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Research Article

Industrial-current-density CO2-to-formate conversion with low overpotentials enabled by disorder-engineered metal sites

Zhiqiang Wang1,§Xiaolong Zu1,§Xiaodong Li1,§Li Li1Yang Wu1Shumin Wang1Peiquan Ling1Yuan Zhao1Yongfu Sun1,2 ( )Yi Xie1,2
Hefei National Laboratory for Physical Sciences at Microscale, University of Science and Technology of China, Hefei 230026, China
Institute of Energy, Hefei Comprehensive National Science Center, Hefei 230031, China

§ Zhiqiang Wang, Xiaolong Zu, and Xiaodong Li contributed equally to this work.

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Abstract

CO2 electroreduction to formate is technically feasible and economically viable, but still suffers from low selectivity and high overpotential at industrial current densities. Here, lattice-distorted metallic nanosheets with disorder-engineered metal sites are designed for industrial-current-density CO2-to-formate conversion at low overpotentials. As a prototype, richly lattice-distorted bismuth nanosheets are first constructed, where abundant disorder-engineered Bi sites could be observed by high-angle annular dark-field scanning transmission electron microscopy image. In-situ Fourier-transform infrared spectra reveal the CO2•−* group is the key intermediate, while theoretical calculations suggest the electron-enriched Bi sites could effectively lower the CO2 activation energy barrier by stabilizing the CO2•−* intermediate, further affirmed by the decreased formation energy from 0.49 to 0.39 eV. As a result, the richly lattice-distorted Bi nanosheets exhibit the ultrahigh current density of 800 mA·cm−2 with 91% Faradaic efficiencies for CO2-to-formate electroreduction, and the formate selectivity can reach nearly 100% at the current density of 200 mA·cm−2 with a very low overpotential of ca. 570 mV, outperforming most reported metal-based electrocatalysts.

Graphical Abstract

The disorder-engineered metal sites on the designed two-dimensional (2D) metallic nanosheets could effectively lower the formation energy of rate-limiting CO2•−* intermediate during CO2 reduction to formate. Moreover, the uniform sites and high electron conductivity of metallic nanosheets offer the designed electrocatalyst a higher opportunity to realize selective CO2 to formate at large current densities.

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Nano Research
Pages 6999-7007

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Cite this article:
Wang Z, Zu X, Li X, et al. Industrial-current-density CO2-to-formate conversion with low overpotentials enabled by disorder-engineered metal sites. Nano Research, 2022, 15(8): 6999-7007. https://doi.org/10.1007/s12274-022-4335-1
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Received: 11 January 2022
Revised: 17 February 2022
Accepted: 15 March 2022
Published: 10 May 2022
© Tsinghua University Press 2022