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Regulating p-orbital of metallic bismuth nanosheets via transition-metal oxides enables advanced CO2 electroreduction

利用过渡金属氧化物调控金属铋纳米片的p轨道从而实现CO2的高效电还原

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Abstract

The interaction of p-d orbitals can be used to efficiently improve electrocatalytic performance. However, the enhanced mechanism of electrocatalytic CO2 reduction reaction (eCO2RR) on main group metals inspired by the p-d orbital interactions is still unclear. Herein, a series of transition-metal oxides (TMOs: Fe2O3, Co3O4, and NiO) are introduced to metallic bismuth (Bi) nanosheets (NSs), which is proposed as a proof of concept for investigating the effect of introduced TMOs on the eCO2RR performance for Bi. Based on the results from in-situ Fourier transform infrared (FTIR) spectra and CO2-temperature programmed deposition (TPD), the TMOs in the Bi/TMOs NSs can enhance the adsorption and/or activation ability of CO2. Density functional theory (DFT) calculations reveal that the regulated adsorption energy of *OCHO and p-orbital of Bi sites can decrease theoretical overpotentials for both the CO2-to-*OCHO process and the *OCHO-to-HCOOH process. Moreover, the electron rearrangement that occurred due to the contact between Bi and TMO can also promote electron transport between the catalyst and reactants. Therefore, under the dual positive effect of thermodynamics and kinetics, the Bi sites in Bi/TMO NSs exhibit the maximum catalytic ability, realizing high catalytic activity and selectivity for HCOOH over a wider potential region. In particular, Bi/Fe2O3 NSs can present the most significant enhancement effect. It can yield a wide potential region of 500 mV with a high FEHCOOH (>90%) and achieve a maximum FEHCOOH of 99.7% (1.11 times that of Bi) at −0.8 VRHE with the HCOOH partial current density of 12.65 mA cm−2 (1.86 times that of Bi). This study establishes a relationship between the enhanced performance and the introduced TMOs and provides a practicable and scalable avenue for rationally engineering high-powered electrocatalysts.

摘要

p-d轨道之间的相互作用是一种提升电催化性能的有效方法. 然而, 其对主族金属的电催化CO2还原(eCO2RR)的增强机制尚不清晰. 因此, 我们向金属Bi纳米片中引入了一系列过渡金属氧化物(TMO: Fe2O3、 Co3O4、NiO), 并以此研究引入TMO对Bi物种eCO2RR性能的影响. 根据原位傅里叶变换红外光谱(FTIR)和CO2-程序升温脱附 (TPD)的结果, Bi/TMO中的TMO可以增强CO2的吸附和活化能力. 密度泛函理论(DFT)计算结果表明, Bi活性位点*OCHO吸附能及p轨道的优化可以降低CO2到*OCHO过程和*OCHO到HCOOH过程的理论过电位. 同时, 由于Bi与TMO之间因复合而发生的电子重排也促进了催化剂与反应物之间的电子传输. 因此, 在热力学和动力学的双重作用下, Bi/TMO中的Bi活性位点表现出最佳的催化能力, 在更宽的电位区间内实现了更高的催化活性和甲酸选择性. 其中, Bi/Fe2O3的增强效果最为显著. 在500 mV的宽电位区间内达到较高的甲酸的法拉第效率(>90%), 在−0.8 VRHE时, 甲酸的法拉第效率达到最大值99.7%(Bi的1.11倍), 甲酸局部电流密度达到12.65 mA cm−2 (Bi的1.86倍). 这一研究不仅建立了 eCO2RR性能增强与引入TMO之间的关系, 也为理性设计高性能电催化剂提供了一条实用的、可扩展的途径.

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Acknowledgements

We gratefully acknowledge the support of this research by the National Natural Science Foundation of China (U20A20250 and 22179035), the Science Fund for Distinguished Young Scholars of Heilongjiang Province (JQ2022B001), the Fundamental Research Funds for Youth Science and Technology Innovation Team Project of Heilongjiang Province (2021-KYYWF-0030), the China Postdoctoral Science Foundation (2019M651313), the Universities Fundamental Research Funds of Heilongjiang Province (RCCXYJ201806 and 2022-KYYWF-1063), and University Nursing Program for Young Scholars with Creative Talents in Heilongjiang Province (UNPYSCT-2020006).

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Authors and Affiliations

  1. Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education of China, School of Chemistry and Materials Science, Heilongjiang University, Harbin, 150080, China

    Weibo Yin  (尹伟勃), Bowen Liu  (刘博文), Xiaolei Wang  (王晓蕾), Wenqian Wang  (王文倩), Zhiyu Ren  (任志宇) & Honggang Fu  (付宏刚)

  2. Key Laboratory of Superlight Materials and Surface Technology of Ministry of Education, College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin, 150001, China

    Zichen Song  (宋子辰)

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  1. Weibo Yin  (尹伟勃)
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Contributions

Author contributions Yin W performed the experiments with help from Fu H, Ren Z and Wang X. Ren Z, Wang X, Yin W and Fu H wrote this paper. All authors contributed to the general discussion.

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Correspondence to Xiaolei Wang  (王晓蕾), Zhiyu Ren  (任志宇) or Honggang Fu  (付宏刚).

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Conflict of interest The authors declare no conflict of interest.

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

Wei-Bo Yin obtained his BSc degree from Heilongjiang University in 2019. He is currently an MSc candidate in inorganic chemisty under the supervision of Prof. Hon-ggang Fu at Heilongjiang University. His current research focuses on the design and synthesis of nanomaterials for energy conversion.

Xiaolei Wang received her BSc and PhD degrees from Jilin University in 2013 and 2016, respectively. During the period of studying for a doctorate (2017–2018), she conducted exchange learning at Kansai University in Japan. Then, she became a lecturer and associate professor of Heilongjiang University in 2018 and 2023, respectively. Her research mainly focuses on the exploring structural reconstruction and active species of catalytic materials under electrocatalytic conditions by in-situ/ex-situ electrochemistry characterization techniques (e.g., Raman spectra, FTIR spectra, XRD, XPS).

Zhiyu Ren received her BSc degree in 2001 and MSc degree in 2004 from Heilongjiang University. Then, she joined Heilongjiang University as an assistant professor. In 2008, she received his PhD degree from Jilin University. She became a full professor in 2014. Her interest focuses on the surface crystal engineering and defect regulation of advanced transition metal-based compounds and carbon-based nanocomposites for electrocatalysis (e.g., water splitting, carbon dioxide reduction, and organic small molecule oxidation).

Honggang Fu received his BSc degree in 1984 and MSc degree in 1987 from Jilin University. Then, he joined Heilongjiang University as an assistant professor. In 1999, he received his PhD degree from Harbin Institute of Technology. He became a full professor in 2000. Currently, he is a Cheung Kong Scholar. His interest focuses on the oxide-based semiconductor nanomaterials for solar energy conversion and photocatalysis, carbon-based nanomaterials for energy conversion and storage, and W (Mo,V)-based catalysts for HER and OER.

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Yin, W., Liu, B., Wang, X. et al. Regulating p-orbital of metallic bismuth nanosheets via transition-metal oxides enables advanced CO2 electroreduction. Sci. China Mater. 67, 1965–1974 (2024). https://doi.org/10.1007/s40843-024-2921-6

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