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Interstitial Sn-doping promotes electrocatalytic CO2-to-formate conversion on bismuth

间隙Sn掺杂促进铋电催化CO2到甲酸盐的转化

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Abstract

Electrochemical CO2 reduction (CO2RR) is a promising technology to mitigate the greenhouse effect and convert CO2 to value-added chemicals. Yet, achieving high catalytic activity, selectivity, and stability for target products is still a big challenge. Herein, interstitially Sn-doped Bi (Snx-Bi, x is the atomic ratio of Sn to Bi, x = 1/2, 1/16, 1/24 or 1/40) nanowire bundles (NBs) are prepared by reducing Sn-doped Bi2S3. Notably, Sn1/24-Bi NBs exhibit ultrahigh formate selectivity over a broad potential window of 1400 mV (Faradaic efficiency over 90% from −0.5 to −1.9 V vs. reversible hydrogen electrode (RHE)) with an industry-compatible current density of −319 mA cm−2 at −1.9 V vs. RHE. Moreover, superior long-term stability for more than 84 h at ∼−200 mA cm−2 is realized. Experimental results and density functional theory (DFT) calculations reveal that interstitially doped Sn optimizes the adsorption affinity of *OCHO intermediate and reduces the electron transfer energy barrier of bismuth catalyst, resulting in the remarkable CO2RR performance. This study provides valuable inspiration for the design of doped electrocatalysts with enhanced catalytic activity, selectivity, and durability for electrochemical CO2-to-formate conversion.

摘要

电化学CO2还原(CO2RR)是一种很有前景的技术, 可以将二氧化 碳转化为多种增值化学品, 从而达到减缓温室效应的目的. 然而, 实现 目标产品的高催化活性、选择性和稳定性仍然是一个很大的挑战. 本 文通过还原Sn掺杂的Bi2S3制备了间隙掺杂的Snx-Bi (x为Sn与Bi的原子 比, x = 1/2, 1/16, 1/24或1/40)纳米线束(NBs). 值得注意的是, Sn1/24-Bi NBs在1400 mV的宽电位窗口内表现出超高的甲酸盐选择性(从−0.5到 −1.9 V vs. 可逆氢电极(RHE), 法拉第效率超过90%), 在−1.9 V vs. RHE 时, 电流密度达到了−319 mA cm−2, 可满足工业使用需求. 此外, 还实现 了在~−200 mA cm−2条件下超过84 h的超长稳定性. 实验结果和密度泛 函理论计算表明, 间隙掺杂Sn优化了*OCHO中间体的吸附亲和力, 降 低了铋催化剂的电子转移能垒, 从而获得了显著的CO2RR性能. 本研究 为设计具有优异催化活性、选择性和耐久性的掺杂型电催化剂用于 CO2RR为甲酸盐提供了启示.

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Acknowledgements

This work was supported by the National Key Research and Development Program of China (2020YFA0710303), the National Natural Science Foundation of China (U1905215, 51672046, 51672047 and 22109025) and the Scientific Research Foundation of Fuzhou University (510936). Huang J acknowledges the support from the Fundamental Research Funds for the Central Universities (2020CDJQY-A072), the Venture and Innovation Support Program for Chongqing Overseas Returnees (cx2020107) and the Natural Science Foundation of Chongqing (cstc2021jcyj-msxmX0945).

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Authors and Affiliations

  1. Key Laboratory of Advanced Materials Technologies, International (Hong Kong Macao and Taiwan) Joint Laboratory on Advanced Materials Technologies, College of Materials Science and Engineering, Fuzhou University, Fuzhou, 350108, China

    Xin Xu  (徐鑫), Yang Wei  (危洋), Linhua Mi  (米林华), Guodong Pan  (潘国栋), Yajun He  (何亚军), Siting Cai  (蔡思婷), Chaoyang Zheng  (郑朝杨), Yaming Jiang  (江雅明), Bin Chen  (陈斌), Liuyi Li  (李留义), Shenghong Zhong  (钟升红) & Yan Yu  (于岩)

  2. Institute of Advanced Interdisciplinary Studies, School of Chemistry and Chemical Engineering, Chongqing University, Chongqing, 400044, China

    Jianfeng Huang  (黄建峰)

  3. Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Binhai New City, Fuzhou, 350207, China

    Wenbin Hu  (胡文彬)

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  1. Xin Xu  (徐鑫)
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  2. Yang Wei  (危洋)
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  3. Linhua Mi  (米林华)
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  6. Siting Cai  (蔡思婷)
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  14. Yan Yu  (于岩)
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Contributions

Author contributions Xu X and Zhong S designed this project. Wei Y performed computational studies and analyzed the data. Xu X, Mi L, Pan G, He Y, Cai S, Zheng C, Jiang Y, and Chen B synthesized the samples, performed XRD, SEM, TEM, XPS, CV, and EIS, and tested the electrocatalytic performance. Xu X and Zhong S wrote the manuscript together. Huang J, Hu W, Yu Y, and Zhong S discussed and revised the manuscript. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Shenghong Zhong  (钟升红), Jianfeng Huang  (黄建峰) or Yan Yu  (于岩).

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Conflict of interest The authors declare that they have no conflict of interest.

Additional information

Supplementary information Experimental details and supporting data are available in the online version of the paper.

Xin Xu is currently a Master student at the College of Materials Science and Engineering, Fuzhou University. His research interest focuses on CO2RR with bismuth-based materials.

Shenghong Zhong received his BSc degree (2011) in chemistry from the University of Science and Technology of China (USTC), and PhD degree (2019) in materials science and engineering from King Abdullah University of Science and Technology (KAUST). Currently, he is an associate professor at Fuzhou University. His research interests mainly focus on non-precious metal nanomaterials, electrocatalysis, aqueous zinc batteries, and liquid metals.

Jianfeng Huang is currently a professor at the Institute of Advanced Interdisciplinary Studies, Chongqing University. He received his BSc degree in chemistry of materials from Nanjing Tech University in 2007, and PhD degree in chemical science from King Abdullah University of Science and Technology (KAUST) in 2015. He did postdoctoral research at École Polytechnique Fédérale de Lausanne (EPFL) (2016–2019). His main research interests are colloidal chemistry, nanoplasmonics and electrocatalysis.

Yan Yu received her BSc, MSc, and PhD degrees from Fuzhou University. She was a postdoctoral fellow at Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, and became a full professor at Fuzhou University in 2011. Her research interest includes environmental remediation, water purification, ecological materials, and photocatalytic CO2 reduction and H2 production.

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Xu, X., Wei, Y., Mi, L. et al. Interstitial Sn-doping promotes electrocatalytic CO2-to-formate conversion on bismuth. Sci. China Mater. 66, 3539–3546 (2023). https://doi.org/10.1007/s40843-023-2495-7

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