Atomic Indium Catalysts for Switching CO₂ Electroreduction Products from Formate to CO

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(18), С. 6877 - 6885

Опубликована: Апрель 15, 2021

Electrochemical reduction of CO2 to chemicals and fuels is an interesting attractive way mitigate greenhouse gas emissions energy shortages. In this work, we report the use atomic catalysts for electroreduction CO. The were anchored on N-doped carbon (InA/NC) through pyrolysis In-based metal–organic frameworks (MOFs) dicyandiamide. It was discovered that InA/NC had outstanding performance selective CO production in mixed electrolyte ionic liquid/MeCN. different from those common materials, which formate/formic acid formed as main product. faradaic efficiency (FE) total current density 97.2% 39.4 mA cm-2, respectively, with a turnover frequency (TOF) ∼40 000 h–1. one highest TOF date all reported. addition, catalyst remarkable stability. Detailed study indicated higher double-layer capacitance, larger adsorption capacity, lower interfacial charge transfer resistance, leading high activity reduction. Control experiments theoretical calculations showed In–N site not only beneficial dissociation COOH* form but also hinders formate formation, selectivity toward instead formate.

Язык: Английский

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Recent advances in MXene-based nanoarchitectures as electrode materials for future energy generation and conversion applications

Coordination Chemistry Reviews, Год журнала: 2021, Номер 435, С. 213806 - 213806

Опубликована: Фев. 15, 2021

Язык: Английский

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Engineering graphitic carbon nitride (g-C₃N₄) for catalytic reduction of CO₂to fuels and chemicals: strategy and mechanism

Green Chemistry, Год журнала: 2021, Номер 23(15), С. 5394 - 5428

Опубликована: Янв. 1, 2021

This review summarises the structural-compositional engineering of carbon nitride (g-C₃N₄) for electrocatalytic and photocatalytic CO₂reduction to chemicals fuels experimentally theoretically.

Язык: Английский

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Highly Efficient CO₂ Electroreduction to Methanol through Atomically Dispersed Sn Coupled with Defective CuO Catalysts

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(40), С. 21979 - 21987

Опубликована: Авг. 4, 2021

Abstract Using renewable electricity to drive CO 2 electroreduction is an attractive way achieve carbon‐neutral energy cycle and produce value‐added chemicals fuels. As important platform molecule clean fuel, methanol requires 6‐electron transfer in the process of reduction. Currently, suffers from poor efficiency low selectivity. Herein, we report first work design atomically dispersed Sn site anchored on defective CuO catalysts for methanol. It exhibits high Faradaic (FE) 88.6 % with a current density 67.0 mA cm −2 remarkable stability H‐cell, which highest FE(methanol) such compared results reported date. The atomic site, adjacent oxygen vacancy support cooperate very well, leading higher double‐layer capacitance, larger adsorption capacity lower interfacial charge resistance. Operando experiments functional theory calculations demonstrate that catalyst beneficial activation via decreasing barrier *COOH dissociation form *CO. obtained key intermediate *CO then bound Cu species further reduction, selectivity toward

Язык: Английский

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Strain Relaxation in Metal Alloy Catalysts Steers the Product Selectivity of Electrocatalytic CO₂ Reduction

ACS Nano, Год журнала: 2022, Номер 16(2), С. 3251 - 3263

Опубликована: Янв. 28, 2022

Strain engineering in bimetallic alloy structures is of great interest electrochemical CO2 reduction reactions (CO2RR), which it simultaneously improves electrocatalytic activity and product selectivity by optimizing the binding properties intermediates. However, a reliable synthetic strategy systematic understanding strain effects CO2RR are still lacking. Herein, we report relaxation used to determine lattice strains bimetal MNi alloys (M = Pd, Ag, Au) realize an outstanding CO2-to-CO Faradaic efficiency 96.6% show durability toward Zn-CO2 battery. Molecular dynamics (MD) simulations predict that strained PdNi (s-PdNi) correlated with increases synthesis temperature, high temperature activation energy drives complete atomic mixing multiple metal atoms allow for regulation strains. Density functional theory (DFT) calculations reveal effectively formation energies *COOH *CO intermediates on s-PdNi surfaces, as also verified situ spectroscopic investigations. This approach provides promising catalyst design, enabling independent optimization reaction improve catalytic simultaneously.

Язык: Английский

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Interatomic Electronegativity Offset Dictates Selectivity When Catalyzing the CO₂ Reduction Reaction

Advanced Energy Materials, Год журнала: 2022, Номер 12(26)

Опубликована: Июнь 1, 2022

Abstract Achieving efficient efficiency and selectivity for the electroreduction of CO 2 to value‐added feedstocks has been challenging, due thermodynamic stability molecules competing hydrogen evolution reaction. Herein, a dual‐single‐atom catalyst consisting atomically dispersed CuN 4 NiN bimetal sites is synthesized with electrospun carbon nanofibers (CuNi‐DSA/CNFs). Theoretical experimental studies reveal strong electron interactions induced by electronegativity offset between Cu Ni atoms. The delicately averaged compensated electronic structures result in an effect that optimizes adsorption strength *COOH intermediate boosts reduction reaction (CO RR) kinetics, notably promoting intrinsic activity catalyst. CuNi‐DSA/CNFs exhibits outstanding FE 99.6% across broad potential window −0.78– −1.18 V (vs reversible electrode), high turnover frequency 2870 h –1 , excellent durability (25 h). Furthermore, aqueous Zn‐CO battery power conversion constructed. This atomic‐level dual‐atom provides appealing direction develop advanced electrocatalysts RR.

Язык: Английский

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In-situ spectroscopic probe of the intrinsic structure feature of single-atom center in electrochemical CO/CO2 reduction to methanol

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

Опубликована: Июнь 9, 2023

While exploring the process of CO/CO2 electroreduction (COxRR) is great significance to achieve carbon recycling, deciphering reaction mechanisms so as further design catalytic systems able overcome sluggish kinetics remains challenging. In this work, a model single-Co-atom catalyst with well-defined coordination structure developed and employed platform unravel underlying mechanism COxRR. The as-prepared exhibits maximum methanol Faradaic efficiency high 65% at 30 mA/cm2 in membrane electrode assembly electrolyzer, while on contrary, reduction pathway CO2 strongly decreased CO2RR. In-situ X-ray absorption Fourier-transform infrared spectroscopies point different adsorption configuration *CO intermediate CORR compared that CO2RR, weaker stretching vibration C-O bond former case. Theoretical calculations evidence low energy barrier for formation H-CoPc-CO- species, which critical factor promoting electrochemical CO methanol.

Язык: Английский

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Stabilizing intermediates and optimizing reaction processes with N doping in Cu2O for enhanced CO2 electroreduction

Applied Catalysis B Environment and Energy, Год журнала: 2022, Номер 308, С. 121191 - 121191

Опубликована: Фев. 7, 2022

Язык: Английский

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Stabilizing copper sites in coordination polymers toward efficient electrochemical C-C coupling

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

Опубликована: Янв. 30, 2023

Electroreduction of carbon dioxide with renewable electricity holds promise for achieving net-zero emissions. Single-site catalysts have been reported to catalyze carbon-carbon (C-C) coupling-the indispensable step more valuable multi-carbon (C2+) products-but were proven be transformed in situ metallic agglomerations under working conditions. Here, we report a stable single-site copper coordination polymer (Cu(OH)BTA) periodic neighboring coppers and it exhibits 1.5 times increase C2H4 selectivity compared its counterpart at 500 mA cm-2. In-situ/operando X-ray absorption, Raman, infrared spectroscopies reveal that the catalyst remains structurally does not undergo dynamic transformation during reaction. Electrochemical kinetic isotope effect analyses together computational calculations show Cu provides suitably-distanced dual sites enable energetically favorable formation an *OCCHO intermediate post rate-determining CO hydrogenation. Accommodation this imposes little changes conformational energy structure C-C coupling. We stably operate full-device CO2 electrolysis industry-relevant current one ampere 67 h membrane electrode assembly. The polymers provide perspective on designing molecularly stable, electrochemical conversion.

Язык: Английский

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The 2022 solar fuels roadmap

Journal of Physics D Applied Physics, Год журнала: 2022, Номер 55(32), С. 323003 - 323003

Опубликована: Май 13, 2022

Abstract Renewable fuel generation is essential for a low carbon footprint economy. Thus, over the last five decades, significant effort has been dedicated towards increasing performance of solar fuels generating devices. Specifically, to hydrogen efficiency photoelectrochemical cells progressed steadily its fundamental limit, and faradaic valuable products in CO 2 reduction systems increased dramatically. However, there are still numerous scientific engineering challenges that must be overcame order turn into viable technology. At electrode device level, conversion efficiency, stability selectivity significantly. Meanwhile, these metrics maintained when scaling up devices while maintaining an acceptable cost footprint. This roadmap surveys different aspects this endeavor: system benchmarking, scaling, various approaches photoelectrodes design, materials discovery, catalysis. Each sections focuses on single topic, discussing state art, key advancements required meet them. The can used as guide researchers funding agencies highlighting most pressing needs field.

Язык: Английский

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