Isolated Tin(IV) Active Sites for Highly Efficient Electroreduction of CO2 to CH4 in Neutral Aqueous Solution DOI

Zhen‐Hua Zhao,

Jia‐Run Huang, Pei‐Qin Liao

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(22)

Опубликована: Фев. 24, 2023

The development of efficient electrocatalysts with non-copper metal sites for electrochemical CO2 reduction reactions (eCO2 RR) to hydrocarbons and oxygenates is highly desirable, but still a great challenge. Herein, stable metal-organic framework (DMA)4 [Sn2 (THO)2 ] (Sn-THO, THO6- = triphenylene-2,3,6,7,10,11-hexakis(olate), DMA dimethylammonium) isolated distorted octahedral SnO62- active reported as an electrocatalyst eCO2 RR, showing exceptional performance RR the CH4 product rather than common products formate CO Sn-based catalysts. partial current density reaches high value 34.5 mA cm-2 , surpassing most copper-based all non-Cu metal-based Our experimental theoretical results revealed that site favors formation key *OCOH species produce can greatly inhibit *OCHO *COOH *HCOOH *CO, respectively.

Язык: Английский

Stabilizing copper sites in coordination polymers toward efficient electrochemical C-C coupling DOI Creative Commons
Yongxiang Liang,

Jiankang Zhao,

Yang Yu

и другие.

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

Процитировано

109
Dinuclear metal synergistic catalysis for energy conversion DOI
Di‐Chang Zhong, Yun‐Nan Gong, Chao Zhang

и другие.

Chemical Society Reviews, Год журнала: 2023, Номер 52(9), С. 3170 - 3214

Опубликована: Янв. 1, 2023

An exclusive review focusing on catalysts exhibiting the dinuclear metal synergistic catalysis (DMSC) effect for energy conversion reactions is presented.

Язык: Английский

Процитировано

82
Direct OC-CHO coupling towards highly C2+ products selective electroreduction over stable Cu0/Cu2+ interface DOI Creative Commons
Xinyu Zhang,

Zhen Xin Lou,

Jiacheng Chen

и другие.

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

Опубликована: Ноя. 24, 2023

Electroreduction of CO2 to valuable multicarbon (C2+) products is a highly attractive way utilize and divert emitted CO2. However, major fraction C2+ selectivity confined less than 90% by the difficulty coupling C-C bonds efficiently. Herein, we identify stable Cu0/Cu2+ interfaces derived from copper phosphate-based (CuPO) electrocatalysts, which can facilitate production with low-energy pathway OC-CHO verified in situ spectra studies theoretical calculations. The CuPO precatalyst shows high Faradaic efficiency (FE) 69.7% towards C2H4 an H-cell, exhibits significant FEC2+ 90.9% under industrially relevant current density (j = -350 mA cm-2) flow cell configuration. interface breaks new ground for structural design electrocatalysts construction synergistic active sites improve activity products.

Язык: Английский

Процитировано

75
Steering CO2 Electroreduction Selectivity U-Turn to Ethylene by Cu–Si Bonded Interface DOI
Wanfeng Xiong, Duan‐Hui Si, Hong-Fang Li

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 146(1), С. 289 - 297

Опубликована: Дек. 22, 2023

Copper (Cu), with the advantage of producing a deep reduction product, is unique catalyst for electrochemical CO2 (CO2RR). Designing Cu-based to trigger CO2RR multicarbon product and understanding accurate structure–activity relationship elucidating reaction mechanisms still remain challenge. Herein, we demonstrate rational design core–shell structured silica-copper (p-Cu@m-SiO2) through Cu–Si direct bonding efficient selective CO2RR. The interface fulfills inversion in selectivity. ratio C2H4/CH4 changes from 0.6 14.4 after silica modification, current density reaches high up 450 mA cm–2. kinetic isotopic effect, situ attenuated total reflection Fourier-transform infrared spectra, functional theory were applied elucidate mechanism. SiO2 shell stabilizes *H intermediate by forming Si–O–H inhibits hydrogen evolution effectively. Moreover, direct-bonded makes bare Cu sites larger charge density. Such stabilized *CHO activated *CO, promoting coupling *CO intermediates form C2H4. This work provides promising strategy designing catalysts C2H4 catalytic activity.

Язык: Английский

Процитировано

57
Efficient strategies for promoting the electrochemical reduction of CO2 to C2+ products over Cu-based catalysts DOI
Huanhuan Yang, Shiying Li, Qun Xu

и другие.

CHINESE JOURNAL OF CATALYSIS (CHINESE VERSION), Год журнала: 2023, Номер 48, С. 32 - 65

Опубликована: Май 1, 2023

Язык: Английский

Процитировано

50
Recent Advances in Electrocatalytic Hydrogenation Reactions on Copper‐Based Catalysts DOI Creative Commons
Min Zheng, Junyu Zhang, Pengtang Wang

и другие.

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

Опубликована: Сен. 27, 2023

Hydrogenation reactions play a critical role in the synthesis of value-added products within chemical industry. Electrocatalytic hydrogenation (ECH) using water as hydrogen source has emerged an alternative to conventional thermocatalytic processes for sustainable and decentralized under mild conditions. Among various ECH catalysts, copper-based (Cu-based) nanomaterials are promising candidates due their earth-abundance, unique electronic structure, versatility, high activity/selectivity. Herein, recent advances application Cu-based catalysts upgrading valuable chemicals systematically analyzed. The properties initially introduced, followed by design strategies enhance activity selectivity. Then, typical on presented detail, including carbon dioxide reduction multicarbon generation, alkyne-to-alkene conversion, selective aldehyde ammonia production from nitrogen-containing substances, amine organic nitrogen compounds. In these catalyst composition nanostructures toward different is focused. co-hydrogenation two substrates (e.g., CO

Язык: Английский

Процитировано

50
Synergistic Effect in a Metal–Organic Framework Boosting the Electrochemical CO2 Overall Splitting DOI
Meng‐Di Zhang, Jia‐Run Huang, Wen Shi

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(4), С. 2439 - 2447

Опубликована: Янв. 19, 2023

It is a very important but still challenging task to develop bifunctional electrocatalysts for highly efficient CO2 overall splitting. Herein, we report stable metal-organic framework (denoted as PcNi-Co-O), composed of (2,3,9,10,16,17,23,24-octahydroxyphthalocyaninato)nickel(II) (PcNi-(O-)8) ligands and the planar CoO4 nodes, When working both cathode anode catalysts (i.e., PcNi-Co-O||PcNi-Co-O), PcNi-Co-O achieved commercial-scale current density 123 mA cm-2 (much higher than reported values (0.2-12 cm-2)) with Faradic efficiency (CO) 98% at low cell voltage 4.4 V. Mechanism studies suggested synergistic effects between two active sites, namely, (i) electron transfer from PcNi sites under electric fields, resulting in raised oxidizability/reducibility CoO4/PcNi respectively; (ii) energy-level matching can reduce energy barrier them improve performance

Язык: Английский

Процитировано

46
MOF-based materials for electrochemical reduction of carbon dioxide DOI

Jian-Mei Huang,

Xiang‐Da Zhang,

Jiayi Huang

и другие.

Coordination Chemistry Reviews, Год журнала: 2023, Номер 494, С. 215333 - 215333

Опубликована: Июль 28, 2023

Язык: Английский

Процитировано

46
Porphyrin-based metal–organic frameworks for photo(electro)catalytic CO2 reduction DOI

Guixiang Ding,

Chunxue Li, Lihui Chen

и другие.

Energy & Environmental Science, Год журнала: 2024, Номер 17(15), С. 5311 - 5335

Опубликована: Янв. 1, 2024

The panorama of the latest developments emerging porphyrin-based MOFs for photo(electro)catalytic CO 2 reduction is shown.

Язык: Английский

Процитировано

44
Continuously Producing Highly Concentrated and Pure Acetic Acid Aqueous Solution via Direct Electroreduction of CO2 DOI
Haolin Zhu, Jia‐Run Huang, Meng‐Di Zhang

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(1), С. 1144 - 1152

Опубликована: Янв. 2, 2024

It is crucial to achieve continuous production of highly concentrated and pure C2 chemicals through the electrochemical CO2 reduction reaction (eCO2RR) for artificial carbon cycling, yet it has remained unattainable until now. Despite one-pot tandem catalysis (dividing eCO2RR into two catalytical reactions CO C2) offering potential significantly enhancing efficiency, its mechanism remains unclear performance unsatisfactory. Herein, we selected different CO2-to-CO catalysts CO-to-acetate construct several catalytic systems acetic acid. Among them, a system comprising covalent organic framework (PcNi-DMTP) metal–organic (MAF-2) as catalysts, respectively, exhibited faradaic efficiency 51.2% with current density 410 mA cm–2 an ultrahigh acetate yield rate 2.72 mmol m–2 s–1 under neutral conditions. After electrolysis 200 h, 1 working electrode can continuously produce 20 mM acid aqueous solution relative purity 95+%. Comprehensive studies revealed that influenced not only by supply–demand relationship electron competition between processes in but also CO-to-C2 catalyst diluted

Язык: Английский

Процитировано

37