Electron‐Rich Bi Nanosheets Promote CO₂⋅⁻ Formation for High‐Performance and pH‐Universal Electrocatalytic CO₂ Reduction

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(11)

Published: Jan. 20, 2023

Electrochemical CO2 reduction reaction (CO2 RR) to chemical fuels such as formate offers a promising pathway carbon-neutral future, but its practical application is largely inhibited by the lack of effective activation molecules and pH-universal feasibility. Here, we report an electronic structure manipulation strategy electron-rich Bi nanosheets, where electrons transfer from Cu donor acceptor in bimetallic Cu-Bi, enabling RR towards with concurrent high activity, selectivity stability (acidic, neutral alkaline) electrolytes. Combined situ Raman spectra computational calculations unravel that promotes ⋅- formation activate molecules, enhance adsorption strength *OCHO intermediate up-shifted p-band center, thus leading superior activity formate. Further integration robust nanosheets into III-V-based photovoltaic solar cell results unassisted artificial leaf solar-to-formate (STF) efficiency 13.7 %.

Language: Английский

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Kinetically matched C–N coupling toward efficient urea electrosynthesis enabled on copper single-atom alloy

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

Published: Nov. 1, 2023

Chemical C-N coupling from CO2 and NO3-, driven by renewable electricity, toward urea synthesis is an appealing alternative for Bosch-Meiser production. However, the unmatched kinetics in NO3- reduction reactions complexity of C- N-species involved co-reduction render challenge coupling, leading to low yield rate Faradaic efficiency. Here, we report a single-atom copper-alloyed Pd catalyst (Pd4Cu1) that can achieve highly efficient electrosynthesis. The regulated matched steering Cu doping level Pd4Cu1/FeNi(OH)2 interface. Charge-polarized Pdδ--Cuδ+ dual-sites stabilize key *CO *NH2 intermediates promote coupling. synthesized Pd4Cu1-FeNi(OH)2 composite achieves 436.9 mmol gcat.-1 h-1 efficiency 66.4%, as well long cycling stability 1000 h. In-situ spectroscopic results theoretical calculation reveal atomically dispersed lattice promotes deep *NH2, Pd-Cu lower energy barrier pivotal between *CO.

Language: Английский

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Fast Screening for Copper‐Based Bimetallic Electrocatalysts: Efficient Electrocatalytic Reduction of CO₂to C₂₊Products on Magnesium‐Modified Copper

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(51)

Published: Oct. 27, 2022

Electroreduction of CO2 (CO2 RR) into high value-added chemicals is an attractive route to achieve carbon neutrality. However, the development efficient catalyst for RR still largely by trial-and-error and very time-consuming. Herein, we built electrocatalyst testing platform featuring a home-built automatic flow cell accelerate discovery catalysts. A fast screening 109 Cu-based bimetallic catalysts in only 55 h identifies Mg combined with Cu as best C2+ products. The thus designed Mg-Cu achieves Faradaic efficiency (FE) products up 80 % current density 1.0 cm-2 at -0.77 V versus reversible hydrogen electrode (RHE). Systematic experiments situ spectroelectrochemistry analyses show that Mg2+ species stabilize Cu+ sites during promote activation, enhancing *CO coverage C-C coupling.

Language: Английский

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Facet Dopant Regulation of Cu₂O Boosts Electrocatalytic CO₂ Reduction to Formate

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 33(16)

Published: Jan. 25, 2023

Abstract Electrochemical carbon dioxide reduction reaction (CO 2 RR) using clean electric energy provides a sustainable route to generate highly‐valuable chemicals and fuels, which is beneficial for realizing the carbon‐neutral cycle. Up now, achieving narrow product distribution highly targeted selectivity over Cu‐based electrocatalysts still big challenge. Herein, sulfur modification on different crystal planes of cuprous oxide (Cu O) demonstrated, results in an improvement formate generation degrees. Experimental density functional theory (DFT) calculations reveal that species modified surface Cu O (100) facet effectively lower formation key intermediate *OCOH compared with (111) facet. As consequence, p‐Block elements effective strategy optimize adsorption during CO RR, leading selective product.

Language: Английский

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Regulating reconstruction of oxide-derived Cu for electrochemical CO ₂ reduction toward n-propanol

Science Advances, Journal Year: 2023, Volume and Issue: 9(43)

Published: Oct. 27, 2023

Oxide-derived copper (OD-Cu) is the most efficient and likely practical electrocatalyst for CO 2 reduction toward multicarbon products. However, inevitable but poorly understood reconstruction from pristine state to working of OD-Cu under strong conditions largely hinders rational construction catalysts products, especially C 3 products like n-propanol. Here, we simulate CuO Cu O into their derived by molecular dynamics, revealing that CuO-derived (CuOD-Cu) intrinsically has a richer population undercoordinated sites higher surficial atom density than counterpart O-derived (Cu OD-Cu) because vigorous oxygen removal. In situ spectroscopes disclose coordination number CuOD-Cu considerably lower OD-Cu, enabling fast kinetics reaction strengthened binding *C intermediate(s). Benefiting rich sites, achieves remarkable n-propanol faradaic efficiency up ~17.9%, whereas dominantly generates formate.

Language: Английский

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Cation-Induced Interfacial Hydrophobic Microenvironment Promotes the C–C Coupling in Electrochemical CO₂ Reduction

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(8), P. 5532 - 5542

Published: Feb. 16, 2024

The electrochemical carbon dioxide reduction reaction (CO2RR) toward C2 products is a promising way for the clean energy economy. Modulating structure of electric double layer (EDL), especially interfacial water and cation type, useful strategy to promote C–C coupling, but atomic understanding lags far behind experimental observations. Herein, we investigate combined effect alkali metal cations on coupling at Cu(100) electrode/electrolyte interface using ab initio molecular dynamics (AIMD) simulations with constrained MD slow-growth approach. We observe linear correlation between water-adsorbate stabilization effect, which manifests as hydrogen bonds, corresponding alleviation in free energy. role larger cation, compared smaller (e.g., K+ vs Li+), lies its ability approach through desolvation coordinates *CO+*CO moiety, partially substituting hydrogen-bonding stabilizing water. Although this only results marginal barrier it creates local hydrophobic environment scarcity bonds owing great ionic radius, impeding surrounding oxygen adsorbed *CO. This skillfully circumvents further hydrogenation *CO C1 pathway, serving predominant factor facilitates coupling. study unveils comprehensive mechanism cation–water–adsorbate interactions that can facilitate optimization electrolyte EDL efficient CO2RR.

Language: Английский

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Defect-induced triple synergistic modulation in copper for superior electrochemical ammonia production across broad nitrate concentrations

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

Published: April 1, 2024

Abstract Nitrate can be electrochemically degraded to produce ammonia while treating sewage it remains grand challenge simultaneously realize high Faradaic efficiency and production rate over wide-range concentrations in real wastewater. Herein, we report the defect-rich Cu nanowire array electrode generated by in-situ electrochemical reduction, exhibiting superior performance nitrate reduction reaction benefitting from triple synergistic modulation. Notably, delivers current density ranging 50 1100 mA cm −2 across wide (1–100 mM) with 90%. Operando Synchrotron radiation Fourier Transform Infrared Spectroscopy theoretical calculations revealed that defective sites enhance adsorption, promote water dissociation suppress hydrogen evolution. A two-electrode system integrating industrial wastewater glycerol oxidation achieves of 550 at −1.4 V 99.9% selectivity conversion 100 h stability, demonstrating outstanding practicability.

Language: Английский

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Engineering Cu(I)/Cu(0) interfaces for efficient ethanol production from CO2 electroreduction

Chem, Journal Year: 2023, Volume and Issue: 10(1), P. 211 - 233

Published: Sept. 21, 2023

Language: Английский

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Probing electrolyte effects on cation-enhanced CO2 reduction on copper in acidic media

Nature Catalysis, Journal Year: 2024, Volume and Issue: 7(7), P. 807 - 817

Published: June 24, 2024

Language: Английский

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N and OH-Immobilized Cu₃ Clusters In Situ Reconstructed from Single-Metal Sites for Efficient CO₂ Electromethanation in Bicontinuous Mesochannels

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(2), P. 1423 - 1434

Published: Jan. 3, 2024

Cu-based catalysts hold promise for electrifying CO2 to produce methane, an extensively used fuel. However, the activity and selectivity remain insufficient due lack of catalyst design principles steer complex reduction pathways. Herein, we develop a concept carbon-supported Cu by regulating active sites' atomic-scale structures engineering carbon support's mesoscale architecture. This aims provide favorable local reaction microenvironment selective pathway methane. In situ X-ray absorption Raman spectroscopy analyses reveal dynamic reconstruction nitrogen hydroxyl-immobilized Cu3 (N,OH-Cu3) clusters derived from atomically dispersed Cu–N3 sites under realistic conditions. The N,OH-Cu3 possess moderate *CO adsorption affinity low barrier hydrogenation, enabling intrinsically CO2-to-CH4 compared C–C coupling with high energy barrier. Importantly, block copolymer-derived fiber support interconnected mesopores is constructed. unique long-range mesochannels offer H2O-deficient prolong transport path CO intermediate, which could suppress hydrogen evolution favor deep toward methane formation. Thus, newly developed consisting in constructed embedded into bicontinuous achieved unprecedented Faradaic efficiency 74.2% at industry-level current density 300 mA cm–2. work explores effective concepts steering desirable pathways interfacial catalytic systems via modulating site atomic level pore architectures supports on create microenvironments.

Language: Английский

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