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Density functional theory studies on hydroxylamine mechanism of cyclohexanone ammoximation on titanium silicalite-1 catalyst

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Abstract

The hydroxylamine mechanism of cyclohexanone ammoximation on defective titanium active site of titanium silicalite-1 (TS-1) was simulated using two-layer ONIOM (M062X/6-31G**:PM6) method. A new energy favorable reaction route was found, which contained two parts: (1) the catalytic oxidation of adsorbed NH3 to form hydroxylamine using the Ti-OOH as an active oxidant formed by reacting H2O2 with the defective Ti active site; (2) the subsequent noncatalytic oximation of desorbed hydroxylamine and cyclohexanone out of TS-1 pores to form cyclohexanone oxime. In the catalytic formation of hydroxylamine on the Ti active site of TS-1, the proposed mechanism of two-step single-proton transfer aided by a lattice oxygen atom bonded to Ti atom need a lower reaction energy than the mechanism proposed before. In the subsequent noncatalytic oximation of hydroxylamine and cyclohexanone, which contained two elementary reaction steps in total, the mechanisms of one-step double-proton transfer in the first elementary reaction step and the subsequent one-step three-proton transfer for the second elementary reaction step were proposed, in which the solvent water molecules played a very important role in assisting and stabilizing the proton transfer processes.

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Acknowledgments

Grateful thanks for support of the National Natural Science Foundation of China (21276180) and the program for Changjiang Scholars and Innovative Research Team in University (IRT0936).

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Authors and Affiliations

  1. Department of Chemical Engineering, School of Chemical Engineering and Technology, Tianjin University, Nankai District, Wei Jin Road 92, Tianjin, 300072, China

    Chang Qing Chu, Yan Ying Qi & Feng Xin

  2. Department of Chemistry, School of Science, Tianjin University, Nankai District, Wei Jin Road 92, Tianjin, 300072, China

    Hai Tao Zhao

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  1. Chang Qing Chu
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  2. Hai Tao Zhao
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  3. Yan Ying Qi
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  4. Feng Xin
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Correspondence to Feng Xin.

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Chu, C.Q., Zhao, H.T., Qi, Y.Y. et al. Density functional theory studies on hydroxylamine mechanism of cyclohexanone ammoximation on titanium silicalite-1 catalyst. J Mol Model 19, 2217–2224 (2013). https://doi.org/10.1007/s00894-013-1768-1

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  • DOI: https://doi.org/10.1007/s00894-013-1768-1

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