Single‐Product Faradaic Efficiency for Electrocatalytic of CO₂ to CO at Current Density Larger than 1.2 A cm⁻² in Neutral Aqueous Solution by a Single‐Atom Nanozyme

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(44)

Published: Sept. 7, 2022

Electroreduction of CO2 to CO is a promising approach for the cycling use , while it still suffers from impractical current density and durability. Here we report single-atom nanozyme (Ni-N5 -C) that achieves industrial-scale performance -to-CO conversion with Faradaic efficiency (FE) exceeded 97 % over -0.8--2.4 V vs. RHE. The at -2.4 RHE reached maximum 1.23 A cm-2 (turnover frequency 69.7 s-1 ) an FE 99.6 %. No obvious degradation was observed 100 hours continuous operation. Compared planar Ni-N4 site, square-pyramidal Ni-N5 site has increase decrease in dz2${{{\rm d}}_{{z}^{2}}}$ dxz/yz orbital energy levels, respectively, as revealed by functional theory calculations. Thus, catalytic more superior activate molecule reduce barriers well promote desorption, thus boosting kinetic activation process activity.

Language: Английский

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Carbon Catalysts for Electrochemical CO₂ Reduction toward Multicarbon Products

Advanced Energy Materials, Journal Year: 2022, Volume and Issue: 12(24)

Published: May 1, 2022

Abstract Electrochemical CO 2 reduction offers a compelling route to mitigate atmospheric concentration and store intermittent renewable energy in chemical bonds. Beyond C 1 , 2+ feedstocks are more desirable due their higher density significant market need. However, the ‐to‐C suffers from barriers of CC coupling complex reaction pathways. Due remarkable tunability over morphology/pore architecture along with great feasibility functionalization modify electronic geometric structures, carbon materials, serving as active components, supports, promoters, provide exciting opportunities tune both adsorption properties intermediates local environment for reduction, offering effective solutions enable steer evolution. general design principles remain ambiguous, causing an impediment rational catalyst refinement application thrusts. This review clarifies insightful advancing materials. First, current performance status challenges discussed strategies outlined promote Further, correlation between composition, structure, morphology catalysts catalytic behavior is elucidated establish mechanisms critical factors determining performance. Finally, future research directions envisioned inspire revolutionary advancements.

Language: Английский

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In Situ Dynamic Construction of a Copper Tin Sulfide Catalyst for High-Performance Electrochemical CO₂ Conversion to Formate

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(16), P. 9922 - 9932

Published: Aug. 1, 2022

Electrochemical reduction of CO2 to produce fuels and chemicals is one the most valuable approaches achieve a carbon-neutral cycle. Recently, diversity catalysts have been developed improve their intrinsic activity efficiency. However, dynamic evolution process in situ construction behavior electrocatalysts under working conditions are typically ignored. Here, we fully reveal phase transformation copper tin sulfide catalyst reconstructed by precatalyst Cu2SnS3 CuS during electrochemical reduction. Furthermore, reaches an outstanding CO2-to-formate conversion with high Faradaic efficiency 96.4% at impressive production rate 124889.9 μmol mg–1 h–1 partial current density −241 mA cm–2 (−669.4 A g–1) flow-cell reactor. Theoretical calculations further demonstrate strong charge interaction between adsorbate substrate accelerate transfer decrease formation energies OCHO* HCOOH* intermediates pathway HCOOH, resulting selectivity for formate on surface catalyst. This work paves way revealing designing optimal catalytic selectivity.

Language: Английский

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In‐Situ Constructuring of Copper‐Doped Bismuth Catalyst for Highly Efficient CO₂ Electrolysis to Formate in Ampere‐Level

Advanced Energy Materials, Journal Year: 2022, Volume and Issue: 13(1)

Published: Nov. 6, 2022

Abstract CO 2 electrochemical reduction (CO RR) can mitigate environmental issues while providing valuable products, yet challenging in activity, selectivity, and stability. Here, a CuS‐Bi S 3 heterojunction precursor is reported that situ reconstruct to Cu‐doped Bismuth (CDB) electrocatalyst during RR. The CDB exhibits an industrial‐compatible current density of −1.1 A cm −2 record‐high formate formation rate 21.0 mmol h −1 at −0.86 V versus the reversible hydrogen electrode toward RR formate, dramatically outperforming currently catalysts. Importantly, ultrawide potential region 1050 mV with high Faradaic efficiency over 90% superior long‐term stability for more than 100 −400 mA also be realized. Experimental theoretical studies reveal remarkable performance results from doping effect Cu which optimizes adsorption *OCHO boosts structural metallic bismuth catalyst. This study provides inspiration design element‐doping electrocatalysts enhance catalytic activity durability.

Language: Английский

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Applications of Metal–Organic Frameworks and Their Derivatives in Electrochemical CO2 Reduction

Nano-Micro Letters, Journal Year: 2023, Volume and Issue: 15(1)

Published: April 30, 2023

Abstract Electrochemically reducing CO 2 to more reduced chemical species is a promising way that not only enables the conversion of intermittent energy resources stable fuels, but also helps build closed-loop anthropogenic carbon cycle. Among various electrocatalysts for electrochemical reduction, multifunctional metal–organic frameworks (MOFs) have been employed as highly efficient and selective heterogeneous due their ultrahigh porosity topologically diverse structures. Up now, great progress has achieved in design synthesis active MOF-related catalysts reduction reaction (CO RR), corresponding mechanisms thoroughly studied. In this review, we summarize recent applying MOFs derivatives RR, with focus on strategies electrolyzers. We first discussed different RR products introduced commonly applied electrolyzer configurations current system. Then, an overview several categories (CO, HCOOH, CH 4 , 3 OH, multi-carbon chemicals) generated from or via was discussed. Finally, offer some insights perspectives future development reduction. aim provide new into field further guide research large-scale applications.

Language: Английский

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