催化学报

催化学报 ›› 2019, Vol. 40 ›› Issue (11): 1686-1692.DOI: 10.1016/S1872-2067(19)63350-4

• 论文 • 上一篇    下一篇

核壳结构MOx/Fe2O3(M=Mo,V,Nb)催化剂上甲醇氧化反应

Pip Helliera,b, Peter P. Wellsc,d, Michael Bowkera,b   

  1. a 卢瑟福-阿普尔顿实验室, 哈韦尔研究综合体, 英国催化中心, 哈韦尔, 英国;
    b 卡迪夫大学化学学院, 卡迪夫, 英国;
    c 南安普顿大学化学学院, 南安普顿, 英国;
    d 哈韦尔科学与创新园区, 钻石光源有限公司, 迪德科特, 英国
  • 收稿日期:2019-01-31 修回日期:2019-03-05 出版日期:2019-11-18 发布日期:2019-09-06
  • 通讯作者: Michael Bowker
  • 基金资助:
    The authors thank HarwellXPS, the EPSRC National Facility for X-Ray Photoelectron Spectroscopy, for their assistance in performing XPS measurements, and EPSRC for support via the UK Catalysis Hub (EP/K014854/1, EP/K014714/1), and EPSRC and Diamond Light Source for funding the studentship to PH.

Methanol oxidation over shell-core MOx/Fe2O3 (M=Mo, V, Nb) catalysts

Pip Helliera,b, Peter P. Wellsc,d, Michael Bowkera,b   

  1. a UK Catalysis Hub, Research Complex at Harwell, Rutherford Appleton Laboratory, Harwell, UK;
    b School of Chemistry, Cardiff University, Cardiff, UK;
    c School of Chemistry, University of Southampton, Southampton, UK;
    d Diamond Light Source Ltd, Harwell Science and Innovation Campus, Didcot, UK
  • Received:2019-01-31 Revised:2019-03-05 Online:2019-11-18 Published:2019-09-06
  • Contact: Michael Bowker
  • Supported by:
    The authors thank HarwellXPS, the EPSRC National Facility for X-Ray Photoelectron Spectroscopy, for their assistance in performing XPS measurements, and EPSRC for support via the UK Catalysis Hub (EP/K014854/1, EP/K014714/1), and EPSRC and Diamond Light Source for funding the studentship to PH.

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摘要： 本文比较了赤铁矿为核，Mo，V和Nb氧化物为壳层的材料在选择性甲醇氧化反应中的性能.Mo和V对甲醛都有很高的选择性，而Nb则没有.Nb的反应模式非常不同，主要表现为脱氢（生成CO）和脱水（生成三甲醚），表明缺乏完整的壳层，同时Raman光谱发现，NbOx的形成过程与Mo和V的并不相同.我们推测这是由于固体材料在形成过程中的流动性差异很大，NbOx需要明显较高（和有害）的焙烧温度，以便为壳层的形成提供足够的流动性.

关键词: 甲醇, 氧化, 甲醛, 钼酸铁, 核壳结构催化剂

Abstract: We present a comparison of Mo, V and Nb oxides as shell materials atop haematite cores used for selective methanol oxidation. While Mo and V both yield high selectivity to formaldehyde, Nb does not. Very different reactivity patterns are seen for Nb, which mainly shows dehydrogenation (to CO) and dehydration (to DME), indicating the lack of a complete shell, while Raman spectroscopy shows that the Mo and V formation process is not followed by NbOx. We suggest this is due to the large differences in mobility within the solid materials during formation, NbOx requiring significantly higher (and deleterious) calcination temperatures to allow sufficient mobility for shell completion.

Key words: Methanol, Oxidation, Formaldehyde, Iron molybdate, Shell-core catalyst