Photolysis of the CO<sub>2</sub> + K/Au(111) System

Farkas, Arnold Péter; Solymosi, F.

doi:10.1021/jp101841b

Cited by 7 publications

(6 citation statements)

References 36 publications

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“…As known CO 2 is a very stable molecule. In previous studies performed on TiO 2 -supported metals [27] and metal single crystals including Au(1 1 1) [28][29][30][31], it was revealed that the donation of electrons from the catalyst to the antibonding p level of CO 2 leads to the formation of reactive negatively charged CO 2 dÀ . Based on this consideration we propose the occurrence of following steps for the reaction of CO 2 and C 2 H 6…”

Section: Discussionmentioning

confidence: 99%

Reactions of ethane with CO2 over supported Au

Tóth¹,

Halasi²,

Solymosi³

2015

Journal of Catalysis

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Reaction of C 2 H 6 with CO 2 Au catalyst Effects of supports Electronic interaction between Au and oxides a b s t r a c tThe dehydrogenation of C 2 H 6 and its reaction with CO 2 have been investigated on Au deposited on various oxides. Both reactions occurred at relatively high temperatures, above 650 K. Ethylene formed in the dehydrogenation process with high selectivity, 94-98%, on most of the catalysts. The conversion of C 2 H 6 varied with the nature of support and fell in the range of 3-19%. Adding CO 2 to C 2 H 6 only slightly influenced the reaction of C 2 H 6 on Au/MgO and Au/Al 2 O 3 , but markedly increased the conversion of C 2 H 6 and changed its reaction pathways on Au deposited on n-type TiO 2 , CeO 2 and ZnO. Taking into account the properties of these oxides, we came to the conclusion that their electric behavior and not their defect structure play a dominant role in the enhanced activity of Au deposited on these supports. Based on the different work functions, an electronic interaction between Au particles and these oxides is proposed, which facilitates the formation of reactive negatively charged CO 2 .

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Section: Discussionmentioning

confidence: 99%

Reactions of ethane with CO2 over supported Au

Tóth¹,

Halasi²,

Solymosi³

2015

Journal of Catalysis

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“…For the optimization of the TS structure, we introduced the image function method together with the level-shift Newton-Raphson method. 38,39 This procedure is effective when one uses an appropriate initial guess, which is close to the transition-state (TS) structure.…”

Section: Theoretical Background: Ap Methodsmentioning

confidence: 99%

Reinvestigation of the Reaction of Ethylene and Singlet Oxygen by the Approximate Spin Projection Method. Comparison with Multireference Coupled-Cluster Calculations

et al. 2010

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We quantify a spin contamination error caused by a broken-symmetry (BS) method on the geometry at the stationary points and barrier heights of the [2 + 2] reaction between singlet oxygen and ethylene, which goes through a diradical intermediate. Several hybrid GGA, hybrid meta-GGA, and long-range corrected hybrid functionals, O3LYP, B3LYP, PBE0, MPW1B95, BHandHLYP, and omegaB97X, are examined to elucidate their original nature without the spin contamination error. For that purpose, the geometry of each reaction step for the BS state as well as its total energy is corrected by using an approximate spin projection method. The CCSD and CCSD(T) single-point calculations are also carried out at optimized geometries at the DFT level to confirm the results of the DFT methods. The single-point calculations by means of Mukherjee's multireference coupled cluster with single and double excitations at CASSCF(10e,8o)-optimized geometries are also presented to assess the DFT methods. After the energy and geometry corrections, the barrier height of each functional is consistent with conventional closed-shell-type reactions even in the reaction involving singlet diradical species. We also find that the spin contamination error on the geometric change is not negligible especially at the early stage of the reaction ( approximately 3 kcal/mol), where the triplet state is the ground state.

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“…importance of the activation of CO 2 appeared in our recent study dealing with the catalytic and photocatalytic reaction of H 2 þ CO 2 on Au deposited on various n-type oxides [52,53].…”

Section: Catalytic Studymentioning

confidence: 99%