The Liu Wen team and its collaborators of the School of Environment reported the new strategy of using oxygen atom capturing the oxygen atoms containing oxygen -containing CO3O4

New pollutants are an important concern of ecological environmental protection in my country today. Advanced oxidation technology is one of the effective technologies for the deep treatment of new pollutants in water.Advanced oxidation is a collective name of a type of technology centered on active species (such as free radicals) attack. It is highly respected due to its advantages such as strong oxidation ability, high response efficiency, fast response speed, and easy operation.In the high -grade oxidation reaction, the regulation and production of active species and the directional degradation and transformation of pollutants are the main scientific issues of attention.In the non -existing high -level oxidation system enhanced by functional materials, the design architecture of the material activity site determines the type and concentration of the active species after the oxidant cracking.

Figure 1. oxygen -containing empty level CO₃O₄Principles of the concept of material architecture and catalytic activity

Researcher Liu Wen, a researcher group of the School of Environmental Science and Engineering of Peking University for many years, has been engaged in the research of high -grade oxidation technology in water treatment, and has developed a variety of specific functional materials that are suitable for different advanced oxidation systems.Active metal -based materials in transitional metal base materials (CLO₂^–) In the high -grade oxidation technology, the selective oxidation of organic pollutants can be achieved by simultaneously generating high -priced metal species and chlorine dioxide.However, the non -existing high -priced metal species on the material interface are different from the average high -priced metal species in chemical forms and evolutionary mechanisms, but they are often confused, so they need to be clearly explored.The research group has explored the traditional CO in the early stage₃O₄Materials catalyze the active species of active species and degradation of pollutants (Environ. Sci. Technol. 2023, 57, 5,1882-1893; cover thesis).On this basis, in the recent research, the research team successfully introduced the light excitement (OVS) to the CO through the UV -induced modification method₃O₄(OV-Co₃O₄) In the catalytic activation of chloroate and the efficient degradation of new pollutants in water.Experimental representation combined theoretical calculation shows that in OV-Co₃O₄/In the high -level oxidation system of chloroate, the introduced oxygen space introduces the generation of low -oriented CO, and then the CLO can be anchored by the capture of oxygen atoms.₂^–EssenceFirst, CLO₂^–After the O -CL crack, the unbuttoned O atom is transferred to the low -coordinated CO atom to form a highly self -spiny ≡CO (IV) = O; since then, ≡CO (IV) = O from CLO₂^–Extract an electron to generate chlorine dioxide CLO₂), And accompanied by the CO atom, returned a lower spin.Stimulate the high -priced cobalt (≡CO (IV) = O) and CLO2 Selective degradation of organic new pollutants (such as sulfa antibiotics).Therefore, this work proposes a new point through the construction of light stimulation of oxygen and empty position as an oxygen atomic capture position, so as to strengthen the non -existing advanced oxidation process, and provides new in the formation of the formation of ≡CO (IV) = O through defective projects.Opinions.

Figure 2. oxygen -containing empty level CO₃O₄Preparation of preparation and results of material representation

Taking the typical antibiotic pollutant Sulfa sulfidazole (SMX) as the target pollutant, degradation dynamic experiments show that the prepared OV-Co₃O₄The enhancement of activity is closely related to the concentration of OVS.Through electronic spinning resonance (ESR) spectrum, UV-visible absorption spectrum and PMSO probe conversion experiment, it has confirmed that the main active species produced after the activation of yam is high-priced cobalt (≡co (IV) = “=”O) and CLO2.Then analyze the effectiveness of the 6 sulfa antibiotics (SAS) of the non -existing high -level oxidation system. Due to the parenting attributes of active species, ≡CO (IV) = O and CLO₂They tend to selectively attack SAS’s rich electronic areas.In addition, the apparent response rate constant (KOBS value) of pollutants degradation (KOBS value) is negatively correlated with the ionization (IP) of pollutant molecules, indicating that the heterocycles replace the base to increase the conscience of SAS.The activation process is oxidized.In order to clarify the selective selective selective system, the potential relationship between the degradation efficiency of 16 representative pollutants and the parent performance was further studied.Studies have found that pollutants with lower IP values (higher conscience activity) correspond to higher degradation rates, which shows that the active species attack after the activation of yam chloroate is mainly based on the parental reaction.

Figure 3. OV-Co₃O₄/Analysis of the degradation performance and structure of the chloroate system to organic pollutants-active relationship analysis

The calculation of density general letters (DFT) reveals the enhanced mechanism of optical OVS on material catalytic activity.Specifically, two steps have gone through two steps, namely the process of oxygen atom transfer (OAT) and electronic transfer (ET).In the first step, CLO₂^–OV-Co₃O₄The OV site capture in the middle of the OV site to form a sub-stable ≡co … O-CL-O ··· CO≡ intermediate, so the solution of O atom (marked O*) is transferred to mix with the surrounded CO atoms.Initial, we define the oxygen atom transfer (OAT) mediated by OVS as “oxygen atom capture effect”.In addition, the rich LAN on OV induces the cracks of O-CL, which produces reactive ≡Coiv-O*-CO≡ species.In the second step, another CLO₂^–Sucked to O*–CO₃O₄, Then electrons quickly from CLO₂Moved to oCoiv-O*-CO≡ to induce CLO₂The generation.After the chloroate is activated, OVS will be filled by O*atoms in Ayrachloride, resulting in a decline in the performance of catalysts after use.After the reaction, the -filled OVS can restore the defect structure by re -exposed to ultraviolet radiation, which shows that OVS that is stimulated by light can be used as sustainable active sites for chloroate activation.

Figure 4. Ayl chloride in OV-Co₃O₄Upper adsorption and activated DFT theory calculation and rail analysis

In summary, this study proposes a new strategy of promoting the activation of yamonate through UV induction method to promote the activation of yamate.XA -ray absorption spectrum (XAS) and DFT computing indicate that light stimulation OVS regulates CO₃O₄The electronic structure and the CO atom of unsaturated coordination are generated, which generates the oxygen atom capture position that is conducive to the adsorption of schlorite.OVS promotes the balance of the O -CL keys. The solution of O*atoms are captured by OVS adjacent Co atoms.(≡Coiv – –CO≡, that is, ≡co (IV) = O).Since the CO 3D orbit that has a pair of spin -spin electrons, ≡CO (IV) = O can be from CLO2^–Extract an electron to form a CLO₂EssenceBased on oxygen atom capture effect, OV-Co₃O₄Bi Yuan Co₃O₄It has stronger chloroate activation capabilities, thereby showing higher pollutant degradation efficiency.In addition, oco (IV) = O and CLO₂It is more inclined to attack rich electronic organic objects, which makes the chloroate activation technology show high selectivity in water purification.This study described the mechanism for strengthening the ≡CO (IV) = O of OVS through oxygen atom capture effects, which provides a feasible strategy for strengthening the non -existing advanced oxidation process through defective projects.