Tailoring O‐Monodentate Adsorption of CO2 Initiates C–N Coupling for Efficient Urea Electrosynthesis with Ultrahigh Carbon Atom Economy DOI Open Access
Min Zhou, Yan Zhang, Hu Li

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 24, 2024

Abstract The thermodynamically and kinetically sluggish electrocatalytic C−N coupling from CO 2 NO 3 − is inert to initially take place while typically occurring after protonation, which severely dwindles urea efficiency carbon atom economy. Herein, we report a single O‐philic adsorption strategy facilitate initial of *OCO subsequent protonation over dual‐metal hetero‐single‐atoms in N −Fe−(N−B) −Cu−N coordination mode (FeN 4 /B CuN @NC), greatly inhibits the formation C‐containing byproducts facilitates electrosynthesis an unprecedented C‐selectivity 97.1 % with yield 2072.5 μg h −1 mg cat. 71.9 Faradaic efficiency, outperforming state‐of‐the‐art electrodes. carbon‐directed antibonding interaction Cu−B elaborated benefit rather than conventional C‐end or bridging O,O‐end modes, can accelerate kinetics initiated protonation. Theoretical results indicate that O‐monodentate pathway benefits thermodynamics *NO rate‐determining step, markedly direct This oriented manipulating reactant patterns initiate specific step universal moderate oxophilic transition metals offers kinetic‐enhanced path for multiple conversion processes.

Language: Английский

Review on strategies for improving the added value and expanding the scope of CO2 electroreduction products DOI
Minghang Jiang, Huaizhu Wang, Mengfei Zhu

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(10), P. 5149 - 5189

Published: Jan. 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.

Language: Английский

Citations

75
Highly Efficient Electroreduction of CO2 to Ethanol via Asymmetric C–C Coupling by a Metal–Organic Framework with Heterodimetal Dual Sites DOI
Zhen‐Hua Zhao, Jia‐Run Huang, Pei‐Qin Liao

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(49), P. 26783 - 26790

Published: Nov. 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.

Language: Английский

Citations

72
Efficient Capture and Electroreduction of Dilute CO2 into Highly Pure and Concentrated Formic Acid Aqueous Solution DOI

Zhenhua Zhao,

Jia‐Run Huang,

Da-Shuai Huang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(20), P. 14349 - 14356

Published: May 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.

Language: Английский

Citations

26
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 DOI Creative Commons
Jitendra N. Tiwari, Krishan Kumar, Moein Safarkhani

et al.

Advanced Science, Journal Year: 2024, Volume and Issue: 11(33)

Published: July 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.

Language: Английский

Citations

24
Atomically Dispersed Cobalt/Copper Dual‐Metal Catalysts for Synergistically Boosting Hydrogen Generation from Formic Acid DOI Creative Commons
Yanzhe Shi,

Bingcheng Luo,

Runqi Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(43)

Published: Sept. 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.

Language: Английский

Citations

25
Recent strategies to improve the electroactivity of metal–organic frameworks for advanced electrocatalysis DOI Creative Commons

Runzhi Wei,

Xiao Li, Aziz B. Ibragimov

et al.

Deleted Journal, Journal Year: 2024, Volume and Issue: 1(2), P. 181 - 206

Published: Aug. 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.

Language: Английский

Citations

11
In situ fabrication of atomically adjacent dual-vacancy sites for nearly 100% selective CH 4 production DOI Creative Commons
Ye He, Sheng Dai, Jianping Sheng

et al.

Proceedings of the National Academy of Sciences, Journal Year: 2024, Volume and Issue: 121(25)

Published: June 10, 2024

The photocatalytic CO

Language: Английский

Citations

10
Revolutionizing electrochemical CO2 reduction to deeply reduced products on non-Cu-based electrocatalysts DOI

Haoming Yu,

Hsiwen Wu,

Yuen Leong Chow

et al.

Energy & Environmental Science, Journal Year: 2024, Volume and Issue: 17(15), P. 5336 - 5364

Published: Jan. 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.

Language: Английский

Citations

9
Electron Localization‐Triggered Proton Pumping Toward Cu Single Atoms for Electrochemical CO2 Methanation of Unprecedented Selectivity DOI
Zhanhu Guo, Peng Zhou, Liqun Jiang

et al.

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(14)

Published: Dec. 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.

Language: Английский

Citations

21
Advances in the Stability of Catalysts for Electroreduction of CO2 to Formic Acid DOI

Dewen Song,

Shipeng Zhang,

Minjun Zhou

et al.

ChemSusChem, Journal Year: 2024, Volume and Issue: 17(14)

Published: Feb. 27, 2024

Abstract The electroreduction of CO 2 to high‐value products is a promising approach for achieving carbon neutrality. Among these products, formic acid stands out as having the most potential industrialization due its optimal economic value in terms consumption and output. In recent years, Faraday efficiency from has reached 90~100 %. However, this high selectivity cannot be maintained extended periods under currents meet industrial requirements. This paper reviews excellent work perspective catalyst stability, summarizing discussing performance typical catalysts. Strategies preparing stable highly active catalysts are also briefly described. review may offer useful data reference valuable guidance future design long‐stability

Language: Английский

Citations

6