Department of Pharmaceutical Engineering, Bengbu Medical College, Bengbu, Anhui 233030, P. R. China.
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, Liaoning 116024, P. R. China.
Inorg Chem. 2023 Apr 10;62(14):5700-5706. doi: 10.1021/acs.inorgchem.3c00250. Epub 2023 Mar 26.
Low-cost high-efficiency H evolution is indispensable for its large-scale applications in the future. In the research, we expect to build high active photocatalysts for sunlight-driven H production by surface engineering to adjust the work function of photocatalyst surfaces, adsorption/desorption ability of substrates and products, and reaction activation energy barrier. Single-atom Pt-doped TiO nanosheets (NSs), mainly including two facets of (001) and (101), with loading of Pt nanoparticles (NPs) at their edges (Pt/TiO-SAP) are successfully prepared by an oxygen vacancy-engaged synthetic strategy. According to the theoretical simulation, the implanted single-atom Pt can change the surface work function of TiO, which benefits electron transfer, and electrons tend to gather at Pt NPs adsorbed at (101) facet-related edges of TiO NSs for H evolution. Pt/TiO-SAP exhibits ultrahigh photocatalytic performance of hydrogen evolution from dry methanol with a quantum yield of 90.8% that is ∼1385 times higher than pure TiO NSs upon 365 nm light irradiation. The high H generation rate (607 mmol g h) of Pt/TiO-SAP is the basis for its potential applications in the transportation field with irradiation of UV-visible light (100 mW cm). Finally, lower adsorption energy for HCHO on Ti sites originated from TiO (001) doping single-atom Pt is responsible for high selective dehydrogenation of methanol to HCHO, and H tends to favorably gather at Pt NPs on the TiO (101) surface to produce H.
低成本、高效率的 H 演化对于其未来的大规模应用是不可或缺的。在研究中，我们期望通过表面工程构建高效的光催化剂，以调整光催化剂表面的功函数、底物和产物的吸附/解吸能力以及反应的活化能垒，从而实现太阳光驱动的 H 生产。通过氧空位参与的合成策略，成功制备了负载在 Pt 纳米粒子（NPs）边缘的单原子 Pt 掺杂 TiO 纳米片（NSs），主要包括（001）和（101）两个晶面。根据理论模拟，嵌入的单原子 Pt 可以改变 TiO 的表面功函数，有利于电子转移，电子倾向于聚集在 Pt NPs 吸附在 TiO NSs 的（101）面相关边缘上，用于 H 演化。Pt/TiO-SAP 在干燥甲醇的光催化制氢中表现出超高的催化性能，量子产率为 90.8%，在 365nm 光照射下比纯 TiO NSs 高约 1385 倍。Pt/TiO-SAP 的高 H 生成速率（607mmol g h）是其在运输领域潜在应用的基础，在 UV-可见光（100mW cm）照射下也具有较高的选择性。最后，TiO（001）掺杂单原子 Pt 导致 Ti 位上 HCHO 的吸附能降低，有利于甲醇向 HCHO 的高选择性脱氢，H 倾向于在 TiO（101）表面的 Pt NPs 上聚集以产生 H。
