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![Cl(2p) XPS spectra: (a) pulsed plasma poly(vinylbenzyl chloride) deposited onto PTFE membrane; (b) following quaternisation with N-butylimidazole; and (c) following palladium(II) chloride complexation to (b). Due to spin-orbit coupling, Cl(2p 1/2 ) components are shifted by 1.6 eV to higher binding energy relative to the Cl(2p 3/2 ) components, with a Cl(2p 3/2 ):Cl(2p 1/2 ) peak area ratio equal to 2:1 [54]. Signal intensity is counts per second.](publication/323312199/figure/fig4/AS:873429985144833@1585253344141/Cl2p-XPS-spectra-a-pulsed-plasma-polyvinylbenzyl-chloride-deposited-onto-PTFE.png)
Cl(2p) XPS spectra: (a) pulsed plasma poly(vinylbenzyl chloride) deposited onto PTFE membrane; (b) following quaternisation with N-butylimidazole; and (c) following palladium(II) chloride complexation to (b). Due to spin-orbit coupling, Cl(2p 1/2 ) components are shifted by 1.6 eV to higher binding energy relative to the Cl(2p 3/2 ) components, with a Cl(2p 3/2 ):Cl(2p 1/2 ) peak area ratio equal to 2:1 [54]. Signal intensity is counts per second.
Source publication
Anisotropic palladium–poly(ionic liquid) catalyst membranes have been prepared by complexation of palladium(II) chloride to poly(ionic liquid) functionalised flexible porous substrates. The practical viability of these low loading (sub 0.1 mol%) palladium catalyst membranes for continuous flow reactions at ambient temperature is demonstrated for th...
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Context 1
... with trapped free radicals contained within the plasma deposited layer [36,53]. The Cl(2p) peak envelope could be fitted to two different chlorine atom environments with Cl(2p 3/2 ) binding energy values of 197.3 ± 0.1 eV and 200.6 ± 0.2 eV corresponding to chloride anions and non-quaternised unreacted benzyl chloride groups respectively [54], Fig. 4. Based on these two Cl(2p 3/2 ) binding energy environments, the level of surface quaternisation was calculated to be 52 ± 9% (this is most likely to be an underestimate due to the XPS sampling depth (2-5 nm) also probing the sub-surface [55,56]). Infrared spectroscopy of the quaternised membranes did not detect any contributions from ...
Context 2
... ionic liquids, Fig. 3 [58]. This was accompanied by the relative Cl(2p 3/2 ) chloride anion peak component at 197.3 ± 0.1 eV within the overall Cl(2p) envelope increasing (as well as a shift towards higher binding energy) due to the incorporation of additional chloride anions accompanying the palladium(II) catalyst complexation process, Fig. ...
Context 3
... equivalent reaction solution loading of 11.1 ± 8 ppm on a mass basis (or 0.061 ± 0.004 mol%) -this is equivalent to ∼1% of the Pd present leaching from an already sub 0.1 mol% catalyst loading during one reaction cycle at 343 K). This is consistent with the negligible drop in product yield with reaction cycle number, Supplementary information Fig. S4. As a control, the Suzuki-Miyaura coupling reaction was run using 4-methoxyiodobenzene and phenylboronic acid reactants under similar reaction conditions in order to rule out the possibility of homocoupled by-product formation. GC-MS analysis of the obtained products showed the presence of only 4-methoxybiphenyl, and an absence of ...
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Nanostructured palladium (Pd) is attractive for diverse applications owing to their unique properties compared to their bulk materials. Here, in this study, we have explored Pd-induced phase separation in functional sulfur containing poly(methyl methacrylate) telopolymer, which allowed synthesis of Pd nanorods with specific crystallographic facets....
Citations
... 399.5, and 531.8 eV that correspond, respectively, to Cl 2p, C 1s, N 1s, and O 1s (Fig. 2) [40]. In the high-resolution C 1s XPS spectrum of AC-BPA (Fig. 2a), the dominant peak centered at 285.5 eV can be attributed to sp 2 (C = C) and sp 3 (C-C) carbon, while the peak at 286.4 eV was due to C-Cl [41]. Surface functionalization of AC with BPA changed the chemical environment of the carbon atoms, as indicated by the appearance of an sp 2 (C = C) peak at a lower binding energy in AC (284.6 eV) and AC-NH 2 (284.2 ...
Interactions between surface functional groups of adsorbents and pollutants are key variables controlling adsorption and degradation. Herein, we presented a new approach to address such variables by modifying the surface of activated carbon (AC) with branched polyamine (BPA) to create an efficient hybrid material for tackling a common air pollutant, i.e., formaldehyde (FA). The hybrid AC-BPA possessed amine, –COOH, –OH, and Cl ⁻ on its surface, facilitating physical, chemical, and reactive adsorption of FA. Consequently, AC-BPA exhibited a high partition coefficient (PC) of 0.64 mol kg − 1 Pa − 1 (82.3 mg g − 1 adsorption capacity), surpassing pristine AC and associated reported systems. AC-BPA performance was further improved under high relative humidity (e.g., 100% RH), achieving an impressive adsorption capacity of 144.3 mg g − 1 and PC of 1.25 mol kg − 1 Pa − 1 . Further, in-situ diffuse reflectance infrared Fourier-transform spectroscopy revealed that AC-BPA catalyzed the chemical transformation of FA into methylol adducts, H 2 O, and CO 2 . This study opens new approaches to the design of high-performance, energy-efficient, and metal-free hybrid materials for reactive adsorption and effective degradation of FA under ambient conditions.
... Due to the spin-orbit interaction, the binding energy of C-Cl 2p 1/2 (202.2 eV) was 1.6 eV larger than that of C-Cl 2p 3/2 (200.6 eV), and the area ratio of the two C-Cl 2p spectra was 1:2 [38,39]. This demonstrates that the GO/DCX HT membrane possesses many unreacted C-Cl bonds included in the DCX crosslinking networks. ...
... The binding energy of organic chlorine was higher than 200 eV (Cl 2p3/2) [38], and thus, C-Cl bonds were present in the GO/DCX HT membrane, as indicated by the Cl 2p3/2 peak (200.6 eV). Due to the spin-orbit interaction, the binding energy of C-Cl 2p1/2 (202.2 eV) was 1.6 eV larger than that of C-Cl 2p3/2 (200.6 eV), and the area ratio of the two C-Cl 2p spectra was 1:2 [38,39]. This demonstrates that the GO/DCX HT membrane possesses many unreacted C-Cl bonds included in the DCX crosslinking networks. ...
Graphene oxide (GO), a carbonaceous 2D nanomaterial, has received significant interest as a next-generation membrane building block. To fabricate high-performance membranes, an effective strategy involves stacking GO nanosheets in laminated structures, thereby creating unique nanochannel galleries. One outstanding merit of laminar GO membranes is that their permselectivity is readily tunable by tailoring the size of the nanochannels. Here, a high-performance GO-based nanofiltration membrane was developed by intercalating an aromatic crosslinker, α,α/-dichloro-p-xylene (DCX), between the layers in laminated GO nanosheets. Owing to the formation of strong covalent bonds between the crosslinker and the GO, the resulting GO laminate membrane exhibited outstanding structural stability. Furthermore, due to the precisely controlled and enlarged interlayer spacing distance of the developed DCX-intercalated GO membrane, it achieved an over two-fold enhancement in water permeability (11 ± 2 LMH bar−1) without sacrificing the rejection performance for divalent ions, contrary to the case with a pristine GO membrane.
... Typical catalytic systems for cross-coupling reactions employ a metallic catalyst (Pd normally), auxiliary ligand to stabilize the metal, Lewis base to neutralize the system, solvent, inert atmosphere, and heating (Diederich and Meijere 2004;Negishi 2002). Efforts have been reported in order to reduce the amount of catalytically active species in reactions (Roy and Uozumi 2018) or replace it with a more eco-friendly and less expensive metal (Ma et al. 2021); reduce the use of auxiliary ligands (Serrano et al. 2022); employ less toxic solvents (Su et al. 2022) and bases (Long et al. 2019); and make the reaction conditions milder through the use of lower temperatures (close to room temperature) , microwave heating (Salih 2022), sonication (Wilson et al. 2018), or elimination of the inert atmosphere (Tian et al. 2022). In addition, the search for new, greener catalytic systems employing biomass sources appears frequently in literature, such as in the use of biomass extracts to prepare metal nanoparticles (NPs) via biogenic routes (Schmitt et al. 2021) or green solvents applied in carbon-carbon and carbon-heteroatom couplings (Peixoto et al. 2022). ...
The production of sustainable catalytic supports for palladium nanoparticles is always desired, even more so through the recovery of biomass residues. In this sense, two different solids were investigated — chitosan/cellulose film and corn stem biochar — as catalytic supports of palladium nanoparticles. The solids were carefully characterized and tested in the Suzuki-Miyaura reaction, a typical cross-coupling reaction. The developed catalytic systems proved to be efficient and sustainable, promoted the formation of target products very well, and demanded green reactants under environmentally appropriate conditions. With the results shown in the manuscript, it is expected to contribute to the valorization of biomass and agro-industrial residues in the development of new catalysts for the chemical industry.
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Ecofriendly supercapacitors (SCs) are fabricated with graphene electrodes printed on recycled‐plastics and utilized seawater as electrolyte. Those devices produced an energy density and capacitance of 50.4 Wh kg⁻¹ and 250.4 F g⁻¹, respectively. Later, a mixture of Bi─Mg─Fe─O (BMO) oxides is added to the SC electrodes and the capacitance of the devices increased up to 209%. Subsequently, SC electrodes are recovered from used/tested devices and utilized as “seed mats” to grow bean plants. For this purpose, pinto bean seeds are wrapped with recycled SC electrodes and later subjected to a germination treatment together with control seeds. The germination parameters are calculated from the bean plants and found that: 1) 100% of the seeds initially wrapped with the SC electrodes germinated, in contrast, only 88.9% of the control seeds germinated and 2) The bean plants grown with the seed mats has the longest roots/shoots. This occurred because the seed mats have Mg/Fe micronutrients on their surface as well as OH/COOH groups (coming from the seawater), which promote the germination and growth of bean plants. The results of this research demonstrated that SC electrodes coated with BMO can be used as a substrate to promote the growth of bean plants, which is of interest for sustainable agriculture.
The thermal activation of the nanoclusters on a support material can enhance their activity and selectivity in heterogeneous catalysis. However, their evolution upon thermal activation remains challenging to study due...
Described herein presents a kind of multisite hybrid ionic liquid‐catalysts and establishes a novel strategy for H 2 S utilization, which has been characterized by multiaspects to reveal internal structural characterization. Through chemical modification, the D101‐based hybrid ILs were used for the direct synthesis of thioamides from the addition of H 2 S and nitriles. D101‐[PMDETA][DMG] can achieve an impressive activity of quantitative conversion for benzonitrile. Reaction kinetics, adsorption thermodynamics, substrate universality, and catalyst cycling experiments have been systematically studied. A first‐order kinetic model was constructed and studied experimentally for the reaction of nitriles with H 2 S to produce thioamides. The internal mechanism was proposed through experiments and confirmed by DFT‐based theoretical calculations. Moreover, D101‐based hybrid ILs can be easily recovered, thus completing the cyclic process of thioamide multiplication. This work not only offers an effective method for the construction of organic‐inorganic hybrid materials but also provides a novel insight into efficient H 2 S conversion.
Pure crystalline Analcime (ANA) zeolite samples were successfully synthesized using various aluminum precursors such as aluminum nitrate (ANA-nit), aluminum sulfate (ANA-sul), aluminum isopropoxide (ANA-isop), sodium aluminate (ANA-sodalu) and aluminum chloride (ANA-chl) to study the influence of various anions on the physicochemical properties of ANA zeolite structure. The physicochemical properties of the samples have been studied using elemental analysis, X-ray diffraction, Fourier-transformed infrared spectroscopy, scanning electron microscope, N2-physisorption, X-ray photon spectroscopy, and diffuse reflectance UV–vis measurements. The synthesized analcime samples exhibited highly crystalline ANA structure; however, the anions present in the Al precursor influenced the crystallite and particle sizes. All the samples possessed a band gap energy of around 3.8 eV. The metachromasy phenomenon of methylene blue (MB) over synthesized Analcime samples was investigated under UV irradiation. The UV–vis absorption spectra of MB solution show a transformation from mono-MB to H-aggregated MB species due to the metachromasy phenomenon occurring over the surface of synthesized analcime samples. The formation of H-aggregated MB species differs for the synthesized ANA samples, which depends on the presence of active species on the ANA surface. The ANA-nit sample exhibited a fast metachromatic phenomenon due to more surface basic sites (e.g., O2−, O−) distributed over different (micro-, meso- and macro-) pores.
