Electron Localization‐Triggered Proton Pumping Toward Cu Single Atoms for Electrochemical CO₂ Methanation of Unprecedented Selectivity

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(14)

Published: Dec. 28, 2023

Abstract Slow multi‐proton coupled electron transfer kinetics and unexpected desorption of intermediates severely hinder the selectivity CO 2 methanation. In this work, a one‐stone‐two‐bird strategy pumping protons improving adsorption configuration/capability enabled by localization is developed to be highly efficient for CH 4 electrosynthesis over Cu single atoms anchored on bismuth vacancies BiVO (Bi 1‐x VO ─Cu), with superior kinetic isotope effect high Faraday efficiency (92%), far outperforming state‐of‐the‐art electrocatalysts Control experiments theoretical calculations reveal that ( V Bi ) not only act as active sites H O dissociation but also induce toward single‐atom sites. The ‐induced pumps *H from atoms, significantly promoting generation stabilization pivotal intermediate (*CHO) selective electrosynthesis. metal new initiators show enormous potential in proton transfer‐involved hydrogenative conversion processes.

Language: Английский

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Atomically Local Electric Field Induced Interface Water Reorientation for Alkaline Hydrogen Evolution Reaction

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(26)

Published: March 8, 2023

Abstract The slow water dissociation process in alkaline electrolyte severely limits the kinetics of HER. orientation H 2 O is well known to affect process, but hard control because its random distribution. Herein, an atomically asymmetric local electric field was designed by IrRu dizygotic single‐atom sites (IrRu DSACs) tune adsorption configuration and orientation, thus optimizing process. intensity DSACs over 4.00×10 10 N/C. ab initio molecular dynamics simulations combined with situ Raman spectroscopy analysis on behavior show that M−H bond length (M=active site) shortened at interface due strong gradient optimized promotes interfacial water. This work provides a new way explore role single atomic hydrogen evolution reaction.

Language: Английский

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Hierarchical Ni/N/C Single‐Site Catalyst Achieving Industrial‐Level Current Density and Ultra‐Wide Potential Plateau of High CO Faradic Efficiency for CO₂ Electroreduction

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 33(20)

Published: Feb. 20, 2023

Abstract The practical applications of CO 2 electroreduction to driven by renewable electricity should simultaneously meet the requests industrial‐level partial current density (J ) at least 100 mA cm −2 , wide potential window high faradic efficiency (FE ), and low cost. Herein, a new strategy is reported construct porous hierarchical Ni/N/C single‐site catalyst with excellent catalytic activity via coating Ni‐containing ZIF‐8 on mesostructured basic magnesium carbonate template followed pyrolysis. abundant micropores facilitate formation numerous edge‐hosted Ni‐N 4 sites intrinsic activity, interconnected macro/mesopores much promote delivery release for full expression activity. Consequently, exhibits J 105–462 range −0.6∼−1.3 V ultra‐wide FE plateau (>90%@−0.4∼−1.3 V), showing great promise application. This study provides general synthetic explore high‐performance M/N/C electrocatalysts.

Language: Английский

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Self‐Polarization Triggered Multiple Polar Units Toward Electrochemical Reduction of CO₂ to Ethanol with High Selectivity

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(26)

Published: April 28, 2023

Electrochemical conversion of CO2 to highly valuable ethanol has been considered a intriguring strategy for carbon neutruality. However, the slow kinetics coupling carbon-carbon (C-C) bonds, especially low selectivity than ethylene in neutral conditions, is significant challenge. Herein, asymmetrical refinement structure with enhanced charge polarization built vertically oriented bimetallic organic frameworks (NiCu-MOF) nanorod array encapsulated Cu2 O (Cu2 O@MOF/CF), which can induce an intensive internal electric field increase C-C producing electrolyte. Particularly, when directly employed O@MOF/CF as self-supporting electrode, faradaic efficiency (FEethanol ) could reach maximum 44.3 % energy 27 at working-potential -0.615 V versus reversible hydrogen electrode (vs. RHE) using -saturated 0.5 M KHCO3 Experimental and theoretical studies suggest that atomically localized fields derived from asymmetric electron distribution tune moderate adsorption *CO assist reduce formation H2 CCHO*-to-*OCHCH3 generation ethanol. Our research offers reference design active selective electrocatalysts reducing multicarbon chemicals.

Language: Английский

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Pyrrolic N anchored atomic Ni–N3–C catalyst for highly effective electroreduction of CO2 into CO

Carbon, Journal Year: 2023, Volume and Issue: 206, P. 62 - 71

Published: Feb. 6, 2023

Language: Английский

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