Heteroatomic Ni, Sn Clusters-Grafted Anatase TiO2 Photocatalysts: Structure, Electron Delocalization, and Synergy for Solar Hydrogen Production
Heteroatomic Ni, Sn Clusters-Grafted Anatase TiO2 Photocatalysts: Structure, Electron Delocalization, and Synergy for Solar Hydrogen Production
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杂原子 Ni、Sn 簇接枝锐钛矿型 TiO2 光催化剂：结构、电子离域和太阳能产氢的协同作用
DOI：
10.1021/acs.jpcc.5b02256
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发表时间：
2015-05-14
影响因子：
3.7
通讯作者：
Long, Jinlin
中科院分区：
文献类型：
--
作者：
Huang, Haowei;Lin, Jinjin;Long, Jinlin
本工作基于金属-金属电荷转移(MMCT)的基本原理，展示了锐钛矿型纳米粒子表面金属活性中心的分子工程。采用表面金属有机化学的方法制备了一系列锡、镍共修饰的TiO2光催化剂。以乙二胺四乙酸二钠溶液光催化制氢为模型反应，评价了材料的光催化性能。结合多种光谱技术对改性剂的化学状态进行了表征。这些结果清楚地揭示了原子隔离的镍和锡中心对太阳能到氢的转化的协同作用。在太阳光照射下，锡、镍共接枝的TiO2光催化剂的产氢能力提高了近10倍。详细的表征表明，这种协同作用与具有八元环结构的[-O-Ti-O-SnO-O-Ni-O-Ti-]杂原子簇合物密切相关。提出了一种电子离域回路，用于有效分离块体TiO2光产生的电荷和Ni-O-Ti分子键产生的激子。
This work shows the molecular engineering of metal active sites on the surface of anatase nanoparticles, based on the fundamental of metal-to-metal charge transfer (MMCT). A series of Sn, Ni-co-modified TiO2 photocatalysts were prepared by use of surface organometallic chemistry. Photocatalytic hydrogen production from ethylenediaminetetraacetic acid disodium salt solution as a model reaction was used to evaluate the photocatalytic properties of the materials. The chemical states of the modifiers were characterized by a combination of various spectroscopic techniques. These results clearly reveal the synergy of atomically isolated Ni and Sn centers for solar-to-hydrogen conversion. A near 10-fold enhancement of hydrogen production is achieved on Sn, Ni-co-grafted TiO2 photocatalysts under solar light irradiation. Detailed characterization suggests that the synergy is closely related to the [-O-Ti-O-Sn-O-Ni-O-Ti-] heteroatomic clusters with the eight-member cyclic structure. An electron-delocalization loop is proposed for efficient separation of charges photogenerated in bulk TiO2 and excitons generated in Ni-O-Ti molecular linkages.