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Frontiers of Environmental Science & Engineering

Front. Environ. Sci. Eng.    2016, Vol. 10 Issue (3) : 447-457     https://doi.org/10.1007/s11783-015-0808-8
RESEARCH ARTICLE |
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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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.

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.
 URL:  
http://journal.hep.com.cn/fese/EN/10.1007/s11783-015-0808-8
http://journal.hep.com.cn/fese/EN/Y2016/V10/I3/447
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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
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