Using microkinetic analysis to search for novel anhydrous formaldehyde production catalysts

SURFACE SCIENCE

卷:641

Article

Li, Han-Jung^1,2  Lausche, Adam C.^1,2  Peterson, Andrew A.³  Hansen, Heine A.⁴  Studt, Felix^1,2  Bligaard, Thomas^1,2 

[1] SIAC Natl Accelerator Lab, SUNCAT Ctr Interface Sci & Catalysis, Menlo Pk, CA 94025 USA

[2] Stanford Univ, Dept Chem Engn, Stanford, CA 94305 USA

[3] Brown Univ, Sch Engn, Providence, RI 02912 USA

[4] Tech Univ Denmark, Dept Energy Convers & Storage, DK-4000 Roskilde, Denmark

关键词: Methanol;    Formaldehyde;    Heterogeneous catalysis;    Density functional theory;    Scaling relations;    Microkinetic model;   

DOI  :  10.1016/j.susc.2015.04.028

来源: Elsevier

【 摘 要 】

Direct dehydrogenation of methanol to produce anhydrous formaldehyde is investigated using periodic density functional theory (DFT) and combining the microkinetic model to estimate rates and selectivities on stepped (211) surfaces under a desired reaction condition. Binding energies of reaction intermediates and transition state energies for each elementary reaction can be accurately scaled with CHO and OH binding energies as the only descriptors. Based on these two descriptors, a steady-state microkinetic model is constructed with a piece-wise adsorbate-adsorbate interaction model that explicitly includes the effects of adsorbate coverage on the rates and selectivities as well as the volcano plots are obtained. Our results show that most of the stepped (211) pure-metallic surfaces such as Au, Pt, Pd, Rh, Ru, Ni, Fe, and Co are located in a region of low activity and selectivity toward CH2O production due to higher rate for CH2O dehydrogenation than CH2O desorption. The selectivities toward CH2O production on Zn, Cu, and Ag surfaces are located on the boundary between the high and low selectivity regions. To find suitable catalysts for anhydrous CH2O production, a large number of A(3)B-type transition metal alloys are screened based on their predicted rates and selectivities, as well as their estimated stabilities and prices. We finally propose several promising candidates for the dehydrogenation of CH3OH. Published by Elsevier B.V.

【 授权许可】

Free