Twin boundary defect engineering in Au cocatalyst to promote alcohol splitting for coproduction of H2 and fine chemicals

Mengqing Li; Mathias Van Der Veer; Xuhui Yang; Bo Weng; Lijuan Shen; Haowei Huang; Xiongbo Dong; Guanhua Wang; Maarten B J Roeffaers; Min-Quan Yang

doi:10.1016/j.jcis.2023.11.171

Twin boundary defect engineering in Au cocatalyst to promote alcohol splitting for coproduction of H₂ and fine chemicals

J Colloid Interface Sci. 2024 Mar:657:819-829. doi: 10.1016/j.jcis.2023.11.171. Epub 2023 Dec 1.

Authors

Affiliations

¹ College of Environmental and Resource Sciences, College of Carbon Neutral Modern Industry, Fujian Key Laboratory of Pollution Control & Resource Reuse, Fujian Normal University, Fuzhou 350007, China.
² cMACS, Department of Microbial and Molecular Systems, KU Leuven, Celestijnenlaan 200F, 3001 Leuven, Belgium; Applied Electrochemistry and Catalysis (ELCAT), University of Antwerp, Campus Drie Eiken, Universiteitsplein 1, 2610 Wilrijk, Belgium.
³ cMACS, Department of Microbial and Molecular Systems, KU Leuven, Celestijnenlaan 200F, 3001 Leuven, Belgium. Electronic address: bo.weng@kuleuven.be.
⁴ cMACS, Department of Microbial and Molecular Systems, KU Leuven, Celestijnenlaan 200F, 3001 Leuven, Belgium.
⁵ Engineering Research Center of Nano-Geomaterials of Ministry of Education, China University of Geosciences, Wuhan 430074, China.
⁶ Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Xiamen 361005, China.
⁷ cMACS, Department of Microbial and Molecular Systems, KU Leuven, Celestijnenlaan 200F, 3001 Leuven, Belgium. Electronic address: maarten.roeffaers@kuleuven.be.
⁸ College of Environmental and Resource Sciences, College of Carbon Neutral Modern Industry, Fujian Key Laboratory of Pollution Control & Resource Reuse, Fujian Normal University, Fuzhou 350007, China. Electronic address: yangmq@fjnu.edu.cn.

PMID: 38086245
DOI: 10.1016/j.jcis.2023.11.171

Abstract

The microstructure of Au metal cocatalyst has been shown to significantly influence its optical and electronic properties. However, the impact of Au defect engineering on photocatalytic activity remains underexplored. In this study, we synthesize different Au-TiO₂ composites by in-situ hybridizing face-centered cubic (F-Au) and twin boundary defect Au (T-Au) nanoparticles (NPs) onto the surface of TiO₂. We find that T-Au NPs with twin defects serve as highly efficient cocatalysts for converting alcohols into their corresponding aldehydes while also generating H₂. The optimized T-Au/TiO₂ composite yields an H₂ evolution rate of 6850 µmol h^-1 g^-1 and a BAD formation rate of 6830 µmol h^-1 g^-1, about 38 times higher than that of blank TiO₂. Compared to F-Au/TiO₂, the T-Au/TiO₂ composite enhances charge separation, extends the lifetime of electrons, and provides more active sites for H₂ reduction. The twin defect also improves alcohol reactant adsorption, boosting overall photocatalytic performance. This research paves the way for more studies on defect engineering in metal cocatalysts for enhanced catalytic activities in organic synthesis and H₂ evolution.

Keywords: Alcohols splitting; Au cocatalyst; H(2) evolution; Photocatalysis; Twin boundary defect.