Enhanced Electrochemical CO2 Reduction to Formate over Phosphate‐Modified In: Water Activation and Active Site Tuning

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(27)

Published: April 26, 2024

Abstract Electrochemical CO 2 reduction reaction (CO RR) offers a sustainable strategy for producing fuels and chemicals. However, it suffers from sluggish activation slow water dissociation. In this work, we construct (P−O) δ− modified catalyst that exhibits high activity selectivity in electrochemical to formate. A combination of situ characterizations kinetic analyses indicate has strong interaction with K + (H O) n , which effectively accelerates dissociation provide protons. attenuated total reflectance surface‐enhanced infrared absorption spectroscopy (ATR‐SEIRAS) measurements together density functional theory (DFT) calculations disclose modification leads higher valence state active site, thus promoting HCOO* formation, while inhibiting competitive hydrogen evolution (HER). As result, the oxide‐derived excellent formate across broad potential window Faradaic efficiency as 92.1 % at partial current ~200 mA cm −2 cathodic −1.2 V vs. RHE an alkaline electrolyte.

Language: Английский

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pH‐Universal Electrocatalytic CO₂ Reduction with Ampere‐Level Current Density on Doping‐Engineered Bismuth Sulfide

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(32)

Published: May 27, 2024

Abstract The practical application of the electrocatalytic CO 2 reduction reaction (CO RR) to form formic acid fuel is hindered by limited activation molecules and lack universal feasibility across different pH levels. Herein, we report a doping‐engineered bismuth sulfide pre‐catalyst (BiS‐1) that S partially retained after electrochemical reconstruction into metallic Bi for RR formate/formic with ultrahigh performance wide range. best BiS‐1 maintains Faraday efficiency (FE) ~95 % at 2000 mA cm −2 in flow cell under neutral alkaline solutions. Furthermore, catalyst shows unprecedentedly high FE (~95 %) current densities from 100 1300 acidic Notably, density can reach 700 while maintaining above 90 membrane electrode assembly electrolyzer operate stably 150 h 200 . In situ spectra functional theory calculations reveals doping modulates electronic structure effectively promotes formation HCOO* intermediate generation. This work develops efficient stable electrocatalysts sustainable production.

Language: Английский

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Steering Geometric Reconstruction of Bismuth with Accelerated Dynamics for CO2 Electroreduction

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(34)

Published: June 5, 2024

Abstract Bismuth‐based materials have emerged as promising catalysts in the electrocatalytic reduction of CO 2 to formate. However, reasons for reconstruction Bi‐based precursors form bismuth nanosheets are still puzzling, especially formation defective sites. Herein, we prepare with vacancy‐rich defects (V‐Bi NS) by rapidly reconstructing Bi 19 Cl 3 S 27 under negative potential. Theoretical analysis reveals that introduction chlorine induces generation intrinsic electric field precursor, thereby increasing electron transfer rate and further promoting metallization trivalent bismuth. Meanwhile, experimental tests verify has a faster than . The formed V‐Bi NS exhibits up 96 % HCOO − Faraday efficiency 400 mA cm −2 partial current densities, its electrochemical active surface area normalized formate density yield 2.2 times higher those intact (I‐Bi NS). Density functional theory calculations indicate vacancies electron‐rich aggregation reduce activation energy *CO radicals stabilize adsorption key intermediate *OCHO, thus facilitating reaction kinetics production.

Language: Английский

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Direct low concentration CO2 electroreduction to multicarbon products via rate-determining step tuning

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Nov. 29, 2024

Direct converting low concentration CO2 in industrial exhaust gases to high-value multi-carbon products via renewable-energy-powered electrochemical catalysis provides a sustainable strategy for utilization with minimized separation and purification capital energy cost. Nonetheless, the electrocatalytic conversion of dilute into value-added chemicals (C2+ products, e.g., ethylene) is frequently impeded by rate weak carbon intermediates' surface adsorption strength. Here, we fabricate range Cu catalysts comprising fine-tuned Cu(111)/Cu2O(111) interface boundary density crystal structures aimed at optimizing rate-determining step decreasing thermodynamic barriers adsorption. Utilizing engineering, attain Faradaic efficiency (51.9 ± 2.8) % partial current (34.5 6.4) mA·cm−2 C2+ feed condition (5% v/v), comparing state-of-art electrolysis. In contrast prevailing belief that activation ( $${{CO}}_{2}+{e}^{-}+\, * \,\to {}^{ }{CO}_{2}^{-}$$ ) governs reaction rate, discover that, under conditions, shifts generation *COOH $${}^{ } {{CO}}_{2}^{-}+{H}_{2}O\to {COOH}+{{OH}}^{-}({aq})$$ Cu0/Cu1+ boundary, resulting better production performance. The development operate resembling waste holds promise reduction. authors report vacuum calcination approach regulating on Cu-based can electro-catalyze low-concentration CO2.

Language: Английский

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Enhancing local K⁺ adsorption by high-density cube corners for efficient electroreduction of CO₂ to C₂₊ products

Chemical Science, Journal Year: 2024, Volume and Issue: 15(28), P. 10858 - 10866

Published: Jan. 1, 2024

Enhancing the field effect and increasing surface of Cu 2 O crystals are beneficial for adsorption *CO intermediates reduction C–C coupling energy barriers, thereby effectively reducing CO to C 2+ products.

Language: Английский

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Steering Geometric Reconstruction of Bismuth with Accelerated Dynamics for CO2 Electroreduction

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(34)

Published: June 5, 2024

Bismuth-based materials have emerged as promising catalysts in the electrocatalytic reduction of CO

Language: Английский

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

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(15), P. 11857 - 11864

Published: July 25, 2024

Low-cost copper (Cu)-based electrocatalysts have been widely established with the special capability of generating C2+ products from CO2 reduction reaction (CO2RR). However, efficient formate production has rarely achieved due to instant most reported Cu-based catalysts upon CO2RR, and derived metallic Cu compromises C1 selectivity. Herein, we demonstrate that incorporation alkali metal ions is intrinsically effective for stabilizing Cu(I)–S bonds by forming ternary sulfides (M–Cu(I)–S, M = Na, K, Rb). The strengthened Cu–S can be well preserved in M–Cu(I)–S during contributing protonation effect thus highly formate. Moreover, also exhibit enhanced electrical conductivity relative Cu2S, favorably promoting kinetics. Accordingly, RbCu7S4 as a representative catalyst achieves Faradaic efficiency 90.4 ± 1.3% at only −0.7 V versus reversible hydrogen electrode (VRHE), high partial current density 272.1 mA cm–2 stable operation over 72 h. This study could provide different series on an industrial scale CO2RR.

Language: Английский

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Conductive Zeolite Supported Indium–Tin Alloy Nanoclusters for Selective and Scalable Formic Acid Electrosynthesis

Advanced Materials, Journal Year: 2024, Volume and Issue: unknown

Published: July 31, 2024

Abstract Upgrading excess CO 2 toward the electrosynthesis of formic acid is significant research and commercial interest. However, simultaneously achieving high selectivity industrially relevant current densities ‐to‐formate conversion remains a grand challenge for practical implementations. Here, an electrically conductive zeolite support strategically designed by implanting Sn ions into skeleton structure Y, which impregnates ultrasmall In 0.2 0.8 alloy nanoclusters supercages tailored 12‐ring framework. The prominent electronic geometric interactions between nanoalloy lead to delocalization electron density that enhances orbital hybridizations active site *OCHO intermediate. Thus, energy barrier rate‐limiting formation step reduced, facilitating electrocatalytic hydrogenation acid. Accordingly, developed electrocatalyst achieves industrial‐level partial 322 mA cm −2 remarkable Faradaic efficiency 98.2% formate production stably maintains above 93% at over 102 h. This work opens up new opportunities zeolite‐based electrocatalysts from electrolysis practically accessible electrocatalysis conversion.

Language: Английский

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Regulating p-orbital electronic configuration of In2O3 by thickness-controlled carbon layer for efficient electrocatalytic CO2 reduction to HCOOH

Applied Catalysis B Environment and Energy, Journal Year: 2024, Volume and Issue: unknown, P. 124596 - 124596

Published: Sept. 1, 2024

Language: Английский

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In Situ and Operando Spectroscopic Techniques for Electrochemical Energy Storage and Conversion Applications

The Journal of Physical Chemistry C, Journal Year: 2024, Volume and Issue: 128(45), P. 19055 - 19070

Published: Nov. 1, 2024

Understanding the mechanisms of action fundamental redox processes is great interest for development more active catalysts and materials energy storage conversion devices. To gain insight into those processes, spectroscopic techniques performed in situ operando are widely used. In this work, we summarize recent advances UV–vis, infrared (IR), Raman, X-ray absorption spectroscopy (XAS), photoelectron (XPS) applications. We then provide an outlook use these techniques, focusing on improving their temporal spatial resolution combining multiple one experiment (i.e., using a multispectroscopy approach). Finally, overview advancements machine learning field our perspective its future

Language: Английский

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