Effect of Bimetallic Dimer-Embedded TiO2(101) Surface on CO2 Reduction: The First-Principles Calculation

Chongyang Li; Cui Shang; Bin Zhao; Gang Zhang; Liangliang Liu; Wentao Yang; Zhiquan Chen

doi:10.3390/ma15072538

Effect of Bimetallic Dimer-Embedded TiO₂(101) Surface on CO₂ Reduction: The First-Principles Calculation

Materials (Basel). 2022 Mar 30;15(7):2538. doi: 10.3390/ma15072538.

Authors

Chongyang Li^{1

2}, Cui Shang³, Bin Zhao⁴, Gang Zhang¹, Liangliang Liu⁵, Wentao Yang⁴, Zhiquan Chen²

Affiliations

¹ College of Electric Power, North China University of Water Resources and Electric Power, Zhengzhou 450045, China.
² Hubei Nuclear Solid Physics Key Laboratory, Department of Physics, Wuhan University, Wuhan 430072, China.
³ Henan Key Laboratory of Magnetoelectronic Information Functional Materials, School of Physics and Electronics Engineering, Zhengzhou University of Light Industry, Zhengzhou 450002, China.
⁴ School of Science, Zhongyuan University of Technology, Zhengzhou 450007, China.
⁵ Key Laboratory for Special Functional Materials of Ministry of Education, Henan University, Kaifeng 475004, China.

Abstract

The first-principles calculation was used to explore the effect of a bimetallic dimer-embedded anatase TiO₂(101) surface on CO₂ reduction behaviors. For the dimer-embedded anatase TiO₂(101) surface, Zn-Cu, Zn-Pt, and Zn-Pd dimer interstitials could stably stay on the TiO₂(101) surface with a binding energy of about -2.36 eV, as well as the electronic states' results. Meanwhile, the results of adsorption energy, structure parameters, and electronic states indicated that CO₂ was first physically and then chemically adsorbed much more stably on these three kinds of dimer-embedded TiO₂(101) substrate with a small barrier energy of 0.03 eV, 0.23 eV, and 0.12 eV. Regarding the reduction process, the highest-energy barriers of the CO₂ molecule on the Zn-Cu dimer-embedded TiO₂(101) substrate was 0.31 eV, which largely benefited the CO₂-reduction reaction (CO₂RR) activity and was much lower than that of the other two kinds of Zn-Pt and Cu-Pt dimer-TiO₂ systems. Simultaneously, the products CO* and *O* of CO₂ reduction were firmly adsorbed on the dimer-embedded TiO₂(101) surface. Our results indicated that a non-noble Zn-Cu dimer might be a more suitable and economical choice, which might theoretically promote the designation of high CO₂RR performance on TiO₂ catalysts.

Keywords: CO2 reduction; TiO2(101); catalyst; dimer; first principles; metal-embedded.

Abstract

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