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Title: Heterogeneous Metal-Free Hydrogenation over Defect-Laden Hexagonal Boron Nitride

Catalytic hydrogenation is an important process used for the production of everything from foods to fuels. Current heterogeneous implementations of this process utilize metals as the active species. Until recently, catalytic heterogeneous hydrogenation over a metal-free solid was unknown; implementation of such a system would eliminate the health, environmental, and economic concerns associated with metal-based catalysts. We report good hydrogenation rates and yields for a metal-free heterogeneous hydrogenation catalyst as well as its unique hydrogenation mechanism. We achieved catalytic hydrogenation of olefins over defect-laden h-BN (dh-BN) in a reactor designed to maximize the defects in h-BN sheets. Good yields (>90%) and turnover frequencies (6 × 10 –5–4 × 10 –3) were obtained for the hydrogenation of propene, cyclohexene, 1,1-diphenylethene, (E)- and (Z)-1,2-diphenylethene, octadecene, and benzylideneacetophenone. Temperature-programmed desorption of ethene over processed h-BN indicates the formation of a highly defective structure. Solid-state NMR (SSNMR) measurements of dh-BN with high and low propene surface coverages show four different binding modes. The introduction of defects into h-BN creates regions of electronic deficiency and excess. Density functional theory calculations show that both the alkene and hydrogen-bond order are reduced over four specific defects: boron substitution for nitrogen (B N), vacancies (V B and Vmore » N), and Stone–Wales defects. SSNMR and binding-energy calculations show that V N are most likely the catalytically active sites. Our work shows that catalytic sites can be introduced into a material previously thought to be catalytically inactive through the production of defects.« less
Authors:
 [1] ;  [1] ;  [2] ;  [2] ;  [2] ;  [2] ;  [2] ; ORCiD logo [3] ; ORCiD logo [3] ;  [1] ;  [2] ; ORCiD logo [4]
  1. Univ. of Central Florida, Orlando, FL (United States). Dept. of Chemistry
  2. Univ. of Central Florida, Orlando, FL (United States). Dept. of Physics
  3. Northwestern Univ., Evanston, IL (United States). International Inst. for Nanotechnology
  4. Univ. of Central Florida, Orlando, FL (United States). Dept. of Physics, Cluster for the Rational Design of Catalysts for Energy Applications and Propulsion and Center for Advanced Turbomachinery and Energy Research
Publication Date:
Grant/Contract Number:
FG02-07ER15842
Type:
Published Article
Journal Name:
ACS Omega
Additional Journal Information:
Journal Volume: 1; Journal Issue: 6; Journal ID: ISSN 2470-1343
Publisher:
American Chemical Society (ACS)
Research Org:
Univ. of Central Florida, Orlando, FL (United States)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Catalysts; Hydrogenation; Organic compounds and Functional groups; Quantum mechanical methods
OSTI Identifier:
1336965
Alternate Identifier(s):
OSTI ID: 1339948

Nash, David J., Restrepo, David T., Parra, Natalia S., Giesler, Kyle E., Penabade, Rachel A., Aminpour, Maral, Le, Duy, Li, Zhanyong, Farha, Omar K., Harper, James K., Rahman, Talat S., and Blair, Richard G.. Heterogeneous Metal-Free Hydrogenation over Defect-Laden Hexagonal Boron Nitride. United States: N. p., Web. doi:10.1021/acsomega.6b00315.
Nash, David J., Restrepo, David T., Parra, Natalia S., Giesler, Kyle E., Penabade, Rachel A., Aminpour, Maral, Le, Duy, Li, Zhanyong, Farha, Omar K., Harper, James K., Rahman, Talat S., & Blair, Richard G.. Heterogeneous Metal-Free Hydrogenation over Defect-Laden Hexagonal Boron Nitride. United States. doi:10.1021/acsomega.6b00315.
Nash, David J., Restrepo, David T., Parra, Natalia S., Giesler, Kyle E., Penabade, Rachel A., Aminpour, Maral, Le, Duy, Li, Zhanyong, Farha, Omar K., Harper, James K., Rahman, Talat S., and Blair, Richard G.. 2016. "Heterogeneous Metal-Free Hydrogenation over Defect-Laden Hexagonal Boron Nitride". United States. doi:10.1021/acsomega.6b00315.
@article{osti_1336965,
title = {Heterogeneous Metal-Free Hydrogenation over Defect-Laden Hexagonal Boron Nitride},
author = {Nash, David J. and Restrepo, David T. and Parra, Natalia S. and Giesler, Kyle E. and Penabade, Rachel A. and Aminpour, Maral and Le, Duy and Li, Zhanyong and Farha, Omar K. and Harper, James K. and Rahman, Talat S. and Blair, Richard G.},
abstractNote = {Catalytic hydrogenation is an important process used for the production of everything from foods to fuels. Current heterogeneous implementations of this process utilize metals as the active species. Until recently, catalytic heterogeneous hydrogenation over a metal-free solid was unknown; implementation of such a system would eliminate the health, environmental, and economic concerns associated with metal-based catalysts. We report good hydrogenation rates and yields for a metal-free heterogeneous hydrogenation catalyst as well as its unique hydrogenation mechanism. We achieved catalytic hydrogenation of olefins over defect-laden h-BN (dh-BN) in a reactor designed to maximize the defects in h-BN sheets. Good yields (>90%) and turnover frequencies (6 × 10–5–4 × 10–3) were obtained for the hydrogenation of propene, cyclohexene, 1,1-diphenylethene, (E)- and (Z)-1,2-diphenylethene, octadecene, and benzylideneacetophenone. Temperature-programmed desorption of ethene over processed h-BN indicates the formation of a highly defective structure. Solid-state NMR (SSNMR) measurements of dh-BN with high and low propene surface coverages show four different binding modes. The introduction of defects into h-BN creates regions of electronic deficiency and excess. Density functional theory calculations show that both the alkene and hydrogen-bond order are reduced over four specific defects: boron substitution for nitrogen (BN), vacancies (VB and VN), and Stone–Wales defects. SSNMR and binding-energy calculations show that VN are most likely the catalytically active sites. Our work shows that catalytic sites can be introduced into a material previously thought to be catalytically inactive through the production of defects.},
doi = {10.1021/acsomega.6b00315},
journal = {ACS Omega},
number = 6,
volume = 1,
place = {United States},
year = {2016},
month = {12}
}