| Energy depletion and environmental pollution are two major problems that need to be solved urgently in today's world.As an efficient and clean energy source,hydrogen is a sustainable alternative to the traditional fossil fuels.The solar photocatalytic hydrogen production is a critical process for the development of hydrogen energy that may help to confront the energy and environmental challenges.Metal organic frameworks(MOFs)have shown promising applications in several research fields due to their properties such as adjustable structure,ultra-high specific surface area and ordered porosity.Particularly,study of MOFs a as photocatalysts has drawn great attention in the fields of photocatalysis and inorganic chemistry.In this thesis work,we designed and synthesized novel metal-organic framework materials based on terpyridine Ru complexes photosensitizers as organic linkers and explore their applications in photocatalytic reactions.The major content of this thesis consists of the following four sections:(1)Design and syntheses of novel bis-4'-carboxy-2,2':6',2''-terpyridine type of ruth enium photosensitizers[RuII(tpy COOH)2](PF6)2 and[RuII(bny COOH)2](PF6)2;and bis-4,4''-bicarboxy-2,2':6',2''-terpyridine type of ruthenium photosensitizers[RuII(tpy(COOH)2)2](PF6)2,[RuII(bny(COOH)2)2](PF6)2,and[RuII(tpy(COOH)2)(bny(COOH)2)](PF6)2 as linkers of metal organic frameworks.(2)Two new two-dimensional MOFs,Fe-Ru(COOH)2 and Cd-Ru(COOH)2,were constructed using the bis-4'-carboxy-2,2':6',2''-terpyridine ruthenium photosensitizer[RuII(tpy COOH)2](PF6)2 as the organic linker and Fe and Cd ions as the metal nodes.Fe-Ru(COOH)2 and Cd-Ru(COOH)2 were exfoliated into two-dimensional nanosheets and applied to photocatalytic proton reduction reactions.Fe-Ru(COOH)2 and Cd-Ru(COOH)2 did not show significant activity for photocatalytic hydrogen production.(3)Four bimetallic MOFs,denoted as CoxNiy-Ru(COOH)2,with different Co/Ni ratios were synthesized by solvothermal methods using[RuII(tpy COOH)2](PF6)2 as an organic linker.CoxNiy-Ru(COOH)2,Fe-Ru(COOH)2 and Cd-Ru(COOH)2are isostructural MOFs.The bimetallic MOFs were exfoliated into two-dimensional nanosheets and assessed as photocatalytic proton reduction catalysts.Among them,Co1Ni2-Ru(COOH)2,exhibits most efficient photocatalytic hydrogen production activity with a turnover number of 654.35?mol g-1(2.5h)and a catalytic rate of 258.14?mol g-1 h-1 under optimized conditions.(4)Four new metal-organic frameworks were constructed by solvothermal methods[RuII(tpy(COOH)2)2](PF6)2 and[RuII(bny(COOH)2)2](PF6)2 as organic linkers and 3d transition metal(Co,Ni,Cu,Zn)ions as nodes.Among them,[RuII(tpy(COOH)2)2](PF6)2 linker and Cu ion afforded the three-dimensional MOF Cu-Ru(COOH)4.[RuII(bny(COOH)2)2](PF6)2linker and Co or Ni metal ions generated the isostructural two-dimensional Co-Ru(bny COOH)4 and Ni-Ru(bny COOH)4 MOFs under different synthetic conditions.The three-dimensional Zn-Ru(bny COOH)4 MOF consists of[Zn3O15C5]cluster nodes. |
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