| In this work,under hydrothermal and conventional synthetic conditions,by using triazole and imidazole nitrogen–containing derivatives as ligands,Through continuously adjusting the raw materials,reaction temperature and p H,etc.fourteen Keggin and homopolymolybdate based compounds were obtained.In terms of characterization,X–ray single crystal diffractometer and IR spectroscopy are mainly used;In terms of properties,the electrochemistry,photocatalysis,Hg2+sensing and electrochemical reduction of CO2 of all compounds were tested.1.Using three different triazole–containing organic ligands,six Keggin–based compounds were obtained,namely the 3D frameworks of 1,2 and 3,the supramolecular 2D layer of 4,and the 1D chain structures of 5 and 6.All these crystalline compounds show good photocatalytic activity for MB.Compounds 1–3and 6 have good electrocatalytic activity for KNO2 and ascorbic acid,which also can be used as electrochemical sensors for nitrite.[Cu(BBYT)2.5(HPMo12O40)]·2H2O(1)[Cu(BBYT)2.5(HPW12O40)]·3H2O(2)[Cu3(BBYT)3(OH)Cl(Si W12O40)]·2H2O(3)[Cu(Tybz)2(HPMo12O40)]·H2O(4)[Cu(Tbz)4(OH)6(H2Si W12O40)](5){Ag4(Tybz)4[H4(Si Mo12O40)2]}·6H2O(6)BBYT=1,4–bis(1,3,4–triazole–1–methyl)benzeneTybz=4–[1,3,4]Triazol–4–ylmethyl–benzylamineTbz=4–Benzyl–4H–[1,3,4]triazole2.Five compounds were constructed by using organic ligands containing triazole,imidazole,pyridine or carboxyl groups and homopolymolybdates.In compounds 7 and 8,the imidazole group in MET ligand does not coordinate with metal atoms.The two N atoms in triazole group link transition metal atoms and Mo8ions to construct a 1D chain.Among them,compound 9 was synthesized by conventional methods.The multi–coordinated octamolybdate anion induces the formation of a 3D framework.Compounds 10 and 11 were constructed by copper–2,2'–bipyridine complex precursors,which are further chelated by octamolybdate.In addition,the photocatalytic performance,electrocatalytic performance,mercury ion sensing properties and catalytic reduction of CO2 of these compounds were also studied experimentally.[Cu(MET)2][H2(?–Mo8O26)](7)[Zn(MET)2(H2O)2][H2(?–Mo8O26)](8)[Cu2(pca)2(H2O)4(?–Mo8O26)0.5]·H2O(9)[Cu(bpy)(Mo2O7)](10){[Cu(bpy)]2(?–Mo8O26)]}·H2O(11)MET=4–(3–Imidazol–1–yl–ethyl)–4H–[1,3,4]triazolepca=2–Pyrazinecarboxylic Acidbpy=2,2'–Bipyridine3.By using Keggin–type anions and the organic ligand MET containing both triazole and imidazole groups,three new Keggin POM based compounds 12–14were successfully synthesized.None of the imidazole groups in the compounds participates in coordination with metal atoms.Among the three compounds,the imidazole group in the organic ligand MET is not involved in coordination,and only depends on the chelation of triazole group.The three compounds all have 0D structure.In addition,the electrochemical properties and mercury ion sensing properties of these compounds were studied.[Cu(MET)4(H2PMo12O40)2]·6H2O(12)[Cu3(MET)4Cl2(H2O)2(H2Si W12O40)2]·2H2O(13)[Cu3(MET)4Cl2(H2O)2(H2Ge Mo12O40)2]·3H2O(14)MET=4–(3–Imidazol–1–yl–ethyl)–4H–[1,3,4]triazole... |
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