Improving CO₂-to-C₂₊ Product Electroreduction Efficiency via Atomic Lanthanide Dopant-Induced Tensile-Strained CuO_x Catalysts

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(17), P. 9857 - 9866

Published: April 24, 2023

Cu is a promising electrocatalyst in CO2 reduction reaction (CO2RR) to high-value C2+ products. However, as important C-C coupling active sites, the Cu+ species usually unstable under conditions. How atomic dopants affect performance of Cu-based catalysts interesting be studied. Herein, we first calculated difference between thermodynamic limiting potentials CO2RR and hydrogen evolution reaction, well *CO binding energy over Cu2O doped with different metals, results indicated that doping Gd into could improve catalyst effectively. On basis theoretical study, designed Gd1/CuOx catalysts. The distinctive electronic structure large ion radii not only keep stable during but also induce tensile strain Gd1/CuOx, resulting excellent for electroreduction Faradic efficiency products reach 81.4% product partial current density 444.3 mA cm-2 at -0.8 V vs reversible electrode. Detailed experimental studies revealed enhanced activation on catalyst, stabilized key intermediate O*CCO, reduced barrier reaction.

Language: Английский

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Stabilizing Copper by a Reconstruction-Resistant Atomic Cu–O–Si Interface for Electrochemical CO₂ Reduction

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(15), P. 8656 - 8664

Published: April 8, 2023

Copper (Cu), a promising catalyst for electrochemical CO2 reduction (CO2R) to multi-electron products, suffers from an unavoidable and uncontrollable reconstruction process during the reaction, which not only may lead deactivation but also brings great challenges exploration of structure-performance relationship. Herein, we present efficient strategy stabilizing Cu with silica synthesize reconstruction-resistant CuSiOx amorphous nanotube catalysts abundant atomic Cu-O-Si interfacial sites. The strong interaction between makes sites ultrastable in CO2R reaction without any apparent reconstruction, thus exhibiting high CO2-to-CH4 selectivity (72.5%) stability (FECH4 remains above 60% after 12 h test). A remarkable conversion rate 0.22 μmol cm-2 s-1 was achieved flow cell device. This work provides very route design highly active stable Cu-based catalysts.

Language: Английский

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Rapid Self-Decomposition of g-C₃N₄ During Gas–Solid Photocatalytic CO₂ Reduction and Its Effects on Performance Assessment

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(8), P. 4560 - 4570

Published: April 4, 2022

We report direct evidence of the rapid self-decomposition graphitic carbon nitride (g-C3N4), a popular photo (electro) catalyst, during gas–solid photocatalytic reaction. Crucially, average rate CO production from light-induced g-C3N4 in Ar is almost equal to that CO2 atmosphere, and products include CO, CO2, NO2, NO2–/NO3–. Using experimental theoretical studies, we reveal chemical instability related adsorbed hydroxyl groups (OHads) on catalyst surface. Specifically, electronic interactions between OHads reduce stability C–N═C bonds, photogenerated charge carriers attack structural units g-C3N4, leading decomposition. Theoretical calculations indicate reaction more thermodynamically favorable than reduction Overall, these findings demonstrate importance need fully consider when evaluating redox performance.

Language: Английский

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Unraveling the Influence of Oxygen Vacancy Concentration on Electrocatalytic CO₂ Reduction to Formate over Indium Oxide Catalysts

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(6), P. 4021 - 4029

Published: March 8, 2023

Rational engineering of oxygen vacancies in a metal oxide-based catalyst represents an effective strategy to regulate catalytic performances by influencing both their electrochemical active surface areas and the microelectronic structure. However, precise control modulation concentration uniformity on still remains inadequately explored poorly elucidated. Herein, we develop facile method prepare series In2O3 nanorods with varying vacancy concentrations for efficient electrolytic CO2 reduction formate. Experimental results theoretical calculations reveal that abundant significantly improve activation promote production *HCOO intermediates, achieving maximum formate Faradaic efficiency 91.2% at −1.27 V vs reversible hydrogen electrode (RHE) high partial current density and, meanwhile, superior stability. The underlying relationship between reaction (CO2RR) performance was further established. This work offers feasible finely tune p-block catalysts highly CO2RR.

Language: Английский

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Modulating adsorbed hydrogen drives electrochemical CO2-to-C2 products

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Aug. 1, 2023

Electrocatalytic CO2 reduction is a typical reaction involving two reactants (CO2 and H2O). However, the role of H2O dissociation, which provides active *H species to multiple protonation steps, usually overlooked. Herein, we construct dual-active sites catalyst comprising atomic Cu nanoparticles supported on N-doped carbon matrix. Efficient electrosynthesis multi-carbon products achieved with Faradaic efficiency approaching 75.4% partial current density 289.2 mA cm-2 at -0.6 V. Experimental theoretical studies reveal that facilitate C-C coupling step through *CHO dimerization, while boost dissociation form *H. The generated migrate modulate coverage NPs, thus promote *CO-to-*CHO. effect single-sites gives rise catalytic performance.

Language: Английский

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Tailoring Coordination Microenvironment of Cu(I) in Metal–Organic Frameworks for Enhancing Electroreduction of CO₂to CH₄

Advanced Functional Materials, Journal Year: 2022, Volume and Issue: 32(36)

Published: June 29, 2022

Abstract The coordination microenvironment of metal active sites in metal–organic frameworks (MOFs) plays a crucial role its performance for electrochemical CO 2 reduction reaction (CO RR). However, it remains challenge to clarify the structure–performance relationship RR catalyzed by MOFs. Herein, series MOFs with different microenvironments Cu(I) (CuCl, CuBr, and CuI) evaluate their performances is synthesized. With increasing radius halogen atom, adsorption capacity increases d‐band center Cu positively shifts Fermi level, leading enhance selectivity CH 4 conversion. CuI gives highest total Faradaic efficiency (FE) 83.2%, FE up 57.2% partial current density 60.7 mA cm −2 at −1.08 V versus reversible hydrogen electrode. Theoretical calculations reveal that shifted site contributes reduced formation energies *CH O 3 intermediates, which potential‐determining step thus facilitates electrocatalytic . This study opens new avenue studying between electroreduction

Language: Английский

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Coupling electrocatalytic cathodic nitrate reduction with anodic formaldehyde oxidation at ultra-low potential over Cu₂O

Energy & Environmental Science, Journal Year: 2023, Volume and Issue: 16(6), P. 2696 - 2704

Published: Jan. 1, 2023

An HCHO oxidation reaction for electrocatalytic ammonia synthesis was developed to replace the sluggish anodic oxygen evolution involving oxidative dehydrogenation and tandem pathways.

Language: Английский

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A Honeycomb‐Like Porous Crystalline Hetero‐Electrocatalyst for Efficient Electrocatalytic CO₂ Reduction

Advanced Materials, Journal Year: 2022, Volume and Issue: 34(44)

Published: Sept. 11, 2022

Abstract Porous heterostructured electrocatalysts with multifunctionality and synergistic effect have much benefit for efficient electrocatalytic CO 2 reduction reaction (CO RR), yet it still remains a daunting challenge to explore heterostructures based on covalent organic frameworks (COFs) metal–organic (MOFs) in this field. Here, series of honeycomb‐like porous crystalline hetero‐electrocatalysts (MCH‐ X , = 1–4, stands the numbered sample obtained from different MOF doses synthesis MCH) are synthesized, these successfully applied RR. The specially designed integrated MOF‐template ultrathin COF‐coating enable adsorption/activation conversion into CH 4 . best them, MCH‐3, shows greatly inhibited H evolution, excellent current density (−398.1 mA cm −2 ), superior (76.7%) physical mixture (38.0%), MOF@COF without morphology (47.7%), bare COF (37.5%) (15.9%) at −1.0 V. Based functional theory calculations various characterizations, vital roles facilitating adsorption/activation, stabilizing intermediates, conquering energy barrier rate‐determining step intensively studied.

Language: Английский

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Chlorine anion stabilized Cu2O/ZnO photocathode for selective CO2 reduction to CH4

Applied Catalysis B Environment and Energy, Journal Year: 2022, Volume and Issue: 321, P. 122035 - 122035

Published: Oct. 1, 2022

Language: Английский

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Enhancing Selective Electrochemical CO₂ Reduction by In Situ Constructing Tensile-Strained Cu Catalysts

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(7), P. 4711 - 4718

Published: March 23, 2023

Heteroatom-doped Cu-based catalysts have been found to show not only enhanced activity of electrochemical CO2 reduction reaction (CO2RR) but also the possibility tune selectivity CO2RR. However, complex and variable nature materials renders it difficult elucidate origin improved performance, which further hinders rational design catalysts. Here, we demonstrate that CO2RR can be tuned by manipulating lattice strain The combined operando ex situ spectroscopic characterizations reveal initial compressively strained Sn-doped CuO could converted tensile-strained Sn/Cu alloy under conditions. In attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEITAS) theoretical calculations favor CO formation due preponderant adsorption *CO much lower free energies *COOH, thus effectively suppressing dimerization process production HCOOH H2. This work provides a strategy performance strain.

Language: Английский

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