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Frontiers of Environmental Science & Engineering

Front. Environ. Sci. Eng.    2016, Vol. 10 Issue (3) : 447-457
Catalytic activities and mechanism of formaldehyde oxidation over gold supported on MnO2 microsphere catalysts at room temperature
Guanglong PANG1,2,Donghui WANG3,Yunhong ZHANG1,*,Chunyan MA2,*(),Zhengping HAO2
1. Institute of Chemical Physics, School of Chemistry, Beijing Institute of Technology, Beijing 100081, China
2. Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China
3. Research Institute of Chemical Defense, Beijing 100191, China
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MnO2 microspheres with various surface structures were prepared using the hydrothermal method, and Au/MnO2 catalysts were synthesized using the sol-gel method. We obtained three MnO2 microspheres and Au/MnO2 samples: coherent solid spheres covered with wire-like nanostructures, solid spheres with nanosheets, and hierarchical hollow microspheres with nanoplatelets and nanorods. We investigated the properties and catalytic activities of formaldehyde oxidation at room temperature. Crystalline structures of MnO2 are the main factor affecting the catalytic activities of these samples, and γ-MnO2 shows high catalytic performance. The excellent redox properties are responsible for the catalytic ability of γ-MnO2. The gold-supported interaction can change the redox properties of catalysts and accelerate surface oxygen species transition, which can account for the catalytic activity enhancement of Au/MnO2. We also studied intermediate species. The dioxymethylene (DOM) and formate species formed on the catalyst surface were considered intermediates, and were ultimately transformed into hydrocarbonate and carbonate and then decomposed into CO2. A proposed mechanism of formaldehyde oxidation over Au/MnO2 catalysts was also obtained.

Keywords MnO2 microspheres      Au/MnO2      formaldehyde oxidation      γ-MnO2     
Corresponding Authors: Yunhong ZHANG,Chunyan MA   
Online First Date: 20 July 2015    Issue Date: 05 April 2016
 Cite this article:   
Guanglong PANG,Donghui WANG,Yunhong ZHANG, et al. Catalytic activities and mechanism of formaldehyde oxidation over gold supported on MnO2 microsphere catalysts at room temperature[J]. Front. Environ. Sci. Eng., 2016, 10(3): 447-457.
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Guanglong PANG
Donghui WANG
Yunhong ZHANG
Chunyan MA
Zhengping HAO
catalyst SBETa)/(m2?g-1) Dpb) /nm Vpc) /(cm3?g-1) Au size d)/nm consumed H2 /(mmol·g-1) HCHO conversion/%
MnO2-S1 217 3.8 0.27 - 3.9 0
MnO2-S2 280 8.6 0.8 - 5.8 22.3
MnO2-S3 52.4 11.6 0.17 - 7.9 30.6
Au/MnO2-S1 58.0 5.5 0.13 7.8 6.7 27.2
Au/MnO2-S2 282 8.7 0.8 10 8.5 49.2
Au/MnO2-S3 52.3 11.3 0.16 11.2 10.8 59.2
Tab.1  Formaldehyde oxidation activities and physical-chemical properties of the MnO2 microspheres and the Au/MnO2 catalysts
Fig.1  XRD patterns of three MnO2 microspheres and the Au/MnO2 catalysts (a, MnO2-S1; b, Au/MnO2-S1; c, MnO2-S2; d, Au/MnO2-S2; e, MnO2-S3; f, Au/MnO2-S3)
Fig.2  N2 adsorption-desorption isotherms (Insert: pore size distribution) of (a) MnO2 microspheres and (b) Au/MnO2 catalysts
Fig.3  FESEM images of MnO2 microspheres (MnO2-S1: (a) (b); MnO2-S2: (c) (d); MnO2-S3: (e) (f))
Fig.4  FESEM, HRTEM images of Au/MnO2 catalysts (Au/MnO2-S1: (a) (b); Au/MnO2-S2: (c) (d); Au/MnO2-S3: (e) (f))
Fig.5  H2-TPR profiles of (a) MnO2 microspheres and (b) Au/MnO2 catalysts
Fig.6  Au 4f XPS spectra of Au/MnO2 and used Au/MnO2-S3 catalysts
Fig.7  In-situ FTIR spectra of formaldehyde adsorption (a) and oxidation (b) on the Au/MnO2-S3 catalyst
1 Salthammer T, Mentese S, Marutzky R. Formaldehyde in the indoor environment. Chemical Reviews, 2010, 110(4): 2536–2572
2 Tang X, Li Y, Huang X, Xu Y, Zhu H, Wang J, Shen W. MnOx–CeO2 mixed oxide catalysts for complete oxidation of formaldehyde: effect of preparation method and calcination temperature. Applied Catalysis B: Environmental, 2006, 62(3-4): 265–273
3 Bai B, Arandiyan H, Li J. Comparison of the performance for oxidation of formaldehyde on nano-Co3O4, 2D-Co3O4, and 3D-Co3O4 catalysts. Applied Catalysis B: Environmental, 2013, 142-143: 677–683
4 Quiroz Torres J, Royer S, Bellat J P, Giraudon J M, Lamonier J F. Formaldehyde: catalytic oxidation as a promising soft way of elimination. ChemSusChem, 2013, 6(4): 578–592
5 Tian H, He J, Liu L, Wang D, Hao Z, Ma C. Highly active manganese oxide catalysts for low-temperature oxidation of formaldehyde. Microporous and Mesoporous Materials, 2012, 151(15): 397–402
6 Ma C, Wang D, Xue W, Dou B, Wang H, Hao Z. Investigation of formaldehyde oxidation over Co3O4-CeO2 and Au/Co3O4–CeO2 catalysts at room temperature: effective removal and determination of reaction mechanism. Environmental Science & Technology, 2011, 45(8): 3628–3634
7 Wang Y, Zhu A, Chen B, Crocker M, Shi C. Three-dimensional ordered mesoporous Co–Mn oxide: a highly active catalyst for “storage–oxidation” cycling for the removal of formaldehyde. Catalysis Communications, 2013, 36: 52–57
8 Tang X, Chen J, Li Y, Li Y, Xu Y, Shen W. Complete oxidation of formaldehyde over Ag/MnOx-CeO2 catalysts. Chemical Engineering Journal, 2006, 118(1-2): 119–125
9 Chen B, Zhu X, Crocker M, Wang Y, Shi C. Complete oxidation of formaldehyde at ambient temperature over γ-Al2O3 supported Au catalyst. Catalysis Communications, 2013, 42: 93–97
10 Zhou L, Zhang J, He J, Hu Y, Tian H. Control over the morphology and structure of manganese oxide by tuning reaction conditions and catalytic performance for formaldehyde oxidation. Materials Research Bulletin, 2011, 46(10): 1714–1722
11 Tian H, He J, Zhang X, Zhou L, Wang D. Facile synthesis of porous manganese oxide K-OMS-2 materials and their catalytic activity for formaldehyde oxidation. Microporous and Mesoporous Materials, 2011, 138(1-3): 118–122
12 Chen H, He J, Zhang C, He H. Self-assembly of novel mesoporous manganese oxide nanostructures and their application in oxidative decomposition of formaldehyde. Journal of Physical Chemistry C, 2007, 111(49): 18033–18038
13 Lamaita L, Peluso M A, Sambeth J E, Thomas H, Mineli G, Porta P. A theoretical and experimental study of manganese oxides used as catalysts for VOCs emission reduction. Catalysis Today, 2005, 107-108: 133–138
14 Fu X, Feng J, Wang H, Ng K M. Fast synthesis and formation mechanism of γ-MnO2 hollow nanospheres for aerobic oxidation of alcohols. Materials Research Bulletin, 2010, 45(9): 1218–1223
15 Li D, Wu X, Chen Y. Synthesis of hierarchical hollow MnO2 microspheres and potential application in abatement of VOCs. Journal of Physical Chemistry C, 2013, 117(21): 11040–11046
16 Yu X, He J, Wang D, Hu Y, Tian H, He Z. Facile controlled synthesis of Pt/MnO2 nanostructured catalysts and their catalytic performance for oxidative decomposition of formaldehyde. Journal of Physical Chemistry C, 2012, 116(1): 851–860
17 Yu X, He J, Wang D, Hu Y C, Tian H, Dong T, He Z. Au–Pt bimetallic nanoparticles supported on nest-likeMnO2: synthesis and application in HCHO decomposition. Journal of Nanoparticle Research, 2012, 14(11): 1260–1273
18 Munaiah Y, Gnana Sundara Raj B, Prem Kumar T, Ragupathy P. Facile synthesis of hollow sphere amorphous MnO2: the formation mechanism, morphology and effect of a bivalent cation-containing electrolyte on its supercapacitive behavior. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2013, 1(13): 4300–4306
19 Sing K S W, Evrett D H, Haul R A W, Moscou L, Pierotti R A, Rouqerol J, Siemieniewska T. Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity. Pure and Applied Chemistry, 1985, 57(4): 603–619
20 Torres J Q, Giraudon J M, Lamonier J F. Formaldehyde total oxidation over mesoporous MnOx catalysts. Catalysis Today, 2011, 176(1): 277–280
21 Li X, Cui Y, Yang X, Dai W, Fan K. Highly efficient and stable Au/Mn2O3 catalyst for oxidative cyclization of 1,4-butanediol to γ-butyrolactone. Applied Catalysis A, General, 2013, 458(10): 63–70
22 Lin X, Uzayisenga V, Li J, Fang P, Wu D Y, Ren B, Tian Z Q. Synthesis of ultrathin and compact Au@MnO2 nanoparticles for shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS). Journal of Raman Spectroscopy : JRS, 2012, 43(1): 40–45
23 Longo A, Liotta L F, Carlo G D, Giannici F, Venezia A M, Martorana A. Structure and the metal support interaction of the Au/Mn oxide catalysts. Chemistry of Materials, 2010, 22(13): 3952–3960
24 Wang L, Liu Y, Chen M, Cao Y, He H Y, Fan K N. MnO2 nanorod supported gold nanoparticles with enhanced activity for solvent-free aerobic alcohol oxidation. Journal of Physical Chemistry C, 2008, 112(17): 6981–6987
25 Wang L C, Huang X S, Liu Q, Liu Y M, Cao Y, He H Y, Fan K N, Zhuang J H. Gold nanoparticles deposited on manganese (III) oxide as novel efficient catalyst for low temperature CO oxidation. Journal of Catalysis, 2008, 259(1): 66–74
26 Ye Q, Zhao J, Huo F, Wang D, Cheng S, Kang T, Dai H. Nanosized Au supported on three-dimensionally ordered mesoporous β-MnO2: highly active catalysts for the low-temperature oxidation of carbon monoxide, benzene, and toluene. Microporous and Mesoporous Materials, 2013, 172: 20–29
27 Durand J P, Senanayake S D, Suib S L, Mullins D R. Reaction of formic acid over amorphous manganese oxide catalytic systems: an in situ study. Journal of Physical Chemistry C, 2010, 114(47): 20000–20006
28 Chen D, Qu Z, Sun Y, Gao K, Wang Y. Identification of reaction intermediates and mechanism responsible for highly active HCHO oxidation on Ag/MCM-41 catalysts. Applied Catalysis B: Environmental, 2013, 142-143: 838–848
29 Kecskés T, Raskó J, Kiss J. FTIR and mass spectrometric studies on the interaction of formaldehyde with TiO2 supported Pt and Au catalysts. Applied Catalysis A: General, 2004, 273(1-2): 55–62
30 Laberty C, Marquez-Alvarez C, Drouet C, Alphonse P, Mirodatos C. CO oxidation over nonstoichiometric nickel manganite spinels. Journal of Catalysis, 2001, 198(2): 266–276
31 Busca G, Lamotte J, Lavalley J, Lorenzelli V. FT-IR study of the adsorption and transformation of formaldehyde on oxide surfaces. Journal of the American Chemical Society, 1987, 109(17): 5197–5202
32 Popova G A, Budneva A A, Andrushkevich T V. Identification of adsorption forms by ir spectroscopy for formaldehyde and formic acid on K3PMo12O40. Reaction Kinetics and Catalysis Letters, 1997, 61(2): 353–362
33 Chen B, Shi C, Crocker M, Wang Y, Zhu A. Catalytic removal of formaldehyde at room temperature over supported gold Catalysts. Applied Catalysis B: Environmental, 2013, 132-133: 245–255
34 Zhao D Z, Shi C, Li X, Zhu A, Jang B W.-L. Enhanced effect of water vapor on complete oxidation of formaldehyde in air with ozone over MnOx catalysts at room temperature. Journal of Hazardous Materials, 2012, 239-240: 362–369
35 Bond G C, Thompson D T. Gold-catalysed oxidation of carbon monoxide. Gold Bulletin, 2000, 33(2): 41–50
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