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New picolinate-functionalized titanium-oxide clusters: syntheses, structures and photocatalytic H2 evolution

Chang Gao,Dexin Wang,Yanshu Liu,Guanyun Zhang,Caiyun Liu,Amir Said,Huihui Niu,Guo Wang,Chen-Ho Tung,Yifeng Wang

Two nanosized titanium-oxide clusters (TOCs), Ti12(μ2-O)14(μ3-O)4PA16 (1; PA = 2-picolinate) and Ti12(μ2-O)18PA18 (2) were synthesized by using 2-picolinic acid and Ti(OiPr)4 in one-pot reactions. Their structures were determined using single-crystal X-ray diffractometry. Although both have the same core composition of Ti12O18, 1 exhibited superior H2 evolution activity of up to 180 μmol h−1 g−1, which is nearly eight times faster than 2. Mechanism studies revealed that 1 could induce the assembly of 2.3 nm PtNPs into 10–30 nm supra-nanoparticle structures, which contributed to the increased H2 evolution rate.