Hybrid Catalyst Coupling Zn Single Atoms and CuNx Clusters for Synergetic Catalytic Reduction of CO2 DOI
Xiao Hu, Xinyu Liu,

Xin Hu

et al.

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

Published: Feb. 2, 2023

Abstract Reverse water‐gas shift (RWGS) reaction is the initial and necessary step of CO 2 hydrogenation to high value‐added products, regulating selectivity still a fundamental challenge. In present study, an efficient catalyst (CuZnN x @C‐N) composed by Zn single atoms Cu clusters stabilized nitrogen sites reported. It contains saturated four‐coordinate Zn‐N 4 low valence CuN clusters. Monodisperse induces aggregation pyridinic N form structures, which show strong Lewis basicity has adsorption for *CO *COOH intermediates, but weak *CO, thus greatly improves conversion selectivity. The calcined at 700 °C exhibits highest 43.6% under atmospheric pressure, 18.33 times Cu‐ZnO close thermodynamic equilibrium rate (49.9%) . catalytic process, not only adsorbs activates H , also cooperates with adjacent structures jointly activate molecules further promotes This synergistic mechanism will provide new insights developing catalysts.

Language: Английский

Accelerating electrochemical CO2 reduction to multi-carbon products via asymmetric intermediate binding at confined nanointerfaces DOI Creative Commons
Jin Zhang, Chenxi Guo, Susu Fang

et al.

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

Published: March 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.

Language: Английский

Citations

182
Cu-Zn-based alloy/oxide interfaces for enhanced electroreduction of CO2 to C2+ products DOI
Ziyang Zhang, Hao Tian, Lei Bian

et al.

Journal of Energy Chemistry, Journal Year: 2023, Volume and Issue: 83, P. 90 - 97

Published: May 11, 2023

Language: Английский

Citations

141
Multiscale CO2 Electrocatalysis to C2+ Products: Reaction Mechanisms, Catalyst Design, and Device Fabrication DOI
Tianxiang Yan, Xiaoyi Chen,

Lata Kumari

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(17), P. 10530 - 10583

Published: Aug. 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.

Language: Английский

Citations

138
C2+ Selectivity for CO2 Electroreduction on Oxidized Cu-Based Catalysts DOI
Haobo Li,

Yunling Jiang,

Xinyu Li

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(26), P. 14335 - 14344

Published: June 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.

Language: Английский

Citations

93
SiO2 assisted Cu0–Cu+–NH2 composite interfaces for efficient CO2 electroreduction to C2+ products DOI
Ziyang Zhang, Hao Tian, Han Jiao

et al.

Journal of Materials Chemistry A, Journal Year: 2023, Volume and Issue: 12(2), P. 1218 - 1232

Published: Dec. 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.

Language: Английский

Citations

77
Why Is C–C Coupling in CO2 Reduction Still Difficult on Dual-Atom Electrocatalysts? DOI
Weijie Yang,

Zhenhe Jia,

Binghui Zhou

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(14), P. 9695 - 9705

Published: July 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

Language: Английский

Citations

51
Tuning Coordination Structures of Zn Sites Through Symmetry‐Breaking Accelerates Electrocatalysis DOI
Yuntong Sun, Wenjun Fan, Yinghao Li

et al.

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(4)

Published: Aug. 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

Language: Английский

Citations

51
Electronic modulation of a single-atom-based tandem catalyst boosts CO2 photoreduction to ethanol DOI
Shuaiqi Gong, Baoxin Ni,

Xiaoyang He

et al.

Energy & Environmental Science, Journal Year: 2023, Volume and Issue: 16(12), P. 5956 - 5969

Published: Jan. 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.

Language: Английский

Citations

49
Palladium-Copper bimetallic catalysts for electroreduction of CO2 and nitrogenous species DOI

Fengchen Zhou,

Junjun Zhang, Yifan Zhang

et al.

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 509, P. 215802 - 215802

Published: March 26, 2024

Language: Английский

Citations

46
Oxygen-Bridged Cu Binuclear Sites for Efficient Electrocatalytic CO2 Reduction to Ethanol at Ultralow Overpotential DOI
Fengfei Xu, Biao Feng, Zhen Shen

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(13), P. 9365 - 9374

Published: March 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.

Language: Английский

Citations

45