Electrochemical reduction of carbon dioxide to multicarbon (C₂₊) products: challenges and perspectives

Energy & Environmental Science, Год журнала: 2023, Номер 16(11), С. 4714 - 4758

Опубликована: Янв. 1, 2023

This review analyzes advanced catalysts and C 2+ synthesis mechanisms based on theoretical explorations in situ / operando characterizations. Triphasic interface optimization is discussed for the potential of industry-compatible stability.

Язык: Английский

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Modulating adsorbed hydrogen drives electrochemical CO2-to-C2 products

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

Опубликована: Авг. 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.

Язык: Английский

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Asymmetric Low-Frequency Pulsed Strategy Enables Ultralong CO₂ Reduction Stability and Controllable Product Selectivity

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(4), С. 2195 - 2206

Опубликована: Янв. 11, 2023

Copper-based catalysts are widely explored in electrochemical CO2 reduction (CO2RR) because of their ability to convert into high-value-added multicarbon products. However, the poor stability and low selectivity limit practical applications these catalysts. Here, we proposed a simple efficient asymmetric low-frequency pulsed strategy (ALPS) significantly enhance Cu-dimethylpyrazole complex Cu3(DMPz)3 catalyst CO2RR. Under traditional potentiostatic conditions, exhibited CO2RR performance with Faradaic efficiency (FE) 34.5% for C2H4 FE 5.9% CH4 as well less than 1 h. We optimized two distinguished ALPS methods toward C2H4, correspondingly. The high selectivities catalytic product (FECH4 = 80.3% above 76.6% within 24 h) (FEC2H4 70.7% 66.8% can be obtained, respectively. ultralong 300 h > 60%) 145 50%) was also recorded method. Microscopy (HRTEM, SAED, HAADF) measurements revealed that method situ generated stabilized extremely dispersive active Cu-based clusters (∼2.7 nm) from Cu3(DMPz)3. Meanwhile, ex spectroscopies (XPS, AES, XANES) XANES indicated this modulated Cu oxidation states, such Cu(0 I) Cu(I II) selectivity. mechanism under by ATR-FTIR, Raman, DFT computation. provide new opportunity boost

Язык: Английский

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Surface passivation for highly active, selective, stable, and scalable CO2 electroreduction

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

Опубликована: Авг. 3, 2023

Electrochemical conversion of CO2 to formic acid using Bismuth catalysts is one the most promising pathways for industrialization. However, it still difficult achieve high production at wide voltage intervals and industrial current densities because Bi are often poisoned by oxygenated species. Herein, we report a Bi3S2 nanowire-ascorbic hybrid catalyst that simultaneously improves selectivity, activity, stability applied voltages. Specifically, more than 95% faraday efficiency was achieved formate formation over potential range above 1.0 V ampere-level densities. The observed excellent catalytic performance attributable unique reconstruction mechanism form defective sites while ascorbic layer further stabilized trapping poisoning hydroxyl groups. When used in an all-solid-state reactor system, newly developed efficient pure 120 hours 50 mA cm-2 (200 cell current).

Язык: Английский

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Coordinating the Edge Defects of Bismuth with Sulfur for Enhanced CO₂ Electroreduction to Formate

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(25)

Опубликована: Апрель 20, 2023

Bismuth-based materials have been recognized as promising catalysts for the electrocatalytic CO2 reduction reaction (ECO2 RR). However, they show poor selectivity due to competing hydrogen evolution (HER). In this study, we developed an edge defect modulation strategy Bi by coordinating defects of bismuth (Bi) with sulfur, promote ECO2 RR and inhibit HER. The prepared demonstrate excellent product selectivity, a high HCOO- Faraday efficiency ≈95 % partial current ≈250 mA cm-2 under alkaline electrolytes. Density function theory calculations reveal that sulfur tends bind defects, reducing coordination-unsaturated sites (*H adsorption sites), regulating charge states neighboring improve *OCHO adsorption. This work deepens our understanding mechanism on bismuth-based catalysts, guiding design advanced catalysts.

Язык: Английский

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The dual-active-site tandem catalyst containing Ru single atoms and Ni nanoparticles boosts CO2 methanation

Applied Catalysis B Environment and Energy, Год журнала: 2022, Номер 323, С. 122190 - 122190

Опубликована: Ноя. 17, 2022

Язык: Английский

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Cascade Dual Sites Modulate Local CO Coverage and Hydrogen-Binding Strength to Boost CO₂ Electroreduction to Ethylene

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(8), С. 5693 - 5701

Опубликована: Фев. 9, 2024

Rationally modulating the binding strength of reaction intermediates on surface sites copper-based catalysts could facilitate C–C coupling to generate multicarbon products in an electrochemical CO2 reduction reaction. Herein, theoretical calculations reveal that cascade Ag–Cu dual synergistically increase local CO coverage and lower kinetic barrier for protonation, leading enhanced asymmetric C2H4. As a proof concept, Cu3N-Ag nanocubes (NCs) with Ag located partial Cu Cu3N unit center are successfully synthesized. The Faraday efficiency current density C2H4 over NCs 7.8 9.0 times those NCs, respectively. In situ spectroscopies combined confirm produce promote *COCHO, significantly enhancing generation Our work provides new insights into catalysis strategy at atomic scale boosting products.

Язык: Английский

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Strong Hydrogen-Bonded Interfacial Water Inhibiting Hydrogen Evolution Kinetics to Promote Electrochemical CO₂ Reduction to C₂₊

ACS Catalysis, Год журнала: 2024, Номер 14(5), С. 3457 - 3465

Опубликована: Фев. 19, 2024

Interfacial water is an important participant in electrochemical CO2 reduction (CO2RR), directly affecting the kinetics of hydrogenation steps occurring CO2RR and competitive hydrogen evolution reaction (HER). However, its structural composition dynamic are difficult to investigate due bulk interference bias dependence. Herein, we adopt situ vibration spectroscopy combined with molecular dynamics simulations probe change interfacial structure on electrified hydrophobic electrode surface further explore mechanism origin suppressed HER activity enhanced multicarbon products' selectivity. We reveal that near exhibits rigid intermolecular bonding interaction, degree which increases a potential. The strong bond makes it hard for reorientation leading longer metal–H distance, inhibits dissociation decreases *H coverage. Moderate coverage not only but also ensures intermediates realizing promoted C–C dimerization. A faradaic efficiency 75.2% products was ultimately achieved. Our results provide insights into understanding role controlling selectivity CO2RR.

Язык: Английский

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Designs of Tandem Catalysts and Cascade Catalytic Systems for CO₂ Upgrading

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(43)

Опубликована: Июнь 20, 2023

Upgrading CO2 into multi-carbon (C2+) compounds through the reduction reaction (CO2 RR) offers a practical approach to mitigate atmospheric while simultaneously producing high value chemicals. The pathways for C2+ production involve multi-step proton-coupled electron transfer (PCET) and C-C coupling processes. By increasing surface coverage of adsorbed protons (*Had ) *CO intermediates, kinetics PCET can be accelerated, thereby promoting production. However, *Had are competitively intermediates on monocomponent catalysts, making it difficult break linear scaling relationship between adsorption energies /*CO intermediate. Recently, tandem catalysts consisting multicomponents have been developed improve or by enhancing water dissociation -to-CO auxiliary sites. In this context, we provide comprehensive overview design principles based products. Moreover, development cascade RR catalytic systems that integrate with downstream catalysis has expanded range potential upgrading Therefore, also discuss recent advancements in systems, highlighting challenges perspectives these systems.

Язык: Английский

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

Chem, Год журнала: 2023, Номер 10(1), С. 211 - 233

Опубликована: Сен. 21, 2023

Язык: Английский

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