Accelerating electrochemical CO2 reduction to multi-carbon products via asymmetric intermediate binding at confined nanointerfaces

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Март 9, 2023

Abstract Electrochemical CO 2 reduction (CO R) to ethylene and ethanol enables the long-term storage of renewable electricity in valuable multi-carbon (C 2+ ) chemicals. However, carbon–carbon (C–C) coupling, rate-determining step R C conversion, has low efficiency poor stability, especially acid conditions. Here we find that, through alloying strategies, neighbouring binary sites enable asymmetric binding energies promote -to-C electroreduction beyond scaling-relation-determined activity limits on single-metal surfaces. We fabricate experimentally a series Zn incorporated Cu catalysts that show increased CO* surface coverage for fast C–C coupling consequent hydrogenation under electrochemical Further optimization reaction environment at nanointerfaces suppresses hydrogen evolution improves utilization acidic achieve, as result, high 31 ± 2% single-pass yield mild-acid pH 4 electrolyte with >80% efficiency. In single flow cell electrolyzer, realize combined performance 91 Faradaic notable 73 efficiency, full-cell energy 24 1% conversion commercially relevant current density 150 mA cm −2 over h.

Язык: Английский

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Cu-Zn-based alloy/oxide interfaces for enhanced electroreduction of CO2 to C2+ products

Journal of Energy Chemistry, Год журнала: 2023, Номер 83, С. 90 - 97

Опубликована: Май 11, 2023

Язык: Английский

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Multiscale CO₂ Electrocatalysis to C₂₊ Products: Reaction Mechanisms, Catalyst Design, and Device Fabrication

Chemical Reviews, Год журнала: 2023, Номер 123(17), С. 10530 - 10583

Опубликована: Авг. 17, 2023

Electrosynthesis of value-added chemicals, directly from CO2, could foster achievement carbon neutral through an alternative electrical approach to the energy-intensive thermochemical industry for utilization. Progress in this area, based on electrogeneration multicarbon products CO2 electroreduction, however, lags far behind that C1 products. Reaction routes are complicated and kinetics slow with scale up high levels required commercialization, posing significant problems. In review, we identify summarize state-of-art progress synthesis a multiscale perspective discuss current hurdles be resolved generation reduction including atomistic mechanisms, nanoscale electrocatalysts, microscale electrodes, macroscale electrolyzers guidelines future research. The review ends cross-scale links discrepancies between different approaches extensions performance stability issues arise industrial environment.

Язык: Английский

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C₂₊ Selectivity for CO₂ Electroreduction on Oxidized Cu-Based Catalysts

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(26), С. 14335 - 14344

Опубликована: Июнь 21, 2023

Design for highly selective catalysts CO2 electroreduction to multicarbon (C2+) fuels is pressing and important. There is, however, presently a poor understanding of selectivity toward C2+ species. Here we report the first time method judiciously combined quantum chemical computations, artificial-intelligence (AI) clustering, experiment development model relationship between product composition oxidized Cu-based catalysts. We 1) evidence that Cu surface more significantly facilitates C-C coupling, 2) confirm critical potential condition(s) this oxidation state under different metal doping components viaab initio thermodynamics computation, 3) establish an inverted-volcano experimental Faradaic efficiency using multidimensional scaling (MDS) results based on physical properties dopant elements, 4) demonstrate design electrocatalysts selectively generate product(s) through co-doping strategy early late transition metals. conclude combination theoretical AI can be used practically relationships descriptors complex reactions. Findings will benefit researchers in designing conversions products.

Язык: Английский

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SiO₂ assisted Cu⁰–Cu⁺–NH₂ composite interfaces for efficient CO₂ electroreduction to C₂₊ products

Journal of Materials Chemistry A, Год журнала: 2023, Номер 12(2), С. 1218 - 1232

Опубликована: Дек. 13, 2023

SiO 2 assisted abundant Cu 0 –Cu + –NH composite interfaces enhance the adsorption and activation of CO H O, strengthen intermediates, promote C–C coupling to produce C 2+ products.

Язык: Английский

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Why Is C–C Coupling in CO₂ Reduction Still Difficult on Dual-Atom Electrocatalysts?

ACS Catalysis, Год журнала: 2023, Номер 13(14), С. 9695 - 9705

Опубликована: Июль 10, 2023

The emerging metal–nitrogen–carbon (M–N–C) dual–atom catalysts (DACs) have been expected to generate multicarbon products in the CO2 reduction reaction (CO2RR) due presence of multimetal sites DACs. Unfortunately, numerous recent experiments suggested that almost no DAC could effectively produce a high quantity products. To uncover reason for this phenomenon, we probed surface states typical homonuclear and heteronuclear DACs explored mechanisms CO2RR by spin-polarized density functional theory calculations with van der Waals interactions. Contrary conventional hypothesis C–C coupling can occur through metal-top sites, Pourbaix analyses indicate CO preferentially occupies bridge between two metals, which would hinder subsequent coupling. Moreover, according energy variation, occurring on is not feasible both thermodynamics kinetics. Based derived microkinetic models CO2RR, formation more favorable than other products, consistent current experimental results. Furthermore, found double-side occupancy also if molecules penetrate carbon layer large defect, lead HCOOH CO2RR. By developing an analytical framework combining state analysis, activity modeling, electronic structure work reveals why remains difficult provides insights into regulating adsorption strength *CO site enhance selectivity at

Язык: Английский

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Tuning Coordination Structures of Zn Sites Through Symmetry‐Breaking Accelerates Electrocatalysis

Advanced Materials, Год журнала: 2023, Номер 36(4)

Опубликована: Авг. 31, 2023

Manipulating the coordination environment of individual active sites in a precise manner remains an important challenge electrocatalytic reactions. Herein, inspired by theoretical predictions, facile procedure to synthesize series symmetry-breaking zinc metal-organic framework (Zn-MOF) catalysts with well-defined structures is presented. Benefiting from optimized microenvironment regulated symmetry-breaking, Zn-N

Язык: Английский

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Electronic modulation of a single-atom-based tandem catalyst boosts CO₂ photoreduction to ethanol

Energy & Environmental Science, Год журнала: 2023, Номер 16(12), С. 5956 - 5969

Опубликована: Янв. 1, 2023

A single-atom-based tandem photocatalyst (In 2 O 3 /Cu–O ) is fabricated for efficient CO -to-ethanol conversion. The electronic interaction between Cu and In promotes C–C coupling of *CO (on site) *COH Cu–O to form OC–COH species.

Язык: Английский

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Lattice Oxygen Activation through Deep Oxidation of Co₄N by Jahn–Teller–Active Dopants for Improved Electrocatalytic Oxygen Evolution

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(33)

Опубликована: Май 27, 2024

Triggering the lattice oxygen oxidation mechanism is crucial for improving evolution reaction (OER) performance, because it could bypass scaling relation limitation associated with conventional adsorbate through direct formation of oxygen-oxygen bond. High-valence transition metal sites are favorable activating oxygen, but deep pre-catalysts suffers from a high thermodynamic barrier. Here, taking advantage Jahn-Teller (J-T) distortion induced structural instability, we incorporate high-spin Mn

Язык: Английский

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Oxygen-Bridged Cu Binuclear Sites for Efficient Electrocatalytic CO₂ Reduction to Ethanol at Ultralow Overpotential

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(13), С. 9365 - 9374

Опубликована: Март 21, 2024

Electrocatalytic CO2 reduction (CO2RR) to alcohols offers a promising strategy for converting waste into valuable fuels/chemicals but usually requires large overpotentials. Herein, we report catalyst comprising unique oxygen-bridged Cu binuclear sites (CuOCu-N4) with Cu···Cu distance of 3.0–3.1 Å and concomitant conventional Cu–N4 mononuclear on hierarchical nitrogen-doped carbon nanocages (hNCNCs). The exhibits state-of-the-art low overpotential 0.19 V (versus reversible hydrogen electrode) ethanol an outstanding Faradaic efficiency 56.3% at ultralow potential −0.30 V, high-stable active-site structures during the CO2RR as confirmed by operando X-ray adsorption fine structure characterization. Theoretical simulations reveal that CuOCu-N4 greatly enhance C–C coupling potentials, while Cu-N4 hNCNC support increase local CO concentration production CuOCu-N4. This study provides convenient approach advanced site catalysts deep understanding mechanism.

Язык: Английский

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