Engineering Cu/TiO2@N-Doped C Interfaces Derived from an Atom-Precise Heterometallic CuII4TiIV5 Cluster for Efficient Photocatalytic Hydrogen Evolution

Yusheng Yuan; Kai Sheng; Suyuan Zeng; Xiguang Han; Liming Sun; Ivor Lončarić; Wenwen Zhan; Di Sun

doi:10.1021/acs.inorgchem.0c00084

Engineering Cu/TiO₂@N-Doped C Interfaces Derived from an Atom-Precise Heterometallic Cu^II₄Ti^IV₅ Cluster for Efficient Photocatalytic Hydrogen Evolution

Inorg Chem. 2020 Apr 20;59(8):5456-5462. doi: 10.1021/acs.inorgchem.0c00084. Epub 2020 Apr 10.

Authors

Yusheng Yuan¹, Kai Sheng^{2

3}, Suyuan Zeng⁴, Xiguang Han¹, Liming Sun¹, Ivor Lončarić⁵, Wenwen Zhan¹, Di Sun²

Affiliations

¹ Jiangsu Key Laboratory of Green Synthetic Chemistry for Functional Materials, Department of Chemistry, School of Chemistry and Chemical Engineering, Jiangsu Normal University, Xuzhou 221116, People's Republic of China.
² Key Laboratory of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, People's Republic of China.
³ School of Aeronautics, Shandong Jiaotong University, Jinan 250037, People's Republic of China.
⁴ Department of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252059, People's Republic of China.
⁵ Division of Theoretical Physics, Ruđer Bošković Institute, Bijenička 54, 10000 Zagreb, Croatia.

PMID: 32275402
DOI: 10.1021/acs.inorgchem.0c00084

Abstract

Engineering interfaces is an effective method to create efficient photocatalysts by reducing the recombination of photogenerated carriers. Still, there is a lack of proficient strategies to construct suitable interfaces. In this work, we design and synthesize an atom-precise heterometallic Cu^II₄Ti^IV₅ cluster, [Ti₅Cu₄O₆(ba)₁₆]·2CH₃CN (1, Hba = benzoic acid), which is used as a precursor for fabricating efficient photocatalytic interfaces. The cluster has a precise composition and structure with hierarchical bimetal atom distribution and favorable binding properties. The resulting Cu/TiO₂@N-doped C interfaces are obtained via the thermal treatment. Combined Cu/TiO₂ with N-doped C interfaces provide multiple channels for the transmission of photogenerated carriers and effectively reduce the recombination probability of photogenerated charge carriers. Consequently, the novel interface structure exhibits an excellent hydrogen evolution rate via the photocatalytic water splliting. Density functional theory calculations also support high activity of the interfaces toward hydrogen evolution. As a proof-of-concept application, we show that choosing well-defined metal clusters as precursors can offer a valuable method for engineering photocatalytically efficient interfaces.