Cu单原子与CuO纳米团簇协同增强TiO2光催化析氢性能

doi:10.1016/S1872-2067(25)64892-3

催化学报 ›› 2026, Vol. 83: 162-171.DOI: 10.1016/S1872-2067(25)64892-3

Cu单原子与CuO纳米团簇协同增强TiO₂光催化析氢性能

张洪文^,¹, 蔡颖慧^,¹, 李秉岳, 山巍, 唐华^*()

青岛大学环境与地理科学学院, 山东青岛 266071

收稿日期:2025-08-01 接受日期:2025-08-27 出版日期:2026-04-18 发布日期:2026-03-04
通讯作者: * 电子信箱: huatang79@163.com (唐华).
作者简介:¹共同第一作者.
基金资助:
国家自然科学基金(22378219);国家自然科学基金(22302106);山东省泰山学者青年项目(tsqn202312170);山东省优秀青年科学基金(海外)(2024HWYQ-069);山东省青创团队计划项目(2023KJ225)

Isolated Cu atoms and CuO nanoclusters synergistically boost hydrogen evolution over TiO₂

Hongwen Zhang^,¹, Yinghui Cai^,¹, Bingyue Li, Wei Shan, Hua Tang^*()

School of Environment and Geography, Qingdao University, Qingdao 266071, Shandong, China

Received:2025-08-01 Accepted:2025-08-27 Online:2026-04-18 Published:2026-03-04
Contact: * E-mail: huatang79@163.com (H. Tang).
About author:¹Contributed equally to this work.
Supported by:
National Science Foundation of China(22378219);National Science Foundation of China(22302106);Taishan Scholar Program of Shandong Province(tsqn202312170);Science Fund for Excellent Young Scholars (Overseas) of Shandong Province(2024HWYQ-069);Technology Support Program for Youth Innovation Team of Shandong Universities(2023KJ225)

摘要/Abstract

摘要：

太阳能转化为氢能是一种极具前景且可持续的策略, 有望缓解全球能源危机并减轻环境污染. 然而, 实现具有实际应用价值的太阳能制氢效率仍面临巨大挑战, 主要原因在于光生载流子空间分离效率不足以及界面反应动力学迟缓. 通过构筑氧化还原活性位点, 可显著提升光催化析氢性能, 已成为近年来的重要研究方向. 本文针对传统方法合成复杂、难以规模化等问题, 提出了一种简便可控的熔盐法制备策略, 实现了在二氧化钛(TiO₂)表面和晶格中协同引入不同价态铜物种, 从而兼顾反应活性与成本效益, 为高效光催化制氢材料的设计提供了新的思路.
本研究采用简易可扩展的熔盐法, 在TiO₂中同时构筑了两类具有互补功能的Cu物种: 一部分Cu以单原子形式嵌入TiO₂晶格中, 形成分散均一的还原活性位点, 可显著降低氢吸附自由能, 促进质子还原半反应; 另一部分Cu物种在表面以超小CuO纳米团簇形式存在, 能够降低甲醇氧化过电位, 加快空穴的消耗速率, 从而有效提升界面电荷分离效率. 在以甲醇为牺牲剂的条件下, 优化后的Cu/TiO₂光催化剂表现出37.6 mmol g^-1 h^-1的析氢速率, 相较于本征TiO₂提升了96倍. 机理研究表明, 单原子Cu位点通过调节TiO₂表面电子结构, 提高了电子参与质子还原的能力, 而CuO纳米团簇则通过促进有机分子氧化反应, 加速了空穴的利用, 从而实现了光生载流子的高效空间分离. 在低浓度(0.1%)牺牲剂条件下, 该光催化剂仍保持较高的氢产率, 并能高效催化多种有机分子的氧化反应, 充分体现了CuO纳米团簇在氧化转化过程中的催化作用. 该研究不仅验证了Cu单原子与CuO纳米团簇在促进还原与氧化半反应中的协同效应, 而且为开发高效、稳定、可规模化制备的光催化制氢材料提供了有力依据.
未来, 随着原子级调控与多功能位点构筑技术的进一步发展, 通过合理设计兼具电子与空穴捕获利用功能的复合活性位点, 将有望突破太阳能制氢效率瓶颈. 本文提出的简便可控双模式Cu改性策略, 为低成本高效光催化剂的设计与应用提供了新范式, 对推动绿色氢能的大规模应用具有重要意义.

关键词: Cu单原子, CuO纳米团簇, 氧化还原活性位点工程, 光催化析氢反应, 有机分子氧化

Abstract:

The conversion of solar energy into hydrogen represents a promising and sustainable approach to addressing the global energy crisis and mitigating environmental pollution. However, achieving the industrial benchmark of solar-to-hydrogen efficiency remains challenging due to the inherently insufficient spatial separation of charge carriers and sluggish interfacial kinetics. Engineering redox-active sites has emerged as an effective approach to enhance photocatalytic hydrogen evolution performance. Herein, a dual-mode copper-modified titanium dioxide photocatalyst (Cu/TiO₂), comprising isolated Cu atoms and CuO nanoclusters, was successfully synthesized via a facile molten salt method. The optimized Cu/TiO₂ exhibited a remarkable hydrogen evolution rate of 37.6 mmol g^-1 h^-1 with methanol as a sacrificial agent, representing a 96-fold enhancement compared to pristine TiO₂. Mechanistic studies revealed that isolated Cu atoms incorporated into the TiO₂ lattice substantially lower the free energy of hydrogen adsorption (*H), thereby promoting the proton reduction half-reaction. Simultaneously, the surface-dispersed CuO nanoclusters were found to reduce the overpotential for methanol oxidation, thereby accelerating the oxidation half-reaction and facilitating overall charge balance during photocatalysis. Furthermore, photocatalytic hydrogen production coupled with the oxidation of various organic molecules was evaluated under a low sacrificial agent concentration (0.1%) over the Cu/TiO₂ photocatalyst, offering a more sustainable and practically relevant assessment of catalyst performance for green energy applications.

Key words: Isolated Cu Atoms, CuO nanoclusters, Engineering redox-active sites, Photocatalytic hydrogen evolution reaction, Organic molecule oxidation

张洪文, 蔡颖慧, 李秉岳, 山巍, 唐华. Cu单原子与CuO纳米团簇协同增强TiO₂光催化析氢性能[J]. 催化学报, 2026, 83: 162-171.

Hongwen Zhang, Yinghui Cai, Bingyue Li, Wei Shan, Hua Tang. Isolated Cu atoms and CuO nanoclusters synergistically boost hydrogen evolution over TiO₂[J]. Chinese Journal of Catalysis, 2026, 83: 162-171.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(25)64892-3

https://www.cjcatal.com/CN/Y2026/V83/I4/162

图/表 7

Fig. 1. Schematic illustration of the synthesis procedure for Cu/TiO2 photocatalysts.

Fig. 2. SEM (a), HRTEM (b-d), HAADF-STEM (e), and EDS mapping (g) images of Cu/TiO2-5.4. (f) XPS Cu 2p spectra of Cu/TiO2-2.6, Cu/TiO2-4.0, and Cu/TiO2-5.4.

Fig. 3. Cu K-edge XANES (a) and EXAFS (b) spectra of Cu/TiO2-5.4. (c) XPS quantitative analysis of Ti, O, and Cu elements.

Fig. 4. Photocatalytic H2 yields (a) and H2 production rates (b) of TiO2 and Cu/TiO2. Photocatalytic H2 yields (c) and H2 production rates (d) of Cu/TiO2 with various morphologies. (e) Stability test of Cu/TiO2. (f) XRD patterns of Cu/TiO2 before irradiation and after stable testing.

Fig. 5. UV-vis DRS (a), Photocurrent-time curves (b), EIS (c), and PL decay profiles (d) of TiO2 and Cu/TiO2. In-situ SER signals of DMPO-e- adducts of TiO2 (e) and Cu/TiO2 (f).

Fig. 6. (a) Free energy diagram of H2 evolution over TiO2, and Cu single atom-TiO2. LSV for HER (b), LSV for methanol oxidation (c), benzyl alcohol oxidation (d), H2 yields (e) and rates (f) of Cu/TiO2 in the oxidation of various organic substrates (each at 0.1 vol%).

Fig. 7. Schematic diagram illustrating the dual-site catalytic mechanism of Cu/TiO2 for photocatalytic HER using methanol as a sacrificial agent.

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Cu单原子与CuO纳米团簇协同增强TiO₂光催化析氢性能

Isolated Cu atoms and CuO nanoclusters synergistically boost hydrogen evolution over TiO₂

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