Copper vulcanization realizes selective carbon dioxide reduction to formate

Liu, Wenqiang; Wen, Yan; Fang, Nan; Wang, Mingmin; Xu, Yong; Huang, Xiaoqing

doi:10.1039/d3cc03263a

Cited by 4 publications

(4 citation statements)

References 27 publications

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“…Notably, the J formate of RbCu 7 S 4 at the relatively low overpotentials (−0.7 and −0.9 V RHE ) are superior to the most reported Cu-based catalysts for formate production (Figure d, Table S2). As a result, it possesses a high formate yield of 4.688 mmol cm –2 h –1 , which is outstanding among the reported Cu-based catalysts (Figure e). − Moreover, increased half-cell energy efficiencies (EE, Figure f) can be achieved for RbCu 7 S 4 (63.3% at −0.7 V RHE ) compared to that of Cu 2 S (42.3%).…”

Section: Resultsmentioning

confidence: 91%

Alkali Metal Ions Stabilizing Copper(I)–Sulfur Bonds for Efficient Formate Production from Electrochemical CO₂ Reduction

Cui,

Wu,

Hou

et al. 2024

ACS Catal.

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Low-cost copper (Cu)-based electrocatalysts have been widely established with the special capability of generating C 2+ products from the CO 2 reduction reaction (CO 2 RR). However, efficient formate production has been rarely achieved due to the instant reduction of most reported Cu-based catalysts upon CO 2 RR, and the derived metallic Cu compromises the C 1 selectivity. Herein, we demonstrate that the incorporation of alkali metal ions is intrinsically effective for stabilizing the Cu(I)−S bonds by forming ternary copper sulfides (M−Cu(I)−S, M = Na, K, and Rb). The strengthened Cu−S bonds can be well preserved in M−Cu(I)−S during the CO 2 RR, contributing to the protonation effect and thus highly efficient production of formate. Moreover, the M−Cu(I)−S catalysts also exhibit enhanced electrical conductivity relative to that of Cu 2 S, favorably promoting the reaction kinetics. Accordingly, the RbCu 7 S 4 as a representative catalyst achieves a Faradaic efficiency of 90.4 ± 1.3% for formate at only −0.7 V versus reversible hydrogen electrode (V RHE ), with a high partial current density of 272.1 mA cm −2 and stable operation over 72 h. This study could provide a different series of Cu-based electrocatalysts for efficient formate production on an industrial scale from the CO 2 RR.

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Section: Resultsmentioning

confidence: 91%

Alkali Metal Ions Stabilizing Copper(I)–Sulfur Bonds for Efficient Formate Production from Electrochemical CO₂ Reduction

Cui,

Wu,

Hou

et al. 2024

ACS Catal.

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“…Direct formate fuel cells (DFFCs), operating under alkaline conditions, have recently garnered significant attention due to their unique advantages. Unlike other fuel cell anode reactants such as hydrogen, methanol, ethanol, and formic acid, formate boasts safer storage and transport, either as a solid or in aqueous solution, with negligible toxicity. − Notably, formate stands out as a carbon–neutral compound, which can be synthesized from CO 2 using renewable energy sources. − The alkaline operational environment of DFFCs also permits the use of non-noble-metal electrocatalysts for the oxygen reduction reaction on the cathode, potentially driving down equipment costs. , However, a major drawback remains: most electrocatalysts exhibit slow formate oxidation reaction (FOR) kinetics in alkaline settings . As such, pioneering efficient anodic catalysts for DFFCs is crucial for their optimized performance and broader adoption.…”

Section: Introductionmentioning

confidence: 99%

Cu-Modified Palladium Catalysts: Boosting Formate Electrooxidation via Interfacially OH_ad-Driven H_ad Removal

Tang,

Li,

Shi

et al. 2024

ACS Appl. Mater. Interfaces

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Direct formate fuel cells have gained traction due to their eco-friendly credentials and inherent safety. However, their potential is hampered by the kinetic challenges of the formate oxidation reaction (FOR) on Pd-based catalysts, chiefly due to the unfavorable adsorption of hydrogen species (H ad ). These species clog the active sites, hindering efficient catalysis. Here, we introduce a straightforward strategy to remedy this bottleneck by incorporating Pd with Cu to expedite the removal of Pd−H ad in alkaline media. Notably, Cu plays a pivotal role in bolstering the concentration of hydroxyl adsorbates (OH ad ) on the surface of catalyst. These OH ad species can react with H ad , effectively unblocking the active sites for FOR. The as-synthesized catalyst of PdCu/C exhibits a superior FOR performance, boasting a remarkable mass activity of 3.62 A mg −1 . Through CO-stripping voltammetry, we discern that the presence of Cu in Pd markedly speeds up the formation of adsorbed hydroxyl species (OH ad ) at diminished potentials. This, in turn, aids the oxidative removal of Pd−H ad , leveraging a synergistic mechanism during FOR. Density functional theory computations further reveal intensified interactions between adsorbed oxygen species and intermediates, underscoring that the Cu−Pd interface exhibits greater oxyphilicity compared to pristine Pd. In this study, we present both experimental and theoretical corroborations, unequivocally highlighting that the integrated copper species markedly amplify the generation of OH ad , ensuring efficient removal of H ad . This work paves the way, shedding light on the strategic design of high-performing FOR catalysts.

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confidence: 99%

“…1,2 Among the various potential products, HCOOH is an important chemical due to its potential applications as an energy storage medium and fuel. 3 Through reasonable catalyst design and reaction condition optimization, achieving efficient HCOOH product has opened up broad prospects for the sustainability and economic viability of the CO 2 RR. 4 Among the diverse p-block metal catalysts, such as In, Sn, Pb, and Bi, In-based electrocatalysts have garnered significant attention on account of their remarkable selectivity, low toxicity, and environmental friendliness for the CO 2 RR to HCOOH.…”

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confidence: 99%

A N-doped carbon-supported In₂O₃ catalyst for highly efficient CO₂ electroreduction to HCOOH

Zhang,

Liang,

et al. 2024

Chem. Commun.

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Copper vulcanization realizes selective carbon dioxide reduction to formate

Abstract: Copper (Cu) is regarded as one of the most promising catalysts for electrochemical carbon dioxide reduction (CO2RR) to C2+ products, which has recently attracted great interests for alleviating the current...

Cited by 4 publications

References 27 publications

Alkali Metal Ions Stabilizing Copper(I)–Sulfur Bonds for Efficient Formate Production from Electrochemical CO₂ Reduction

Alkali Metal Ions Stabilizing Copper(I)–Sulfur Bonds for Efficient Formate Production from Electrochemical CO₂ Reduction

Cu-Modified Palladium Catalysts: Boosting Formate Electrooxidation via Interfacially OH_ad-Driven H_ad Removal

A N-doped carbon-supported In₂O₃ catalyst for highly efficient CO₂ electroreduction to HCOOH

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Copper vulcanization realizes selective carbon dioxide reduction to formate

Abstract: Copper (Cu) is regarded as one of the most promising catalysts for electrochemical carbon dioxide reduction (CO2RR) to C2+ products, which has recently attracted great interests for alleviating the current...

Cited by 4 publications

References 27 publications

Alkali Metal Ions Stabilizing Copper(I)–Sulfur Bonds for Efficient Formate Production from Electrochemical CO2 Reduction

Alkali Metal Ions Stabilizing Copper(I)–Sulfur Bonds for Efficient Formate Production from Electrochemical CO2 Reduction

Cu-Modified Palladium Catalysts: Boosting Formate Electrooxidation via Interfacially OHad-Driven Had Removal

A N-doped carbon-supported In2O3 catalyst for highly efficient CO2 electroreduction to HCOOH

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Alkali Metal Ions Stabilizing Copper(I)–Sulfur Bonds for Efficient Formate Production from Electrochemical CO₂ Reduction

Alkali Metal Ions Stabilizing Copper(I)–Sulfur Bonds for Efficient Formate Production from Electrochemical CO₂ Reduction

Cu-Modified Palladium Catalysts: Boosting Formate Electrooxidation via Interfacially OH_ad-Driven H_ad Removal

A N-doped carbon-supported In₂O₃ catalyst for highly efficient CO₂ electroreduction to HCOOH