Abstract
Designing efficient and cost-effective bifunctional catalysts is desirable for carbon dioxide and oxygen reduction reactions (CO2RR and ORR) to address carbon neutralization and energy conversion. Herein, a bifunctional CO2RR and ORR catalyst for aqueous Zn-air battery (ZAB) self-driving CO2RR electrolysis is developed using atomically dispersed niobium anchored onto N-doped ordered mesoporous carbon (Nb-N-C). The Nb-N-C atomic catalyst demonstrates aqueous CO2RR activity with CO Faradaic efficiency up to 90%, ORR activity with a half-wave potential of 0.84 V vs. reversible hydrogen electrode, and ZAB activity with a peak power density of 115.6 mW cm−2, owing to the high Nb atom-utilization efficiency and ordered mesoporous structure. Furthermore, two-unit ZABs in series, serving as the power source for the self-powered CO2 electrolysis system, continuously convert CO2 to CO with average productivity of 3.75 µmol h−1 \(\rm{mg_{cat}}^{-1}\) during the first 10 h. Moreover, theoretical calculations exhibit that atomic Nb anchored to N-doped carbon can form Nb-N coordination bonds, effectively reducing the energy barriers of potential-determining *COOH for CO2RR and *O formation for ORR.
摘要
设计廉价和高效的双功能催化剂应用于CO2还原和O2还原反应 (CO2RR和ORR)是实现碳中和的理想选择. 因此, 本文研制出铌原子分散固定在氮掺杂有序介孔碳(Nb-N-C)上的双功能CO2RR和ORR催化剂用于锌-空气电池(ZAB)自驱动CO2RR. 得益于高铌原子利用率和有序介孔结构, Nb-N-C催化剂展现出高达90%的CO法拉第效率, ORR的半 波电位活性为0.84 V, ZAB的峰值功率活性为115.6 mW cm−2. 此外, 采用两个串联的ZABs单元作为自供能CO2RR系统的电源, 能够连续将 CO2 转化为CO. 该自供能系统前10 小时的CO 平均产率为 3.75 µmol h−1 \(\rm{mg_{cat}}^{-1}\). 理论计算表明, 铌原子分散固定在氮掺杂的碳上形成Nb–N配位键, 从而有效地降低CO2RR的决速中间体*COOH和ORR的决速中间体*O的生成能垒.
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Acknowledgements
This work was financially supported by the National Natural Science Foundation of China (22075211, 21601136, 22109118, 51971157, and 51621003).
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Author contributions Gao S and Wang T conducted the experiment; Gao S designed this study, analyzed the data and wrote the paper; Jin M performed the theoretical calculation; Hu G did some characterizations. Yang H, Zhang S, Liu Q, Liu X and Luo J performed some data analysis and offered helpful suggestions. All authors contributed to the general discussion.
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Sanshuang Gao received his MS degree from the College of Materials Science and Engineering, Anhui University of Science and Technology, China, in 2018. His research interests mainly focus on the design, synthesis and applications of nanomaterials.
Guangzhi Hu received his PhD degree from the Chinese Academy of Sciences in 2010. After post-doctoral research at the Nano Carbon Materials Research Laboratory of the Department of Physics, Umeå University, Sweden, he joined the Chinese Academy of Sciences. Currently, he is a full-time professor at the Institute for Ecological Research and Pollution Control of Plateau Lakes, Yunnan University. His research interests focus on the application of functional nanomaterials in energy and environment.
Jun Luo received his BS (2001) and PhD (2006) degrees from Tsinghua University. Then, he worked as a postdoc at Warwick University and a research fellow at Oxford University. He joined Tsinghua University as an associate professor. In 2015, he moved to Tianjin University of Technology. Currently, He is a full professor at Shenzhen Institute for Advanced Study, University of Electronic Science and Technology of China. His research interests focus on low-dimensional materials and their electron microscopy.
Xijun Liu received his PhD degree from the College of Science, Beijing University of Chemical Technology in 2014. Then, he joined the School of Materials Science and Engineering, Tianjin University of Technology. Currently, he is a full-time professor at the School of Resource, Environments and Materials, Guangxi University. His current scientific interests focus on nanomaterials, heterogeneous catalysis, and materials design for catalysts and energy conversion/storage devices.
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Gao, S., Wang, T., Jin, M. et al. Bifunctional Nb-N-C atomic catalyst for aqueous Zn-air battery driving CO2 electrolysis. Sci. China Mater. 66, 1013–1023 (2023). https://doi.org/10.1007/s40843-022-2236-8
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DOI: https://doi.org/10.1007/s40843-022-2236-8