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![Importance of Cu(110) for effective passivation
a–c, SEM images of formate-treated single-crystalline surfaces after exposure to 0.1 M sodium hydroxide for 12 h: Cu(110)-FA (a), Cu(100)-FA (b) and Cu(111)-FA (c). d, Comparison of adsorption free energies of O2 and Cl⁻ at 298 K on a clean Cu(110) surface and on Cu(110)-FA with surface co-passivation by [Cu(μ-HCOO)(OH)2]2 and O²⁻. e, Comparison of the mass of dissolved Cu(ii) from Cu-FA/DT, Cu-FA and Cu after the salt spray test in 5% NaCl at 47 °C for 96 h. The data are averages of three independent measurements. Error bars represent the standard errors. f, Optical photographs of Cu-FA/DT (1), Cu-FA (2) and Cu (3) foils after a 10-min exposure to Na2S (50 mM).
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Importance of Cu(110) for effective passivation a–c, SEM images of formate-treated single-crystalline surfaces after exposure to 0.1 M sodium hydroxide for 12 h: Cu(110)-FA (a), Cu(100)-FA (b) and Cu(111)-FA (c). d, Comparison of adsorption free energies of O2 and Cl⁻ at 298 K on a clean Cu(110) surface and on Cu(110)-FA with surface co-passivation by [Cu(μ-HCOO)(OH)2]2 and O²⁻. e, Comparison of the mass of dissolved Cu(ii) from Cu-FA/DT, Cu-FA and Cu after the salt spray test in 5% NaCl at 47 °C for 96 h. The data are averages of three independent measurements. Error bars represent the standard errors. f, Optical photographs of Cu-FA/DT (1), Cu-FA (2) and Cu (3) foils after a 10-min exposure to Na2S (50 mM). Source data
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Owing to its high thermal and electrical conductivities, its ductility and its overall non-toxicity1–3, copper is widely used in daily applications and in industry, particularly in anti-oxidation technologies. However, many widespread anti-oxidation techniques, such as alloying and electroplating1,2, often degrade some physical properties (for exam...
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... Metallic materials, particularly copper (Cu), have attracted significant attention for mitigating electromagnetic loss and power dissipation under high-radio-frequency (RF) conditions owing to their high-conductivity properties [1][2][3]. Enhancing the electrical conductivity of Cu has become a long-standing topic in meeting the requirements of high-throughput information processing that is driven by the development of the modern electronics industry [4]. Aiming at enhancing the conductivity of Cu materials, much research has focused on processing optimizations and microstructure modulations. ...
High-radio-frequency (RF) conductivity is required in advanced electronic materials to reduce the electromagnetic loss and power dissipation of electronic devices. Graphene/copper (Gr/Cu) multilayers possess higher conductivity than silver under direct current conditions. However, their RF conductivity and detailed mechanisms have rarely been evaluated at the micro scale. In this work, the RF conductivity of copper–copper (P-Cu), monolayer-graphene/copper (S-Gr/Cu), and multilayer-graphene/copper (M-Gr/Cu) multilayer structures were evaluated using scanning microwave impedance microscopy (SMIM) and dielectric resonator technique. The results indicated that the order of RF conductivity was M-Gr/Cu < P-Cu < S-Gr/Cu at 3 GHz, contrasting with P-Cu < M-Gr/Cu < S-Gr/Cu at DC condition. Meanwhile, the same trend of M-Gr/Cu < P-Cu < S-Gr/Cu was also observed using the dielectric resonator technique. Based on the conductivity-related Drude model and scattering theory, we believe that the microwave radiation can induce a thermal effect at S-Gr/Cu interfaces, leading to an increasing carrier concentration in S-Gr. In contrast, the intrinsic defects in M-Gr introduce additional carrier scattering, thereby reducing the RF conductivity in M-Gr/Cu. Our research offers a practical foundation for investigating conductive materials under RF conditions.
... [13,26,27] This is attributed to the dense self-assembly layer of the carboxyl group from formic acid on the copper surface, leading to the creation of a protective antioxidant film layer. [28,29] Consequently, this layer impedes the adsorption of oxygen or chloride ions onto the metallic copper surface, thereby enhancing its resistance to corrosion. [26,[30][31][32][33][34] Thioglycolic acid (TGA) [35][36][37][38][39][40][41] was expected to have better adsorption stability on copper surfaces because the molecule contains both sulfhydryl group and carboxyl groups. ...
... This further validates the preference for TGA over O 2 adsorption and suggests TGA's ability to interact on the Cu surface first, forming a self-assembled layer that modifies the properties of Cu surfaces and possibly inhibits O 2 corrosion. This result is also consistent with the reported in the literature by Zheng et al. [28] Furthermore, we also compared the antioxidant properties of TGA molecule with HCOOH, 3-amino-1,2,4-triazol, benzotriazole and 1-hydroxybenzotriazol on copper surface. It can be seen that TGA has better antioxidant properties on copper surface in Fig. S2 and Supporting Information. ...
Copper is widely used in everyday life and industrial production because of its good electrical and thermal conductivity. To overcome copper oxidation and maintain its good physical properties, small organic molecules adsorbed on the surface of copper make a passivated layer to further avoid copper corrosion. In this work, we have investigated thioglycolic acid (TGA, another name is mercaptoacetic acid) adsorbed on copper surfaces by using density functional theory (DFT) calculations and a periodical slab model. We first get five stable adsorption structures, and the binding interaction between TGA and Cu(111) surfaces by using density of states (DOS), indicating that the most stable configuration adopts a triple‐end binding model. Then, we analyze the vibrational Raman spectra of TGA adsorbed on the Cu(111) surface and make vibrational assignments according to the vibrational vectors. Finally, we explore the temperature effect of the thermodynamically Gibbs free energy of TGA on the Cu(111) surface and the antioxidant ability of the small organic molecular layer of copper oxidation on the copper surface. Our calculated results further provide evidences to interpret the stability of adsorption structures and antioxidant properties of copper.
... However, for batteries to be an economical and reliable form of automotive energy storage, the next generation of higher energydensity LIBs must have high-cutoff voltages and structural stabilities. Herein, the internal component stability should be noticed and strengthened less prone to degradation or failures 19 (e.g., corrosion the of current collector 8,[20][21][22][23][24][25][26] and spoilage of electrode materials 24,16,27 ). ...
State-of-the-art lithium-ion batteries inevitably suffer from electrode corrosion over long-term operation, such as corrosion of Al current collectors. However, the understanding of Al corrosion and its impacts on the battery performances have not been evaluated in detail. The passivation, its breakdown, and corrosion of the Al resulted in the deterioration of the solid/solid interface and electrode integrity. Additionally, localized diffusion of F − /Al 3+ brought the irreversible current detrimental to the Coulomb efficiency (1.14% loss). Eventually, the behavior led to extensive capacity damage (>20%) to battery performance until lifespan. During the battery cycling, the passivation layer greater than 20 nm was generated near the median voltage. When the charging voltage rose, the passivation layer was squeezed and deformed by the newly generated Al-F-O particles, resulting in stress corrosion cracks. The passivation layer peeled off, and the nano-passivation layer material was regenerated as the voltage continued to rise. The above results were repeated, and the Al matrix was continuously consumed. The passivity breakdown with localized corrosion was derived from ethylene carbonate adsorption, which was highly correlated to the charge voltages, especially at 4.4 V and 4.8 V. The results will serve as a benchmark for electrode corrosion of other advanced energy storage materials, which is crucial for electrode engineering and performance modulation using interfacial design. One of the application dilemmas of lithium-ion batteries (LIBs) in portable electronic devices is the requirement to manage the physical-chemical stability of multiple external/internal components. The internal components all contain separators 1,2 , current collectors 3-8 , electrolytes 9-13 , and electrodes 14-18. Due to the high energy density of LIBs, their application has also penetrated the automotive market in the form of plug-in hybrid and electric vehicles. However, for batteries to be an economical and reliable form of automotive energy storage, the next generation of higher energy-density LIBs must have high-cutoff voltages and structural stabilities. Herein, the internal component stability should be noticed and strengthened less prone to degradation or failures 19 (e.g., corrosion the of current collector 8,20-26 and spoilage of electrode materials 24,16,27). Al/Cu are the most concerned materials for the cathode/anode current collectors in lithium-based and other rechargeable energy batteries attributed to their cost-efficiencies, high electrical conductivity, and chemical/electrochemical inertness 28,29. However, metal corrosion degrades metallic materials and their structures, which behave as Cu oxidation and Al dissolution for LIBs' current collectors. Degradation of Cu is an important aspect, as this component contributes significantly to the battery weight and cost. The inertness of Al originates from the original oxide film, which is composed of two layers, i.e., hard crystalline hydro-soft aluminite (Al 2 O 3 ·H 2 O) with fine holes and the middle layer is a dense amorphous alumina (Al 2 O 3) barrier layer 30. Inevitably, the Al substrate will be exposed to aggressive electrolytes and be attacked despite its natural oxide film 4,22,31-35. The attacking effects from liquid organic electrolytes (i.e., ester-based electrolytes) are distinct from those in aqu-eous environments 36. The former mechanism exposure is indispensable for the development of energy storage materials. The subsequent corrosion may be related to the contaminates and side reactions/products of the electrolytes, such as HF generated from LiPF 6 hydrolysis in the presence of a trace amount of water, LiTFSI, and LiFSI 20,22,37-39. The parasitic corrosive reactions of the electrolyte are reflected as undesired interfacial interactions , which contain the chemical corrosion of current collectors and the dissolution of electrodes. The latter dissolution has been examined in several literature 16,40-42. In contrast to the latter, the chemical/electro-chemical corrosion and failure of current collectors at multiple charge voltages need to be evaluated corresponding to the battery performance, especially at >4.5 V. Thus, it is urgent to determine the corrosion influence
... Hence, corrosion inhibition involves suppressing the adsorption and reaction activities of these corrosive species [82]. Organic compounds containing heteroatoms, such as N, O, and S, exhibit robust adsorption onto the copper surface, forming stable steric structures that impede the adsorption of corrosive species onto the metallic substrate [83]. For instance, thiol molecules have the capability to form self-assembled monolayers (SAMs) on the copper surface, effectively inhibiting the adsorption of water molecules and mitigating subsequent degradation [12]. ...
... However, even small molecules such as formate can be utilized for the surface passivation of copper. In their work, Peng et al. [83] introduced an innovative solvothermal treatment method for copper in the presence of sodium formate, aiming to enhance corrosion resistance (Fig. 12). During the process, the copper surface underwent crystallographic reconstruction and formed an extremely thin coordination layer. ...
... During the process, the copper surface underwent crystallographic reconstruction and formed an extremely thin coordination layer. Specifically, formates acted as ligands and coordinated with Cu(II) on the reconstructed Cu (110) to Na 2 S (50 mM) [83]. Copyright 2020, Springer Nature. ...
... Weathering steels, fortified with corrosion-resistant elements, provide a promising solution to meet the growing demand for steel materials in severe marine atmospheric corrosion environments with high Cl − concentrations while maintaining mechanical properties [1][2][3][4] . The meticulous composition design of weathering steels plays a crucial role in establishing a rust layer capable of withstanding intrusion by Cl − , thus ensuring the viability of coating-free weathering steels [5][6][7][8] . ...
... Simultaneously, influenced by both high Cl − ion concentrations and the ensuing acidic environment, a substantial quantity of β-FeOOH forms via the sequence: FeCl 2 → β-Fe 2 (OH) 3 Cl → GR1(Cl − ) → β-FeOOH [54] . This phase transformation leads to the establishment of a stable rust layer characterized by the composite structure of Layer A, Layer B, and Layer C. ...
... Consequently, the prevailing manifestation of Cl within the rust layer of the experimental steels in this study is predominantly in the form of β-FeOOH. The presence of β-FeOOH also rationalizes the occurrence of minor microcracks and the relatively subdued microhardness values detected within Layer C. In more specific terms, the generation of β-FeOOH involves a multifaceted transformation process, proceeding as follows: FeCl 2 → β-Fe 2 (OH) 3 Cl → GR1(Cl − ) → β-FeOOH [54] . Importantly, owing to its relatively lower density (3.0 g cm − ³), the associated volume changes that arise upon its formation can potentially disrupt the structural integrity of the rust layer. ...
... [30] It is known that surfactants can form a uniform assembly layer at the solid/liquid interface via surface enrichment phenomenon, which has already been widely applied on the anti-corrosion of metal. [31,32] In this regard, RÀ Cu was submersed into the solutions of the as-prepared surfactants to obtain the surfactant modified Cu (XÀ MÀ Cu, X represents the different structure of surfactants). The preparation process of 1-MÀ Cu was shown in Figure 2B to illustrate the modification Scheme. ...
Electroreduction of CO2 into valuable chemicals and fuels is a promising strategy to mitigate energy and environmental problems. However, it usually suffers from unsatisfactory selectivity for a single product and inadequate electrochemical stability. Herein, we report the first work to use cationic Gemini surfactants as modifiers to boost CO2 electroreduction to formate. The selectivity, activity and stability of the catalysts can be all significantly enhanced by Gemini surfactant modification. The Faradaic efficiency (FE) of formate could reach up to 96 %, and the energy efficiency (EE) could achieve 71 % over the Gemini surfactants modified Cu electrode. In addition, the Gemini surfactants modified commercial Bi2O3 nanosheets also showed an excellent catalytic performance, and the FE of formate reached 91 % with a current density of 510 mA cm⁻² using the flow cell. Detailed studies demonstrated that the double quaternary ammonium cations and alkyl chains of the Gemini surfactants played a crucial role in boosting electroreduction CO2, which can not only stabilize the key intermediate HCOO* but also provide an easy access for CO2. These observations could shine light on the rational design of organic modifiers for promoted CO2 electroreduction.
... XPS and Co L-edge XAS, known for their surface sensitivity, offer detailed information about the surface cobalt metal species. 44,45 The average oxidation state of Co changes ( Fig. 2a) depending on the type of metal dopants, indicating that these dopants uniquely modify the electronic structure of CSO. 46 Unlike XPS, which offers surface-specific information, the Co K-edge XAS data provide insights into the bulk properties. ...
Universal incorporation of metals into cobalt spinel oxide (CSO) has emerged as a versatile and promising strategy to enhance catalytic performance. However, the uncontrolled reactivity of early transition metal and...
... The degradation of a metal is highly influenced by the environmental cues including physical, chemical and biological ones [17][18][19][20][21][22]. It has known that small molecules and ions can influence metal corrosion [23][24][25][26][27][28]. As early as in 1982, Clark and Williams addressed the question of the effects of proteins on metallic corrosion and pioneered the study of unwelcome corrosion at that time for those permanent metals including aluminum, chromium, cobalt, copper, molybdenum, nickel, titanium and Co-Cr-Mo alloy [29]. ...
Corrodible metals are the newest kind of biodegradable materials and raise a new problem of the corrosion products. However, the removal of the precipitated products has been unclear and even largely ignored in publications. Herein, we find that albumin, an abundant macromolecule in serum, enhances the solubility of corrosion products of iron in blood mimetic Hank’s solution significantly. This is universal for other main biodegradable metals such as magnesium, zinc and polyester-coated iron. Albumin also influences corrosion rates in diverse trends in Hank’s solution and normal saline. Based on quantitative study theoretically and experimentally, both the effects on corrosion rates and soluble fractions are interpreted by a unified mechanism, and the key factor leading to different corrosion behaviors in corrosion media is the interference of albumin to the Ca/P passivation layer on the metal surface. This work has illustrated that the interactions between metals and media macromolecules should be taken into consideration in the design of the next-generation metal-based biodegradable medical devices in the formulism of precision medicine. The improved Hank’s solution in the presence of albumin and with a higher content of initial calcium salt is suggested to access biodegradable metals potentially for cardiovascular medical devices, where the content of calcium salt is calculated after consideration of chelating of calcium ions by albumin, resulting in the physiological concentration of free calcium ions.
... Our study will likely expand the application scenarios of Cu under various extreme operating conditions. Cu is widely used in the modern semiconductor industry as electrical connectors due to its high conductivity [1][2][3][4][5] . However, the susceptibility of Cu to oxidation greatly limits its advanced applications 6 . ...
... For example, Cu will lose more than 99.99999% of its electrical conductivity at 200°C in air for only 30 min 7 . Conventional organic coating 8 and sacrificial anode 9 anticorrosion techniques have made significant success in traditional industries, unfortunately, these methods typically rely on a thick coating and fail to comply with the miniaturisation requirements of the integrated circuits industry 1,2 . Currently, the rise of two-dimensional (2D) materials has provided new opportunities for the development of anticorrosion technology [10][11][12] . ...
The atomic-thick anticorrosion coating for copper (Cu) electrodes is essential for the miniaturisation in the semiconductor industry. Graphene has long been expected to be the ultimate anticorrosion material, however, its real anticorrosion performance is still under great controversy. Specifically, strong electronic couplings can limit the interfacial diffusion of corrosive molecules, whereas they can also promote the surficial galvanic corrosion. Here, we report the enhanced anticorrosion for Cu simply via a bilayer graphene coating, which provides protection for more than 5 years at room temperature and 1000 h at 200 °C. Such excellent anticorrosion is attributed to a nontrivial Janus-doping effect in bilayer graphene, where the heavily doped bottom layer forms a strong interaction with Cu to limit the interfacial diffusion, while the nearly charge neutral top layer behaves inertly to alleviate the galvanic corrosion. Our study will likely expand the application scenarios of Cu under various extreme operating conditions.
... [2,3] Surface passivation with thiolate and formate modifications and morphological optimization to eliminate low-coordination sites could efficiently retard the oxidation, but this strategy might not be suitable for the metal catalysts because of the elimination of the desired active sites. [4][5][6] Alloying and electroplating, chemical etching, photo and thermal reduction have been used to minimize the metal oxidation or remove the oxidized species for supported metal nanoparticles, [7][8][9][10][11][12] but it is difficult to prepare oxidationresistant metal nanoparticle-based catalysts. ...
The metal surfaces tend to be oxidized in air through dissociation of the O−O bond of oxygen to reduce the performances in various fields. Although several ligand modification routes have alleviated the oxidation of bulky metal surfaces, it is still a challenge for the oxidation resistance of small‐size metal nanoparticles. Herein, we fixed the small‐size Pd nanoparticles in tin‐contained MFI zeolite crystals, where the tin acts as an electron donor to efficiently hinder the oxidation of Pd by weakening the adsorption of molecular oxygen and suppressing the O−O cleavage. This oxidation‐resistant Pd catalyst exhibited superior performance in directly synthesizing hydrogen peroxide from hydrogen and oxygen, with the productivity of hydrogen peroxide at ≈10,170 mmol gPd⁻¹ h⁻¹, steadily outperforming the catalysts tested previously. This work leads to the hypothesis that tin is an electron donor to realize oxidation‐resistant Pd within zeolite crystals for efficient catalysis to overcome the limitation of generally supported Pd catalysts and further motivates the use of oxidation‐resistant metal nanoparticles in various fields.
