journal article·2021-03-22

Regulating the Spin State of Nickel in Molecular Catalysts for Boosting Carbon Dioxide Reduction

Xiang Wang, Yubin Fu, Diana Tranca, Kaiyue Jiang, Jinhui Zhu, Jichao Zhang, Sheng Han, Changchun Ke, Chenbao Lu, Xiaodong Zhuang

ACS Applied Energy Materials· Volume 4· Issue 3
Publisher page

Abstract

Molecular catalysts have been extensively studied for fundamental understanding of the catalytic mechanism of specific active sites for carbon dioxide (CO2) reduction, and nitrogen-coordinated transition metal centers are considered active sites for high-efficiency catalysis. However, different spin states of the same metal atom have rarely been studied. In this study, a hydrazine-pretreatment strategy is presented toward high-spin-state nickel centers in nickel(II) phthalocyanine and porphyrin. Such high-spin-state nickel centers possess abundant unpaired 3d electrons and exhibit considerably enhanced activity for CO2 reduction. The high-spin-state nickel(II) phthalocyanine displays a higher CO faradaic efficiency than that of ground-state nickel(II) phthalocyanine (98.5% vs 93.2% at −0.7 V; the ratio of CO and H2 generated by high-spin-state nickel(II) phthalocyanine is approximately 5 times that generated by ground-state nickel(II) phthalocyanine). And the CO faradaic efficiency of nickel porphyrin increased from approximately 0% (ground state) to 25.0% (high spin state). Operando X-ray absorption fine structure analysis demonstrates that the high-spin-state nickel exhibits a stronger adsorption of CO2 and intermediates, which is beneficial to CO2 reduction. Theoretical calculations reveal that the high-spin-state nickel center shows a smaller highest–lowest occupied molecular orbital gap, which favors the production of the key intermediate *COOH, thus accelerating CO2 reduction.
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Research context

OpenAlex topics: CO2 Reduction Techniques and Catalysts · Carbon dioxide utilization in catalysis · Covalent Organic Framework Applications

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

Affiliations

College of Chemistry and Chemical Engineering, Shanghai University of Engineering Science, Shanghai 201620, China

The meso-Entropy Matter Lab, State Key Laboratory of Metal Matrix Composites, Shanghai Key Laboratory of Electrical Insulation and Thermal Ageing, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China

Center for Advancing Electronics Dresden (cfaed) & Department of Chemistry and Food Chemistry, Technische Universität Dresden 01062 Dresden, Germany

Shanghai Synchrotron Radiation Facility, Zhangjiang Laboratory, Shanghai Advanced Research Institute, Chinese Academy of Sciences, No. 239, Zhangheng Road, Shanghai 201204, China

School of Chemical and Environmental Engineering, Shanghai Institute of Technology, Haiquan Road 100, Shanghai 201418, China

School of Mechanical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China

College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001, Henan, China

Funding

Science and Technology Commission of Shanghai Municipality · NSFC Young Scientists Fund · China Postdoctoral Science Fund · NSFC · the Key Science and Technology Project in Henan Province · National Key Research and Development Program of China

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