Abstract
In recent years, metal-organic frameworks (MOFs) have been extensively investigated as electrocatalysts due to their highly efficient electroreduction of CO2. Herein, the electrocatalytic CO2 reduction reaction was investigated by growing helical Cu-porphyrinic MOF Cu meso-tetra(4-carboxyphenyl)porphyrin (TCPP) on Cu(OH)2 nanoarrays (H-CuTCPP@Cu(OH)2) using a sacrificial template method. The electrocatalytic results showed that the H-CuTCPP@Cu(OH)2 nanoarrays exhibited a high acetic acid Faradaic efficiency (FE) of 26.1% at −1.6 V vs. Ag/Ag+, which is much higher than the value of 19.8% obtained for non-helical CuTCPP@Cu(OH)2 (nH-CuTCPP@Cu(OH)2). The higher efficiency may be because space was more effectively utilized in the helical MOF nanoarrays, resulting in a greater number of active catalytic sites. Furthermore, in situ diffuse reflectance infrared Fourier transform spectra showed that the H-CuTCPP@Cu(OH)2 nanoarrays have much stronger CO linear adsorption, indicating a better selectivity of acetic acid than that of nH-CuTCPP@Cu(OH)2. In this study, we develop new helical nanomaterials and propose a new route to enhance the reduction of CO2.
摘要
金属-有机框架(MOF)因其高的比表面积、可调的孔道结构等特 点, 近年来在电催化二氧化碳还原领域受到了广泛的关注. 本文中, 我 们首次采用牺牲模板法在Cu(OH) 2 纳米阵列上生长具有螺旋形貌的铜-卟啉基MOF CuTCPP (H-CuTCPP@Cu(OH) 2), 并研究了其电催化二氧 化碳还原性能. 电催化性能显示, 在−1.6 V vs. Ag/Ag+ 电势下, H-CuTCPP@Cu(OH) 2 表现出二氧化碳还原成乙酸的高效性能, 其法拉第 效率高达26.1%, 并优于非螺旋CuTCPP (nH-CuTCPP@Cu(OH)2) (19.8%). 这是因为螺旋MOF纳米阵列具有更有效的催化空间并提供了 更多催化活性位点. 此外, 原位红外光谱证实了H-CuTCPP@Cu(OH)2 对一氧化碳具有更强的线性吸附, 因此具有更高的乙酸选择性. 这项工 作不仅开发了新型螺旋纳米材料, 也为提高电催化二氧化碳还原性能 提供了一种新的途径.
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Acknowledgements
This work was supported by the National Key Research and Development Program of China (2018YFA0208600), the National Natural Science Foundation of China (21872148 and 21601189), the Youth Innovation Promotion Association of the Chinese Academy of Sciences (2018339) and Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China (2021ZR131).
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Xiao YH performed the experiments, analyzed the data, and wrote the manuscript draft under the guidance of Gu ZG and Zhang J; Zhang YX helped with the SEM measurements; Zhai R provided research suggestions. All authors contributed to the general discussion.
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Experimental details and supporting data are available in the online version of the paper.
Yi-Hong Xiao received his BS degree in 2017 from Fujian Normal University. He is currently a PhD student under the supervision of Prof. Zhi-Gang Gu and Prof. Jian Zhang at Fujian Institute of Research on the Structure of Matter (FJIRSM), Chinese Academy of Sciences (CAS). His current research interests focus on the preparation and photo/electric properties of composite MOF films.
Zhi-Gang Gu obtained his PhD degree from Karlsruhe Institute of Technology (KIT) in 2014 and then worked as a postdoctoral fellow at KIT. In 2015 he became an associate professor, and in 2018 he was promoted to a professor at FFJIRSM, CAS. His recent research focuses on the controllable assembly and functionalities of surface-coordinated metal-organic framework thin films (SUR-MOFs).
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Xiao, YH., Zhang, YX., Zhai, R. et al. Helical copper-porphyrinic framework nanoarrays for highly efficient CO2 electroreduction. Sci. China Mater. 65, 1269–1275 (2022). https://doi.org/10.1007/s40843-021-1835-8
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DOI: https://doi.org/10.1007/s40843-021-1835-8