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Multivalent Sn species synergistically favours the CO2-into-HCOOH conversion

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Abstract

Although Sn-based catalysts have recently achieved considerable improvement in selective electro-catalyzing CO2 into HCOOH, the role of various valence Sn species is not fully understood due to the complexity and uncertainty of their evolution during the reaction process. Here, inspired by the theoretical simulations that the concomitant multivalent Sn (Sn0, Sn11 and SnIV) can significantly motivate the intrinsic activity of Sn-based catalyst, the Sn/SnO/SnO2 nanosheets were proposed to experimentally verify the synergistic effect of multivalent Sn species on the CO2-into-HCOOH conversion. During CO2 reduction reaction, the Sn/SnO/SnO2 nanosheets, which are prepared by the sequential hydrothermal reaction, calcined crystallization and low-temperature H2 treatment, exhibit a high FEHCOOH of 89.6% at −0.9 VRHE as well as a large cathodic current density. Systematic experimental and theoretical results corroborate that multivalent Sn species synergistically energize the CO2 activation, the HCOO* adsorption, and the electron transfer, which make Sn/SnO/SnO2 favour the conversion from CO2 into HCOOH in both thermodynamics and kinetics. This proof-of-concept study establishes a relationship between the enhanced performance and the multivalent Sn species, and also provides a practicable and scalable avenue for rational engineering high-powered electrocatalysts.

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Acknowledgements

We gratefully acknowledge the support by the National Natural Science Foundation of China (Nos. 21631004 and 21901065), the Natural Science Foundation of Heilongjiang Province of China (No. LH2020B019), the Youth Science and Technology Innovation Team Project of Heilongjiang Province (No. RCYJTD201803), and the University Nursing Program for Young Scholars with Creative Talents in Heilongjiang Province (No. UNPYSCT-2018009).

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Authors and Affiliations

  1. 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

    Jun Wu, Ziehen Song & Guiling Wang

  2. Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education of the People’s Republic of China, Heilongjiang University, Harbin, 150080, China

    Xue Bai, Zhiyu Ren, Shichao Du, Lei Zhao, Bowen Liu & Honggang Fu

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  1. Jun Wu
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  2. Xue Bai
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  3. Zhiyu Ren
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Correspondence to Zhiyu Ren, Guiling Wang or Honggang Fu.

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Wu, J., Bai, X., Ren, Z. et al. Multivalent Sn species synergistically favours the CO2-into-HCOOH conversion. Nano Res. 14, 1053–1060 (2021). https://doi.org/10.1007/s12274-020-3149-2

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