Insight into the efficient oxidation of methyl-ethyl-ketone over hierarchically micro-mesostructured Pt/K-(Al)SiO2 nanorod catalysts: Structure-activity relationships and mechanism

[Display omitted] •Hierarchically micro-mesostructured K-(Al)SiO2 supports were successfully prepared.•Monodispersed Pt was created by ethylene glycol reduction and colloid impregnation.•Pt/K-Al-SiO2 nanorod catalysts exhibit superior performance for MEK oxidation.•Role of K and Al and structure-act...

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Published inApplied catalysis. B, Environmental Vol. 226; pp. 220 - 233
Main Authors Jiang, Zeyu, He, Chi, Dummer, Nicholas F., Shi, Jianwen, Tian, Mingjiao, Ma, Chunyan, Hao, Zhengping, Taylor, Stuart H., Ma, Mudi, Shen, Zhenxing
Format Journal Article
LanguageEnglish
Published Elsevier B.V 15.06.2018
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Abstract [Display omitted] •Hierarchically micro-mesostructured K-(Al)SiO2 supports were successfully prepared.•Monodispersed Pt was created by ethylene glycol reduction and colloid impregnation.•Pt/K-Al-SiO2 nanorod catalysts exhibit superior performance for MEK oxidation.•Role of K and Al and structure-activity relationships of catalysts were studied.•MEK destruction mechanism was investigated and proposed by in situ DRIFTS and DFT. Hierarchically micro-mesostructured Pt/K-Al-SiO2 catalysts with regular nanorod (Pt/KA-NRS) and spherical nanoflower-like (Pt/KA-SNFS) morphologies were prepared. The existence of Al atoms generates Brønsted acid sites and reduces silanol groups over the supports, promoting the dispersion of Pt nanoparticles and stability of catalysts. Potassium atoms balance the negative charge of supports and enhance O2 mobility. The Pt/KA-NRS catalysts exhibit unexceptionable low temperature activity, CO2 selectivity, and stability for MEK oxidation. Amongst, 0.27 wt.% Pt/KA-NRS completely converts MEK at just 170 °C (activation energy as low as 37.22 kJ·mol−1), more than 100 °C lower than other typical Pt/Pd supported catalysts reported in the literature. Diacetyl and 2,3-butandiol are the main intermediates during MEK activation, which convert into H2O and CO2 through aldehydes and acids. The excellent catalytic activity of Pt/KA-NRS is ascribed to their regular morphology, high Pt0 content and dispersion, excellent MEK adsorption capacity and superior O2/CO2 desorption capability under low temperature.
AbstractList [Display omitted] •Hierarchically micro-mesostructured K-(Al)SiO2 supports were successfully prepared.•Monodispersed Pt was created by ethylene glycol reduction and colloid impregnation.•Pt/K-Al-SiO2 nanorod catalysts exhibit superior performance for MEK oxidation.•Role of K and Al and structure-activity relationships of catalysts were studied.•MEK destruction mechanism was investigated and proposed by in situ DRIFTS and DFT. Hierarchically micro-mesostructured Pt/K-Al-SiO2 catalysts with regular nanorod (Pt/KA-NRS) and spherical nanoflower-like (Pt/KA-SNFS) morphologies were prepared. The existence of Al atoms generates Brønsted acid sites and reduces silanol groups over the supports, promoting the dispersion of Pt nanoparticles and stability of catalysts. Potassium atoms balance the negative charge of supports and enhance O2 mobility. The Pt/KA-NRS catalysts exhibit unexceptionable low temperature activity, CO2 selectivity, and stability for MEK oxidation. Amongst, 0.27 wt.% Pt/KA-NRS completely converts MEK at just 170 °C (activation energy as low as 37.22 kJ·mol−1), more than 100 °C lower than other typical Pt/Pd supported catalysts reported in the literature. Diacetyl and 2,3-butandiol are the main intermediates during MEK activation, which convert into H2O and CO2 through aldehydes and acids. The excellent catalytic activity of Pt/KA-NRS is ascribed to their regular morphology, high Pt0 content and dispersion, excellent MEK adsorption capacity and superior O2/CO2 desorption capability under low temperature.
Author Dummer, Nicholas F.
Shi, Jianwen
Taylor, Stuart H.
Ma, Chunyan
Hao, Zhengping
He, Chi
Ma, Mudi
Jiang, Zeyu
Tian, Mingjiao
Shen, Zhenxing
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  email: chi_he@xjtu.edu.cn
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  givenname: Jianwen
  surname: Shi
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  organization: Center of Nanomaterials for Renewable Energy, State Key Laboratory of Electrical Insulation and Power Equipment, School of Electrical Engineering, Xi’an Jiaotong University, Xi'an 710049, Shaanxi, China
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  givenname: Mingjiao
  surname: Tian
  fullname: Tian, Mingjiao
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  givenname: Chunyan
  surname: Ma
  fullname: Ma, Chunyan
  organization: Department of Environmental Nano-materials, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, PR China
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  givenname: Zhengping
  surname: Hao
  fullname: Hao, Zhengping
  organization: Department of Environmental Nano-materials, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, PR China
– sequence: 8
  givenname: Stuart H.
  surname: Taylor
  fullname: Taylor, Stuart H.
  organization: Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff, CF10 3AT, UK
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  givenname: Mudi
  surname: Ma
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  organization: Department of Environmental Science and Engineering, State Key Laboratory of Multiphase Flow in Power Engineering, School of Energy and Power Engineering, Xi'an Jiaotong University, Xi'an 710049, Shaanxi, PR China
– sequence: 10
  givenname: Zhenxing
  surname: Shen
  fullname: Shen, Zhenxing
  organization: Department of Environmental Science and Engineering, State Key Laboratory of Multiphase Flow in Power Engineering, School of Energy and Power Engineering, Xi'an Jiaotong University, Xi'an 710049, Shaanxi, PR China
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Snippet [Display omitted] •Hierarchically micro-mesostructured K-(Al)SiO2 supports were successfully prepared.•Monodispersed Pt was created by ethylene glycol...
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SubjectTerms Activation mechanism
Al-K decorated silica
Catalytic oxidation
Methyl-ethyl-ketone
Monodispersed Pt sites
Title Insight into the efficient oxidation of methyl-ethyl-ketone over hierarchically micro-mesostructured Pt/K-(Al)SiO2 nanorod catalysts: Structure-activity relationships and mechanism
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