Surface Cleavage Of Emerging Contaminants Excited By H₂O₂ Assisted Cu-based Catalyst

The combined pollution caused by emerging contaminants（ECs）represented by persistent organic pollutants,endocrine disruptors,antibiotics,etc.in water environment has become one of the urgent environmental problems to be solved presently.To solve this international problem,many water treatment technologies have emerged,including activated carbon adsorption,mem-brane filtration and biofilters,but in most cases the treatment effect is inhibited by compound pollutants,so the detection rate of ECs in various water environment is still high.Although advanced oxidation processes（AOPs）are unanimously considered as one of the most efficient water treatment technologies for organic pollutant removal,they often require excessive energy and resources to achieve effluent discharge standards,resulting in excessive and unnecessary consumption.China’s"14th Five-Year Plan"clearly states that it is necessary to build a precise,scientific and systematic environmental management system,improve the waste utilization rate of sewage and garbage,and realize the peak of carbon emissions by 2030,indicating that the key to environmental management nowadays lies in achieving"energy saving and consumption reduction The key to environmental management now is to achieve"energy saving"and"waste reuse".Aiming at this problem,this work will base on the Dual Reaction Center（DRC）catalytic system,using the in situ doping of Cu on the catalyst surface to construct Dual Reaction Centers with electron-poor/rich microregions,driving the electron-donating action of ECs in the elec-tron-poor centers by trace H₂O₂.ECs are removed via dual pathways during this process,which greatly reduces the energy consumption of wastewater treatment and therefore breaks through the bottleneck problem of wastewater treatment.This work will provide the theoretical basis and practical solutions for establishing new high-efficiency and low-consumption water treatment technologies.1.DRC catalyst Cu Co-ZnOnps-CMs（CCZO-CMs）with typical surface electron-poor/rich microregions were constructed by hydrothermal in situ doping of Cu and Co species into ZnO crystals,and the surface electron directed distribution structure was revealed by a series of char-acterization techniques.It was found that the lattice substitution of Cu and Co for Zn contributed to the electron directed distribution on the surface of CCZO-CMs and successfully formed sur-face electron-poor/rich microregions.In the wastewater purification process,the CCZO-CMs/H₂O₂ system exhibited excellent removal performance for a variety of refractory ECs,such as ciprofloxacin（CIP）with a removal efficiency of more than 95%within 30 min,and the efficient removal of CIP was achieved in a wide p H range（3-9）.CCZO-CMs also showed sig-nificant deep treatment effects on the secondary effluent,which is difficult to be treated bio-chemically in actual printing and dyeing wastewater,demonstrating excellent prospects for prac-tical applications.It is found that the system could remove ECs such as endocrine disruptors,antibiotics,pesticides,dyes,etc.from water under natural conditions at room temperature and pressure by reducing trace H₂O₂ and DO to ROS in the electron-rich center,which breaks the micro-equilibrium of potential difference of DRCs on the catalyst surface,driving the electron donating effect of ECs in the electron-poor center.The synergistic connection of surface DRCs achieves high-efficiency and low-consumption removal of ECs.2.Based on the above work,one of the rural wastes,chicken manure,was used as a raw material for preparation of DRC catalysts to reduce the cost of catalyst preparation and further optimize the consumption of energy and resources for the water purification process.An in situ synthesis method of impregnation-programmed warming calcination was used to form Cu-Chicken Manure-nanoparticles（CCM-Nps）by anchoring Cu species on chicken manure pre-cursors.TEM and SEM techniques revealed the microscopic morphology of CCM-Nps,con-firming that the resource technology successfully transformed the irregular waste into a regular flake catalyst;XPS and EPR techniques revealed the structure and electronic properties of the CCM-Nps surface,demonstrating that the introduction of Cu species successfully tuned the electron distribution on the surface in a directional manner,forming DRC catalyst with surface electron-poor/rich microregions.The DRC catalysts obtained by resourcelized conversion ena-bled to remove ECs efficiently and rapidly in a very short time.For example,endocrine inter-feron bisphenol A（BPA）reached a removal rate of more than 70% in CCM-Nps/H₂O₂ system within 1 min,and was completely removed within 60 min with high adaptability to a wide range of pH values（3-10）.In addition,only a trace amount of H₂O₂ was consumed during the whole process,achieving a synergistic reduction of energy consumption at the front-end and back-end.Experimental and theoretical studies have confirmed that the directional transfer of electrons and the generation of cation-πinteractions in the process of resource utilization lead to the for-mation of electron-poor/rich microregions.The activation of this special structure for DO in water and trace H₂O₂ could break the electron-donating energy barrier of ECs,resulting in a continuous transfer of electrons and energy from ECs to the surface of CCM-Nps through inter-facial interactions,thus significantly reduce the demand of external resources and energy for the reaction system.This study breaks the bottleneck of huge energy consumption in the traditional Fenton system,and is also expected to promote the resourceful use of rural waste and the sus-tainable development of environmental elements.