The Active Molybdenum Oxide Phase in the Methanol Oxidation to Formaldehyde (Formox Process): A DFT Study

被引:33
|
作者
Rellan-Pinerio, Marcos [1 ]
Lopez, Nuria [1 ]
机构
[1] Inst Chem Res Catalonia ICIQ, Tarragona 43007, Spain
关键词
density functional calculations; iron; molybdenum; oxidation; reaction mechanisms; TOTAL-ENERGY CALCULATIONS; IRON-MOLYBDATE CATALYSTS; SELECTIVE OXIDATION; METAL-OXIDE; FT-IR; QUANTITATIVE-DETERMINATION; TURNOVER FREQUENCIES; RAMAN-SPECTROSCOPY; FERRIC MOLYBDATE; (MO3)(3) M;
D O I
10.1002/cssc.201500315
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Methanol is oxidised to formaldehyde by the Formox process, in which molybdenum oxides, usually doped with iron, are the catalyst. The active phase of the catalysts and the reasons for the selectivity observed are still unknown. We present a density functional theory based study that indicates the unique character of (MoMoIV)-Mo-VI pairs as the most active and selective sites and indicates the active sites on the surface, the controlling factors of selectivity, and the role of the dopant. Iron reduces the energy requirements of the redox (MoMoIV)-Mo-VI pair by acting as an electron reservoir that sets in if required. Our present study paves the way towards a better understanding of the process.
引用
收藏
页码:2231 / 2239
页数:9
相关论文
共 50 条
  • [21] KINETICS OF VAPOR-PHASE OXIDATION OF METHANOL AND FORMALDEHYDE BY OXYGEN ON VANADIUM OXIDE CATALYST
    MEDVEDEV.YG
    BULAKH, AY
    CHUCHMAR.SK
    ZHURNAL FIZICHESKOI KHIMII, 1974, 48 (08): : 2122 - 2124
  • [22] Oxidation of methanol to formaldehyde on supported vanadium oxide catalysts compared to gas phase molecules
    Döbler, Jens
    Pritzsche, Marc
    Sauer, Joachim
    Journal of the American Chemical Society, 2005, 127 (31): : 10861 - 10868
  • [23] Oxidation of methanol to formaldehyde on supported vanadium oxide catalysts compared to gas phase molecules
    Döbler, J
    Pritzsche, M
    Sauer, J
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (31) : 10861 - 10868
  • [24] Regeneration of the iron-molybdenum catalyst for partial oxidation of methanol to formaldehyde
    Babichev, I. V.
    Ilyin, A. A.
    Rumyantsev, R. N.
    Ilyin, A. P.
    Kuryleva, K. V.
    RUSSIAN JOURNAL OF APPLIED CHEMISTRY, 2015, 88 (04) : 590 - 594
  • [25] Regeneration of the iron-molybdenum catalyst for partial oxidation of methanol to formaldehyde
    I. V. Babichev
    A. A. Ilyin
    R. N. Rumyantsev
    A. P. Ilyin
    K. V. Kuryleva
    Russian Journal of Applied Chemistry, 2015, 88 : 590 - 594
  • [26] The Nature of the Molybdenum Surface in Iron Molybdate. The Active Phase in Selective Methanol Oxidation
    Brookes, Catherine
    Wells, Peter P.
    Dimitratos, Nikolaos
    Jones, Wilm
    Gibson, Emma K.
    Morgan, David J.
    Cibin, Giannantonio
    Nicklin, Chris
    Mora-Fonz, David
    Scanlon, David O.
    Catlow, C. R. A.
    Bowker, Mike
    JOURNAL OF PHYSICAL CHEMISTRY C, 2014, 118 (45): : 26155 - 26161
  • [27] Highly Stable Apatite Supported Molybdenum Oxide Catalysts for Selective Oxidation of Methanol to Formaldehyde: Structure, Activity and Stability
    Thrane, Joachim
    Elvebakken, Christopher Falholt
    Juelsholt, Mikkel
    Christiansen, Troels Lindahl
    Jensen, Kirsten M. O.
    Hansen, Lars Pilsgaard
    Lundegaard, Lars Fahl
    Mentzel, Uffe Vie
    Thorhauge, Max
    Jensen, Anker Degn
    Hoj, Martin
    CHEMCATCHEM, 2021, 13 (23) : 4954 - 4975
  • [28] Hydroxyapatite supported molybdenum oxide catalyst for selective oxidation of methanol to formaldehyde: studies of industrial sized catalyst pellets
    Thrane, Joachim
    Mentzel, Uffe Vie
    Thorhauge, Max
    Hoj, Martin
    Jensen, Anker Degn
    CATALYSIS SCIENCE & TECHNOLOGY, 2021, 11 (03) : 970 - 983
  • [29] CONVERSION OF METHYL RADICALS TO METHANOL AND FORMALDEHYDE OVER MOLYBDENUM OXIDE CATALYSTS
    PAK, S
    ROSYNEK, MP
    LUNSFORD, JH
    JOURNAL OF PHYSICAL CHEMISTRY, 1994, 98 (45): : 11786 - 11790
  • [30] Catalytic oxidation of methanol to formaldehyde in the gas phase.
    Waters, T
    O'Hair, RAJ
    Wedd, AG
    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2001, 222 : U590 - U591