Ethane Dehydrogenation on Single and Dual Centers of Ga-modified γ-Al2O3
Abstract
Density-functional theory calculations and microkinetic analysis are used to investigate the efficacy of Ga-modified γ-Al2O3 (110) surfaces for the catalytic dehydrogenation of ethane and elucidate the synergy between Ga and Al sites. The model surfaces are modified by either Ga grafting or doping. We consider and analyze numerous active sites and rank them using microkinetic analysis. The kinetic parameters obtained from microkinetic modelling are compared with experimental values for ethane dehydrogenation over Ga2O3-Al2O3 mixed oxides prepared by co-precipitation. The dominant reaction pathway proceeds via heterolytic C-H bond dissociation to a surface proton and a metal-carbanion intermediate that undergoes β-hydride elimination. We find that grafted Ga sites are catalytically inactive. In contrast, Ga-doped sites exhibit fivefold enhancement in catalytic activity when compared to the sites on pristine Al2O3, owed to the synergy between neighboring AlIII and GaIV sites. Furthermore, we model and investigate the effect of surface hydroxylation, demonstrate how surface water interferes with the aforementioned synergy between AlIII and GaIV sites and discuss the implications for the catalytic activity of the modified surfaces. Here, an increase in the partial pressure of H2O significantly increases the apparent activation energies of dehydrogenation and interestingly changes the most active site.
- Publication Date:
- Research Org.:
- RAPID Manufacturing Inst., Newark, DE (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Energy Efficiency Office. Advanced Manufacturing Office
- OSTI Identifier:
- 1768841
- Grant/Contract Number:
- EE0007888
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Catalysis
- Additional Journal Information:
- Journal Volume: 11; Journal Issue: 3; Journal ID: ISSN 2155-5435
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; ethane; dehydrogenation; Ga-modified alumina; grafted-Ga; Ga doping; density-functional theory; kinetics; microkinetic modeling; hydrocarbons; oxides; activation energy; organic reactions; catalysts
Citation Formats
Batchu, Sai Praneet, Wang, Hsuan-Lan, Chen, Weiqi, Zheng, Weiqing, Caratzoulas, Stavros, Lobo, Raul F., and Vlachos, Dionisios G. Ethane Dehydrogenation on Single and Dual Centers of Ga-modified γ-Al2O3. United States: N. p., 2021.
Web. doi:10.1021/acscatal.0c03536.
Batchu, Sai Praneet, Wang, Hsuan-Lan, Chen, Weiqi, Zheng, Weiqing, Caratzoulas, Stavros, Lobo, Raul F., & Vlachos, Dionisios G. Ethane Dehydrogenation on Single and Dual Centers of Ga-modified γ-Al2O3. United States. https://doi.org/10.1021/acscatal.0c03536
Batchu, Sai Praneet, Wang, Hsuan-Lan, Chen, Weiqi, Zheng, Weiqing, Caratzoulas, Stavros, Lobo, Raul F., and Vlachos, Dionisios G. Wed .
"Ethane Dehydrogenation on Single and Dual Centers of Ga-modified γ-Al2O3". United States. https://doi.org/10.1021/acscatal.0c03536. https://www.osti.gov/servlets/purl/1768841.
@article{osti_1768841,
title = {Ethane Dehydrogenation on Single and Dual Centers of Ga-modified γ-Al2O3},
author = {Batchu, Sai Praneet and Wang, Hsuan-Lan and Chen, Weiqi and Zheng, Weiqing and Caratzoulas, Stavros and Lobo, Raul F. and Vlachos, Dionisios G.},
abstractNote = {Density-functional theory calculations and microkinetic analysis are used to investigate the efficacy of Ga-modified γ-Al2O3 (110) surfaces for the catalytic dehydrogenation of ethane and elucidate the synergy between Ga and Al sites. The model surfaces are modified by either Ga grafting or doping. We consider and analyze numerous active sites and rank them using microkinetic analysis. The kinetic parameters obtained from microkinetic modelling are compared with experimental values for ethane dehydrogenation over Ga2O3-Al2O3 mixed oxides prepared by co-precipitation. The dominant reaction pathway proceeds via heterolytic C-H bond dissociation to a surface proton and a metal-carbanion intermediate that undergoes β-hydride elimination. We find that grafted Ga sites are catalytically inactive. In contrast, Ga-doped sites exhibit fivefold enhancement in catalytic activity when compared to the sites on pristine Al2O3, owed to the synergy between neighboring AlIII and GaIV sites. Furthermore, we model and investigate the effect of surface hydroxylation, demonstrate how surface water interferes with the aforementioned synergy between AlIII and GaIV sites and discuss the implications for the catalytic activity of the modified surfaces. Here, an increase in the partial pressure of H2O significantly increases the apparent activation energies of dehydrogenation and interestingly changes the most active site.},
doi = {10.1021/acscatal.0c03536},
journal = {ACS Catalysis},
number = 3,
volume = 11,
place = {United States},
year = {Wed Jan 13 00:00:00 EST 2021},
month = {Wed Jan 13 00:00:00 EST 2021}
}
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