Direct Molten Polymerization Synthesis of Highly Active Samarium Manganese Perovskites with Different Morphologies for VOC Removal.

A morphology-controlled molten polymerization route was developed to synthesize SmMnO3 (SMO) perovskite catalysts with netlike (SMO-N), granular-like (SMO-G), and bulk (SMO-B) structures. The SMO perovskites were formed directly by a molten polymerization method, and their morphologies were controlled by using the derivative polymers as templates. Among all catalysts, the porous SMO-N exhibited the highest activity, over which the toluene, benzene, and o-xylene were completely oxidized to CO2 at 240, 270, and 300 °C, respectively, which was comparable to that of typical noble-metal catalysts. The apparent activation energies of toluene over SMO-N (56.4 kJ·mol-1) was much lower than that of SMO-G (70.8 kJ·mol-1) and SMO-B (90.1 kJ·mol-1). Based on the results of scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and H2 temperature-programmed reduction characterization, we deduce that the excellent removal efficiency of volatile organic compounds (VOCs) over SMO-N catalyst was attributable to the special structure, high surface Mn4+/Mn3+ and Olatt/Oads molar ratios, and strong reducibility. Due to the high activity, low cost, and simple preparation strategy, the SMO catalyst is a promising catalyst for VOC removal.

[1]  Luyu Wang,et al.  A 3D Calcium Spirobifluorene Metal-Organic Framework: Single-Crystal-to-Single-Crystal Transformation and Toluene Detection by a Quartz Crystal Microbalance Sensor. , 2018, Inorganic chemistry.

[2]  Son H. Doan,et al.  Alternative pathways to α,β-unsaturated ketones via direct oxidative coupling transformation using Sr-doped LaCoO3 perovskite catalyst , 2019, Royal Society Open Science.

[3]  L. M. Gandía,et al.  Effect of the temperature of calcination on the catalytic performance of manganese- and samarium-manganese-based oxides in the complete oxidation of acetone , 2004 .

[4]  X. Verykios,et al.  Catalytic oxidation of toluene over binary mixtures of copper, manganese and cerium oxides supported on γ-Al2O3 , 2011 .

[5]  Zhenxing Shen,et al.  Sphere-Shaped Mn3O4 Catalyst with Remarkable Low-Temperature Activity for Methyl-Ethyl-Ketone Combustion. , 2017, Environmental science & technology.

[6]  Yadong Li,et al.  Catalysis based on nanocrystals with well-defined facets. , 2012, Angewandte Chemie.

[7]  Zhengjian Xu,et al.  Hydrolysis driving redox reaction to synthesize Mn-Fe binary oxides as highly active catalysts for the removal of toluene , 2017 .

[8]  A. Giroir‐Fendler,et al.  Catalytic oxidation of 1,2-dichloropropane over supported LaMnOx oxides catalysts , 2017 .

[9]  P. Ruiz,et al.  Structuration of LaMnO3 perovskite catalysts on ceramic and metallic monoliths: Physico-chemical characterisation and catalytic activity in methane combustion , 2008 .

[10]  G. Guo,et al.  In situ poly(methyl methacrylate)-templating generation and excellent catalytic performance of MnOx/3DOM LaMnO3 for the combustion of toluene and methanol , 2013 .

[11]  Yazhou Wang,et al.  Morphologically controlled synthesis of porous spherical and cubic LaMnO3 with high activity for the catalytic removal of toluene. , 2014, ACS applied materials & interfaces.

[12]  V. Pârvulescu,et al.  Supported perovskites for total oxidation of toluene , 2005 .

[13]  Shuiyuan Cheng,et al.  Nanosized Ag/α-MnO2 catalysts highly active for the low-temperature oxidation of carbon monoxide and benzene , 2011 .

[14]  P. Magnoux,et al.  Catalytic oxidation of Volatile Organic Compounds (VOCs) mixture (isopropanol/o-xylene) on zeolite catalysts , 2007 .

[15]  W. Shim,et al.  Catalytic combustion of VOCs over a series of manganese oxide catalysts , 2010 .

[16]  C. Au,et al.  Controlled preparation and high catalytic performance of three-dimensionally ordered macroporous LaMnO3 with nanovoid skeletons for the combustion of toluene , 2012 .

[17]  S. Martin,et al.  Airborne observations reveal elevational gradient in tropical forest isoprene emissions , 2017, Nature Communications.

[18]  Guiying Li,et al.  Visible-light-enhanced photothermocatalytic activity of ABO(3)-type perovskites for the decontamination of gaseous styrene , 2017 .

[19]  C. Au,et al.  Strontium-Doped Lanthanum Cobaltite and Manganite: Highly Active Catalysts for Toluene Complete Oxidation , 2008 .

[20]  Junhua Li,et al.  A Facile Method for in Situ Preparation of the MnO2/LaMnO3 Catalyst for the Removal of Toluene. , 2016, Environmental science & technology.

[21]  B. Nayak,et al.  Temperature-mediated phase transformation, pore geometry and pore hysteresis transformation of borohydride derived in-born porous zirconium hydroxide nanopowders , 2016, Scientific Reports.

[22]  B. Kasprzyk-Hordern,et al.  Catalytic ozonation of chlorinated VOCs on ZSM-5 zeolites and alumina: Formation of chlorides , 2017 .

[23]  J. Chen,et al.  Homogeneous Introduction of CeO y into MnO x -based Catalyst for Oxidation of Aromatic VOCs , 2018 .

[24]  M. Zawadzki,et al.  Properties and catalytic performance for propane combustion of LaMnO3 prepared under microwave-assisted glycothermal conditions: Effect of solvent diols , 2017 .

[25]  A. Samimi,et al.  Synthesis and adsorption performance of a modified micro-mesoporous MIL-101(Cr) for VOCs removal at ambient conditions , 2018, Chemical Engineering Journal.

[26]  F. J. Maldonado-Hódar,et al.  Design of low-temperature Pt-carbon combustion catalysts for VOC's treatments. , 2010, Journal of hazardous materials.

[27]  F. Teng,et al.  Catalytic behavior of hydrothermally synthesized La0.5Sr0.5MnO3 single-crystal cubes in the oxidation of CO and CH4 , 2007 .

[28]  Haiqun Chen,et al.  Low-temperature preparation of magnetically separable Fe3O4@CuO-RGO core-shell heterojunctions for high-performance removal of organic dye under visible light , 2016 .

[29]  D. Fino,et al.  Mesoporous manganese oxides prepared by solution combustion synthesis as catalysts for the total oxidation of VOCs , 2015 .

[30]  B. Su,et al.  Influence of hierarchically porous niobium doped TiO2 supports in the total catalytic oxidation of model VOCs over noble metal nanoparticles , 2013 .

[31]  Wenjie Shen,et al.  Low-temperature oxidation of CO catalysed by Co3O4 nanorods , 2009, Nature.

[32]  Lei Zhang,et al.  Preparation of three-dimensionally ordered macroporous La0.6Sr0.4Fe0.8Bi0.2O3−δ and their excellent catalytic performance for the combustion of toluene , 2013 .

[33]  L. Nazar,et al.  A Comprehensive Approach toward Stable Lithium–Sulfur Batteries with High Volumetric Energy Density , 2017 .

[34]  A. Giroir‐Fendler,et al.  LaMnO3 perovskite oxides prepared by different methods for catalytic oxidation of toluene , 2014 .

[35]  Junhua Li,et al.  Selective Dissolution of A-Site Cations in ABO3 Perovskites: A New Path to High-Performance Catalysts. , 2015, Angewandte Chemie.

[36]  Eric C. Njagi,et al.  Gas-Phase Total Oxidation of Benzene, Toluene, Ethylbenzene, and Xylenes Using Shape-Selective Manganese Oxide and Copper Manganese Oxide Catalysts , 2012 .

[37]  A. Giroir‐Fendler,et al.  Catalytic oxidation of toluene by SrTi1-XBXO3 (B = Cu and Mn) with dendritic morphology synthesized by one pot hydrothermal route , 2018 .

[38]  Siwen Wang,et al.  Ball milling synthesized MnOx as highly active catalyst for gaseous POPs removal: significance of mechanochemically induced oxygen vacancies. , 2015, Environmental science & technology.

[39]  Lei Zhang,et al.  Lysine-aided PMMA-templating preparation and high performance of three-dimensionally ordered macroporous LaMnO3 with mesoporous walls for the catalytic combustion of toluene , 2012 .

[40]  C. Au,et al.  A comparative study of bulk and 3DOM-structured Co3O4, Eu0.6Sr0.4FeO3, and Co3O4/Eu0.6Sr0.4FeO3: Preparation, characterization, and catalytic activities for toluene combustion , 2012 .

[41]  Craig M. Brown,et al.  Unravelling Solid-State Redox Chemistry in Li1.3Nb0.3Mn0.4O2 Single-Crystal Cathode Material , 2018 .

[42]  Zhong‐Yong Yuan,et al.  New Pd/hierarchical macro-mesoporous ZrO2, TiO2 and ZrO2-TiO2 catalysts for VOCs total oxidation , 2006 .

[43]  S. Siffert,et al.  Total oxidation of toluene over noble metal based Ce, Fe and Ni doped titanium oxides , 2014 .

[44]  J. Jia,et al.  A facile method for scalable preparation of mesoporous structured SmMnO3 perovskites sheets for efficient catalytic oxidation of toluene , 2018 .

[45]  N. Locoge,et al.  VOC ternary mixture effect on ppb level photocatalytic oxidation: Removal kinetic, reaction intermediates and mineralization , 2017 .

[46]  C. Au,et al.  In situ PMMA-templating preparation and excellent catalytic performance of Co3O4/3DOM La0.6Sr0.4CoO3 for toluene combustion , 2013 .

[47]  H. Arandiyan,et al.  Dual-templating synthesis of three-dimensionally ordered macroporous La(0.6)Sr(0.4)MnO3-supported Ag nanoparticles: controllable alignments and super performance for the catalytic combustion of methane. , 2013, Chemical communications.

[48]  Yuan Gao,et al.  Electrically Conductive Coordination Polymer for Highly Selective Chemiresistive Sensing of Volatile Amines. , 2018, Inorganic chemistry.

[49]  A. Giroir‐Fendler,et al.  Relationship between catalytic deactivation and physicochemical properties of LaMnO3 perovskite catalyst during catalytic oxidation of vinyl chloride , 2016 .