Date

2011

Author

Kurnaz, Emine

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Propylene epoxidation reaction was investigated on catalytic surfaces of chlorinated copper(I) oxide and ruthenium(IV) oxide using periodic density functional theory (DFT). Cu2O(001) and (110) surface of RuO2 was selected to generate chlorinated surfaces to be used in the study. Besides epoxidation, other reactions that compete with epoxidation were also studied such as formations of allyl-radical, acrolein, acetone on chlorinated Cu2O(001) and formations of propionaldehyde, allyl-radical and acetone on chlorinated RuO2(110) surface. Path of each reaction was determined by CI-NEB method and transition state analyses. Generally accepted stable surface intermediate mechanism was utilized in reactions to final products. The surface intermediate favorable on the surfaces in this study was determined to be the intermediate that is not preferable on metallic surfaces under low oxygen. On chlorinated Cu2O(001) surface, formation of propylene oxide, acetone and acrolein have higher probability than gas phase allyl-radical since the desorption energy of allyl-radical was calculated to be 70kcal/mol which is a relatively high value. In fact it is desirable since gas phase allyl-radical is known to be the precursor of combustion products. On chlorinated RuO2(110) surface, desorption Propylene epoxidation reaction was investigated on catalytic surfaces of chlorinated copper(I) oxide and ruthenium(IV) oxide using periodic density functional theory (DFT). Cu2O(001) and (110) surface of RuO2 was selected to generate chlorinated surfaces to be used in the study. Besides epoxidation, other reactions that compete with epoxidation were also studied such as formations of allyl-radical, acrolein, acetone on chlorinated Cu2O(001) and formations of propionaldehyde, allyl-radical and acetone on chlorinated RuO2(110) surface. Path of each reaction was determined by CI-NEB method and transition state analyses. Generally accepted stable surface intermediate mechanism was utilized in reactions to final products. The surface intermediate favorable on the surfaces in this study was determined to be the intermediate that is not preferable on metallic surfaces under low oxygen. On chlorinated Cu2O(001) surface, formation of propylene oxide, acetone and acrolein have higher probability than gas phase allyl-radical since the desorption energy of allyl-radical was calculated to be 70kcal/mol which is a relatively high value. In fact it is desirable since gas phase allyl-radical is known to be the precursor of combustion products. On chlorinated RuO2(110) surface, desorption observed to be possible on chlorinated RuO2(110) surface but not possible on chlorinated Cu2O(001). When activation barriers and desorption energies of all possible reactions are compared on chlorinated RuO2(110) surface; gas phase propylene oxide generated directly seems as the preferable product with allylradical although it was computed to have high desorption energy. Comparison of activation barriers obtained in this study on chlorinated Cu2O(001) with the barriers of nonchlorinated surface revealed chlorine slightly increases the activation barrier of unwanted allylic hydrogen stripping and hence slightly decreases the probability of occurance. When chlorine is placed closer to reaction site, activation barrier of allylic hydrogen stripping reaction increases further. The effect of chlorine might be electronic since the charge of oxygen at reaction site slightly becomes less negative when the place of chlorine gets closer to the reaction site on the surface. Similar comparison between chlorinated and nonchlorinated RuO2(110) surfaces revealed that chlorine addition does not improve the surface toward propylene oxide formation, rather it is detrimental as chlorine addition caused a decrease in unwanted allylic hydrogen stripping reaction.

Subject Keywords

Chemical engineering., Organic compounds.

URI

http://etd.lib.metu.edu.tr/upload/12613918/index.pdf
https://hdl.handle.net/11511/21199

Collections

Graduate School of Natural and Applied Sciences, Thesis