Research On The Preparation Of ZnO Composites Growth By 3D Printing ABS/TPU/CaSiO₃ Skeleton Hydrothermal Heating Method

The problem of environmental pollution has become a global problem affecting human life and health.ZnO is a photocatalyst with high photosensitivity,high stability,low toxicity,simple synthesis and low price.There have been a large number of literature reports that it has a good effect on the degradation of organic pollutants in wastewater.However,in practical applications,nano-ZnO generally in powder form,it is difficult to recycle after use and the cost is high.Based on this,we tried to load nano-ZnO powder on the 3D printed polymer skeleton to achieve its immobilization.Compared with other photocatalysts with high photosensitivity,ZnO has a low synthesis temperature,does not require high-temperature calcination,and can meet the use conditions of most plastic polymers.Therefore,in this paper,acrylonitrile-butadiene-styrene copolymer(ABS),thermoplastic polyurethane(TPU)and calcium silicate(CaSiO₃)are melt blended to prepare ABS/TPU/CaSiO₃composite wire,which is made by fused deposition molding(FDM)the ABS/TPU/CaSiO₃3D printing skeleton was obtained and ZnO was grown in situ by hydrothermal method to obtain the ZnO-ABS/TPU/CaSiO₃(ZnO-ATC)composite material,which realized the immobilization of ZnO on the 3D skeleton.Then,with rhodamine B(Rh B)as the target pollutant,the photocatalytic-adsorption synergistic removal ability of ZnO-ATC composite material was studied,and its removal mechanism was studied in depth.The research work mainly includes the following parts:Firstly,ABS/TPU/CaSiO₃3D printing wire was prepared by melt blending technology.After FDM was formed,ZnO-ATC composite was prepared by hydrothermal growth method.The introduction of calcium silicate provided active sites for the growth of ZnO,and it brings a certain adsorption capacity to the framework.The ZnO-ATC composite material was characterized by XRD,SEM,TEM,XPS and BET experiments,and the adsorption and photocatalytic properties of the material to Rh B(50 mg/L)were tested at the same time.The results showed that:ZnO was successfully loaded on the surface of the ATC framework.Under dark conditions,the adsorption rate of ZnO-ATC to Rh B was 75.78%at 8 h;while under ultraviolet light,the removal rate of rhodamine B under the synergistic effect of ZnO-ATC photocatalysis and adsorption reached 93.12%after 8h,the removal rate remained above 85.73%after 5 cycles test,reflecting the material's excellent dye removal performance and cycle stability.Secondly,by changing the amount of citric acid(complexing agent)during the hydrothermal reaction,the ZnO morphology(rods,flakes,flowers,balls,etc.)grown on the surface of the 3D printed ATC skeleton was adjusted,and the Rh B removal performance was tested.When the addition amount of citric acid is 0.8g and the ZnO morphology is spherical,the ZnO-ATC composite has the best Rh B removal performance,and the removal rate of Rh B reaches 98.44%under ultraviolet light irradiation for 5 hours,indicating that the preparation under this condition that the obtained ZnO-ATC material has good performance of removing dyes through photocatalysis-adsorption synergistic effect.Finally,by introducing?-Fe₂O₃,the light response range of the material was extended to the visible light band,and?-Fe₂O₃/ZnO-ATC composite materials with different Zn/Fe ratios were synthesized,and the Rh B removal performance was tested.When n(Zn):n(Fe)=150:1,the composite material has the best Rh B removal performance under the sunlight simulated by the xenon lamp,which can reach 98.21%in 3 hours,and it can still maintain after 5 times of repeated use.The better performance indicates that the composite material has good visible light photocatalytic degradation and recycling performance.