Although attaining a high porosity in TiO₂ is critical to enhancing its photocatalytic and photoelectric activities, its synthesis has been challenging owing to the high reactivity of conventional Ti precursors and the laborious template removal process. Thus, we herein report a versatile method for preparing hierarchically porous organic-functionalized TiO₂ (HiPOTs) using Ti-oxo clusters consisting of a rigid reactive ligand, para-aminobenzoate (p-ABA). The presence of p-ABA as a structure-directing template is crucial to obtain microporous structures with sufficiently high yields. The HiPOTs gradually transform from hierarchically micro/mesoporous structures into mesoporous structures during a sol–gel process. The Brunauer–Emmett–Teller surface areas of the HiPOTs range from 242 to 739 m²/g, which are among the highest reported for porous TiO₂ materials. The presence of p-ABA on the HiPOT surface decreases the band gap of TiO₂ to 2.7 eV, and prolonging the sol–gel process releases greater quantities of p-ABA, thereby increasing the band gap and the crystallinity of the anatase phase. Interestingly, unlike conventional TiO₂, which experiences rapid charge recombination, the Ti³⁺ oxidation states of HiPOTs are successfully isolated during UV irradiation and can be applied as a proof of concept to generate reactive oxygen species such as ¹O₂ and ^•O₂⁻.

尽管在TiO _2中获得高孔隙度对于增强其光催化和光电活性至关重要，但由于常规Ti前体的高反应活性和费力的模板去除工艺，其合成一直具有挑战性。因此，我们在此报告了一种通用的方法，该方法使用由刚性反应性配体对氨基苯甲酸酯（p -ABA）组成的Ti-氧代簇制备分级多孔有机功能化TiO ₂（HiPOT）。p的存在-ABA作为结构指导模板对于获得具有足够高产率的微孔结构至关重要。在溶胶-凝胶过程中，HiPOTs从分层的微/中孔结构逐渐转变为中孔结构。HiPOT的Brunauer-Emmett-Teller表面积为242至739 m ² / g，是多孔TiO ₂材料中报道的最高值。在HiPOT表面上存在p -ABA将TiO ₂的带隙减小到2.7 eV，并且延长溶胶-凝胶过程会释放更多的p -ABA，从而增加了带隙和锐钛矿相的结晶度。有趣的是，与传统的TiO ₂不同，它经历快速电荷复合，使Ti ³⁺ HiPOTs的氧化态被成功地在UV辐照期间分离并且可应用于作为概念证明，以产生活性氧物质，例如¹ Ò ₂和^• ö ₂ ^- 。