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Selective Conversions of light alkanes that take place on metal compounds

hatrick2 - Posted on 02 February 2012

Project Description: 

Selective conversions of light alkanes to molecules with functional groups are of great industrial and fundamental interest, especially nowadays because the oil price remains at a high level and oil depletion in three to five decades is widely expected. Nature has a large body of cheap light alkanes. Whether or not these cheap feedstocks can be utilized to produce more valuable commodities, lies in the avaliablity of high active and product selective catalysts. Our aim is to design, synthesis of new catalysts and understand how the catalytic process undergoes on these catalysts, mainly for the oxidative conversion of alkanes to alkenes.

Researcher name: 
Xufeng Lin
Researcher position: 
Associate Professor
Researcher email: 
hatrick2@hku.hk
Researcher name: 
David L. Phillips
Researcher position: 
Professor
Researcher email: 
phillips@hku.hk
Research Project Details
Project Duration: 
04/2011 to 03/2014
Project Significance: 
(1) To understand the detailed unit steps for how alkanes reacts with transition metal oxide clusters (2) To help design a rational catalysts
Results Achieved: 
(1) More "well-ordered" Fe, Ni catalysts has been synthesized, and their corresponding performance on conversion of ethane to ethylene has been evaluated. (2) The kinetics of the oxidation of ethane, methane on various type of catalysts has been examined. (3) Model catalysts of Ni3Ox reacting with ethane were examined by quantum chemical calculation. We found the less x value leads to the high initial ethylene selectivity. List of publications: (X. F. Lin) 1. The mechanism for dehydration of glycerol on zeolites: a combined experimental and computational study X. F. Lin, Y. H. Lv, Y. Y. Qu, Y. Y. Xi, J. Sun, C. G. Liu, D. L. Phillips In preparation for Journal of Catalysis 2. Unraveling the reaction mechanism for nickel-catalyzed oxidative dehydrogenation of ethane by DFT: The C-H bond activation step and its following pathways X. F. Lin, Y. Y. Xi, J. Sun J. Phys. Chem. C, In Press. 3. Computational interpretation of the stereoselectivity for a dirhodium tetracarboxylate- catalyzed amidation reaction X. F. Lin, J. Sun, Y. Y. Xi, Bo Pang, Computational and Theoretical Chemistry, 2011, 963, 284. 4. How racemic secondary alkyl electrophiles proceed to enantioselective products in Negishi cross-coupling reactions X. F. Lin, J. Sun, Y. Y. Xi, D. L. Lin Oragnometallics, 2011, 30, 3284. 5．Oxidative dehydrogenation of ethane with oxygen catalyzed by K-Y zeolite supported first-row transition metals X. F. Lin, K. R. Poeppelmeier, E. Weitz, Applied catalysis A-General, 2010, 381, 114. 6．Oxidative dehydrogenation (ODH) of ethane with O2 as oxidant on selected transition metal-loaded zeolites X. F. Lin, C. A. Hoel, W. M. H. Sachtler, K. R. Poeppelmeier, E. Weitz, Journal of Catalysis, 2009, 265, 54. 7. A DFT Study on the Mechanism of Rh2(II,II)-Catalyzed Intramolecular Amination of Carbamates X. F. Lin, C. Y. Zhao, C. M. Che, Z. F. Ke, D. L. Phillips, Chem. Asian J. 2008, 2, 1101. 8. Surface-enhanced Raman scattering in the ultraviolet spectral region: UV-SERS on rhodium and ruthenium electrodes B. Ren, X. F. Lin, Z. L. Yang, G. K. Liu, R. F. Aroca, B. W. Mao, Z. Q. Tian, J. Am. Chem. Soc. 2003, 125, 9598. 9. Electrochemical and surface-enhanced Raman spectroscopic studies on the adsorption and electrooxidation of C1 molecules on a roughened Rh electrode X. F. Lin, B. Ren, Z. Q. Tian, J. Phys. Chem. B 2004, 108, 981. 10. Reaction mechanism and stereoselectivity of ruthenium-Porphyrin-catalyzed intramolecular amidation of sulfamate ester: A DFT computational study X. F. Lin, C. M. Che, D. L. Phillips, J. Org. Chem., 2008, 73, 529. 11. Density functional theory study of water-assisted deprotonation of the C8- intermediate in the reaction of the 2-Fluorenylnitrenium ion with guanosine to form a C8 adduct Z. Guo, X. F. Lin, C. Y. Zhao, D. L. Phillilps, Journal of Molecular Structure- Theochem, 2008, 848, 119. 12. Density functional theory studies of negishi alkyl-alkyl cross-coupling reactions catalyzed by a methyiterpyridyl-Ni(I) complex, X. F. Lin, D. L. Phillips, J. Org. Chem., 2008, 73, 3680 13. Modeling SN2 reactions in methanol solution by ab initio calculation of nucleophile solvent-substrate clusters X. F. Lin, C. Y. Zhao, D. L. Phillips, J. Org. Chem., 2005, 70, 9279. 14. Water-catalyzed O-H Insertion/HI elimination reactions of isodihalomethanes (CH2X-I, where X = Cl, Br, I) with water and the dehalogenation of dihalomethanes in water-solvated environments X. F. Lin, X. G. Guan, W. M. Kwok. C. Y. Zhao, Y. Du, Y. L. Li, D. L. Phillips, J. Phys. Chem. A , 2005, 109, 981. 15. Water-catalyzed dehalogenation reactions of the isomer of CBr4 and its reaction products and a comparison to analogous reactions of the isomers of di- and trihalomethanes C. Y. Zhao, X. F. Lin, W. M. Kwok, X. G. Guan, Y. Du, D. Q. Wang, K. F. Hung, D. L. Phillips, Chem. Euro. J., 2005, 11, 1093. 16. An ab initio study of the reactions of CH2X-X (X = Cl, Br, I)isopolyhalomethanes with nCH3OH X. F. Lin, C. Y. Zhao, D. L. Phillips, Molecular Simulation, 2005, 31, 483. 17. Ab initio investigation of the O-Y (Y = CH3, H) insertion/HI elimination reactions of CH2I-I with CH3OH and H2O: comparison of methanol and water catalyzed reactions X. F. Lin, C. Y. Zhao, D. L. Phillips, Chem. Phys. Lett. 2004, 397, 488. 18. Ultraviolet photolysis of CH2I2 in methanol: O-H insertion and HI elimination reactions to form a dimethoxymethane product X. G. Guan, X. F. Lin, W. M. Kwok, Y. Du, Y. L. Li, C. Y. Zhao, D. Q. Wang, D. L. Phillips J. Phys. Chem. A 2005, 109, 1247 19. Surface-enhanced Raman spectroscopy with ultraviolet excitation X. F. Lin, B. Ren, Z. L. Yang, G. K. Liu, Z. Q. Tian, J. Raman Spectrosc. 2005, 36, 606. 20. Electrochemically roughened rhodium electrode as a substrate for surface-enhanced Raman spectroscopy B. Ren, X. F. Lin, J. W. Yan, B. W. Mao, Z. Q. Tian, J. Phys. Chem. B 2003, 107, 899. 21. Optimizing detection sensitivity on surface-enhanced Raman scattering of transition-metal electrodes with confocal Raman microscopy B. Ren, X. F. Lin, Y. X. Jiang, P. G. Cao, Y. Xie, Q. J. Huang, Z. Q. Tian, Appl. Spectrosc. 2003, 57, 419. 22. An investigation of the adsorption of pyrazine and pyridine on nickel electrodes by in situ surface-enhanced Raman spectroscopy Q. J. Huang, X.F.Lin, Z. L. Yang, J. W. Hu, Z. Q. Tian, J. Electroanal. Chem. 2004, 563, 121-131. 23. Probing different adsorption behavior of CO on Pt at solid/liquid and solid/gas interfaces by Raman spectroscopy with a three-phase Raman cell B. Ren, L. Cui, X. F. Lin, Z. Q. Tian, Chem. Phys. Lett. 2003, 376, 130-13518. 24. Surface-enhanced Raman scattering from transition metals with special surface morphology and nanoparticle shape Z. Q. Tian, Z. L. Yang, B. Ren, J. F. Li, Y. Zhang, X. F. Lin, J. W. Hu, D. Y. Wu, Faraday Discussions 2006, 132, 159 25. Confocal microprobe Raman spectroscopy for investigating the electrochemical interface B. Ren, F. M. Liu, X. F. Lin, Z. Q. Tian, Chin. J. Electrochem. 2001, 7, 41 26. Rh as a Ubiquitous Substrates for surface enhanced Raman spectroscopy B. Ren, X. F. Lin, Z. Q. Tian, Chin. J. Electrochem. 2001, 7, 55 27. In situ Raman spectroscopic studies on the reduction of the surface oxides of rhodium at solid/liquid and solid/gas interfaces X. F. Lin, B. Ren, Y. Y. Liao, W.Y. Hu, Z. Q. Tian, Chin. J. Light Scattering 2002, 14, 111.
Remarks: 
To understand the support effect on the transition metal catalyzed conversion of alkanes with density functional theory calculation, as well as to build larger size of model metal oxide clusters, a powerful computational resource is highly desired to speed up the computational process. Therefore, HPC will help up greatly in understanding the reaction mechnanism as well as in catalyst design.