Zheng Hongshun, Zi Baoye, Zhou Tong, Qiu Guoyang, Luo Zhongge, Lu Qingjie, Santiago Alain Rafael Puente, Zhang Yumin, Zhao Jianhong, Zhang Jin, He Tianwei, Liu Qingju
National Center for International Research on Photoelectric and Energy Materials, Yunnan Key Laboratory for Micro/nano Materials & Technology, School of Materials Science and Engineering, Yunnan University, Kunming 650091, China.
Southwest United Graduate School, Kunming 650091, China.
Nanoscale Horiz. 2024 Aug 19;9(9):1532-1542. doi: 10.1039/d4nh00196f.
The development of high-activity photocatalysts is crucial for the current large-scale development of photocatalytic hydrogen applications. Herein, we have developed a strategy to significantly enhance the hydrogen photocatalytic activity of Cu/Pr di-atom co-modified TiO architectures by selectively anchoring Cu single atoms on the oxygen vacancies of the TiO surface and replacing a trace of Ti atoms in the bulk with rare earth Pr atoms. Calculation results demonstrated that the synergistic effect between Cu single atoms and Pr atoms regulates the electronic structure of Cu/Pr-TiO, thus promoting the separation of photogenerated carriers and their directional migration to Cu single atoms for the photocatalytic reaction. Furthermore, the d-band center of Cu/Pr-TiO, which is located at -4.70 eV, optimizes the adsorption and desorption behavior of H*. Compared to TiO, Pr-TiO, and Cu/TiO, Cu/Pr-TiO displays the best H* adsorption Gibbs free energy (-0.047 eV). Furthermore, experimental results confirmed that the photogenerated carrier lifetime of Cu/Pr-TiO is not only the longest (2.45 ns), but its hydrogen production rate (34.90 mmol g h) also significantly surpasses those of Cu/TiO (13.39 mmol g h) and Pr-TiO (0.89 mmol g h). These findings open up a novel atomic perspective for the development of optimal hydrogen activity in dual-atom-modified TiO photocatalysts.
高活性光催化剂的开发对于当前光催化制氢应用的大规模发展至关重要。在此，我们开发了一种策略，通过将铜单原子选择性地锚定在TiO表面的氧空位上，并在体相中用稀土Pr原子取代微量的Ti原子，显著提高Cu/Pr双原子共修饰TiO结构的光催化产氢活性。计算结果表明，铜单原子与Pr原子之间的协同效应调节了Cu/Pr-TiO的电子结构，从而促进了光生载流子的分离及其向铜单原子的定向迁移以进行光催化反应。此外，位于-4.70 eV的Cu/Pr-TiO的d带中心优化了H的吸附和解吸行为。与TiO、Pr-TiO和Cu/TiO相比，Cu/Pr-TiO表现出最佳的H吸附吉布斯自由能（-0.047 eV）。此外，实验结果证实，Cu/Pr-TiO的光生载流子寿命不仅最长（2.45 ns），而且其产氢速率（3~4.90 mmol g h）也显著超过Cu/TiO（13.39 mmol g h）和Pr-TiO（0.89 mmol g h）。这些发现为双原子修饰的TiO光催化剂中最佳产氢活性的开发开辟了一个新的原子视角。
