Review on strategies for improving the added value and expanding the scope of CO₂ electroreduction products

Chemical Society Reviews, Год журнала: 2024, Номер 53(10), С. 5149 - 5189

Опубликована: Янв. 1, 2024

This review summarizes promising strategies including the design of catalysts and construction coupled electrocatalytic reaction systems, aimed at achieving selective production various products from CO 2 electroreduction.

Язык: Английский

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Highly Efficient Electroreduction of CO₂ to Ethanol via Asymmetric C–C Coupling by a Metal–Organic Framework with Heterodimetal Dual Sites

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(49), С. 26783 - 26790

Опубликована: Ноя. 28, 2023

The electroreduction of CO2 into value-added liquid fuels holds great promise for addressing global environmental and energy challenges. However, achieving highly selective yielding multi-carbon oxygenates through the electrochemical reduction reaction (eCO2RR) is a formidable task, primarily due to sluggish asymmetric C-C coupling reaction. In this study, novel metal-organic framework (CuSn-HAB) with unprecedented heterometallic Sn···Cu dual sites (namely, pair SnN2O2 CuN4 bridged by μ-N atoms) was designed overcome limitation. CuSn-HAB demonstrated an impressive Faradic efficiency (FE) 56(2)% eCO2RR alcohols, current density 68 mA cm-2 at low potential -0.57 V (vs RHE). Notably, no significant degradation observed over continuous 35 h operation specified density. Mechanistic investigations revealed that, in comparison copper site, site exhibits higher affinity oxygen atoms. This enhanced plays pivotal role facilitating generation key intermediate *OCH2. Consequently, compared homometallic Cu···Cu (generally ethylene product), were proved be more thermodynamically favorable between *CO *OCH2, leading formation *CO-*OCH2, which ethanol product.

Язык: Английский

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Efficient Capture and Electroreduction of Dilute CO₂ into Highly Pure and Concentrated Formic Acid Aqueous Solution

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(20), С. 14349 - 14356

Опубликована: Май 14, 2024

High-purity CO2 rather than dilute (15 vol %, CO2/N2/O2 = 15:80:5, v/v/v) similar to the flue gas is currently used as feedstock for electroreduction of CO2, and liquid products are usually mixed up with cathode electrolyte, resulting in high product separation costs. In this work, we showed that a microporous conductive Bi-based metal–organic framework (Bi-HHTP, HHTP 2,3,6,7,10,11-hexahydroxytriphenylene) can not only efficiently capture from under humidity but also catalyze adsorbed into formic acid current density 80 mA cm–2 Faradaic efficiency 90% at very low cell voltage 2.6 V. Importantly, performance atmosphere was close high-purity atmosphere. This first catalyst maintain exceptional eCO2RR presence both O2 N2. Moreover, by using feedstock, 1 working electrode coating Bi-HHTP continuously produce 200 mM aqueous solution relative purity 100% least 30 h membrane assembly (MEA) electrolyzer. The does contain electrolytes, such highly concentrated pure be directly an electrolyte fuel cells. Comprehensive studies revealed might ascribed ability micropores on lower Gibbs free energy formation key intermediate *OCHO open Bi sites.

Язык: Английский

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Materials Containing Single‐, Di‐, Tri‐, and Multi‐Metal Atoms Bonded to C, N, S, P, B, and O Species as Advanced Catalysts for Energy, Sensor, and Biomedical Applications

Advanced Science, Год журнала: 2024, Номер 11(33)

Опубликована: Июль 1, 2024

Abstract Modifying the coordination or local environments of single‐, di‐, tri‐, and multi‐metal atom (SMA/DMA/TMA/MMA)‐based materials is one best strategies for increasing catalytic activities, selectivity, long‐term durability these materials. Advanced sheet supported by metal atom‐based have become a critical topic in fields renewable energy conversion systems, storage devices, sensors, biomedicine owing to maximum utilization efficiency, precisely located centers, specific electron configurations, unique reactivity, precise chemical tunability. Several offer excellent support are attractive applications energy, medical research, such as oxygen reduction, production, hydrogen generation, fuel selective detection, enzymatic reactions. The strong metal–metal metal–carbon with metal–heteroatom (i.e., N, S, P, B, O) bonds stabilize optimize electronic structures atoms due interfacial interactions, yielding activities. These provide models understanding fundamental problems multistep This review summarizes substrate structure‐activity relationship different active sites based on experimental theoretical data. Additionally, new synthesis procedures, physicochemical characterizations, biomedical discussed. Finally, remaining challenges developing efficient SMA/DMA/TMA/MMA‐based presented.

Язык: Английский

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Atomically Dispersed Cobalt/Copper Dual‐Metal Catalysts for Synergistically Boosting Hydrogen Generation from Formic Acid

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

Опубликована: Сен. 11, 2023

The development of practical materials for (de)hydrogenation reactions is a prerequisite the launch sustainable hydrogen economy. Herein, we present design and construction an atomically dispersed dual-metal site Co/Cu-N-C catalyst allowing significantly improved dehydrogenation formic acid, which available from carbon dioxide green hydrogen. active centers consist specific CoCuN6 moieties with double-N-bridged adjacent metal-N4 clusters decorated on nitrogen-doped support. At optimal conditions performance nanostructured material (mass activity 77.7 L ⋅ gmetal-1 h-1 ) up to 40 times higher compared commercial 5 % Pd/C. In situ spectroscopic kinetic isotope effect experiments indicate that promoted acid follows so-called formate pathway C-H dissociation HCOO* as rate-determining step. Theoretical calculations reveal Cu in moiety synergistically contributes adsorption intermediate raises d-band center Co favor activation thereby lower reaction energy barrier.

Язык: Английский

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Electron Localization‐Triggered Proton Pumping Toward Cu Single Atoms for Electrochemical CO₂ Methanation of Unprecedented Selectivity

Advanced Materials, Год журнала: 2023, Номер 36(14)

Опубликована: Дек. 28, 2023

Abstract Slow multi‐proton coupled electron transfer kinetics and unexpected desorption of intermediates severely hinder the selectivity CO 2 methanation. In this work, a one‐stone‐two‐bird strategy pumping protons improving adsorption configuration/capability enabled by localization is developed to be highly efficient for CH 4 electrosynthesis over Cu single atoms anchored on bismuth vacancies BiVO (Bi 1‐x VO ─Cu), with superior kinetic isotope effect high Faraday efficiency (92%), far outperforming state‐of‐the‐art electrocatalysts Control experiments theoretical calculations reveal that ( V Bi ) not only act as active sites H O dissociation but also induce toward single‐atom sites. The ‐induced pumps *H from atoms, significantly promoting generation stabilization pivotal intermediate (*CHO) selective electrosynthesis. metal new initiators show enormous potential in proton transfer‐involved hydrogenative conversion processes.

Язык: Английский

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In situ fabrication of atomically adjacent dual-vacancy sites for nearly 100% selective CH ₄ production

Proceedings of the National Academy of Sciences, Год журнала: 2024, Номер 121(25)

Опубликована: Июнь 10, 2024

The photocatalytic CO

Язык: Английский

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Experimental and Theoretical Insights into Single Atoms, Dual Atoms, and Sub‐Nanocluster Catalysts for Electrochemical CO₂ Reduction (CO₂RR) to High‐Value Products

Advanced Materials, Год журнала: 2024, Номер 36(52)

Опубликована: Ноя. 26, 2024

Abstract Electrocatalytic carbon dioxide (CO 2 ) conversion into valuable chemicals paves the way for realization of recycling. Downsizing catalysts to single‐atom (SACs), dual‐atom (DACs), and sub‐nanocluster (SNCCs) has generated highly active selective CO transformation reduced products. This is due introduction numerous sites, unsaturated coordination environments, efficient atom utilization, confinement effect compared their nanoparticle counterparts. Herein, recent Cu‐based SACs are first reviewed newly emerged DACs SNCCs expanding catalysis electrocatalytic reduction RR) high‐value products discussed. Tandem SAC–nanocatalysts (NCs) (SAC–NCs) also discussed RR Then, non‐Cu‐based SACs, DACs, SAC–NCs, theoretical calculations various transition‐metal summarized. Compared previous achievements less‐reduced products, this review focuses on double objective achieving full increasing selectivity formation rate toward C–C coupled with additional emphasis stability catalysts. Finally, through combined experimental research, future outlooks offered further develop over isolated atoms sub‐nanometal clusters.

Язык: Английский

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Revolutionizing electrochemical CO₂ reduction to deeply reduced products on non-Cu-based electrocatalysts

Energy & Environmental Science, Год журнала: 2024, Номер 17(15), С. 5336 - 5364

Опубликована: Янв. 1, 2024

Producing deeply reduced (>2 e − per carbon atom) products from the electrochemical CO 2 reduction reaction on non-Cu-based catalysts is an attractive and sustainable approach for utilization.

Язык: Английский

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Recent strategies to improve the electroactivity of metal–organic frameworks for advanced electrocatalysis

Deleted Journal, Год журнала: 2024, Номер 1(2), С. 181 - 206

Опубликована: Авг. 4, 2024

Abstract Metal–organic frameworks (MOFs) have emerged as promising materials in the realm of electrocatalysis due to their high surface area, tunable porosity, and versatile chemical functionality. However, practical application has been hampered by inherent limitations such low electrical conductivity a limited number active metal sites. Researchers addressed these challenges through various strategies, including enhancing incorporating conductive nanoparticles, modifying structure composition MOFs replacing nodes functionalizing linkers, preparing catalysts thermal processes decarburization conversion into oxides, phosphides (MPs), sulfides (MSs). This review provided comprehensive summary strategies that were employed enhance electroactivity for improved electrocatalytic performance recent years. It also explored future directions potential innovations design synthesis MOF‐based electrocatalysts, offering valuable insights advancing sustainable energy technologies.

Язык: Английский

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