| With the rapid development of modern industry,environmental pollution has become a global problem that can not be ignored.Water pollution caused by heavy metal ions and organic dyes with the characteristics of high toxicity,carcinogenicity and bioaccumulation has caused great harm to the ecological environment and human health.Therefore,a green and efficient solution to heavy metal/organic dye water pollution has become a research focus in recent years.Among all kinds of water treatment technology,adsorption method shows broad application prospect.Porous material as the core material of adsorption process plays an important role in its adsorption and separation performance.Therefore,the development of new and efficient porous adsorption materials has become one of the urgent problems in the research of heavy metal/organic dye wastewater treatment materials.Aiming at this problem,in this paper,the preparation of a new type of porphyrin(Poryrin)conjugated polymer microporous and membrane materials were studied systematically its adsorption of heavy metal ions removal performance and the performance of photocatalytic degradation of organic dyes,providing new research ideas and basic research of the application of data to porous materials in removing pollution of heavy metal ions(waste)water/organic dyes.The main research contents are as follows:(1)5,10,15,20-tetraphenyl(4-bromophenyl)porphyrins and different alkynyl aromatic compounds(1,3,5-triacetylene benzene,1,4-diacetylene benzene)were selected as monomers.By adjusting the polymerization solvent(toluene,DMF),Four new porphyrin-conjugated microporous polymers were successfully prepared by sonogashira-Hagihara coupling reaction catalyzed by Pd(II)/Cu(I),which were Por-CMP-1,Por-CMP-2,Por-CMP-3 and Por-CMP-4.Various characterization analyses and tests revealed that Por-CMP-1?4 was amorphous porous material with good thermal and physicochemical stability.N2-adsorption/desorption tests showed that the specific surface area of Por-CMP-1?4 was 541.47 m2·g-1,614.58 m2·g-1,382.38 m2·g-1 and 677.90 m2·g-1,respectively.The pore volumes were 0.314 m3/g,0.122 m3/g,0.109 m3/g and 0.771 m3/g,respectively.The pore size distribution mainly concentrated in the range of 0?20 nm,belongs to the mesoporous range,with excellent porosity.(2)Adsorption properties of porphyrin-conjugated microporous polymer(Por-CMP-1?4)showed that Por-CMP-1?4 exhibited good selective adsorption properties for Zn(II),Cu(II)and Pb(II).Among them,Por-CMP-3 had the best adsorption performance for Zn(II),with a maximum adsorption capacity of 640mg·g-1 and an adsorption efficiency of 80%.The adsorption capacities for Cu(II)and Pb(II)are 334 mg·g-1and the adsorption efficiencies are 42%.The adsorption kinetics and adsorption isotherms showed that the adsorption behavior of Por-CMP-3 for Zn(II)ions was in accordance with the quasi-first-order adsorption kinetics and Langmuir isotherm adsorption model.Preliminary analysis of the adsorption mechanism shows that the selective adsorption mechanism of Por-CMP-1?4 on Zn(II),Cu(II)and Pb(II)metal ions may be realized through chelation.The four nitrogen atoms in the porphyrin ring have lone pair electrons,which can interact with metal ions to form stable chelation coordination bonds.Thus,these metal ions can be selectively removed effectively.(3)Porphyrin conjugated microporous polymer Por-CMP-1/Por-CMP-3 and nano zero-valent iron(n ZVI)were selected as raw materials.The nanostructured zero-valent iron porphyrin conjugated microporous polymer composites(Por-CMP-1@n ZVI and Por-CMP-3@n ZVI)were successfully prepared by liquid phase synthesis.Infrared spectroscopy,SEM,EDS,XPS and XRD were used to characterize the nanosized zero-valent iron,which was successfully loaded on the surface of porphyrin-based conjugated microporous polymer.Using copper mesh as membrane carrier,nano zero-valent iron(n ZVI),Por-CMP-1,Por-CMP-3,Por-CMP-1@n ZVI and Por-CMP-3@n ZVI as membrane materials,Five kinds of membrane materials were successfully prepared,namely,Por-CMP-1 membrane,Por-CMP-3 membrane,nanosized zero-valent iron(n ZVI)membrane,Por-CMP-1@n ZVI membrane and Por-CMP-3@n ZVI membrane.Studies on the photocatalytic degradation of methylene blue by five membrane materials showed that the photocatalytic degradation efficiency of Por-CMP-1 and Por-CMP-3 membranes was 80%and 83%,respectively,under the conditions of visible light and 3 h reaction.Compared with the above two membrane materials,the photocatalytic efficiency of Por-CMP-1@n ZVI and Por-CMP-3@n ZVI films for methylene blue increased by 10%,and the photocatalytic degradation efficiency reached 91%and 93%,respectively.The nanoscale pore cavities and pore channels of the polymer loaded with nanometer zero-valent iron can provide a favorable way for the diffusion of methylene blue molecules in the catalytic process,improving the photocatalytic degradation efficiency. |
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