Article

Graphene Oxide as an Ideal Substrate for Hydrogen Storage

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Abstract

Organometallic nanomaterials hold the promise for molecular hydrogen (H(2)) storage by providing nearly ideal binding strength to H(2) for room-temperature applications. Synthesizing such materials, however, faces severe setbacks due to the problem of metal clustering. Inspired by a recent experimental breakthrough ( J. Am. Chem. Soc. 2008 , 130 , 6992 ), which demonstrates enhanced H(2) binding in Ti-grafted mesoporous silica, we propose combining the graphene oxide (GO) technique with Ti anchoring to overcome the current synthesis bottleneck for practical storage materials. Similar to silica, GO contains ample hydroxyl groups, which are the active sites for anchoring Ti atoms. GO can be routinely synthesized and is much lighter than silica. Hence, higher gravimetric storage capacity can be readily achieved. Our first-principles computations suggest that GO is primarily made of low-energy oxygen-containing structural motifs on the graphene sheet. The Ti atoms bind strongly to the oxygen sites with binding energies as high as 450 kJ/mol. This is comparable to that of silica and is indeed enough to prevent the Ti atoms from clustering. Each Ti can bind multiple H(2) with the desired binding energies (14-41 kJ/mol-H(2)). The estimated theoretical gravimetric and volumetric densities are 4.9 wt % and 64 g/L, respectively.

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... In that study, 5.5 wt% and 40 g L −1 of hydrogen gas was captured between the modified graphene layers under cryogenic conditions [129]. Graphene oxides and their alkali metal hybrids increased the hydrogen storage capacity of these carriers by increasing the interlayer spacing of graphite sheets [127,129,130]. Nevertheless, even reduced graphene oxide hybridized with various active metals has been unable to meet the DOE requirement so far [130]. ...
... In that study, 5.5 wt% and 40 gL −1 of hydrogen gas was captured between the modified graphene layers under cryogenic conditions [129]. Graphene oxides and their alkali metal hybrids increased the hydrogen storage capacity of these carriers by increasing the interlayer spacing of graphite sheets [127,129,130]. Nevertheless, even reduced graphene oxide hybridized with various active metals has been unable to meet the DOE requirement so far [130]. ...
... Graphene oxides and their alkali metal hybrids increased the hydrogen storage capacity of these carriers by increasing the interlayer spacing of graphite sheets [127,129,130]. Nevertheless, even reduced graphene oxide hybridized with various active metals has been unable to meet the DOE requirement so far [130]. ...
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Globally, reducing CO2 emissions is an urgent priority. The hydrogen economy is a system that offers long-term solutions for a secure energy future and the CO2 crisis. From hydrogen production to consumption, storing systems are the foundation of a viable hydrogen economy. Each step has been the topic of intense research for decades; however, the development of a viable, safe, and efficient strategy for the storage of hydrogen remains the most challenging one. Storing hydrogen in polymer-based carriers can realize a more compact and much safer approach that does not require high pressure and cryogenic temperature, with the potential to reach the targets determined by the United States Department of Energy. This review highlights an outline of the major polymeric material groups that are capable of storing and releasing hydrogen reversibly. According to the hydrogen storage results, there is no optimal hydrogen storage system for all stationary and automotive applications so far. Additionally, a comparison is made between different polymeric carriers and relevant solid-state hydrogen carriers to better understand the amount of hydrogen that can be stored and released realistically.
... Organometallic frameworks, with their well-defined structures and versatile metal centers, introduce unique properties, allowing for precise engineering of redox-active sites and enhancing device performance [135]. Combining them with graphene oxide creates a synergistic effect [136], with graphene oxide's high surface area and excellent electrical conductivity (for rGO) serving as an ideal support matrix [136,137]. This collaboration optimizes charge transfer, stability, and overall electrochemical performance. ...
... The integration of organometallic compounds with graphene oxide nanocomposites represents a promising frontier in the quest for sustainable and eco-friendly energy solutions [137]. This review provides a comprehensive exploration of the achievements and potential of these innovative materials in advancing eco-energy applications. ...
Article
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Combining organometallic frameworks with graphene oxide presents a fresh strategy to enhance the electrochemical capabilities of supercapacitors, contributing to the advancement of sustainable energy solutions. Continued refinement of materials and device design holds promise for broader applications across energy storage and conversion systems. This featured application underscores the inventive utilization of organometallic frameworks on graphene oxide, shedding light on the creation of superior energy storage devices for eco-friendly solutions. This review article delves into the synergistic advancements resulting from the fusion of organometallic frameworks with gra-phene oxide, offering a thorough exploration of their utility in sustainable eco-energy solutions. This review encompasses various facets, including synthesis methodologies, amplified catalytic performances, and structural elucidations. Through collaborative efforts, notable progressions in photocatalysis, photo-voltaics, and energy storage are showcased, illustrating the transformative potential of these hybrids in reshaping solar energy conversion and storage technologies. Moreover, the environmentally conscious features of organometallic-graphene oxide hybrids are underscored through their contributions to environmental remediation, addressing challenges in pollutant elimination, water purification, and air quality enhancement. The intricate structural characteristics of these hybrids are expounded upon to highlight their role in tailoring material properties for specific eco-energy applications. Despite promising advancements, challenges such as scalability and stability are candidly addressed, offering a pragmatic view of the current research landscape. The manuscript concludes by providing insights into prospective research avenues, guiding the scientific community towards surmounting hurdles and fully leveraging the potential of organometallic-graphene oxide hybrids for a sustainable and energy-efficient future.
... When eight hydrogen molecules are adsorbed by Mg-doped GO, a high value of (5.3 wt%) hydrogen storage is reached at 200 K without external pressure. Wang et al. [72][73][74] reported that GO decorated with Pd enhanced the hydrogen storage capacity compared to pristine GO. Moreover transition metal oxides dispersed on GO 73 like GO/V 2 O 5 (1.36 wt%) and GO/TiO 2 (1.26 wt%) also have increased the hydrogen storage capacity compared to that for bare V 2 O 5 (0.16 wt%) and TiO 2 (0.58 wt%). ...
... H 2 adsorption capability of GO frameworks has already been discussed. [67][68][69][70][71][72][73][74] As for the metal-doped GO, there are a lot of positively charged metal atoms and negatively charged oxygen atoms on the graphene sheets. Usually an electrical eld is developed around the metal ion and oxygen to adsorb hydrogen molecules; the metal site is more active to adsorb hydrogen than oxygen sites and the hydroxyl group present on the GO surface lowers the hydrogen storage due to the formation of water. ...
Article
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GO undergoes synergistic interaction with MO nanoparticles and the hybrid can be used as a heterogeneous catalyst for the photocatalytic degradation of dyes.
... [2][3][4] Typically, storage requires the hydrogen molecules to be as densely packed as possible so that the maximum volumetric density can be achieved with the lowest feasible amount of additional material. 5,6 One method of storing hydrogen this way is having other materials absorb the gas within their chemical structure through a process known as physisorption. 7 Hydrogen storage materials such as metal borohydrides have been applied for generating hydrogen with the support of various catalysts, [8][9][10][11] however, a major limitation of using the metal borohydride materials for hydrogen storage lies in their nonrecyclability. ...
Article
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In this study, the hydrogen uptake of five carbon-based materials; graphite flakes, graphene oxide, graphene, multi-walled carbon nanotubes, activated carbon, mesoporous carbon, and carbon microspheres was explored. The characteristic techniques used to confirm the materials included powder X-ray diffraction, attenuated total reflection Fourier transform infrared spectroscopy, transmission electron microscopy, and scanning electron microscopy. Nitrogen adsorption isotherms, Brunnauer-Emmett-Teller surface area and pore size distributions were measured at liquid nitrogen temperature (77K). The hydrogen storage capacity was studied at constant temperature, 77K and pressure from ambient pressure up to 1 bar. This study found that mesoporous carbon had the highest percentage of hydrogen uptake (18%), while activated carbon had the lowest percentage of hydrogen uptake (2%).
... The macroscopic uniformity of GO alignment is mainly determined by processing conditions. These layered GO films can be used for applications of hydrogen storage, membranes, and ion conductors [30][31][32]. Also, GO can be adopted for transparent conductive films, used for flexible electronics, solar cells, batteries, chemical sensors, touch screens, etc. [33][34][35][36][37]. GO-based nanomaterials have been extensively studied for various biomedical applications including bio-sensing, cellular imaging, disease detection, drug-carriers, tissue engineering, and antibacterial materials [38,39]. ...
... The addition of transition metal and alkali metal catalysts can also increase the adsorption capacity of graphene. Graphene materials with the addition of titanium atoms can achieve a hydrogen storage density of 4.9 wt%, while graphene with the addition of lighter metals also shows a significant increase in hydrogen storage capacity [20]. ...
Article
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Nowadays, global warming and energy scarcity have prompted mankind to develop new energy technologies. Given that new energy generation technologies such as solar and wind energy are subject to climatic conditions with factors such as unstable power generation, the storage process of electrical energy is particularly important. Therefore, the importance of hydrogen energy and its storage technology has received increasing attention from researchers based on the advantages of its wide distribution, high calorific value, and lack of greenhouse gas production.This paper summarizes the current research status of various hydrogen storage technologies, and at the same time assesses and compares the gap between each hydrogen storage technology and the commercialization standard. Based on the analysis, two key routes for the future development of hydrogen storage technologies are proposed.
... Therefore, keeping in mind researchers should take all these aspects necessary steps to enhance its dispersibility and to reduce the aggregation of GO. All kinds of surface-modified GO were synthesised via chemical modification or attaching a stabilizer such as a soluble polymer or a surfactant to graft different functional groups on the surfaces [123][124][125]. Introduction of nitrogen bearing groups on GO surface shows paramount significance in uranium removal. ...
Article
Carbon-based adsorbents such as activated carbon, biochar, and graphene materials are the most promising candidates for removing uranium from an aqueous solution. These materials could acquire different surface charges under different pH conditions and therefore are capable of adsorbing diverse uranium species from water. Another significant aspect of carbon-based adsorbents is their tunable surface characteristic to promote the targeted removal of uranium ions. In this review, we have summarized recent studies based on the strategies used for uranium species removal using afore mentioned carbon-based adsorbents. Different techniques used to prepare such adsorbents for the effective removal of uranium from wastewater has been discussed focusing the surface functionalization protocols. Discussions has been furnished on the key mechanisms involved in the uranium removal using the highlighted adsorbentswith reference to adsorption kinetics and isotherm models. The performance of various carbon-based adsorbents has been compared in terms of partition coefficient to assess their usefulness towards uranium removal applications. Further, a concise summary on DFT analysis has been supplied to elucidate uranium removal mechanisms by various carbon adsorbents. It is expected that this article will address the literature gapin the current status of carbon-based adsorbents for uranium removal with the perspectives of future works and challenges in this area.
... Graphene (GR) has attracted a great deal of attention due to its intriguing properties, which include an extremely large surface area (2630 m 2 g − 1 ), high optical transmittance (97.7 %), high mechanical fracture strength (125 GPa), excellent thermal conductivity (5000 W m − 1 K − 1 ), and superb charge-carrier mobility (200,000 cm2 V − 1 s − 1 ) [27][28][29][30][31][32][33][34]. Its exceptional qualities have opened the door to many applications including tissue engineering [35], molecular drug delivery [36], cancer treatment [37], energy storage [38], and catalysis [39], among which BS and GS have piqued the public curiosity [29,34,[40][41][42][43][44][45]. First, graphene-based sensors are more sensitive than silicon-based devices owing to the large specific surface area and atomic thickness of graphene layers, which directly bring complete carbon atoms into touch with analytes [46]. ...
Article
Sensors play a significant role in modern technologies and devices used in industries, hospitals, healthcare, nanotechnology, astronomy, and meteorology. Sensors based upon nanostructured materials have gained special attention due to their high sensitivity, precision accuracy, and feasibility. This review discusses the fabrication of graphene-based biosensors and gas sensors, which have highly efficient performance. Significant developments in the synthesis routes to fabricate graphene-based materials with improved structural and surface properties have boosted their utilization in sensing applications. The higher surface area, better conductivity, tunable structure, and atom-thick morphology of these hybrid materials have made them highly desirable for the fabrication of flexible and stable sensors. Many publications have reported various modification approaches to improve the selectivity of these materials. In the current work, a compact and informative review focusing on the most recent developments in graphene-based biosensors and gas sensors has been designed and delivered. The research community has provided a complete critical analysis of the most robust case studies from the latest fabrication routes to the most complex challenges. Some significant ideas and solutions have been proposed to overcome the limitations regarding the field of biosensors and hazardous gas sensors.
... Hydrogen storage happens under adsorption or absorption over carbon and metallic materials. Carbonaceous materials such as CNTs [149] and graphene [150] have demonstrated great capabilities for the storage of hydrogen. CNTs-G hybrids have theoretically indicated the potential to store hydrogen gas. ...
Article
Due to the global concerns on limited non-renewable energy resources, developing accessible renewable energy systems and expanding electrochemical energy-related devices are serious necessities. Recently, carbon-based metal-free materials have played a crucial role in electrochemical devices. Carbon-based metal-free electrocatalysts have been recognized as proper alternatives for the replacement of frequently used Pt in these devices. Carbon nanotubes-graphene (CNTs-G) hybrids are three-dimensional (3D) carbonaceous structures that have attracted researchers’ interest in the last decade. Because of the unique properties of sp²-hybridized carbon nanostructures viz. superb mechanical, electrical, and catalytic performances, plus recent extensive applications in various aspects, CNTs and graphene families are considered prospective heterostructure materials for next-generation technologies. Moreover, carbon-based materials have demonstrated excellent performance in key reactions like oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER) that occur on the surface of catalysts or electrodes in electrochemical energy conversion/storage devices. The ability to accept functional groups and dopants, create defects, present a large surface area, high porosity, and superior electrolyte penetration, facilitate ion transport, accelerate charge transfer, and capability to form robust attachments between CNTs and graphene have made the CNTs-G hybrid materials suitable candidates in energy-related areas. This review discusses the recent achievements of 3D CNTs-G hybrid heterostructures from synthesis and theoretical concepts to developments and applications in oxygen- and hydrogen- involving electrocatalysts and energy-related devices such as batteries and supercapacitors. Significantly, research gaps and critical issues are identified in order to pave the way for the future study of CNTs-G hybrid materials.
... 44 These characteristics lead to a broad development space in areas such as heterogeneous catalysis, sensors, solar cells, and gas storage. [45][46][47][48][49] Yang et al. synthesized polydispersed graphene sheets modied with an amine derivative, 50 and the amine-functionalized graphene oxide can stabilize metal nanoparticles and distribute them well, avoiding aggregation and thus increasing the catalytic activity. [51][52][53][54][55][56] Recently, Ma et al. prepared a graphene-based Pd hybrid catalyst modied with DNA (called DNA-G-Pd), which could chelate Pd via dative bonding, showing enhanced catalytic activity toward the Suzuki reaction. ...
Article
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Pd-Pd/PdO nanoclusters well dispersed on intercalated graphene oxide (GO) (denoted as GO@PPD-Pd) were prepared and characterized. GO@PPD-Pd exhibited high catalytic activity (a TOF value of 60 705 h-1) during the Suzuki coupling reaction, and it could be reused at least 6 times. The real active centre was Pd(200)-Pd(200)/PdO(110, 102). A change in the Pd facets on the surface of PdO was a key factor leading to deactivation, and the aggregation and loss of active centres was also another important reason. The catalytic mechanism involved heterogeneous catalysis, showing that the catalytic processes occurred at the interface, including substrate adsorption, intermediate formation, and product desorption. The real active centres showed enhanced negative charge due to the transfer of electrons from the carrier and ligands, which could effectively promote the oxidative addition reaction, and Pd(200) and the heteroconjugated Pd/PdO interface generated in situ also participated in the coupling process, synergistically boosting activity. Developed GO@PPD-Pd was a viable heterogeneous catalyst that may have practical applications owing to its easy synthesis and stability, and this synergistic approach can be utilized to develop other transition-metal catalysts.
... Functional groups such as hydroxyls, carbonyls, and carboxyls trap hydrogen molecules via hydrogen bonds that are stronger than the London dispersive force [128]. Moreover, oxygen-containing functional groups not only form gaps between graphene layers but also creates suitable conditions for loading metal nanoparticles in order to create higher hydrogen capacities [10,129]. Graphitic carbons, which are sp 2 hybridized and have a sheet-like structure, interact using van der Waals forces. ...
Article
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With the rapid growth in demand for effective and renewable energy, the hydrogen era has begun. To meet commercial requirements, efficient hydrogen storage techniques are required. So far, four techniques have been suggested for hydrogen storage: compressed storage, hydrogen liquefaction, chemical absorption, and physical adsorption. Currently, high-pressure compressed tanks are used in the industry; however, certain limitations such as high costs, safety concerns, undesirable amounts of occupied space, and low storage capacities are still challenges. Physical hydrogen adsorption is one of the most promising techniques; it uses porous adsorbents, which have material benefits such as low costs, high storage densities, and fast charging–discharging kinetics. During adsorption on material surfaces, hydrogen molecules weakly adsorb at the surface of adsorbents via long-range dispersion forces. The largest challenge in the hydrogen era is the development of progressive materials for efficient hydrogen storage. In designing efficient adsorbents, understanding interfacial interactions between hydrogen molecules and porous material surfaces is important. In this review, we briefly summarize a hydrogen storage technique based on US DOE classifications and examine hydrogen storage targets for feasible commercialization. We also address recent trends in the development of hydrogen storage materials. Lastly, we propose spillover mechanisms for efficient hydrogen storage using solid-state adsorbents.
... Recently, graphene oxide (GO) has received a great attention, which is an oxygenated derivative of graphene, due to its remarkable properties such as large specific surface area, high electrons mobility, prominent mechanical properties with low density and high complex permittivity values enabling it to become a material with bright prospecting in various applications [16][17][18][19][20][21][22][23][24]. GO is a twodimensional carbon-based nanoscale material obtained by oxidization of graphite crystals. ...
Article
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Nano-graphene oxide, nano-(GO), was prepared via a modified Hummer’s method. Hence, superconducting composites of type (GO)x/(Cu0.25Tl0.75)Ba2Ca3Cu4O12−δ, x = 0.00, 0.25, 0.50, 0.75, 1.00, 1.50 and 2.00 wt%, were prepared via the solid-state reaction technique at 850 °C under ambient pressure. The prepared nano-(GO) was characterized using X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy, transmission electron microscopy, high-resolution transmission electron microscopy and the selected-area electron diffraction pattern. The composites samples of type (GO)x/(Cu0.25Tl0.75)Ba2Ca3Cu4O12−δ were characterized using XRD and scanning electron microscopy. The electrical properties of the prepared samples were investigated using the electrical resistivity measurements. The results showed that the samples retained their superconductivity for all x values with a maximum enhancement in the phase formation, the superconducting transition temperature and the activation energy at x = 0.75 wt%.
... In graphene technology, a special role is played by chemically reduced exfoliated graphene oxide (rGO) [1][2][3][4] since this new class of materials enables low-cost and large-scale applications for a wide variety of uses ranging from food packaging 5 to energy conservation 6 and from medical implants 7 to environmental protection. 8 Remarkably, in contrast to pristine graphene, rGO shows better dispersibility in water, polar organic solvents 9 and polymer matrices, which makes it more suitable for many applications such as in nanocomposite materials, 1,10 (bio)sensing, 11,12 and drug delivery. ...
Article
For large-scale graphene applications, such as the production of polymer-graphene nanocomposites, exfoliated graphene oxide (GO) and its reduced form (rGO) are presently considered to be very suitable starting materials, showing enhanced chemical reactivity with respect to pristine graphene, in addition to suitable electronic properties (i.e., tunable band gap). Among other chemical processes, a suitable way to obtain surface decoration of graphene is through a direct one-step Diels-Alder (DA) reaction, e.g. through the use of dienophile or diene moieties. However, the feasibility and extent of decoration largely depends on the specific graphene microstructure that in the case of rGO sheets is not easy to control and generally presents a high degree of inhomogeneity owing to various on-plane functionalization (e.g., epoxide and hydroxyl groups) or in-plane lattice defects. In an effort to gain some insights into the covalent functionalization of variably reduced GO samples, we present a combined experimental and theoretical study on the DA cycloaddition reaction of maleimide, a dienophile functional unit well-suited for chemical conjugation of polymers and macromolecules. In particular, we considered both mildly and strongly reduced GOs. Using thermogravimetry, Raman and X-Ray photoelectron spectroscopy, and elemental analysis we show evidence of variable chemical reactivity of rGO as a function of the residual oxygen content. Moreover, from quantum mechanical calculations carried out at the DFT level on different graphene reaction sites, we provide a more detailed molecular view to interpret experimental findings and to assess the reactivity series of different graphene modifications.
... Graphene film (GF) with high mechanical flexibility, superior electrical conductivity, and high specific surface area shows DOI: 10.1002/advs.202105004 great potentials in supercapacitors, [1][2][3][4] gas sensors, [5,6] hydrogen storage, [7,8] electrodes, [9] and field emission displays. [10,11] The synthetic strategies of GF can be mainly divided into two routes: 1) top-down synthesis from the assembly of graphene flakes and its derivative; [12][13][14][15] this method enables the GF production with relatively low cost, but suffers from the dilemma of graphene thickness uncontrollability and tedious fabrication procedures; 2) bottom-up synthesis from carbon source molecule by chemical vapor deposition (CVD) method. ...
Article
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Graphene films, fabricated by chemical vapor deposition (CVD) method, have exhibited superiorities in high crystallinity, thickness controllability, and large-scale uniformity. However, most synthesized graphene films are substrate-dependent, and usually fragile for practical application. Herein, a freestanding graphene film is prepared based on the CVD route. By using the etchable fabric substrate, a large-scale papyraceous freestanding graphene fabric film (FS-GFF) is obtained. The electrical conductivity of FS-GFF can be modulated from 50 to 2800 Ω sq⁻¹ by tailoring the graphene layer thickness. Moreover, the FS-GFF can be further attached to various shaped objects by a simple rewetting manipulation with negligible changes of electric conductivity. Based on the advanced fabric structure, excellent electrical property, and high infrared emissivity, the FS-GFF is thus assembled into a flexible device with tunable infrared emissivity, which can achieve the adaptive camouflage ability in complicated backgrounds. This work provides an infusive insight into the fabrication of large-scale freestanding graphene fabric films, while promoting the exploration on the flexible infrared camouflage textiles.
... Details for the characterization methods are shown in the SI. Epoxy and hydroxyl groups are in proximity as nearest neighbors but located at the opposite sides of the basal plane, 38 and carboxyl and carbonyl groups are present at the periphery. 39 According to XPS characterization (Table S4), models of FG and OD were determined to be C 70 (C−O− C) 8 (CO) 9 (C−OH) 13 and C 15 (CO) 4 (COOH) 6 , respectively. ...
... GO is a form of graphene with chemical modification and a high oxidation degree, which possesses colloidal stability in biologic media and carries a negative surface charge with the epoxide and hydroxyl functional group [5]. GO is applicable in various fields, such as hydrogen storage [6], catalysis [7], electrochemical devices [8], and separation membranes [9]. In addition, the biological applications of GO have been intensively studied recently because of their potential for bacterial inhibition [10], biosensors [11,12], and drug delivery vectors [13][14][15]. ...
Article
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The mass production of graphene oxide (GO) unavoidably elevates the chance of human exposure, as well as the possibility of release into the environment with high stability, raising public concern as to its potential toxicological risks and the implications for humans and ecosystems. Therefore, a thorough assessment of GO toxicity, including its potential reliance on key physicochemical factors, which is lacking in the literature, is of high significance and importance. In this study, GO toxicity, and its dependence on oxidation level, elemental composition, and size, were comprehensively assessed. A newly established quantitative toxicogenomic-based toxicity testing approach, combined with conventional phenotypic bioassays, were employed. The toxicogenomic assay utilized a GFP-fused yeast reporter library covering key cellular toxicity pathways. The results reveal that, indeed, the elemental composition and size do exert impacts on GO toxicity, while the oxidation level exhibits no significant effects. The UV-treated GO, with significantly higher carbon-carbon groups and carboxyl groups, showed a higher toxicity level, especially in the protein and chemical stress categories. With the decrease in size, the toxicity level of the sonicated GOs tended to increase. It is proposed that the covering and subsequent internalization of GO sheets might be the main mode of action in yeast cells.
... 41 Also, Ti-atom-decorated substrates are promising for hydrogen storage. 42,43 Overall, Ti doping may uniquely improve the photocatalytic activity of 2D J-MoSSe for hydrogen generation by the water-splitting reaction. In this work, we systematically study the geometric, electronic, optical absorption, and surface adsorption properties of doped 2D J-MoSSe with intrinsic vacancies and extrinsic Ti doping. ...
Chapter
The need for renewable and clean energy sources is growing at an alarming rate to keep pace with the human population, keeping in mind the adverse impact of pollution from various non-renewable energy fuels. Hydrogen is a significant replacement of these non-renewable pollution creating energy sources. Thus, hydrogen storage materials have bagged enormous importance in the recent generations. Graphene-based materials have proved their reliability for hydrogen storage applications. The large surface area/volume ratio of graphene nanocomposites play important role for their usage in hydrogen storage. Better hydrogen storage ability and improved adsorption/desorption mechanism is observed when the nanoparticles are dispersed over graphene owing to its high surface area, by attenuating the agglomeration of the nanoparticles and providing better pathways for chemi-physisorption of hydrogen in these nanocomposites. In this chapter, the recent advances of graphene and graphene-based materials, and their composites for hydrogen storage devices have been discussed. Keywords: Doping; Graphene composites; Green energy; Hydrogen storage; Spillover.
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The hydrogen storage capacity of M-decorated (M ¼ Li and B) 2D beryllium hydride is investigated using first-principles calculations based on density functional theory. The Li and B atoms were calculated to be successfully and chemically decorated on the Surface of the a-BeH2 monolayer with a large binding energy of 2.41 and 4.45eV/atom. The absolute value was higher than the cohesive energy of Li and B bulk (1.68, 5.81eV/atom). Hence, the Li and B atoms are strongly bound on the beryllium hydride monolayer without clustering. Our findings show that the hydrogen molecule interacted weakly with B/a-BeH2(B-deco- rated beryllium hydride monolayer) with a low adsorption energy of only 0.0226 eV/H2 but was strongly adsorbed on the introduced active site of the Li atom in the decorated BeH2 with an improved adsorption energy of 0.472 eV/H2. Based on density functional theory, the gravimetric density of 28H2/8li/a-BeH2) could reach 14.5 wt.% higher than DOE's target of 6.5 wt. % (the criteria of the United States Department of Energy). Therefore, our research indicates that the Li-decorated beryllium hydride monolayer could be a candidate for further investigation as an alternative material for hydrogen storage. © 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
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The hydrogen storage capacity of M-decorated (M = Li and B) 2D beryllium hydride is investigated using first-principles calculations based on density functional theory. The Li and B atoms were calculated to be successfully and chemically decorated on the Surface of the α-BeH2 monolayer with a large binding energy of 2.41 and 4.45eV/atom. The absolute value was higher than the cohesive energy of Li and B bulk (1.68, 5.81eV/atom). Hence, the Li and B atoms are strongly bound on the beryllium hydride monolayer without clustering. Our findings show that the hydrogen molecule interacted weakly with B/α-BeH2(B-decorated beryllium hydride monolayer) with a low adsorption energy of only 0.0226 eV/H2 but was strongly adsorbed on the introduced active site of the Li atom in the decorated BeH2 with an improved adsorption energy of 0.472 eV/H2. Based on density functional theory, the gravimetric density of 28H2/8li/α-BeH2) could reach 14.5 wt.% higher than DOE's target of 6.5 wt. % (the criteria of the United States Department of Energy). Therefore, our research indicates that the Li-decorated beryllium hydride monolayer could be a candidate for further investigation as an alternative material for hydrogen storage.
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Using hydrogen energy as an alternative renewable source of fuel is no longer an unrealized dream, it now has real-world application. The influence of nanomaterials on various aspects of hydrogen energy, such as hydrogen production, storage, and safety, is considerable. In this review, we present a brief overview of the nanomaterials that have been used as photocatalysts during hydrogen production. The use of nanomaterials and nanomaterial composites for hydrogen storage is also reviewed. The specific use of graphene and its associated nanocomposites, as well as the milestones reached through its application are elaborated. The need to widen the applicability of graphene and its allied forms for hydrogen energy applications is stressed in the future perspectives. Hydrogen energy is our future hope as an alternative renewable fuel, and graphene has the potential to become the future of hydrogen energy generation.
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Hydrogen adsorption on pristine graphene (PG), graphene with defect (GD), and transition metal (TM) (Ag, Au, Cu, and Fe) doped graphene is systematically investigated for potential hydrogen storage using density functional theory. The stability of the TM atom doped graphene has been analysed by studying the binding energy and the electron density distribution. The TM atom-doped GD shows better binding energy and electron density overlap than PG; therefore, the TM/GD system has been considered and analysed for hydrogen adsorption. The hydrogen adsorption property is studied by examining the adsorption energy, mode of H2, density of states (DOS), charge density difference, and Löwdin charges before and after adsorption to find a better TM/GD system for hydrogen storage. The Fe/GD system shows higher hydrogen adsorption energy and hydrogen in its stable Kubas mode. Furthermore, two to five H2 molecule adsorption and desorption is studied. The increase in the number of H2, which changes the DOS at the Fermi level, suggests that one can predict H2 concentration by measuring conductivity changes. The present work is focused on studying the interaction between H2 and TM/GD systems, which will help understand the basic adsorption mechanism for practical hydrogen storage.
Article
In the current work, symmetrically carbazole linked Zn(II) and Co(II) phthalocyanines (Pcs) have been succesfully synthesized and characterized through Fouirer Transform Infrared (FT-IR), Ultraviolet-visible (UV-Vis) spectroscopies, Matrix-assisted laser desorption - ionisation-time of flight mass spectrometry (MALDI-TOF MS) along with proton and carbon Nuclear Magnetic Resonance (¹H and ¹³C- NMR) spectroscopies.. The electrochemical performance of the targeted metallo- phthalocyanines was demonstrated with cyclic voltammetry (CV), and square wave voltammetry (SWV). The final phthalocyanines were used as hybrid materials for the preparation of the modified glassy carbon electrode (GCE). The hybrid materials were then deposited on GCE via an electropolymerization or electrodeposition method. The surface morphologies of the hybrid electrodes were investigated using scanning electron microscope/energy dispersive using X-Ray (SEM/EDX). IR, UV-Vis and Raman spectroscopies were carried out to evaluate the surface of the hybrid electrodes. The N-ethylcarbazole moiety and redox active Zn(II), Co(II) metal centers were employed in order to improve the sensing performance of targeted compounds. Furthermore, hybrid material-graphene modified GCEs have been designed to compare and rise the analytical activity. The sensing properties of the designed electrodes was investigated to detect electrochemically active biomolecules namely, dopamine (DA), ascorbic acid (AA), and uric acid (UA) in both phosphate buffered saline (PBS) and tap water sample. The Grp/ Ply(Car-CoPc)/GCE electrode was only detected DA with a limit of detection (LOD) of 16 nM. On the other hand, LOD values of Grp(Car-CoPc)/GCE were determined by voltammetric analyses as 3.38 μM and 0.62 μM for AA and UA, respectively. Sensing performances of the designed electrodes were eximined for the concurrently determination of DA and UA using differential pulse voltammetry (DPV) method.
Article
Proton conductors, particularly hydrated solid membranes, have various applications in sensors, fuel cells, and cellular biological systems. Unraveling the intrinsic proton transfer mechanism is critical for establishing the foundation of proton conduction. Two scenarios on electrical conduction, the Grotthuss and the vehicle mechanisms, have been reported by experiments and simulations. But separating and quantifying the contributions of these two components from experiments is difficult. Here, we present the conductive behavior of a two-dimensional layered proton conductor, graphene oxide membrane (GOM), and find that proton hopping is dominant at low water content, while ion diffusion prevails with increasing water content. This change in the conduction mechanism is attributable to the layers of water molecules in GOM nanosheets. The overall conductivity is greatly improved by forming one layer of water molecules. It reaches the maximum with two layers of water molecules, resulting from creating a complete hydrogen-bond network within GOM. When more than two layers of water molecules enter the GOM nanosheets, inducing the breakage of the ordered lamellar structure, protons spread in both in-plane and out-of-plane directions inside the GOM. Our results validate the existence of two conduction mechanisms and show their distinct contributions to the overall conductivity. Furthermore, these findings provide an optimization strategy for the design of realizing the fast proton transfer in materials with water participation.
Article
The latest structural model of graphene oxide (GO) consists of two parts: large sheet of lightly oxidized graphene (FG) and small highly oxidized debris (ODs) in the form of “GO=FG+ODs”. Given the new model, this study focused on the roles of ODs played in the adsorption of aromatic compounds on GO. Firstly, π-conjugation, hydrophobicity, and surfaces charges of GO were examined to reveal how ODs stripping affected the surface property. Then, microscopic adsorption process was captured to reveal the behaviour of ODs during the adsorption process. Finally, isothermal and kinetics experiments were carried out to explore the effects of ODs striping on adsorption capacity and adsorption rate of GO. The results showed that ODs play key roles during the adsorption process and serves as important adsorption sites towards aromatic compounds. The adsorption was enhanced upon the significant stripping of ODs and was mainly attributed to the weakened electrostatic repulsion, increased π-π interaction, and increased hydrophobic interaction between GO and the aromatic compounds. Therefore, ODs should be considered during the development of GO-based environmental nanomaterials for applications.
Article
Graphene oxide (GO) nanomaterials are being extensively explored for a wide spectrum of applications, ranging from water desalination to fuel cell applications, due to their tunable mechanical, thermal, and electrical properties. In this paper, we have investigated the influence of the hydrophobic extent on the adsorption of water on 2D GO surfaces by performing a series of grand canonical Monte Carlo simulations at various relative pressures, P/P0, at 298 K and discuss the implications of our findings on proton transport characteristics. HR is defined as the ratio of the hydrophobic to hydrophilic areas on the GO surface. The structure of adsorbed water is studied by analyzing density distributions and hydrogen bonds. At moderate relative pressures of P/P0 < 0.6, a monolayer of adsorbed water, spanning the hydrophilic and hydrophobic regions of the GO surface, is observed for HR = 0, 0.5 and 1, and at higher pressures, a percolating hydrogen-bonded network is formed, which results in the formation of a thick water film. At intermediate water pressures, bridging water networks form across the hydrophobic regions. The GO surface of HR = 1 is seen to have a strong signature of a Janus surface, displaying increased fluctuations in adsorbed water molecules and hydrogen bonds. Our results suggest that if there is sufficient hydrophilicity on the GO surface, a relative humidity between 70 and 80% results in the formation of a fully formed contact water layer hydrogen-bonded with the surface functional groups along with a second layer of adsorbed water molecules. This coincides with hydration levels at which a maximum in the proton conductivity has been reported on 2D GO surfaces. Molecular dynamics simulations reveal a higher reorientational relaxation time at lower water hydration and the rotational entropy of interfacial water at lower hydration is higher than that of bulk water, indicating broader rotational phase space sampling.
Chapter
A key step in the preparation of single‐atom catalysts is related to the choice of the support, since it allows or not the deposition or embedding of the metal atom in a strongly interacting environment. To reach such atomic dispersion, and thus avoid clustering, metal adsorption energy on a particular support has to be higher than its cohesive energy. In this sense, the use of theoretical and computational methods has been very valuable to describe, at the atomic scale, the geometric and electronic properties of oxide surfaces and carbon‐based supports. The adsorption mode of a single‐metal atom on those supports, which may (or may not) present defects, as well as the induced modifications of the electronic structures have helped experimentalists to determine efficient metal–support combinations for catalysis applications. This review tentatively summarizes recent efforts to better understand metal–support interactions on carbon as well as oxide supports, with the aim of describing and rationalizing the catalytic results by means of reaction pathway investigations, including spillover phenomena, thanks to density functional theory.
Article
Development of empirical potentials with accurate parameterization is indispensable while modeling large-scale systems. Herein, we report accurate parameterization of an anisotropic dressed pairwise potential model (PPM) for probing the adsorption of noble gases, He, Ne, Ar and Kr on boron nitride sheets. For the noble gas binding on B48N48H24, we carried out a least-squares fit analysis of the dispersion and dispersionless contributions of the interaction potential separately. The transferability of the parameters for a range of molecular model systems of boron nitride is further established. The dressed PPM is then used in conjunction with a global optimization technique, namely particle swarm optimization (PSO) to assess the possibility of performing large-scale simulations with the PPM-PSO methodology. The results obtained for the adsorption of 2-5 noble gases on BN sheets establish the proof-of-concept, encouraging the pursuit of large-scale simulations using the PPM-PSO approach.
Article
Development of excellent surface-enhanced Raman scattering (SERS) substrate with high sensitivity, low limit of detection (LOD), good uniformity and high stability are still challenging in practical application. Herein, we prepared a diamond-multilayer graphene nanohybrid (DMGN) film with unique three-dimensional (3D) porous wall-like morphology as a new SERS substrate, through a microwave plasma chemical vapor deposition (MPCVD) method. A simple wet-chemical oxidation treatment performed on DMGN substrate resulted in an obvious improvement in LOD value, from 10⁻⁹ mol/L to 10⁻¹¹ mol/L, and enhancement factor (EF), from 4.2 × 10⁴ to 3.9 × 10⁶, for the detection of Rhodamine B (RhB), simultaneously along with good homogeneity and long-term stability. More importantly, the oxidized DMGN (ODMGN) substrate also exhibited good SERS performance for the detection of a real explosive (FOX-7), including low LOD of 10⁻⁶ mol/L and large EF of 527. Finally, first-principles density functional theory (DFT) simulation revealed that SERS enhancement of ODMGN substrate was mainly attributed to the transfer electron between HN- functional group of FOX-7 and the -OH and O functional groups of ODMGN substrate. These unique 3D porous nanohybrid films showed momentous potential to realize a SERS substrate with excellent performance.
Article
Electrochemical energy storage has become a key part of portable medical and electronic devices, as well as ground and aerial vehicles. Unfortunately, conventionally produced supercapacitors and batteries often cannot be easily integrated into many emerging technologies such as smart textiles, smart jewelry, paper magazines or books, and packages with data-collection or other unique capabilities, electrical cables, flexible wearable electronics and displays, flexible solar cells, epidermal sensors, and others in order to enhance their design aesthetics, convenience, system simplicity, and reliability. In addition, conventional energy storage devices that cannot conform to various shapes, are typically limited to a single function, and cannot additionally provide, for example, load bearing functionality or impact/ballistic protection to reduce the system weight or volume. Commercial devices cannot be activated by various stimuli, be able to self-destroy or biodegrade over time, trigger drug release, operate as sensors, antennas, or actuators. However, a growing number of future technologies will demand batteries and hybrid devices with the abilities to seamlessly integrate into systems and adapt to various shapes, forms, and design functions. Here we summarize recent progress and challenges made in the development of mostly nanostructured and nanoengineered materials as well as fabrication routes for energy storage devices that offer (i) multifunctionality, (ii) mechanical resiliency and flexibility and (iii) integration for more elegant, lighter, smaller and smarter designs. The geometries of device structures and materials are considered to critically define their roles in mechanics and functionality. With these understandings, we outline a future roadmap for the development, scaleup, and manufacturing of such materials and devices.
Article
In this work, we synthesized a novel, free-standing, flexible sodium-bentonite-fabricated graphene (SBG) composite membrane. The prepared SBG membrane was successfully employed for the selective separation of oil and water. SBG-fabricated filter paper and cotton cloth membranes were easily prepared using simple vacuum filtration and coating methods. The SBG composite membrane exhibited switchable wettability properties, which rendered it capable of switching the surface into either hydrophilic/oleophobic or hydrophobic/oleophilic with the selective treatment of water or oil/organic solvent, respectively. The prepared SBG composite was characterized using X-ray diffraction, thermo-gravimetric analysis, X-ray photoelectron spectroscopy and scanning electron microscopy. The as-prepared membrane has high efficiency (>98%) to separate oil–water mixtures, a good recyclability (96% efficiency after 10 cycles), a high flux of 625 Lm⁻² h⁻¹, and a good oil rejection ratio (>97%). The SBG composite can easily be scaled to separate the oil–water mixture for industrial applications. Furthermore, the advantages of the membrane are its easy preparation, self-cleaning property, switchable wettability property (hydrophilic/oleophobic to hydrophobic/oleophilic and vice versa), high flux and excellent recyclability for the selective separation of oil/organic solvents and water from their mixtures.
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A multiple robot control architecture including a plurality of robotic agricultural machines including a first and second robotic agricultural machine. Each robotic agricultural machine including at least one controller configured to implement a plurality of finite state machines Within an individual robot control architecture (IRCA) and a global information module (GIM) communicatively coupled to the IRCA. The GIMs of the first and second robotic agricultural machines being configured to cooperate to cause said first robotic agricultural machine and said second agricultural machine to perform at least one agricultural task.
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The detailed chemical structure of graphite oxide (GO), a layered material prepared from graphite almost 150 years ago and a precursor to chemically modified graphenes, has not been previously resolved because of the pseudo-random chemical functionalization of each layer, as well as variations in exact composition. Carbon-13 (13C) solid-state nuclear magnetic resonance (SSNMR) spectra of GO for natural abundance 13C have poor signal-to-noise ratios. Approximately 100% 13C-labeled graphite was made and converted to 13C-labeled GO, and 13C SSNMR was used to reveal details of the chemical bonding network, including the chemical groups and their connections. Carbon-13–labeled graphite can be used to prepare chemically modified graphenes for 13C SSNMR analysis with enhanced sensitivity and for fundamental studies of 13C-labeled graphite and graphene.
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We present an efficient scheme for calculating the Kohn-Sham ground state of metallic systems using pseudopotentials and a plane-wave basis set. In the first part the application of Pulay's DIIS method (direct inversion in the iterative subspace) to the iterative diagonalization of large matrices will be discussed. Our approach is stable, reliable, and minimizes the number of order N-atoms(3) operations. In the second part, we will discuss an efficient mixing scheme also based on Pulay's scheme. A special ''metric'' and a special ''preconditioning'' optimized for a plane-wave basis set will be introduced. Scaling of the method will be discussed in detail for non-self-consistent calculations. It will be shown that the number of iterations required to obtain a specific precision is almost independent of the system size. Altogether an order N-atoms(2) scaling is found for systems up to 100 electrons. If we take into account that the number of k points can be implemented these algorithms within a powerful package called VASP (Vienna ab initio simulation package). The program and the techniques have been used successfully for a large number of different systems (liquid and amorphous semiconductors, liquid simple and transition metals, metallic and semiconducting surfaces, phonons in simple metals, transition metals, and semiconductors) and turned out to be very reliable.
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Solid-state 13C NMR spectra of graphite oxide (GO) and its derivatives prompt us to propose a new structural model. The spectra of GO treated with KI and the course of the thermal decomposition of GO reveal the presence of epoxide groups, responsible for the oxidating nature of the material. GO is built of aromatic “islands” of variable size which have not been oxidized, and are separated from each other by aliphatic 6-membered rings containing C–OH, epoxide groups and double bonds. The carbon grid is nearly flat; a small degree of warping is caused by the carbons attached to OH groups, which are in a slightly distorted tetrahedral configuration.
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The exact density functional for the ground-state energy is strictly self-interaction-free (i.e., orbitals demonstrably do not self-interact), but many approximations to it, including the local-spin-density (LSD) approximation for exchange and correlation, are not. We present two related methods for the self-interaction correction (SIC) of any density functional for the energy; correction of the self-consistent one-electron potenial follows naturally from the variational principle. Both methods are sanctioned by the Hohenberg-Kohn theorem. Although the first method introduces an orbital-dependent single-particle potential, the second involves a local potential as in the Kohn-Sham scheme. We apply the first method to LSD and show that it properly conserves the number content of the exchange-correlation hole, while substantially improving the description of its shape. We apply this method to a number of physical problems, where the uncorrected LSD approach produces systematic errors. We find systematic improvements, qualitative as well as quantitative, from this simple correction. Benefits of SIC in atomic calculations include (i) improved values for the total energy and for the separate exchange and correlation pieces of it, (ii) accurate binding energies of negative ions, which are wrongly unstable in LSD, (iii) more accurate electron densities, (iv) orbital eigenvalues that closely approximate physical removal energies, including relaxation, and (v) correct longrange behavior of the potential and density. It appears that SIC can also remedy the LSD underestimate of the band gaps in insulators (as shown by numerical calculations for the rare-gas solids and CuCl), and the LSD overestimate of the cohesive energies of transition metals. The LSD spin splitting in atomic Ni and $s$-${}d$ interconfigurational energies of transition elements are almost unchanged by SIC. We also discuss the admissibility of fractional occupation numbers, and present a parametrization of the electron-gas correlation energy at any density, based on the recent results of Ceperley and Alder.
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An exact stochastic simulation of the Schroedinger equation for charged Bosons and Fermions was used to calculate the correlation energies, to locate the transitions to their respective crystal phases at zero temperature within 10 percent, and to establish the stability at intermediate densities of a ferromagnetic fluid of electrons.
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Although graphite is known as one of the most chemically inert materials, we have found that graphene, a single atomic plane of graphite, can react with atomic hydrogen, which transforms this highly conductive zero-overlap semimetal into an insulator. Transmission electron microscopy reveals that the obtained graphene derivative (graphane) is crystalline and retains the hexagonal lattice, but its period becomes markedly shorter than that of graphene. The reaction with hydrogen is reversible, so that the original metallic state, the lattice spacing, and even the quantum Hall effect can be restored by annealing. Our work illustrates the concept of graphene as a robust atomic-scale scaffold on the basis of which new two-dimensional crystals with designed electronic and other properties can be created by attaching other atoms and molecules.
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Transition metal (TM) atoms bound to fullerenes are proposed as adsorbents for high density, room temperature, ambient pressure storage of hydrogen. C60 or C48B12 disperses TMs by charge transfer interactions to produce stable organometallic buckyballs (OBBs). A particular scandium OBB can bind as many as 11 hydrogen atoms per TM, ten of which are in the form of dihydrogen that can be adsorbed and desorbed reversibly. In this case, the calculated binding energy is about 0.3 eV/H(2), which is ideal for use on board vehicles. The theoretical maximum retrievable H2 storage density is approximately 9 wt %.
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We perform an extensive combinatorial search for optimal nanostructured hydrogen-storage materials among various metal-decorated polymers using first-principles density-functional calculations. We take into account the zero-point vibration as well as the pressure- and temperature-dependent adsorption-desorption probability of hydrogen molecules. An optimal material we identify is Ti-decorated cis-polyacetylene with reversibly usable gravimetric and volumetric density of 7.6 wt % and 63 kg/m(3), respectively, near ambient conditions. We also propose "thermodynamically usable hydrogen capacity" as a criterion for comparing different storage materials.
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Using first-principles density-functional electronic structure calculations, we propose functionalized organic molecules decorated with titanium atoms as high-capacity hydrogen storage materials. We study six kinds of functional groups which form complexes with Ti atoms and find that each complex is capable of binding up to six H2 molecules. Among such complexes, Ti-decorated ethane-1,2-diol can store H2’s with the maximum gravimetric density of 13 wt% and, under ambient conditions, a practically usable capacity of 5.5 wt%. We also present various forms of storage materials which are obtained by modifying well-known nanomaterials using Ti-functional group complexes.
Article
We propose a system that can store molecular hydrogen in densities up to ∼100 g/L. Our ab initio calculations predict the existence of an oxidized calcium dihydrogen complex, which holds up to eight H2, i.e., Ca(ion)(H2)8. The dihydrogen binding to the Ca is via a weak electron-donation mechanism from the occupied H2 σ orbital to the unoccupied, but bound, Ca 3d orbitals. Because of the high concentration of the hydrogen in such complexes, even in calcium-intercalated pillared graphite, one can obtain reversible hydrogen storage denser than that of liquid hydrogen, 70 g/L.
Article
We study the pyridinelike nitrogen-doped graphene (PNG) with dispersed transition metal (TM) atoms as a potential hydrogen storage medium using the pseudopotential density functional method. It is found that highly localized states near the Fermi level, which are derived from the nitrogen defects, contribute to strong TM bindings and favorable hydrogen adsorption in the PNG. The strong TM binding prevents the metal aggregation and improves the material stability. The hydrogen molecular binding energy in TM+PNG complex is shown to be optimistic for room temperature storage and release.
Article
Physical Sciences SymposiaAtomic and Electronic Structure of Graphene-OxideArticle author querymkhoyan k [PubMed] [Google Scholar]contryman a [PubMed] [Google Scholar]silcox j [PubMed] [Google Scholar]stewart d [PubMed] [Google Scholar]eda g [PubMed] [Google Scholar]mattevi c [PubMed] [Google Scholar]miller s [PubMed] [Google Scholar]chhowalla m [PubMed] [Google Scholar]KA Mkhoyana1, AW Contrymana2, J Silcoxa2, DA Stewarta2, G Edaa3, C Mattevia3, S Millera3 and M Chhowallaa3a1 University of Minnesota
Article
Carbon materials have been at the forefront of hydrogen storage research. However, without improvements in the hydrogen binding strength, as provided by transition-metal dopants, they will not meet practical targets. We performed ab initio density functional theory simulations on titanium-atom dopants adsorbed on the native defects of an (8,0) nanotube. Adsorption on a vacancy strongly binds titanium, preventing nanoparticle coalescence (a major issue for atomic dopants). The defect-modulated Ti adsorbs five H2 molecules with H2 binding energies in the range from −0.2 to −0.7 eV/H2, desirable for practical applications. Molecular dynamics simulations indicate that this complex is stable at room temperature, and simulation of a C112Ti16H160 unit cell finds that a structure with 7.1 wt % hydrogen storage is stable.
Article
A Monte Carlo based scheme for the formation of graphite oxide (GO) was developed and implemented. A Rosenbluth factor was used to select intermediate structures in an attempt to form stable, low-energy, and realistic GO. The scheme resulted in the production of GO that has an interplanar spacing of 5.8 Å, in good agreement with the experimental value (5.97 Å). Epoxide and hydroxyl functional groups dominate the basal planes, a finding that is consistent with experiment. Individual sheets are wrinkled with an average root-mean-square deviation of 0.33 ± 0.04 Å. Hydrogen bonding between hydroxyl groups and between hydroxyl and epoxide groups has significant impact on the stability of many structures. Molecular dynamics simulations, guided by forces from electronic structure calculations, were performed to examine the behavior of GO when heated to room (300 K) and thermal exfoliation (1323 K) temperatures. Hydrogen-transfer reactions that catalyze the migration of epoxide groups were observed at both temperatures. At 1323 K, the evolution of CO was also observed, and the mechanisms for this process have been elucidated. This process provides a plausible explanation of the source of the 30% carbon mass loss that occurs during the experimental thermal exfoliation of GO. The mechanical properties of GO were examined and compared to those of graphene. Although significantly weaker in tensile deformation than graphene (fracture stress = 116 GPa), GO (fracture stress = 63 GPa) potentially has great strength provided it does not contain large holes. An epoxide line defect, recently reported as playing an important role in the failure of oxidized graphene, was also examined. The observed very large fracture stress (97 GPa) suggests that this structure does not play a major role in the fracture process.
Article
An approach for electronic structure calculations is described that generalizes both the pseudopotential method and the linear augmented-plane-wave (LAPW) method in a natural way. The method allows high-quality first-principles molecular-dynamics calculations to be performed using the original fictitious Lagrangian approach of Car and Parrinello. Like the LAPW method it can be used to treat first-row and transition-metal elements with affordable effort and provides access to the full wave function. The augmentation procedure is generalized in that partial-wave expansions are not determined by the value and the derivative of the envelope function at some muffin-tin radius, but rather by the overlap with localized projector functions. The pseudopotential approach based on generalized separable pseudopotentials can be regained by a simple approximation.
Article
Based on density functional calculations, optimized structures of graphite oxide are found for various coverages by oxygen and hydroxyl groups, as well as their ratio corresponding to the minimum of total energy. The model proposed describes well-known experimental results. In particular, it explains why it is so difficult to reduce the graphite oxide up to pure graphene. Evolution of the electronic structure of graphite oxide with the coverage change is investigated.
Article
Hydrogen storage : A family of Ti‐substituted boranes (see figure) having optimum electronic structures and the ability to absorb hydrogen has been designed computationally. Substantial binding energies and gravimetric densities of hydrogen storage show their potential as hydrogen storage materials. The computational study invites experimental synthesis of the novel borane family and offers a guide to searching for new hydrogen storage materials. magnified image Based on the Wade–Mingos n +1 rule for the closo ‐boranes (B n H n ²⁻ ), a family of Ti‐substituted closo ‐boranes has been designed computationally. Due to the isolobal relation of Ti to a BH ²⁻ group, these Ti‐substituted boranes have n +1 pairs of skeletal electrons to fulfill the bonding requirement for such stable cages. The reported representatives, B 4 H 4 Ti 2 H 2 in particular, not only have stable electronic structures but also superior capability to adsorb hydrogen. The optimal binding energies and high gravimetric densities of hydrogen storage indicate their potential to store hydrogen for practical applications. Simultaneously achieving electronic stability and optimal hydrogen uptake may provide a way of overcoming the issue of aggregation in designing transition‐metal‐decorated hydrogen storage materials. This study invites experimental realization of novel boranes and provides new ideas for searching for hydrogen storage materials.
Article
Step-by-step controllable thermal reduction of individual graphene oxide sheets, incorporated into multiterminal field effect devices, was carried out at low temperatures (125-240 degrees C) with simultaneous electrical measurements. Symmetric hysteresis-free ambipolar (electron- and hole-type) gate dependences were observed as soon as the first measurable resistance was reached. The conductivity of each of the fabricated devices depended on the level of reduction (was increased more than 10(6) times as reduction progressed), strength of the external electrical field, density of the transport current, and temperature.
Article
Significant enhancement in mechanical stiffness (10-200%) and fracture strength (approximately 50%) of graphene oxide paper, a novel paperlike material made from individual graphene oxide sheets, can be achieved upon modification with a small amount (less than 1 wt %) of Mg(2+) and Ca(2+). These results can be readily rationalized in terms of the chemical interactions between the functional groups of the graphene oxide sheets and the divalent metals ions. While oxygen functional groups on the basal planes of the sheets and the carboxylate groups on the edges can both bond to Mg(2+) and Ca(2+), the main contribution to mechanical enhancement of the paper comes from the latter.
Article
We elucidate the atomic and electronic structure of graphene oxide (GO) using annular dark field imaging of single and multilayer sheets and electron energy loss spectroscopy for measuring the fine structure of C and O K-edges in a scanning transmission electron microscope. Partial density of states and electronic plasma excitations are also measured for these GO sheets showing unusual pi* + sigma* excitation at 19 eV. The results of this detailed analysis reveal that the GO is rough with an average surface roughness of 0.6 nm and the structure is predominantly amorphous due to distortions from sp3 C-O bonds. Around 40% sp3 bonding was found to be present in these sheets with measured O/C ratio of 1:5. These sp2 to sp3 bond modifications due to oxidation are also supported by ab initio calculations
Article
Owing to their high uptake capacity at low temperature and excellent reversibility kinetics, metal-organic frameworks have attracted considerable attention as potential solid-state hydrogen storage materials. In the last few years, researchers have also identified several strategies for increasing the affinity of these materials towards hydrogen, among which the binding of H(2) to unsaturated metal centers is one of the most promising. Herein, we review the synthetic approaches employed thus far for producing frameworks with exposed metal sites, and summarize the hydrogen uptake capacities and binding energies in these materials. In addition, results from experiments that were used to probe independently the metal-hydrogen interaction in selected materials will be discussed.
Article
We present a sampling method for Brillouin-zone integration in metals which converges exponentially with the number of sampling points, without the loss of precision of normal broadening techniques. The scheme is based on smooth approximants to the delta and step functions which are constructed to give the exact result when integrating polynomials of a prescribed degree. In applications to the simple-cubic tight-binding band as well as to band structures of simple and transition metals, we demonstrate significant improvement over existing methods. The method promises general applicability in the fields of total-energy calculations and many-body physics.
Article
Generalized gradient approximations (GGA{close_quote}s) for the exchange-correlation energy improve upon the local spin density (LSD) description of atoms, molecules, and solids. We present a simple derivation of a simple GGA, in which all parameters (other than those in LSD) are fundamental constants. Only general features of the detailed construction underlying the Perdew-Wang 1991 (PW91) GGA are invoked. Improvements over PW91 include an accurate description of the linear response of the uniform electron gas, correct behavior under uniform scaling, and a smoother potential. {copyright} {ital 1996 The American Physical Society.}
Article
We report a first-principles study, which demonstrates that a single Ti atom coated on a single-walled nanotube (SWNT) binds up to four hydrogen molecules. The first H2 adsorption is dissociative with no energy barrier while the other three adsorptions are molecular with significantly elongated H-H bonds. At high Ti coverage we show that a SWNT can strongly adsorb up to 8 wt % hydrogen. These results advance our fundamental understanding of dissociative adsorption of hydrogen in nanostructures and suggest new routes to better storage and catalyst materials.
Article
Recent efforts in finding materials suitable for storing hydrogen with large gravimetric density have focused attention on carbon-based nanostructures. Unfortunately, pure carbon nanotubes and fullerenes are unsuitable as hydrogen storage materials because of the weak bonding of the hydrogen molecules to the carbon frame. It has been shown very recently that coating of carbon nanostructures with isolated transition metal atoms such as Sc and Ti can increase the binding energy of hydrogen and lead to high storage capacity (up to 8 wt % hydrogen, which is 1.6 times the U.S. Department of Energy target set for 2005). This prediction has led to a great deal of excitement in the fuel cell community [see The Fuel Cell Review, http://fcr.iop.org/articles/features/2/7/4]. However, this prediction depends on the assumption that the metal atoms coated on the fullerene surface will remain isolated. Using first-principles calculations based on density functional theory, we show that Ti atoms would prefer to cluster on the C60 surface, which can significantly alter the nature of hydrogen bonding, thus affecting not only the amount of stored hydrogen but also their thermodynamics and kinetics.
Article
The storage of gases in porous adsorbents, such as activated carbon and carbon nanotubes, is examined here thermodynamically from a systems viewpoint, considering the entire adsorption-desorption cycle. The results provide concrete objective criteria to guide the search for the "Holy Grail" adsorbent, for which the adsorptive delivery is maximized. It is shown that, for ambient temperature storage of hydrogen and delivery between 30 and 1.5 bar pressure, for the optimum adsorbent the adsorption enthalpy change is 15.1 kJ/mol. For carbons, for which the average enthalpy change is typically 5.8 kJ/mol, an optimum operating temperature of about 115 K is predicted. For methane, an optimum enthalpy change of 18.8 kJ/mol is found, with the optimum temperature for carbons being 254 K. It is also demonstrated that for maximum delivery of the gas the optimum adsorbent must be homogeneous, and that introduction of heterogeneity, such as by ball milling, irradiation, and other means, can only provide small increases in physisorption-related delivery for hydrogen. For methane, heterogeneity is always detrimental, at any value of average adsorption enthalpy change. These results are confirmed with the help of experimental data from the literature, as well as extensive Monte Carlo simulations conducted here using slit pore models of activated carbons as well as atomistic models of carbon nanotubes. The simulations also demonstrate that carbon nanotubes offer little or no advantage over activated carbons in terms of enhanced delivery, when used as storage media for either hydrogen or methane.
Article
Intermolecular interactions between H2 and ligands, metals, and metal-ligand complexes determine the binding affinities of potential hydrogen storage materials (HSM), and thus their extent of potential for practical use. A brief survey of current activity on HSM is given. The key issue of binding strengths is examined from a basic perspective by surveying the distinct classes of interactions (dispersion, electrostatics, orbital interactions) in first a general way, and then in the context of calculated binding affinities for a range of model systems.
Article
A metal-organic framework, PCN-9, containing entatic metal centers, has been synthesized and crystallographically characterized. The H2 and CH4 adsorption enthalpies of PCN-9 are among the highest reported thus far.
Article
Use of the tritopic bridging ligand 1,3,5-benzenetristetrazolate (BTT3-) enables formation of [Mn(DMF)6]3[(Mn4Cl)3(BTT)8(H2O)12]2.42DMF.11H2O.20CH3OH, featuring a porous metal-organic framework with a previously unknown cubic topology. Crystals of the compound remain intact upon desolvation and show a total H2 uptake of 6.9 wt % at 77 K and 90 bar, which at 60 g H2/L provides a storage density 85% of that of liquid hydrogen. The material exhibits a maximum isosteric heat of adsorption of 10.1 kJ/mol, the highest yet observed for a metal-organic framework. Neutron powder diffraction data demonstrate that this is directly related to H2 binding at coordinatively unsaturated Mn2+ centers within the framework.
Article
A porous hybrid inorganic/organic material, NaNi3(OH)(SIP)2 [SIP = 5-sulfoisophthalate][1], is shown to strongly bind molecular hydrogen at coordinatively unsaturated metal sites. A combination of H2 sorption isotherms, temperature programmed desorption, and inelastic neutron scattering spectroscopy show the existence of a considerable number of such strong binding sites in [1] along with other sites where hydrogen is more weakly physisorbed. The overall capacity for hydrogen of this material as well as the much stronger binding of hydrogen than in typical porous material represent an important step toward a possible utilization of porous media for hydrogen storage.
Article
We investigate the potential for hydrogen storage of a new class of nanomaterials, metal-diboride nanotubes. These materials have the merits of a high density of binding sites on the tubular surfaces without the adverse effects of metal clustering. Using the TiB2 (8,0) and (5,5) nanotubes as prototype examples, we show through first-principles calculations that each Ti atom can host two intact H2 units, leading to a retrievable hydrogen storage capacity of 5.5 wt %. Most strikingly, the binding energies fall in the desirable range of 0.2-0.6 eV per H2 molecule, endowing these structures with the potential for room-temperature, near-ambient-pressure applications.
Article
In order to understand the fact that H2 molecule is only useful chemically when the two H's are split apart in controlled fashion, there is a need to be aware of how activation of H2 occurs on metal complexes and on enzymes in naturelike hydrogenases. Recently, the detailed mechanism at the molecular level by which the H-H union splits to form, for instance, a metal dihydride complex, has been established. The breakthrough is due to the fact that H2 contains only a strongly bonded electron pair always assumed to be inert to further chemical interaction. The H2 binds side-on to the metal center primarily via donation of its two σ electrons to a vacant d orbital and forms a stable dihydrogen complex. Such a complex can encompass interaction of any σ bond with a metal center and therefore termed σ complex. It is notable to mention that such relationships can be defined facts, like octohedral Fe(II) d6 centers are favorable for reversible molecular H2 binding rather than irreversible formation of catalytically inactive hydride complexes. In addition, to increase the electrophilicity of the metal center to promote reversible H2 binding rather than irreversible formation of catalytically inactive hydride complexes must be presumed under the CO ligands.
Article
We investigate Raman spectra of graphite oxide and functionalized graphene sheets with epoxy and hydroxyl groups and Stone-Wales and 5-8-5 defects by first-principles calculations to interpret our experimental results. Only the alternating pattern of single-double carbon bonds within the sp2 carbon ribbons provides a satisfactory explanation for the experimentally observed blue shift of the G band of the Raman spectra relative to graphite. To obtain these single-double bonds, it is necessary to have sp3 carbons on the edges of a zigzag carbon ribbon.
Article
Oxidation of graphite may be carried out by reaction with meta-chloroperoxybenzoic acid to yield graphite epoxide. Scanning tunneling microscopy (STM) showed that the functionalization occurs at the edges rather than on the basal plane of the graphite. Quantification of the epoxide content is possible through the deepoxidation reaction using MeReO3/PPh3.
Article
Low-coordinate Ti (III) fragments with controlled geometries designed specifically for sigma-H2 binding were grafted onto mesoporous silica using tri- and tetrabenzyl Ti precursors. The hydrogen storage capacity was tested as a function of precursor and precursor loading level. At an optimal loading level of 0.2 mol equiv tetrabenzyl Ti the total storage capacity at -196 degrees C was 21.45 wt % and 34.10 kg/m(3) at 100 atm, and 3.15 wt % and 54.49 kg/m(3) for a compressed pellet under the same conditions. The adsorption value of this material was 1.66 wt %, which equates to an average of 2.7 H2 per Ti center. The adsorption isotherms did not reach saturation at 60 atm, suggesting that the theoretical maximum of 5 H2 per Ti in this system may be reached at higher pressures. The binding enthalpies rose with surface coverage to a maximum of 22.15 kJ/mol, which is more than double that of the highest recorded previously and within the range predicted for room temperature performance. The adsorption values of 0.99 at -78 degrees C and 0.69 at 25 degrees C demonstrate retention of 2.4 H2 and 1.1 H2 per Ti at these temperatures, respectively. These findings suggest that Kubas binding of H2 may be exploited at ambient temperature to enhance the storage capacities of high-pressure cylinders currently used in hydrogen test vehicles.
Article
The role of exposed metal sites in increasing the H2 storage performances in metal-organic frameworks (MOFs) has been investigated by means of IR spectrometry. Three MOFs have been considered: MOF-5, with unexposed metal sites, and HKUST-1 and CPO-27-Ni, with exposed Cu(2+) and Ni(2+), respectively. The onset temperature of spectroscopic features associated with adsorbed H2 correlates with the adsorption enthalpy obtained by the VTIR method and with the shift experienced by the H-H stretching frequency. This relationship can be ascribed to the different nature and accessibility of the metal sites. On the basis of a pure energetic evaluation, it was observed that the best performance was shown by CPO-27-Ni that exhibits also an initial adsorption enthalpy of -13.5 kJ mol(-1), the highest yet observed for a MOF. Unfortunately, upon comparison of the hydrogen amounts stored at high pressure, the hydrogen capacities in these conditions are mostly dependent on the surface area and total pore volume of the material. This means that if control of MOF surface area can benefit the total stored amounts, only the presence of a great number of strong adsorption sites can make the (P, T) storage conditions more economically favorable. These observations lead to the prediction that efficient H2 storage by physisorption can be obtained by increasing the surface density of strong adsorption sites.
A MetalOrganic Framework with Entatic Metal Centers Exhibiting High Gas Adsorption Affinity Figure 6. Z4 structure on HGO fully loaded with H 2 . It has a 2 2 Ti periodicity, and the OO separation on the same side is d OO
  • S Q Ma
  • H C Zhou
Ma, S. Q.; Zhou, H. C. A MetalOrganic Framework with Entatic Metal Centers Exhibiting High Gas Adsorption Affinity. J. Am. Chem. Soc. 2006, 128, 11734–11735. Figure 6. Z4 structure on HGO fully loaded with H 2. It has a 2 2 Ti periodicity, and the OO separation on the same side is d OO
We performed LDA calculations for Ti at the Z2 site. The binding energies for the first and second adsorbed H 2 are 65 and 33 kJ
  • J Phys
J. Phys.: Condens. Matter 2007, 19, 386220-1–386220-8. We performed LDA calculations for Ti at the Z2 site. The binding energies for the first and second adsorbed H 2 are 65 and 33 kJ/mol-H 2, respectively (see Table 1), in line with the prediction.
  • J Chattopadhyay
  • A Mukherjee
  • C E Hamilton
  • J Kang
  • S Chakraborty
  • W Guo
  • K F Kelly
  • A R Barron
  • W E Billups
  • Epoxide
Chattopadhyay, J.; Mukherjee, A.; Hamilton, C. E.; Kang, J.; Chakraborty, S.; Guo, W.; Kelly, K. F.; Barron, A. R.; Billups, W. E. Graphite Epoxide. J. Am. Chem. Soc. 2008, 130, 5414– 5415.
United States Patent Application
  • R K Prud 'homme
  • I A Aksay
  • D Adamson
  • A Abdala
Prud'homme, R. K.; Aksay, I. A.; Adamson, D.; Abdala, A. United States Patent Application 20090054272.