Harmonizing the Electronic Structures of the Adsorbate and Catalysts for Efficient CO2 Reduction

An Zhang; Yongxiang Liang; Huiping Li; Xinyu Zhao; Yuliang Chen; Boyan Zhang; Wenguang Zhu; Jie Zeng

doi:10.1021/acs.nanolett.9b02782

Harmonizing the Electronic Structures of the Adsorbate and Catalysts for Efficient CO₂ Reduction

Nano Lett. 2019 Sep 11;19(9):6547-6553. doi: 10.1021/acs.nanolett.9b02782. Epub 2019 Aug 16.

Authors

An Zhang¹, Yongxiang Liang¹, Huiping Li², Xinyu Zhao¹, Yuliang Chen¹, Boyan Zhang¹, Wenguang Zhu², Jie Zeng¹

Affiliations

¹ Hefei National Laboratory for Physical Sciences at the Microscale, Key Laboratory of Strongly-Coupled Quantum Matter Physics of Chinese Academy of Sciences, National Synchrotron Radiation Laboratory, Key Laboratory of Surface and Interface Chemistry and Energy Catalysis of Anhui Higher Education Institutes, Department of Chemical Physics , University of Science and Technology of China , Hefei , Anhui 230026 , P.R. China.
² International Center for Quantum Design of Functional Materials, Hefei National Laboratory for Physical Sciences at the Microscale, Synergetic Innovation Center of Quantum Information and Quantum Physics, Department of Physics, School of Physical Sciences , University of Science and Technology of China , Hefei , Anhui 230026 , P.R. China.

PMID: 31414823
DOI: 10.1021/acs.nanolett.9b02782

Abstract

In CO₂ electroreduction, the critical bottleneck lies in the CO₂ activation which requires high overpotentials. CO₂ activation is related to both the electronic structures of catalysts and those of adsorbates, thus an ideal catalyst should match its electronic structures with those of the adsorbate. Here, we harmonized the electronic structures of the adsorbate and Mn-doped In₂S₃ nanosheets for efficient CO₂ reduction. The introduction of Mn dopants into In₂S₃ nanosheets enhanced both the Faradaic efficiency (FE) for carbonaceous products and current density (j). At -0.9 V vs RHE, Mn-doped In₂S₃ nanosheets exhibited a remarkable FE of 92% for carbonaceous product at a high j of 20.1 mA cm^-2. Mechanistic studies revealed that Mn doping enabled the harmonic overlaps between the p orbitals of O atoms and d orbitals of Mn atoms near the conduction band edge of Mn-doped In₂S₃ nanosheets during the activation of CO₂. Due to the unique electronic structures of the coadsorbed configurations, Mn-doped In₂S₃ nanosheets exhibited an energy barrier for CO₂ activation into HCOO* lower than that over pristine In₂S₃ nanosheets.

Keywords: CO activation; CO electroreduction; charge transfer; harmonic electronic structures; orbital overlap.