Abstract
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.
Similar content being viewed by others
References
Salthammer T, Mentese S, Marutzky R. Formaldehyde in the indoor environment. Chemical Reviews, 2010, 110(4): 2536–2572
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
Bai B, Arandiyan H, Li J. Comparison of the performance for oxidation of formaldehyde on nano-Co3O4, 2D-Co3O4, and 3DCo3O4 catalysts. Applied Catalysis B: Environmental, 2013, 142–143: 677–683
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
Torres J Q, Giraudon J M, Lamonier J F. Formaldehyde total oxidation over mesoporous MnO x catalysts. Catalysis Today, 2011, 176(1): 277–280
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 -butyrolactone. Applied Catalysis A, General, 2013, 458(10): 63–70
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
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
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
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
Ye Q, Zhao J, Huo F, Wang D, Cheng S, Kang T, Dai H. Nanosized Au supported on three-dimensionally ordered mesoporous ß-MnO2: highly active catalysts for the low-temperature oxidation of carbon monoxide, benzene, and toluene. Microporous and Mesoporous Materials, 2013, 172: 20–29
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
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
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
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
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
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
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
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 MnO x catalysts at room temperature. Journal of Hazardous Materials, 2012, 239–240: 362–369
Bond G C, Thompson D T. Gold-catalysed oxidation of carbon monoxide. Gold Bulletin, 2000, 33(2): 41–50
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Rights and permissions
About this article
Cite this article
Pang, G., Wang, D., Zhang, Y. et al. Catalytic activities and mechanism of formaldehyde oxidation over gold supported on MnO2 microsphere catalysts at room temperature. Front. Environ. Sci. Eng. 10, 447–457 (2016). https://doi.org/10.1007/s11783-015-0808-8
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11783-015-0808-8