Caged-Cation-Induced Lattice Distortion in Bronze TiO2 for Cohering Nanoparticulate Hydrogen Evolution Electrocatalysts

Gaoxin Lin; Qiangjian Ju; Lijia Liu; Xuyun Guo; Ye Zhu; Zhuang Zhang; Chendong Zhao; Yingjie Wan; Minghui Yang; Fuqiang Huang; Jiacheng Wang

doi:10.1021/acsnano.2c04513

Caged-Cation-Induced Lattice Distortion in Bronze TiO₂ for Cohering Nanoparticulate Hydrogen Evolution Electrocatalysts

ACS Nano. 2022 Jun 28;16(6):9920-9928. doi: 10.1021/acsnano.2c04513. Epub 2022 Jun 17.

Authors

Gaoxin Lin^{1

2}, Qiangjian Ju^{1

2}, Lijia Liu³, Xuyun Guo⁴, Ye Zhu⁴, Zhuang Zhang^{1

2}, Chendong Zhao^{1

2}, Yingjie Wan^{1

2}, Minghui Yang⁵, Fuqiang Huang^{1

6}, Jiacheng Wang^{1

2

7}

Affiliations

¹ State Key Lab of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 201899, China.
² Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China.
³ Department of Chemistry, Western University, 1151 Richmond Street, London, ON N6A5B7, Canada.
⁴ Department of Applied Physics, Research Institute for Smart Energy, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong, China.
⁵ School of Environmental Science and Technology, Dalian University of Technology, Dalian, Liaoning 116024, China.
⁶ State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China.
⁷ Hebei Provincial Key Laboratory of Inorganic Nonmetallic Materials, College of Materials Science and Engineering, North China University of Science and Technology, Tangshan 063210, China.

PMID: 35713656
DOI: 10.1021/acsnano.2c04513

Abstract

Defect engineering provides a promising approach for optimizing the trade-off between support structures and active nanoparticles in heterojunction nanostructures, manifesting efficient synergy in advanced catalysis. Herein, a high density of distorted lattices and defects are successfully formed in bronze TiO₂ through caging alkali-metal Na cations in open voids (Na-TiO₂(B)), which could efficiently cohere nanoparticulate electrocatalysts toward alkaline hydrogen evolution reaction (HER). The RuMo bimetallic nanoparticles could directionally anchor on Na-TiO₂(B) with a certain angle of ∼22° due to elimination of the lattice mismatch, thus promoting uniform dispersion and small sizing of supported nanoparticles. Moreover, caging Na ions could significantly enhance the hydrophilicity of the substrate in RuMo/Na-TiO₂(B), leading to the strengthening synergy of water dissociation and hydrogen desorption. As expected, this Na-caged nanocomposite catalyst rich with structural perturbations manifests a 6.4-fold turnover frequency (TOF) increase compared to Pt/C. The study provides a paradigm for designing stable nano-heterojunction catalysts with lattice-distorted substrates by caging cations toward advanced electrocatalytic transformations.

Keywords: bronze TiO2; caged cations; electrocatalysis; lattice distortion; synergistic effect.