Electrocatalysis for CO₂conversion: from fundamentals to value-added products

Chemical Society Reviews, Год журнала: 2021, Номер 50(8), С. 4993 - 5061

Опубликована: Янв. 1, 2021

This timely and comprehensive review mainly summarizes advances in heterogeneous electroreduction of CO₂: from fundamentals to value-added products.

Язык: Английский

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Electrocatalytic Refinery for Sustainable Production of Fuels and Chemicals

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(36), С. 19572 - 19590

Опубликована: Фев. 19, 2021

Abstract Compared to modern fossil‐fuel‐based refineries, the emerging electrocatalytic refinery (e‐refinery) is a more sustainable and environmentally benign strategy convert renewable feedstocks energy sources into transportable fuels value‐added chemicals. A crucial step in conducting e‐refinery processes development of appropriate reactions optimal electrocatalysts for efficient cleavage formation chemical bonds. However, compared well‐studied primary (e.g., O 2 reduction, water splitting), mechanistic aspects materials design complex are yet be settled. To address this challenge, herein, we first present fundamentals heterogeneous electrocatalysis some reactions, then implement these establish framework by coupling situ generated intermediates (integrated reactions) or products (tandem reactions). We also set principles strategies efficiently manipulate reaction pathways.

Язык: Английский

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Active Site Engineering in Porous Electrocatalysts

Advanced Materials, Год журнала: 2020, Номер 32(44)

Опубликована: Июль 14, 2020

Abstract Electrocatalysis is at the center of many sustainable energy conversion technologies that are being developed to reduce dependence on fossil fuels. The past decade has witnessed significant progresses in exploitation advanced electrocatalysts for diverse electrochemical reactions involved electrolyzers and fuel cells, such as hydrogen evolution reaction (HER), oxygen reduction (ORR), CO 2 (CO RR), nitrogen (NRR), (OER). Herein, recent research advances made porous these five important reviewed. In discussions, an attempt highlight advantages multiobjective optimization surface active sites including not only their density accessibility but also intrinsic activity. First, current knowledge about electrocatalytic briefly summarized. Then, mechanisms above‐mentioned (HER, ORR, RR, NRR, OER), challenges faced by reactions, efforts meet using examined. Finally, future directions synthetic strategies leading materials, insights into sites, standardized tests performance requirements discussed.

Язык: Английский

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Highly Electrocatalytic Ethylene Production from CO₂ on Nanodefective Cu Nanosheets

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(31), С. 13606 - 13613

Опубликована: Июль 13, 2020

The electrochemical synthesis of chemicals from carbon dioxide, which is an easily available and renewable resource, great importance. However, to achieve high product selectivity for desirable C2 products like ethylene a big challenge. Here we design Cu nanosheets with nanoscaled defects (2-14 nm) the production dioxide. A Faradaic efficiency 83.2% achieved. It proved that can enrich reaction intermediates hydroxyl ions on electrocatalyst, thus promoting C-C coupling formation.

Язык: Английский

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Stabilizing Cu²⁺ Ions by Solid Solutions to Promote CO₂ Electroreduction to Methane

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(5), С. 2079 - 2084

Опубликована: Янв. 28, 2022

Copper is the only metal catalyst that can perform electrocatalytic CO2 reduction reaction (CRR) to produce hydrocarbons and oxygenates. Its surface oxidation state determines pathway various products. However, under cathodic potential of CRR conditions, chemical composition most Cu-based catalysts inevitably undergoes electroreduction from Cu2+ Cu0 or Cu1+ species, which generally coupled with phase reconstruction formation new active sites. Since initial sites are hard retain, there have been few studies about for CRR. Herein we propose a solid-solution strategy stabilize ions by incorporating them into CeO2 matrix, works as self-sacrificing ingredient protect species. In situ spectroscopic characterization density functional theory calculations reveal compared conventionally derived Cu sites, species in solid solution (Cu-Ce-Ox) significantly strengthen adsorption *CO intermediate, facilitating its further hydrogenation CH4 instead dimerization give C2 As result, different other catalysts, Cu-Ce-Ox delivered high Faradaic efficiency 67.8% low value 3.6% C2H4.

Язык: Английский

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Identification of Cu(100)/Cu(111) Interfaces as Superior Active Sites for CO Dimerization During CO₂ Electroreduction

Journal of the American Chemical Society, Год журнала: 2021, Номер 144(1), С. 259 - 269

Опубликована: Дек. 28, 2021

The electrosynthesis of valuable multicarbon chemicals using carbon dioxide (CO2) as a feedstock has substantially progressed recently but still faces considerable challenges. A major difficulty lines in the sluggish kinetics forming carbon-carbon (C-C) bonds, especially neutral media. We report here that oxide-derived copper crystals enclosed by six {100} and eight {111} facets can reduce CO2 to products with high Faradaic efficiency 74.9 ± 1.7% at commercially relevant current density 300 mA cm-2 1 M KHCO3 (pH ∼ 8.4). By combining experimental computational studies, we uncovered Cu(100)/Cu(111) interfaces offer favorable local electronic structure enhances *CO adsorption lowers C-C coupling activation energy barriers, performing superior Cu(100) Cu(111) surfaces, respectively. On this catalyst, no obvious degradation was observed over 50 h continuous operation.

Язык: Английский

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Recent advances in innovative strategies for the CO₂ electroreduction reaction

Energy & Environmental Science, Год журнала: 2020, Номер 14(2), С. 765 - 780

Опубликована: Дек. 15, 2020

This review underlines innovative design strategies for CO₂RR system, also distinctively presents the current status and new trend.

Язык: Английский

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Architectural Design for Enhanced C₂ Product Selectivity in Electrochemical CO₂ Reduction Using Cu-Based Catalysts: A Review

ACS Nano, Год журнала: 2021, Номер 15(5), С. 7975 - 8000

Опубликована: Май 6, 2021

Electrochemical CO2 reduction to value-added chemicals and fuels is a promising approach mitigate the greenhouse effect arising from anthropogenic emission energy shortage caused by depletion of nonrenewable fossil fuels. The generation multicarbon (C2+) products, especially hydrocarbons oxygenates, great interest for industrial applications. To date, Cu only metal known catalyze C–C coupling in electrochemical reaction (eCO2RR) with appreciable efficiency kinetic viability produce wide range C2 products aqueous solutions. Nonetheless, poor product selectivity associated main technical problem application eCO2RR technology on global scale. Based extensive research efforts, delicate rational design electrocatalyst architecture using principles nanotechnology likely significantly affect adsorption energetics some key intermediates hence inherent pathways. In this review, we summarize recent progress that has been achieved tailoring efficient conversion target products. By considering experimental computational results, further analyze underlying correlations between catalyst its toward Finally, major challenges are outlined, directions future development suggested.

Язык: Английский

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Hierarchical Copper with Inherent Hydrophobicity Mitigates Electrode Flooding for High-Rate CO₂ Electroreduction to Multicarbon Products

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(21), С. 8011 - 8021

Опубликована: Апрель 29, 2021

Copper is currently the material with most promise as catalyst to drive carbon dioxide (CO2) electroreduction produce value-added multicarbon (C2+) compounds. However, a copper on carbon-based gas diffusion layer electrode often has poor stability-especially when performing at high current densities-owing electrolyte flooding caused by hydrophobicity decrease of during operation. Here, we report bioinspired that mimics unique hierarchical structuring Setaria's hydrophobic leaves. This structure endows CO2 reduction sufficient build robust gas-liquid-solid triple-phase boundary, which can not only trap more close active surface but also effectively resist even under high-rate We consequently achieved C2+ production rate 255 ± 5.7 mA cm-2 64 1.4% faradaic efficiency, well outstanding operational stability 300 over 45 h in flow reactor, largely outperforming its wettable counterparts.

Язык: Английский

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Linking the Dynamic Chemical State of Catalysts with the Product Profile of Electrocatalytic CO₂ Reduction

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(32), С. 17254 - 17267

Опубликована: Март 8, 2021

Abstract The promoted activity and enhanced selectivity of electrocatalysts is commonly ascribed to specific structural features such as surface facets, morphology, atomic defects. However, unraveling the factors that really govern direct electrochemical reduction CO 2 (CO RR) still very challenging since state dynamic difficult predict under working conditions. Moreover, theoretical predictions from viewpoint thermodynamics alone often fail specify actual configuration a catalyst for RR process. Herein, we re‐survey recent studies with emphasis on revealing chemical Cu sites conditions extracted by in situ/operando characterizations, further validate critical link between product profile RR. This point view provides generalizable concept chemical‐state‐driven offers an inspiration both fundamental understanding efficient design.

Язык: Английский

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