Construction And Properties Of Copper-based Heterostructured Photocatalytic Nanomaterials

Advanced oxidation technology is considered to be a promising means to deal with the pollution of organic matter in environmental water and has received important attention,in which photocatalysis and Fenton/Fenton-like methods are effective for the degradation of various pollutants.However,there are still many problems such as unsatisfactory catalytic degradation efficiency and low stability of catalytic materials,and heterostructured semiconductor-based photocatalytic materials are one of the effective means to solve the problem.In this paper,a series of copper-based heterostructure catalytic materials were developed and applied to the catalytic degradation of trichloroacetic acid（TCAA）,nitrophenol（p-NP）and tetracycline（TC）in environmental water.Based on the regulation of the electronic structure of the catalyst surface by the components,the regulation of the surface structure of the catalyst with the help of nano-synthesis technology,and the synergistic effect between different phases in the alloy-metal oxide heterostructure,the designed and prepared catalysts are effective for environmental water bodies.The organic pollutants showed good degradation performance.The main research contents are as follows:（1）Through the hydrothermal-seed growth process,a novel core-sheath heterostructure Cu/Cu₂O-Zn O-Fe₃O₄nanocatalytic material was constructed.The efficient inactivation of CRB and the rapid degradation of TCAA were confirmed by the performance test of photodegradation of drinking water disinfection by-product TCAA in synergy with the inactivation of chlorine-resistant bacteria（CRB）.Benefiting from the nanowire structure of the material,the material exhibits excellent bactericidal properties with the help of ion release and generated reactive oxygen species.Meanwhile,under simulated sunlight,TCAA can be efficiently degraded by the surface reaction of catalytic materials.Within the range of performance effect concentrations,the cell growth rates of Cu/Cu₂O-Zn O-Fe₃O₄were 50%and 10%higher than those of Cu/Cu₂O and Cu/Cu₂O-Zn O,respectively,after 10 h of Hela cell culture medium,indicating that its lower cytotoxicity.（2）The Cu Ni-Cu₂O/Ni Al O_xlayered nanocatalysts were prepared by a phase transformation-in situ reduction process,and the precipitated Cu Ni nanoalloys and Cu₂O nanophases were uniformly distributed on both sides of the layered Ni Al O_xnanosheets.Based on the planar structure of nanosheets,utilizing Cu Ni with tunable electron density,combined with the photocatalytic synergy of Cu₂O,the obtained layered Cu Ni-Cu₂O/Ni Al O_xexhibits catalytic effects on the environmental pollutant p-nitrofen（p-NP）(14 mg·L^-1)to the valuable chemical raw material intermediate nitroamine（p-AP）with high efficiency,the conversion time is only 32 s(the reaction rate constant k is 0.1779 s^-1),and no significant performance decay in 27 cycles.Moreover,the reductive conversion of 20 g·L^-1high concentration p-NP to p-AP can be achieved within 20 min.（3）3D nano-cluster-like reduced mixed oxides re-Cu Ni Fe-MMOs assembled by nanosheets were prepared through a hydrothermal-solvothermal reduction process,and applied to the degradation of tetracyclines（TCs）by environmental organic pollution.Based on the strong interaction and synergy between in-situ alloys and metal mixed oxides（MMOs）in 2D heterostructures,the main reactive oxygen species·O₂ˉspecies generated under visible light,re-Cu Ni Fe-MMOs exhibit Fenton-like photocatalytic degradation of TCs without the addition of oxidants.100%degradation of tetracycline can be achieved within 4 min(K=1.65 min^-1),and the photocatalytic degradation rate of 95.5%can be maintained for 12 cycles.The research provides a green and efficient solution ideas for degrading tetracycline-like environmental pollutants.（4）3D sea urchin-like Cu/Cu₂O-Al₂O₃nanocomposites were prepared through a hydrothermal-etching-hydrogen reduction process,and their catalytic degradation performance for TCs was investigated.Based on the abundant defects on the surface,the photocatalytic effect of Cu₂O,and the fast transfer of photogenerated electrons by Cu,the Cu/Cu₂O-Al₂O₃exhibits highly efficient catalytic degradation activity for TCs.