Facet Engineering to Regulate Surface States of Topological Crystalline Insulator Bismuth Rhombic Dodecahedrons for Highly Energy Efficient Electrochemical CO2 Reduction

Huan Xie; Tan Zhang; Ruikuan Xie; Zhufeng Hou; Xuecong Ji; Yongyu Pang; Shaoqing Chen; Maria-Magdalena Titirici; Hongming Weng; Guoliang Chai

doi:10.1002/adma.202008373

Facet Engineering to Regulate Surface States of Topological Crystalline Insulator Bismuth Rhombic Dodecahedrons for Highly Energy Efficient Electrochemical CO₂ Reduction

Adv Mater. 2021 Aug;33(31):e2008373. doi: 10.1002/adma.202008373. Epub 2021 Jun 26.

Authors

Huan Xie^{1

2

3}, Tan Zhang^{4

5

6}, Ruikuan Xie^{1

2

3}, Zhufeng Hou^{1

2

3}, Xuecong Ji^{4

5

6}, Yongyu Pang^{1

2

3}, Shaoqing Chen⁷, Maria-Magdalena Titirici⁸, Hongming Weng^{4

5

6}, Guoliang Chai^{1

2

3}

Affiliations

¹ State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002, P. R. China.
² School of Chemical Science, University of Chinese Academy of Sciences, Beijing, 100049, China.
³ Fujian Science and Technology Innovation Laboratory for Optoelectronic Information of China, Fuzhou, Fujian, 350108, P. R. China.
⁴ Beijing National Research Center for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing, 100190, China.
⁵ School of Physical Sciences, University of Chinese Academy of Sciences, Beijing, 100049, China.
⁶ Songshan Lake Materials Laboratory, Dongguan, Guangdong, 523808, China.
⁷ Department of Materials Science and Engineering, Southern University of Science and Technology, Shenzhen, Guangdong, 518055, P. R. China.
⁸ Department of Chemical Engineering, Imperial College London, London, SW7 2AZ, UK.

PMID: 34174114
DOI: 10.1002/adma.202008373

Abstract

Bismuth (Bi) is a topological crystalline insulator (TCI), which has gapless topological surface states (TSSs) protected by a specific crystalline symmetry that strongly depends on the facet. Bi is also a promising electrochemical CO₂ reduction reaction (ECO₂ RR) electrocatalyst for formate production. In this study, single-crystalline Bi rhombic dodecahedrons (RDs) exposed with (104) and (110) facets are developed. The Bi RDs demonstrate a very low overpotential and high selectivity for formate production (Faradic efficiency >92.2%) in a wide partial current density range from 9.8 to 290.1 mA cm^-2 , leading to a remarkably high full-cell energy efficiency (69.5%) for ECO₂ RR. The significantly reduced overpotential is caused by the enhanced *OCHO adsorption on the Bi RDs. The high selectivity of formate can be ascribed to the TSSs and the trivial surface states opening small gaps in the bulk gap on Bi RDs, which strengthens and stabilizes the preferentially adsorbed *OCHO and mitigates the competing adsorption of *H during ECO₂ RR. This study describes a promising application of Bi RDs for high-rate formate production and high-efficiency energy storage of intermittent renewable electricity. Optimizing the geometry of TCIs is also proposed as an effective strategy to tune the TSSs of topological catalysts.

Keywords: Bi rhombic dodecahedrons; electrochemical CO 2 reduction; high energy efficiency; surface states; topological crystalline insulators.

Abstract

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