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Bimetallic phthalocyanine heterostructure used for highly selective electrocatalytic CO2 reduction

双金属酞菁异质结构高选择性电催化CO2还原

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Abstract

Heterogeneous molecular catalysts, such as metal phthalocyanines, are efficient electrocatalysts for CO2 reduction reaction (CO2RR). However, the rational design and synthesis of a molecular catalyst-based heterostructure for CO2RR remains challenging. Herein, we developed a crystalline bimetallic phthalocyanine heterostructure electrocatalyst (CoPc/FePc HS), which achieved an excellent CO2-to-CO conversion efficiency (99%) and outstanding long-term stability after 10 h of electrocatalysis. Density functional theory calculations revealed that the enhancement of CO2RR performance could be attributed to the distinct electron transfer pattern between FePc and CoPc. The heterostructural engineering in molecular catalysts would inspire a unique approach for improving CO2RR performance.

摘要

自工业革命以来, 化石燃料的大量消耗导致大气中CO2浓度显著 增加, 引发了全球气候变暖等问题. 电化学CO2还原能够利用可再生能 源产生的间歇性电力可持续地将CO2转化为高附加值化学品或燃料, 是 实现碳中和的有效途径. 目前, 非均相分子催化剂如金属酞菁能够有效 催化CO2还原反应(CO2RR), 但是分子催化剂异质结构的合理设计与合 成仍极具挑战. 基于此, 我们发展了一种具有高结晶度的双金属酞菁异 质结构(CoPc/FePc HS), 其电催化CO2还原为CO的法拉第效率高达 99%, 并在运行10小时后性能基本保持不变. 密度泛函理论计算表明, FePc和CoPc之间不同的电子转移模式能够有效提高CO2RR性能. 构筑 分子催化剂异质结构有望成为CO2RR性能提升的有效策略.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (22071172, 91833306, 21875158, 51633006, and 51733004).

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Author notes

  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Department of Chemistry, School of Science, Tianjin University, Tianjin, 300072, China

    Chenhuai Yang  (杨宸槐), Zengqiang Gao  (高增强), Shuyu Li  (李舒豫), Junjun Li  (李俊俊), Yating Zhu  (朱亚廷), Zhicheng Zhang  (张志成) & Wenping Hu  (胡文平)

  2. College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang, 330022, China

    Dingjia Wang  (王定佳) & Xuejiao J. Gao  (高雪娇)

  3. Collaborative Innovation Center of Technology and Equipment for Biological Diagnosis and Therapy in Universities of Shandong, Institute for Advanced Interdisciplinary Research (iAIR), University of Jinan, Jinan, 250022, China

    Haiqing Wang  (王海青)

  4. SZU-NUS Collaborative Innovation Centre for Optoelectronic Science & Technology, International Collaborative Laboratory of 2D Materials for Optoelectronics Science and Technology of Ministry of Education, Institute of Microscale Optoelectronics, Shenzhen University, Shenzhen, 518060, China

    Wenjuan Yang  (杨文娟)

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  1. Chenhuai Yang  (杨宸槐)
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  2. Zengqiang Gao  (高增强)
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Contributions

Zhang Z, Gao XJ, and Hu W conceived and supervised this study; Yang C, Gao Z, Zhang Z, and Gao XJ wrote the paper; Li S, Li J, Zhu Y, and Wang H carried out the materials fabrication, characterizations, and electrochemical measurements; Wang D, Yang W, and Gao XJ performed the DFT calculations and computational models; All authors contributed to discussions and manuscript review.

Corresponding authors

Correspondence to Xuejiao J. Gao  (高雪娇) or Zhicheng Zhang  (张志成).

Additional information

Xuejiao J. Gao received her PhD degree from the School of Chemistry and Chemical Engineering, University of Chinese Academy of Sciences (Beijing) in 2017. Then, she joined the College of Chemistry and Chemical Engineering, Jiangxi Normal University as an associate professor. Her research interests focus on surface and interface chemistry of nanomaterials and its application in biomimetic catalysis.

Zhicheng Zhang is a Professor of Tianjin University, China. He obtained his PhD degree from China University of Petroleum (Beijing) in 2012. Then he joined Tsinghua University as a postdoctoral researcher. In 2014, he worked as a research fellow at Nanyang Technological University, Singapore. In 2019, he joined Tianjin University as a full Professor. His research interests focus on the design and synthesis of functional metal-based nanomaterials and their applications in energy conversion and catalysis.

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The authors declare no conflict of interest.

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Yang, C., Gao, Z., Wang, D. et al. Bimetallic phthalocyanine heterostructure used for highly selective electrocatalytic CO2 reduction. Sci. China Mater. 65, 155–162 (2022). https://doi.org/10.1007/s40843-021-1749-5

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