| Metal-organic framework materials has characteristics of large specific surface area,unsaturated metal active sites,flexible pore structure and has been widely used in gas adsorption,ctroncatalysis,organic catalysis,fluorescence sensing,energy storage.In order to take advantage of its morphology features?pore system and composition diversity,composite materials based on MOFs,various functional materials based on MOFs materials?MOF source materials?,such as MOF composite,MOF derivatives brings new opportunities and challenges for MOFs.Based on the design synthesis,modification research and application function expansion of MOFs materials,we successfully synthesized three types of MOF-based materials and explored their applications in dye adsorption,heterogeneous organic catalysis,and electrocatalysis.According to the different properties of MOF-based functional materials,main contents of this paper are as follows:Part one,we summarize the structural characteristics,preparation,and research frontiers of metal organic framework materials.Secondly,their applications of dye adsorption and electrocatalysis properties for the hydrogen evolution reaction?HER?and oxygen evolution reaction?OER?were also been discussed and the research progress of the latest research results were summarized.The advantages of MOF as the source material for the preparation of metal sulfides and their effects on dye adsorption and electrocatalytic performance are was discussed.Finally,the basis and research contents of this paper are introduced.Part two,5'-?3,5-dicarboxyphenyl?-[1,1':3',1''-terphenyl]-3,3",5,5-tetracarboxylic acid?H6BHB?is an organic component,we have synthesized four cases heterogeneous homogeneous bulk MOFs[NH2?CH3?2][M3??3-OH??H2O?3?BHB?]?CTGU-10?{[M=Co3,Co2Ni,CoNi2,Ni3,labeled as CTGU-10a1-10d1]}.Based on the electrocatalytic oxygen evolution?OER?performance of bulk CTGU-10 series materials,the corresponding nano-spheres and nano-banded MOFs hierarchical structure?CTGU-10a2-d2?were synthesized and the electrocatalytic OER properties of bulk and them were compared.Among these,CTGU-10c2 is the best material for the OER.Both DFT and experiments show that the remarkable OER performance of CTGU-10c2 is due to the presence of hierarchical nanobelt architecture and the Ni-Co coupling effect.This work confirmed that the introduction of heterometallic clusters and the nanosheet strategy to construct MOF nanostructures is an effective way to improve the electrocatalytic performance of MOF materials.The results have been published in journal?Angew.Chem.Int.Ed.,2019,58,1-6?and apply for an invention patent?CN201810027272.9?Part three,Two isomorphic metal-organic frameworks?Zn/Mn-MOFs?were synthesized under solvothermal conditions by using ligand 5'-?3,5-dicarboxyphenyl?-[1,1':3',1''-terphenyl]-3,3",5,5"-tetracarboxylicacid?H6BHB?,and the porosity was 54.6%.We choose them as a carrier to embed Ag NPs through solution infiltration,resulting in two kinds of composite materials.The nitrophenol reduction reaction was used as a probe to investigate the properties.It is found that the Ag@Mn-MOF composite has a high ability to catalytically reduce nitrophenol,and the rate constant is 3.2×10-2 s-1.We applied for one invention patent?CN201810644587.8?Part four,a series of CuS@NOTT-101-x?x=20,40,60,80,100,120??composites have been successfully fabricated through a convenient MOFs-templated in-situ vulcanization strategy.Highly dispersed ultrafine CuS particles evenly embedded on the surface or within the pore structure of resulting composite frameworks,which are beneficial to introduce hierarchical architecture and exclusive active sites.As a result,the composite exhibits excellent adsorption and electrocatalytic properties.Remarkably,the optimal composite?CuS@NOTT-101-80?possesses a highest adsorption capacity of 500mg g-1 for RhB 6G at a low concentration?30 mg/L?among the previously reported MOFs/MOF-based composites,and demonstrates an outstanding performance towards hydrogen evolution reaction.We applied for one invention patent?CN201710730539.6?.We use the same strategy to generate a highly active and stable hybrid catalyst containing good conductive Fe3S4 ultrasmall nanosheets attached on the surface of 3D MIL-53?Fe?for hydrogen evolution reaction in acidic solutions.By modulating the Fe3S4/MIL-53?Fe?ratio,the Fe3S4?52.1 wt%?/MIL-53 hybrid catalyst with ideal hierarchical nanostructure and composition exhibited high HER activity.Above results have been published in international journal,Chemical Communications?Chem.Commun.,2019,55,4570-4574?and apply for an invention patent?CN201810026817.4?. |
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