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Tunable titanium metal–organic frameworks with infinite 1D Ti–O rods for efficient visible-light-driven photocatalytic H₂ evolution

Li, Changqing, Xu, Hui, Gao, Junkuo, Du, Wenna, Shangguan, Liqing, Zhang, Xin, Lin, Rui-Biao, Wu, Hui, Zhou, Wei, Liu, Xinfeng, Yao, Juming, Chen, Banglin
Journal of materials chemistry A 2019 v.7 no.19 pp. 11928-11933
absorption, coordination polymers, hydrogen, hydrogen production, ligands, light, photocatalysis, photocatalysts, surface area, titanium
Infinite 1D Ti–O rod-based metal–organic frameworks (MOFs) are promising photocatalysts for water splitting due to their high optical response and favourable photo-redox properties and stability, but have not been explored yet. In this study, three isoreticular porous 1D rod-based Ti-MOFs ZSTU-1, ZSTU-2 and ZSTU-3 are successfully constructed from infinite [Ti₆(μ₃-O)₆(μ₂-OH)₆]ₙ secondary building units (SBUs) and tritopic carboxylate linkers 4,4′,4′′-nitrilotribenzoic acid (H₃TCA), 1,3,5-tris(4-carboxyphenyl)benzene (H₃BTB) and tris(4′-carboxybiphenyl)amine (H₃BTCA), respectively. Their porosities systematically increase with the larger and longer organic linkers. The two MOFs ZSTU-1 and ZSTU-3 built from the triphenylamino-based ligands can absorb visible light, exhibiting much better photocatalytic performance than ZSTU-2 as shown by the H₂ production rate of ZSTU-1 and ZSTU-3 being 3–4 times higher than that of ZSTU-2. The photocatalytic H₂ production rates for ZSTU-1, ZSTU-2, and ZSTU-3 are 1060 μmol g⁻¹ h⁻¹, 350 μmol g⁻¹ h⁻¹ and 1350 μmol g⁻¹ h⁻¹, respectively. The extraordinary photocatalytic activity of ZSTU-3 is attributed to its visible light absorption, large surface area, and favorable charge separation.