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The Reduction-Coupled Oxo Activation (ROA) Mechanism Responsible for the Catalytic Selective Activation and Functionalization of n-Butane to Maleic Anhydride by Vanadium Phosphate Oxide

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Abstract

We report here the results of density functional theory quantum mechanical (QM) studies of the detailed chemical mechanism underlying the n-butane selective oxidation to form maleic anhydride (MA) on vanadyl pyrophosphate [(VO)2P2O7] and vanadyl phosphate [VOPO4] surfaces. This QM-derived mechanism differs substantially from previous suggestions but is in excellent agreement with key experimental observations. We find that the O(1)=P bond of the oxidized X1 phase of the VOPO4 surface is the active site for initiating the VPO chemistry, by extracting the H from the n-butane C–H bond. This contrasts sharply with previous suggestions, all of which involved the V=O bonds. The ability of O(1)=P to cleave alkane C–H bonds arises from a new unique mechanism that decouples the proton transfer and electron transfer components of this H atom transfer reaction. We find that the juxtaposition of a highly reducible V+5 next to the P=O bond but coupled via a bridging oxygen dramatically enhances the activity of the P=O bond to extract the proton from an alkane, while simultaneously transferring the electron to the V to form V+4. This Reduction-Coupled Oxo Activation (ROA) mechanism had not been known prior to these QM studies, but we believe that it may lead to a new strategy in designing selective catalysts for alkane activation and functionalization, and indeed it may be responsible for the selective oxidation by a number of known mixed metal oxide catalysts. To demonstrate the viability of this new ROA mechanism, we examine step by step the full sequence of reactions from n-butane to MA via two independent pathways. We that find that every step is plausible, with a highest reaction barrier of 21.7 kcal/mol.

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Acknowledgments

This work was supported mainly by NSF (CHE-1214158) but was initiated with support from the Center for Catalytic Hydrocarbon Functionalization, an Energy Frontier Reserch Center, DOE DE-SC0001298 with some additional support from Chevron USA Inc (Robert Sexton and Oleg Mironov).

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Authors and Affiliations

  1. Materials and Process Simulation Center (139-74), California Institute of Technology, Pasadena, CA, 91125, USA

    Mu-Jeng Cheng, William A. Goddard III & Ross Fu

Authors
  1. Mu-Jeng Cheng
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  2. William A. Goddard III
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  3. Ross Fu
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Corresponding author

Correspondence to William A. Goddard III.

Additional information

This talk is dedicated to Robert Karl Grasselli, who in 1979 introduced me to the wonderful world of mixed metal (amm)oxidation catalysts. He and the excellent group he put together at SOHIO provided the experiments that yielded key mechanistic information that stimulated our theory and computation studies. Bob is an inspiration to us with his deep thinking and encyclopedic knowledge, all aimed at furthering the science of catalysis. His enormous contributions to heterogeneous catalysis have had a dramatic impact on industry and on the chemical concepts underlying selective oxidation catalysis. I want also to thank Jerry Ebner and John Gleaves for their amazing discoveries made at Monsanto back when it was a leading catalysis innovator, and for the deep insights into the mechanism from their TAP reactor studies.

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Cheng, MJ., Goddard, W.A. & Fu, R. The Reduction-Coupled Oxo Activation (ROA) Mechanism Responsible for the Catalytic Selective Activation and Functionalization of n-Butane to Maleic Anhydride by Vanadium Phosphate Oxide. Top Catal 57, 1171–1187 (2014). https://doi.org/10.1007/s11244-014-0284-6

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