Effects of catalyst crystal structure on the oxidation of propene to acrolein

Zhai, Zheng; Wütschert, Maïté; Licht, Rachel B.; Bell, Alexis T.

doi:10.1016/j.cattod.2015.06.011

Effects of catalyst crystal structure on the oxidation of propene to acrolein

Journal Article · Tue Jul 14 00:00:00 EDT 2015 · Catalysis Today

DOI:https://doi.org/10.1016/j.cattod.2015.06.011· OSTI ID:1571060

Zhai, Zheng ^[1]; Wütschert, Maïté ^[1]; Licht, Rachel B. ^[1]; Bell, Alexis T. ^[1]

University of California, Berkeley, CA (United States)

Bismuth molybdate is realized to be active for the oxidation of propene to acrolein and its activity can be altered by substitution of other elements (e.g. Fe, V, W) into the scheelite phase of α-Bi₂Mo₃O₁₂. Our report has further revealed that the apparent activation energy for acrolein formation correlates with the band gap of the catalyst measured at reaction temperature. It is, therefore, of interest to establish to how the crystal structure of the catalyst affects the activation energy. We report here an investigation of propene oxidation conducted over Bi, Mo, V oxides having the aurivillius structure with the composition Bi₄V_2-xMo_xO_11+x/2(x = 0-1) and compare them with oxides having the scheelite structure with the composition Bi_2-x/3Mo_xV_1-xO₁₂(x = 0-1). The aurivillius-phase catalysts again show a correlation between the apparent activation energy and the band gap of the oxide, and the only difference being that for a given band gap, the apparent activation energy for the aurivillius-phase catalysts is 1.5 kcal/mol higher than that for the scheelite-phase catalysts. This difference is attributed to the lower heat of propene adsorption on the aurivillius-phase catalysts. An additional finding is that for catalysts with band gaps greater than ~2.1 eV, the acrolein selectivity is ~75% for the conditions used and independent of the propene conversion. When the band gap falls below ~2.1 eV, the intrinsic selectivity to acrolein decreases rapidly and then decreases further with increasing propene conversion. This pattern shows that when the activity of oxygen atoms at the catalyst surface becomes very high, two processes become more rapid - the oxidation of the intermediate from which acrolein is formed and the sequential combustion of acrolein to CO₂.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1571060

Alternate ID(s):: OSTI ID: 1396937

Journal Information:: Catalysis Today, Journal Name: Catalysis Today Journal Issue: C Vol. 261; ISSN 0920-5861

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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