Fe掺杂对ε-MnO2的催化氧化甲苯性能影响Effects of Fe doping on catalytic oxidation of ε-MnO2 for toluene
杨硕,齐子韬,杨春亚,王晓祥,李伟,李素静
摘要(Abstract):
挥发性有机污染物(VOCs)的治理是环保的重要课题,催化氧化是十分有效的治理技术。为开发高效的催化剂,以甲苯为研究对象,采用简便的共沉淀法制备一系列Fe掺杂的ε-MnO_2催化剂。其中,Fe_1Mn_5对甲苯氧化的催化活性最高,转化率为90%时的反应温度t_(90)为237℃。此外,该催化剂表现出优异的长期运行稳定性和良好的耐水性。通过一系列表征分析,结果表明,Fe的掺杂促进了Fe_1Mn_5氧化物上氧空位的产生,提升了催化剂表面吸附氧物种比例,从而提高了其低温还原性。同时,原位红外分析结果表明,Fe掺杂所产生的表面吸附氧物种促进了甲苯甲基的快速脱氢过程,并促进芳香环中C═C键的断裂。
关键词(KeyWords): 催化氧化;FeMn氧化物;甲苯;构效关系
基金项目(Foundation): 浙江省“尖兵”研发项目(2022C03073);; 浙江省“领雁”研发项目(2022C03146);; 浙江省重点研发项目(2021C03165)
作者(Author): 杨硕,齐子韬,杨春亚,王晓祥,李伟,李素静
参考文献(References):
- [1] CAO X L, SPARLING M, DABEKA R. Occurrence of 13 volatile organic compounds in foods from the canadian total diet study[J].Food Additives and Contaminants Part A-Chemistry Analysis Control Exposure&Risk Assessment, 2016, 33(2):373-382.
- [2] MADRONICH S. Ethanol and ozone[J]. Nature Geoscience, 2014, 7(6):395-397.
- [3] HUANG H B, XU Y, FENG Q Y, et al. Low temperature catalytic oxidation of volatile organic compounds:A review[J]. Catalysis Science&Technology, 2015, 5(5):2649-2669.
- [4] WANG Y Q, XUE Y F, ZHAO C C, et al. Catalytic combustion of toluene with La0.8Ce0.2MnO3 supported on CeO2 with different morphologies[J]. Chemical Engineering Journal, 2016, 300:300-305.
- [5] WANG Q Y, LI Y X, SERRANO-LOTINA A, et al. Operando investigation of toluene oxidation over 1D Pt@CeO2 derived from Pt cluster-containing MOF[J]. Journal of the American Chemical Society, 2021, 143(1):196-205.
- [6] HE C, JIANG Z Y, MA M D, et al. Understanding the promotional effect of Mn2O3 on micro-/mesoporous hybrid silica nanocubic-supported Pt catalysts for the low-temperature destruction of methyl ethyl ketone:An experimental and theoretical study[J]. ACS Catalysis, 2018, 8(5):4213-4229.
- [7] HU P Y, AMGHOUZ Z, HUANG Z W, et al. Surface-confined atomic silver centers catalyzing formaldehyde oxidation[J].Environmental Science&Technology, 2015, 49(4):2384-2390.
- [8] VEITH G M, LUPINI A R, RASHKEEV S, et al. Thermal stability and catalytic activity of gold nanoparticles supported on silica[J].Journal of Catalysis, 2009, 262(1):92-101.
- [9] LAMAITA L, PELUSO M A, SAMBETH J E, et al. A theoretical and experimental study of manganese oxides used as catalysts for VOCs emission reduction[J]. Catalysis Today, 2005, 107/108:133-138.
- [10] YANG X Q, YU X L, LIN M Y, et al. Enhancement effect of acid treatment on Mn2O3 catalyst for toluene oxidation[J]. Catalysis Today, 2019, 327:254-261.
- [11] JIANG X D, XU W C, LAI S F, et al. Integral structured Co-Mn composite oxides grown on interconnected Ni foam for catalytic toluene oxidation[J]. RSC Advances, 2019, 9(12):6533-6541.
- [12] DONG C, QU Z P, JIANG X, et al. Tuning oxygen vacancy concentration of MnO2 through metal doping for improved toluene oxidation[J]. Journal of Hazardous Materials, 2020, 391:122181.
- [13] ZHAO L L, ZHANG Z P, LI Y S, et al. Synthesis of Cea MnOx hollow microsphere with hierarchical structure and its excellent catalytic performance for toluene combustion[J]. Applied Catalysis B:Environmental, 2019, 245:502-512.
- [14] LI Z, YAN Q H, JIANG Q H, et al. Oxygen vacancy mediated Cuy Co3-y Fe1Ox mixed oxide as highly active and stable toluene oxidation catalyst by multiple phase interfaces formation and metal doping effect[J]. Applied Catalysis B:Environmental, 2020, 269:118827.
- [15] KHAN A, CHEN P, BOOLCHAND P, et al. Modified nano-crystalline ferrites for high-temperature WGS membrane reactor applications[J]. Journal of Catalysis, 2008, 253(1):91-104.
- [16] SHAKIR I, SARFRAZ M, ALI Z, et al. Magnetically separable and recyclable graphene-MgFe2O4 nanocomposites for enhanced photocatalytic applications[J]. Journal of Alloys and Compounds, 2016, 660:450-455.
- [17] WANG P F, WANG J, AN X W, et al. Generation of abundant defects in Mn-Co mixed oxides by a facile agar-gel method for highly efficient catalysis of total toluene oxidation[J]. Applied Catalysis B:Environmental, 2021, 282:119560.
- [18] XU Y, DHAINAUT J, ROCHARD G, et al. Hierarchical porous ε-MnO2 from perovskite precursor:Application to the formaldehyde total oxidation[J]. Chemical Engineering Journal, 2020, 388:124146.
- [19] ZHENG Y F, SU Y, PANG C H, et al. Interface-enhanced oxygen vacancies of CoCuOx catalysts in situ grown on monolithic Cu foam for VOC catalytic oxidation[J]. Environmental Science&Technology, 2022, 56(3):1905-1916.
- [20] SI W Z, WANG Y, PENG Y, et al. Selective dissolution of a-site cations in ABO3 perovskites:A new path to high-performance catalysts[J]. Angewandte Chemie International Edition, 2015, 54(27):7954-7957.
- [21] ZHANG Y H. Electronegativities of elements in valence states and their applications 1. Electronegativities of elements in valence states[J]. Inorganic Chemistry, 1982, 21(11):3886-3889.
- [22] YANG W H, SU Z A, XU Z H, et al. Comparative study of α-, β-, γ-and δ-MnO2 on toluene oxidation:Oxygen vacancies and reaction intermediates[J]. Applied Catalysis B:Environmental, 2020, 260:118150.
- [23] ZHOU J, QIN L F, XIAO W, et al. Oriented growth of layered-MnO2 nanosheets over α-MnO2 nanotubes for enhanced room-temperature HCHO oxidation[J]. Applied Catalysis B:Environmental, 2017, 207:233-243.
- [24] PELUSO M A, GAMBARO L A, PRONSATO E, et al. Synthesis and catalytic activity of manganese dioxide(type OMS-2)for the abatement of oxygenated VOCs[J]. Catalysis Today, 2008, 133/134/135:487-492.
- [25] TENG Y, WANG X D, LIAO J F, et al. Atomically thin defect-rich Fe-Mn-O hybrid nanosheets as high efficient electrocatalyst for water oxidation[J]. Advanced Functional Materials, 2018, 28(34):1802463.
- [26] CARN?J, FERRANDON M, BJ?RNBOM E, et al. Mixed manganese oxide-platinum catalysts for total oxidation of model gas from wood boilers[J]. Applied Catalysis A:General, 1997, 155(2):265-281.
- [27] YANG W H, PENG Y, WANG Y, et al. Controllable redox-induced in-situ growth of MnO2 over Mn2O3 for toluene oxidation:Active heterostructure interfaces[J]. Applied Catalysis B:Environmental, 2020, 278:119279.
- [28] RONG S P, ZHANG P Y, LIU F, et al. Engineering crystal facet of α-MnO2 nanowire for highly efficient catalytic oxidation of carcinogenic airborne formaldehyde[J]. ACS Catalysis, 2018, 8(4):3435-3446.
- [29] WU J L, XIA Q B, WANG H H, et al. Catalytic performance of plasma catalysis system with nickel oxide catalysts on different supports for toluene removal:Effect of water vapor[J]. Applied Catalysis B:Environmental, 2014, 156/157:265-272.
- [30] AUGUGLIARO V, KISCH H, LODDO V, et al. Photocatalytic oxidation of aromatic alcohols to aldehydes in aqueous suspension of home prepared titanium dioxide:2. Intrinsic and surface features of catalysts[J]. Applied Catalysis A:General, 2008, 349(1/2):189-197.
- [31] SUN H, LIU Z G, CHEN S, et al. The role of lattice oxygen on the activity and selectivity of the OMS-2 catalyst for the total oxidation of toluene[J]. Chemical Engineering Journal, 2015, 270:58-65.
- [32] LI K Z, CHEN J J, BAI B Y, et al. Bridging the reaction route of toluene total oxidation and the structure of ordered mesoporous Co3O4:The roles of surface sodium and adsorbed oxygen[J]. Catalysis Today, 2017, 297:173-181.
- [33] MO S P, ZHANG Q, LI J Q, et al. Highly efficient mesoporous MnO2 catalysts for the total toluene oxidation:Oxygen-Vacancy defect engineering and involved intermediates using in situ DRIFTS[J]. Applied Catalysis B:Environmental, 2020, 264:118464.
- [34] RONG S P, ZHANG P Y, YANG Y J, et al. MnO2 framework for instantaneous mineralization of carcinogenic airborne formaldehyde at room temperature[J]. ACS Catalysis, 2017, 7(2):1057-1067.