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Ultra-fine Cu clusters decorated hydrangea-like titanium dioxide for photocatalytic hydrogen production

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Abstract

Hydrogen, with the merits of zero emissions and high energy density, is one of the promising green energy sources. Seeking for high efficiency and low-cost catalysts is one of the key issues for hydrogen evolution and its practical applications. Nano-structured metal co-catalysts are widely used to improve the photocatalytic performance via surface electronic structure/properties optimization of the catalyst. Herein, we report ultra-fine (~ 1 nm) Cu clusters decorated hydrangea-like TiO2 systems for photocatalytic hydrogen evolution. The pristine hydrangea-like TiO2 support shows a promising performance of hydrogen evolution (1.8 mmol·h−1·g−1), which is ~ 10.7 times higher than that of the commercial P25 (168 μmol·h−1·g−1). After ultra-fine Cu clusters decoration, a maximal hydrogen evolution performance (3.7 mmol·h−1·g−1) is achieved in the optimized system 6Cu–TiO2 (6 wt%). Experimental and theoretical studies demonstrate that the ultra-fine Cu clusters decoration could promote the charge separation and transfer process effectively. The Cu clusters also act as reaction sites for reduction of H2O to H2. These results are of great importance for the study of Cu-based co-catalyst systems and also shed light on the development of other non-noble metal co-catalysts in photocatalysis hydrogen evolution.

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摘要

氢能是一种最具前景的绿色能源, 具有零排放和高能量密度等优点。因此, 寻找一种高效且具有低成本的催化剂是产氢领域的关键问题之一, 且有助于光催化产氢技术的工业应用。金属纳米助催化剂可以通过优化催化剂的表面电子结构来提高催化剂的活性。在本篇文章中, 我们报道了铜超小纳米团簇(~ 1 nm)修饰的类绣球花状TiO2催化剂, 将其应用于光催化产氢。结果表明, 类绣球花状TiO2具有良好的产氢性能(1.8 mmol h-1 g-1), 约为商业P25 (168 μmol h-1 g-1)性能的10.7倍。铜超小纳米团簇修饰后, 6Cu-TiO2催化剂(6 wt%)的光催化产氢性能达到最优(3.7 mmol h-1 g-1)。实验和理论研究表明, 铜超小纳米团簇修饰可以有效促进催化剂光生载流子的分离和转移。其次, 铜团簇还可以作为活性反应位点, 将H2O还原为H2。该工作对铜基助催化剂体系的研究具有重要意义, 也为其他非贵金属助催化剂在光催化析氢方面的研究提供了启示。

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Nos. 11874356, 11904039, 51772035 and 52071041), the Project for Fundamental and Frontier Research in Chongqing (Nos. cstc2019jcyjjqX0002 and cstc2020jcyj-msxmX0777) and the Fundamental Research Funds for the Central Universities (No. 106112016CDJZR308808). The work conducted at Chongqing Institute of Green and Intelligent Technology (Chinese Academy of Sciences) is also supported by Key Research Program of Frontier Sciences, CAS (No. QYZDB-SSW-SLH016).

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Authors and Affiliations

  1. College of Physics and State Key Laboratory of Coal Mine Disaster Dynamics and Control, Chongqing University, Chongqing, 401331, China

    Ya-Jie Feng, Yang Wang, Jiang-Ping Ma, You-Yu Duan, Xu Lu & Xiao-Yuan Zhou

  2. Chongqing Institute of Green and Intelligent Technology, Chinese Academy of Sciences, Chongqing, 400722, China

    Ya-Jie Feng & Guo-Yu Wang

  3. Institute of Microstructure and Properties of Advanced Materials, Beijing University of Technology, Beijing, 100124, China

    Kai-Wen Wang

  4. Analytical and Testing Center, Chongqing University, Chongqing, 401331, China

    Jie Liu & Bin Zhang

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  1. Ya-Jie Feng
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  2. Yang Wang
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Feng, YJ., Wang, Y., Wang, KW. et al. Ultra-fine Cu clusters decorated hydrangea-like titanium dioxide for photocatalytic hydrogen production. Rare Met. 41, 385–395 (2022). https://doi.org/10.1007/s12598-021-01815-z

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