journal article·2022-10-25

Molecular Assembled Electrocatalyst for Highly Selective CO2 Fixation to C2+ Products

Peng Wang, Tan Li, Qiqi Wu, Ruian Du, Qinghua Zhang, Wei-Hsiang Huang, Chi-Liang Chen, Yan Fan, Haonan Chen, Yanyan Jia, Sheng Dai, Yongcai Qiu, Keyou Yan, Yuanyuan Meng, Geoffrey I. N. Waterhouse, Lin Gu, Yun Zhao, Wei-Wei Zhao, Guangxu Chen

ACS Nano· Volume 16· Issue 10
Publisher page

Abstract

In certain metalloenzymes, multimetal centers with appropriate primary/secondary coordination environments allow carbon–carbon coupling reactions to occur efficiently and with high selectivity. This same function is seldom realized in molecular electrocatalysts. Herein we synthesized rod-shaped nanocatalysts with multiple copper centers through the molecular assembly of a triphenylphosphine copper complex (CuPPh). The assembled molecular CuPPh catalyst demonstrated excellent electrochemical CO2 fixation performance in aqueous solution, yielding high-value C2+ hydrocarbons (ethene) and oxygenates (ethanol) as the main products. Using density functional theory (DFT) calculations, in situ X-ray absorption spectroscopy (XAS) and quasi-in situ X-ray photoelectron spectroscopy (XPS), and reaction intermediate capture, we established that the excellent catalytic performance originated from the large number of double copper centers in the rod-shaped assemblies. Cu–Cu distances in the absence of CO2 were as long as 7.9 Å, decreasing substantially after binding CO2 molecules indicating dynamic and cooperative function. The double copper centers were shown to promote carbon–carbon coupling via a CO2 transfer-coupling mechanism involving an oxalate (OOC–COO) intermediate, allowing the efficient production of C2+ products. The assembled CuPPh nanorods showed high activity, excellent stability, and a high Faradaic efficiency (FE) to C2+ products (65.4%), with performance comparable to state-of-the-art copper oxide-based catalysts. To our knowledge, our findings demonstrate that harnessing metalloenzyme-like properties in molecularly assembled catalysts can greatly improve the selectivity of CO2RR, promoting the rational design of improved CO2 reduction catalysts.
Source: openalex_inverted_index · Quality: baseline

Research context

OpenAlex topics: CO2 Reduction Techniques and Catalysts · Ionic liquids properties and applications · Electrocatalysts for Energy Conversion

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

School of Environment and Energy, State Key Laboratory of Luminescent Materials and Devices, Guangdong Provincial Key Laboratory of Atmospheric Environment and Pollution Control, South China University of Technology, Guangzhou510006, China

Institute of Physics, Chinese Academy of Sciences, Beijing100190, China

National Synchrotron Radiation Research Center, 101 Hsin-Ann Road, Hsinchu Science Park, Hsinchu30076, Taiwan

Graduate Institute of Applied Science and Technology, National Taiwan University of Science and Technology (NTUST), Taipei10607, Taiwan

Medical Device Research & Testing Center, South China University of Technology, Guangzhou510006, China

Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Centre, Frontiers Science Center for Materiobiology and Dynamic Chemistry, Institute of Fine Chemicals, School of Chemistry and Molecular Engineering, East China University of Science & Technology, Shanghai200237, China

College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan030002, China

School of Chemical Sciences, The University of Auckland, Auckland1142, New Zealand

State Key Laboratory of Analytical Chemistry for Life Science, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing210023, China

Funding

Guangdong Science and Technology Department · Guangdong Province Introduction of Innovative R&D Team · MacDiarmid Institute for Advanced Materials and Nanotechnology · China Postdoctoral Science Foundation · Guangzhou Science and Technology Program key projects · Royal Society Te Aparangi · Energy Education Trust of New Zealand · National Natural Science Foundation of China · Natural Science Foundation of Guangdong Province

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