Preparation Of Copper Ion Surface Imprinted Materials And Their Catalytic Properties

Copper-containing wastewater is widely polluted and toxic,which has seriously threatened the ecological environment and human health.Adsorption method is a common metal copper removal method,which is widely used in enrichment and separation of metal copper by physicochemical adsorption.Due to the complex contamination situation in the environmental medium and the high risk of environmental pollution,a technology for efficient removal and selective identification of target ions is required.Surface ion blotting technology has high selectivity for the formation of specific recognition sites for target ions by selecting appropriate functional monomers,crosslinkers and substrate materials.In this paper,graphene oxide（GO）as the parent material,ferric oxide（Fe₃O₄/M）as the magnetic component,and divalent copper ion Cu（II）as the template ion were successfully prepared by combining organic-inorganic hybrid functional monomer ATPES（silane coupling agent 350）-MAA（methacrylic acid）and crosslinking agent ethylene glycol methacrylate（EGDMA）,and copper ion surface imprinted polymer（MS/MGO-Cu-iip）.In this paper,the optimal synthesis and reaction conditions of the material were determined by functional monomer feeding ratio experiment,kinetic and thermodynamic analysis.In addition,after the adsorption of heavy metals in 5 cycles of imprinted materials,the adsorbent adsorption capacity decreases,and an economical and efficient means is required for waste treatment to effectively use imprinted materials,and the copper ion imprinted materials prepared in this paper not only solve the problem of copper pollution in sewage,but also use copper ion imprinted materials as an efficient catalyst active ingredient,directly and indirectly catalytic degradation tetracycline,which greatly improves the economic value of material recycling and environmental protection.The magnetic recovery of MS/MGO-Cu-iip and its catalytic degradation of tetracycline（TC）as a heterogeneous catalyst combined with oxygen is the highlight of this study,and the main conclusions of this paper are as follows:（1）The feeding ratio of silane coupling agent（APTES）and methacrylic acid（MAA）is an important factor in the adsorption performance of materials.The optimal synthesis conditions were:APTES 14 m L,MAA 51 m L,Cu（II）8 mmol,MGO 0.5 g.The influence of Zn（II）,Pb（II）,Cd（II）and Ni（II）as contrast ions of Cu（II）was investigated.showed that the factor affecting the adsorption capacity was the ion radius of the metal ion,and in the binary system,the adsorption capacity of Cu（II）decreased by MS/MGO-Cu-iip,but the effect was limited.MS/MGO-Cu-iip has a high selective adsorption effect on copper ions.（2）MS/MGO-Cu-iip was characterized by scanning electron microscopy（SEM）,magnetic susceptibility analysis（VSM）,specific surface area,pore size analysis（BET）,and X-ray crystal diffraction characterization analysis（XRD）.The results showed that the surface of the MS/MGO-Cu-iip material was irregular and had a rich imprinted hole structure before the reaction,and the imprinted holes successfully captured copper ions after the reaction,resulting in the full filling of the adsorption site.Compared with magnetic graphene oxide（MGO）,the preparation of imprinted materials leads to a certain weakening of the saturation magnetic field strength of MS/MGO-Cu-iip,but the material is still superparamagnetic.The saturation magnetization strength of the two was 42.2 emu/g and 57.3 emu/g,respectively.BET analysis showed that the surface imprinted material was mesoporous material,and the specific surface areas of MGO and MS/MGO-Cu-iip were 88.54 m²/g and 155.55 m²/g,respectively.Fe₃O₄ was successfully bound to GO,and the crosslinking process did not change the basic structure of the material.After 5 cycles of MS/MGO-Cu-iip,the available reaction sites were continuously reduced,and its adsorption performance for Cu（II）gradually decreased to less than 80%.（3）In order to make the circulating imprinted material"turn waste into treasure".The catalytic degadation of antibiotic contaminant tetracycline（TC）was carried out for the efficient utilization of MS/MGO-Cu-iip as a heterogeneous catalyst.The results showed that the removal effect of MS/MGO-Cu-iip activated reactive oxygen species（ROS）on TC was better than that of GO or MGO alone under different material dosages and initial TC dosage.It is worth noting that due to the intervention of copper ions,heterogeneous catalysts also have good TC removal effect under neutral conditions compared with traditional Fenton reactions.In the radical quenching test,O₂·^-is the main active free radical of the TC removal reaction.In addition,according to the nitrogen and desorption tests,the adsorption rate and degradation rate of TC TO MS/MGO-Cu-iip were 30.98%and 63.10%,respectively.Among them,the direct degradation rate and indirect degradation rate of MS/MGO-Cu-iip to TC were 45.93%and 17.17%,respectively.