Liquid-Phase Hydrogenation of 1-Phenyl-1-propyne on the Pd<sub>1</sub>Ag<sub>3</sub>/Al<sub>2</sub>O<sub>3</sub> Single-Atom Alloy Catalyst: Kinetic Modeling and the Reaction Mechanism
This research was focused on studying the performance of the Pd<sub>1</sub>Ag<sub>3</sub>/Al<sub>2</sub>O<sub>3</sub> single-atom alloy (SAA) in the liquid-phase hydrogenation of di-substituted alkyne (1-phenyl-1-propyne), and development of a kinetic...
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2021-12-01
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| author | Alexander V. Rassolov Igor S. Mashkovsky Galina N. Baeva Galina O. Bragina Nadezhda S. Smirnova Pavel V. Markov Andrey V. Bukhtiyarov Johan Wärnå Alexander Yu. Stakheev Dmitry Yu. Murzin |
| author_facet | Alexander V. Rassolov Igor S. Mashkovsky Galina N. Baeva Galina O. Bragina Nadezhda S. Smirnova Pavel V. Markov Andrey V. Bukhtiyarov Johan Wärnå Alexander Yu. Stakheev Dmitry Yu. Murzin |
| author_sort | Alexander V. Rassolov |
| collection | DOAJ |
| description | This research was focused on studying the performance of the Pd<sub>1</sub>Ag<sub>3</sub>/Al<sub>2</sub>O<sub>3</sub> single-atom alloy (SAA) in the liquid-phase hydrogenation of di-substituted alkyne (1-phenyl-1-propyne), and development of a kinetic model adequately describing the reaction kinetic being also consistent with the reaction mechanism suggested for alkyne hydrogenation on SAA catalysts. Formation of the SAA structure on the surface of PdAg<sub>3</sub> nanoparticles was confirmed by DRIFTS-CO, revealing the presence of single-atom Pd<sub>1</sub> sites surrounded by Ag atoms (characteristic symmetrical band at 2046 cm<sup>−1</sup>) and almost complete absence of multiatomic Pd<sub>n</sub> surface sites (<0.2%). The catalyst demonstrated excellent selectivity in alkyne formation (95–97%), which is essentially independent of P(H<sub>2</sub>) and alkyne concentration. It is remarkable that selectivity remains almost constant upon variation of 1-phenyl-1-propyne (1-Ph-1-Pr) conversion from 5 to 95–98%, which indicates that a direct alkyne to alkane hydrogenation is negligible over Pd<sub>1</sub>Ag<sub>3</sub> catalyst. The kinetics of 1-phenyl-1-propyne hydrogenation on Pd<sub>1</sub>Ag<sub>3</sub>/Al<sub>2</sub>O<sub>3</sub> was adequately described by the Langmuir-Hinshelwood type of model developed on the basis of the reaction mechanism, which suggests competitive H<sub>2</sub> and alkyne/alkene adsorption on single atom Pd<sub>1</sub> centers surrounded by inactive Ag atoms. The model is capable to describe kinetic characteristics of 1-phenyl-1-propyne hydrogenation on SAA Pd<sub>1</sub>Ag<sub>3</sub>/Al<sub>2</sub>O<sub>3</sub> catalyst with the excellent explanation degree (98.9%). |
| first_indexed | 2024-03-10T03:26:35Z |
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| institution | Directory Open Access Journal |
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| language | English |
| last_indexed | 2024-03-10T03:26:35Z |
| publishDate | 2021-12-01 |
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| spelling | doaj.art-a56de66d915b4aa3894f931d8cf6676a2023-11-23T09:50:32ZengMDPI AGNanomaterials2079-49912021-12-011112328610.3390/nano11123286Liquid-Phase Hydrogenation of 1-Phenyl-1-propyne on the Pd<sub>1</sub>Ag<sub>3</sub>/Al<sub>2</sub>O<sub>3</sub> Single-Atom Alloy Catalyst: Kinetic Modeling and the Reaction MechanismAlexander V. Rassolov0Igor S. Mashkovsky1Galina N. Baeva2Galina O. Bragina3Nadezhda S. Smirnova4Pavel V. Markov5Andrey V. Bukhtiyarov6Johan Wärnå7Alexander Yu. Stakheev8Dmitry Yu. Murzin9N.D. Zelinsky Institute of Organic Chemistry RAS, Leninsky Prospect 47, 119991 Moscow, RussiaN.D. Zelinsky Institute of Organic Chemistry RAS, Leninsky Prospect 47, 119991 Moscow, RussiaN.D. Zelinsky Institute of Organic Chemistry RAS, Leninsky Prospect 47, 119991 Moscow, RussiaN.D. Zelinsky Institute of Organic Chemistry RAS, Leninsky Prospect 47, 119991 Moscow, RussiaN.D. Zelinsky Institute of Organic Chemistry RAS, Leninsky Prospect 47, 119991 Moscow, RussiaN.D. Zelinsky Institute of Organic Chemistry RAS, Leninsky Prospect 47, 119991 Moscow, RussiaSynchrotron Radiation Facility SKIF, Boreskov Institute of Catalysis SB RAS, Nikol’skiy Prospekt 1, 630559 Kol’tsovo, RussiaLaboratory of Industrial Chemistry and Reaction Engineering, Faculty of Science and Engineering, Åbo Akademi University, FI-20500 Turku, FinlandN.D. Zelinsky Institute of Organic Chemistry RAS, Leninsky Prospect 47, 119991 Moscow, RussiaLaboratory of Industrial Chemistry and Reaction Engineering, Faculty of Science and Engineering, Åbo Akademi University, FI-20500 Turku, FinlandThis research was focused on studying the performance of the Pd<sub>1</sub>Ag<sub>3</sub>/Al<sub>2</sub>O<sub>3</sub> single-atom alloy (SAA) in the liquid-phase hydrogenation of di-substituted alkyne (1-phenyl-1-propyne), and development of a kinetic model adequately describing the reaction kinetic being also consistent with the reaction mechanism suggested for alkyne hydrogenation on SAA catalysts. Formation of the SAA structure on the surface of PdAg<sub>3</sub> nanoparticles was confirmed by DRIFTS-CO, revealing the presence of single-atom Pd<sub>1</sub> sites surrounded by Ag atoms (characteristic symmetrical band at 2046 cm<sup>−1</sup>) and almost complete absence of multiatomic Pd<sub>n</sub> surface sites (<0.2%). The catalyst demonstrated excellent selectivity in alkyne formation (95–97%), which is essentially independent of P(H<sub>2</sub>) and alkyne concentration. It is remarkable that selectivity remains almost constant upon variation of 1-phenyl-1-propyne (1-Ph-1-Pr) conversion from 5 to 95–98%, which indicates that a direct alkyne to alkane hydrogenation is negligible over Pd<sub>1</sub>Ag<sub>3</sub> catalyst. The kinetics of 1-phenyl-1-propyne hydrogenation on Pd<sub>1</sub>Ag<sub>3</sub>/Al<sub>2</sub>O<sub>3</sub> was adequately described by the Langmuir-Hinshelwood type of model developed on the basis of the reaction mechanism, which suggests competitive H<sub>2</sub> and alkyne/alkene adsorption on single atom Pd<sub>1</sub> centers surrounded by inactive Ag atoms. The model is capable to describe kinetic characteristics of 1-phenyl-1-propyne hydrogenation on SAA Pd<sub>1</sub>Ag<sub>3</sub>/Al<sub>2</sub>O<sub>3</sub> catalyst with the excellent explanation degree (98.9%).https://www.mdpi.com/2079-4991/11/12/3286single-atom alloy catalystalkynealkene selectivityhydrogenation1-phenyl-1-propynekinetic modeling |
| spellingShingle | Alexander V. Rassolov Igor S. Mashkovsky Galina N. Baeva Galina O. Bragina Nadezhda S. Smirnova Pavel V. Markov Andrey V. Bukhtiyarov Johan Wärnå Alexander Yu. Stakheev Dmitry Yu. Murzin Liquid-Phase Hydrogenation of 1-Phenyl-1-propyne on the Pd<sub>1</sub>Ag<sub>3</sub>/Al<sub>2</sub>O<sub>3</sub> Single-Atom Alloy Catalyst: Kinetic Modeling and the Reaction Mechanism Nanomaterials single-atom alloy catalyst alkyne alkene selectivity hydrogenation 1-phenyl-1-propyne kinetic modeling |
| title | Liquid-Phase Hydrogenation of 1-Phenyl-1-propyne on the Pd<sub>1</sub>Ag<sub>3</sub>/Al<sub>2</sub>O<sub>3</sub> Single-Atom Alloy Catalyst: Kinetic Modeling and the Reaction Mechanism |
| title_full | Liquid-Phase Hydrogenation of 1-Phenyl-1-propyne on the Pd<sub>1</sub>Ag<sub>3</sub>/Al<sub>2</sub>O<sub>3</sub> Single-Atom Alloy Catalyst: Kinetic Modeling and the Reaction Mechanism |
| title_fullStr | Liquid-Phase Hydrogenation of 1-Phenyl-1-propyne on the Pd<sub>1</sub>Ag<sub>3</sub>/Al<sub>2</sub>O<sub>3</sub> Single-Atom Alloy Catalyst: Kinetic Modeling and the Reaction Mechanism |
| title_full_unstemmed | Liquid-Phase Hydrogenation of 1-Phenyl-1-propyne on the Pd<sub>1</sub>Ag<sub>3</sub>/Al<sub>2</sub>O<sub>3</sub> Single-Atom Alloy Catalyst: Kinetic Modeling and the Reaction Mechanism |
| title_short | Liquid-Phase Hydrogenation of 1-Phenyl-1-propyne on the Pd<sub>1</sub>Ag<sub>3</sub>/Al<sub>2</sub>O<sub>3</sub> Single-Atom Alloy Catalyst: Kinetic Modeling and the Reaction Mechanism |
| title_sort | liquid phase hydrogenation of 1 phenyl 1 propyne on the pd sub 1 sub ag sub 3 sub al sub 2 sub o sub 3 sub single atom alloy catalyst kinetic modeling and the reaction mechanism |
| topic | single-atom alloy catalyst alkyne alkene selectivity hydrogenation 1-phenyl-1-propyne kinetic modeling |
| url | https://www.mdpi.com/2079-4991/11/12/3286 |
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