Among the numerous transition metal catalysts,manganese-based compounds are considered as promising peroxymonosulfate(PMS)catalysts due to their low cost and environmental friendliness,such as cryptomelane manganese o...Among the numerous transition metal catalysts,manganese-based compounds are considered as promising peroxymonosulfate(PMS)catalysts due to their low cost and environmental friendliness,such as cryptomelane manganese oxide(K_(2-x)Mn_(8)O_(16):abbreviation KMnO).However,the limited catalytic performance of KMnO limits its practical application.In this work,iron-doped KMnO(Fe-KMnO)was prepared by one-step hydrothermal method to optimize its catalytic performance.Compared with KMnO/PMS system,Fe-KMnO/PMS system possessed more excellent removal efficiency of tetracycline(TC).Meanwhile,the Fe-KMnO/PMS system also exhibited good practical application potential and excellent stability.The mechanism of Fe-KMnO activation of PMS was further analyzed in detail.It was found that Fe participated in the redox of high-valent Mn,which promoted the activation of PMS.Moreover,The Fe site as an adsorption site enhanced the TC enrichment ability of the catalyst,reducing the mass transfer resistance and further enhancing the TC removal ability of Fe-KMnO/PMS system.This work not only provides an excellent PMS catalyst,but also offers new insights into the mechanism of PMS activation by bimetallic manganese-based catalysts.展开更多
In this paper,the combined addition of copper or iron and sulphate ions onto TiO_(2) prepared by a simple sol-gel method is studied for formic acid photocatalytic conversion.A wide structural and morphological charact...In this paper,the combined addition of copper or iron and sulphate ions onto TiO_(2) prepared by a simple sol-gel method is studied for formic acid photocatalytic conversion.A wide structural and morphological characterization of the different photocatalysts was performed by X-ray diffraction(XRD),N_(2)-physisorption for BET surface area measurements,scanning and transmission electronic microscopies(SEM and TEM),UV-Vis diffuse spectroscopy(DRS)and X-ray photoelectron spectroscopy(XPS),in order to correlate the physico-chemical properties of the materials to their photocatalytic efficiencies for formic acid oxidation.Results have shown important differences among the catalysts depending on the metal added.Sulphated TiO_(2)/Cu(1%Cu)was the best photocatalyst obtaining about 100% formic acid conversion in only 5 min.The appropriate physico-chemical features of this photocatalyst,given by the addition of combined copper and sulphate ions,explain its excellence in photocatalytic reaction.展开更多
基金supported by the National Natural Science Foundation of China (21806115)Sichuan Science and Technology Program (2020YJ0149)+1 种基金the Power Construction of China (P42819,DJ-ZDXM-2019-42)the Supported by Sichuan Science and Technology Program (2021ZDZX0012)。
文摘Among the numerous transition metal catalysts,manganese-based compounds are considered as promising peroxymonosulfate(PMS)catalysts due to their low cost and environmental friendliness,such as cryptomelane manganese oxide(K_(2-x)Mn_(8)O_(16):abbreviation KMnO).However,the limited catalytic performance of KMnO limits its practical application.In this work,iron-doped KMnO(Fe-KMnO)was prepared by one-step hydrothermal method to optimize its catalytic performance.Compared with KMnO/PMS system,Fe-KMnO/PMS system possessed more excellent removal efficiency of tetracycline(TC).Meanwhile,the Fe-KMnO/PMS system also exhibited good practical application potential and excellent stability.The mechanism of Fe-KMnO activation of PMS was further analyzed in detail.It was found that Fe participated in the redox of high-valent Mn,which promoted the activation of PMS.Moreover,The Fe site as an adsorption site enhanced the TC enrichment ability of the catalyst,reducing the mass transfer resistance and further enhancing the TC removal ability of Fe-KMnO/PMS system.This work not only provides an excellent PMS catalyst,but also offers new insights into the mechanism of PMS activation by bimetallic manganese-based catalysts.
基金This work was supported by a grant from the National Research Foundation of Korea(NRF)funded by the Ministry of Science and ICT(MSIT)of the Korean government(2021R1A3B1068304).The authors also acknowledge the support provided by a grant from the NRF funded by MSIT of the Korean government(RS-2023-00243840)and Brain Pool program(RS-2023-00222393).D.W.Boukhvalov acknowledges support from Jiangsu Innovative and Entrepreneurial Talents Project,and the Ministry of Science and Education of Russian Federation(FEUZ-2023-0013).
文摘通过氮掺杂TiO_(2)(N-TiO_(2))浸渍蜂窝过滤器构建了一系列原型光催化空气净化器(AP(N_(x)-C_(y)))系统,并用于在UV-LED光(1 W)照射条件下光催化分解0.5-5 ppm甲醛(CH_(2)O)蒸汽.在上述催化过滤器系统中,Nx和Cy分别代表N/Ti摩尔比(0-20)和N-TiO_(2)浓度(2-20 mg mL^(-1)).光催化分解实验结果表明,AP(N_(10)-C_(10))的性能最好,其催化CH2O转化为CO_(2)的转化率最高,循环反应10次后CO_(2)产率仍达到89.2%,在干燥空气中的清洁空气输送速率为9.45 L min^(-1).N10-C10的电荷载流子寿命(τa:1.70 ns)优于其他样品(如纯TiO_(2)的电荷载流子寿命为1.37 ns),这表明N缺陷(No)有助于降低带隙(3.10 eV)和产生氧空位OVs-Ti^(3+),这与密度泛函理论(DFT)模拟结果一致.采用原位漫反射红外傅里叶变换、电子顺磁共振和DFT分析等多种方法研究了CH_(2)O的光催化氧化途径.结果表明,氧化过程涉及多个能量有利的中间步骤(例如CH2O以CH_(2)O_(2)的形式在TiO_(2)-OV{110}表面的桥连O/OH基团上发生放热共价吸附,随后通过催化脱氢/氧化反应直接生成CO_(2):CH_(2)O_(2)/HCOO^(-)+•OH→H_(2)O+CO_(2)).这些步骤与具有N杂质的{101}表面上化学活性Ti原子的态密度计算结果一致.预计No缺陷和OVs的存在将通过降低活化能垒来影响反应能量和中间产物,从而在加湿条件下实现有效的矿化.综上,本文为设计和构建先进的光催化系统,并用于环境空气中醛类挥发性有机物(VOCs)的有效矿化提供了新思路.
文摘In this paper,the combined addition of copper or iron and sulphate ions onto TiO_(2) prepared by a simple sol-gel method is studied for formic acid photocatalytic conversion.A wide structural and morphological characterization of the different photocatalysts was performed by X-ray diffraction(XRD),N_(2)-physisorption for BET surface area measurements,scanning and transmission electronic microscopies(SEM and TEM),UV-Vis diffuse spectroscopy(DRS)and X-ray photoelectron spectroscopy(XPS),in order to correlate the physico-chemical properties of the materials to their photocatalytic efficiencies for formic acid oxidation.Results have shown important differences among the catalysts depending on the metal added.Sulphated TiO_(2)/Cu(1%Cu)was the best photocatalyst obtaining about 100% formic acid conversion in only 5 min.The appropriate physico-chemical features of this photocatalyst,given by the addition of combined copper and sulphate ions,explain its excellence in photocatalytic reaction.
