Cheng Fangyuan, Lin Guoming, Hu Xiuli, Xi Shaobo, Xie Kui
CAS Key Laboratory of Design and Assembly of Functional Nanostructures, and Fujian Provincial Key Lab of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002, China.
Nat Commun. 2019 Aug 9;10(1):3618. doi: 10.1038/s41467-019-11623-w.
Porous single-crystalline (P-SC) titanium dioxide in large size would significantly enhance their photoelectrochemical functionalities owing to the structural coherence and large surface area. Here we show the growth of P-SC anatase titanium dioxide on an 2 cm scale through a conceptually different lattice reconstruction strategy by direct removal of K/P from KTiOPO lattice leaving the open Ti-O skeleton simultaneously recrystallizing into titanium dioxide. The (101) facet dominates the growth of titanium dioxide while the relative titanium densities on different parent crystal facets control the microstructures. Crystal growth in reducing atmospheres produces P-SC TiO (n = 7~38) in magneli phases with enhanced visible-infrared light absorption and conductivity. The P-SC TiO shows enhanced exciton lifetime and charge mobility. The P-SC TiO boosts photoelectrochemical oxidation of benzene to phenol with P-SC TiO showing 60.1% benzene conversion and 99.6% phenol selectivity at room temperature which is the highest so far to the best of our knowledge.
大尺寸的多孔单晶（P-SC）二氧化钛由于其结构连贯性和大表面积，将显著增强其光电化学功能。在此，我们展示了通过一种概念上不同的晶格重构策略，在2厘米尺度上生长P-SC锐钛矿型二氧化钛，即通过直接从KTiOPO晶格中去除K/P，留下开放的Ti-O骨架，同时重结晶为二氧化钛。（101）面主导二氧化钛的生长，而不同母晶面上的相对钛密度控制微观结构。在还原气氛中进行晶体生长会产生具有增强的可见-红外光吸收和导电性的Magnéli相的P-SC TiO（n = 7~38）。P-SC TiO表现出增强的激子寿命和电荷迁移率。P-SC TiO促进了苯向苯酚的光电化学氧化，在室温下，P-SC TiO的苯转化率为60.1%，苯酚选择性为99.6%，据我们所知，这是目前最高的。
