Mechanism of selective benzene hydroxylation catalyzed by iron-containing zeolites
Abstract
A direct, catalytic conversion of benzene to phenol would have wide-reaching economic impacts. Fe zeolites exhibit a remarkable combination of high activity and selectivity in this conversion, leading to their past implementation at the pilot plant level. There were, however, issues related to catalyst deactivation for this process. Mechanistic insight could resolve these issues, and also provide a blueprint for achieving high performance in selective oxidation catalysis. Recently, we demonstrated that the active site of selective hydrocarbon oxidation in Fe zeolites, named α-O, is an unusually reactive Fe(IV)=O species. Here in this paper, we apply advanced spectroscopic techniques to determine that the reaction of this Fe(IV)=O intermediate with benzene in fact regenerates the reduced Fe(II) active site, enabling catalytic turnover. At the same time, a small fraction of Fe(III)-phenolate poisoned active sites form, defining a mechanism for catalyst deactivation. Density-functional theory calculations provide further insight into the experimentally defined mechanism. The extreme reactivity of α-O significantly tunes down (eliminates) the rate-limiting barrier for aromatic hydroxylation, leading to a diffusion-limited reaction coordinate. This favors hydroxylation of the rapidly diffusing benzene substrate over the slowly diffusing (but more reactive) oxygenated product, thereby enhancing selectivity. This defines a mechanism to simultaneously attain highmore »
- Authors:
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1482162
- Alternate Identifier(s):
- OSTI ID: 1490261; OSTI ID: 1490638
- Grant/Contract Number:
- AC02-06CH11357; AC02-76SF00515; DGE-11474; CHE-1660611; Munger; Pollock; Reynolds; Robinson; Smith & Yoedicke Stanford Graduate Fellowship; 12L0715N; V417018N; G0A2216N; Gerhard Casper Stanford Graduate Fellowship; P41GM103393
- Resource Type:
- Journal Article: Published Article
- Journal Name:
- Proceedings of the National Academy of Sciences of the United States of America
- Additional Journal Information:
- Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 115 Journal Issue: 48; Journal ID: ISSN 0027-8424
- Publisher:
- National Academy of Sciences, Washington, DC (United States)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis; spectroscopy; zeolites
Citation Formats
Snyder, Benjamin E. R., Bols, Max L., Rhoda, Hannah M., Vanelderen, Pieter, Böttger, Lars H., Braun, Augustin, Yan, James J., Hadt, Ryan G., Babicz, Jr., Jeffrey T., Hu, Michael Y., Zhao, Jiyong, Alp, E. Ercan, Hedman, Britt, Hodgson, Keith O., Schoonheydt, Robert A., Sels, Bert F., and Solomon, Edward I. Mechanism of selective benzene hydroxylation catalyzed by iron-containing zeolites. United States: N. p., 2018.
Web. doi:10.1073/pnas.1813849115.
Snyder, Benjamin E. R., Bols, Max L., Rhoda, Hannah M., Vanelderen, Pieter, Böttger, Lars H., Braun, Augustin, Yan, James J., Hadt, Ryan G., Babicz, Jr., Jeffrey T., Hu, Michael Y., Zhao, Jiyong, Alp, E. Ercan, Hedman, Britt, Hodgson, Keith O., Schoonheydt, Robert A., Sels, Bert F., & Solomon, Edward I. Mechanism of selective benzene hydroxylation catalyzed by iron-containing zeolites. United States. https://doi.org/10.1073/pnas.1813849115
Snyder, Benjamin E. R., Bols, Max L., Rhoda, Hannah M., Vanelderen, Pieter, Böttger, Lars H., Braun, Augustin, Yan, James J., Hadt, Ryan G., Babicz, Jr., Jeffrey T., Hu, Michael Y., Zhao, Jiyong, Alp, E. Ercan, Hedman, Britt, Hodgson, Keith O., Schoonheydt, Robert A., Sels, Bert F., and Solomon, Edward I. 2018.
"Mechanism of selective benzene hydroxylation catalyzed by iron-containing zeolites". United States. https://doi.org/10.1073/pnas.1813849115.
@article{osti_1482162,
title = {Mechanism of selective benzene hydroxylation catalyzed by iron-containing zeolites},
author = {Snyder, Benjamin E. R. and Bols, Max L. and Rhoda, Hannah M. and Vanelderen, Pieter and Böttger, Lars H. and Braun, Augustin and Yan, James J. and Hadt, Ryan G. and Babicz, Jr., Jeffrey T. and Hu, Michael Y. and Zhao, Jiyong and Alp, E. Ercan and Hedman, Britt and Hodgson, Keith O. and Schoonheydt, Robert A. and Sels, Bert F. and Solomon, Edward I.},
abstractNote = {A direct, catalytic conversion of benzene to phenol would have wide-reaching economic impacts. Fe zeolites exhibit a remarkable combination of high activity and selectivity in this conversion, leading to their past implementation at the pilot plant level. There were, however, issues related to catalyst deactivation for this process. Mechanistic insight could resolve these issues, and also provide a blueprint for achieving high performance in selective oxidation catalysis. Recently, we demonstrated that the active site of selective hydrocarbon oxidation in Fe zeolites, named α-O, is an unusually reactive Fe(IV)=O species. Here in this paper, we apply advanced spectroscopic techniques to determine that the reaction of this Fe(IV)=O intermediate with benzene in fact regenerates the reduced Fe(II) active site, enabling catalytic turnover. At the same time, a small fraction of Fe(III)-phenolate poisoned active sites form, defining a mechanism for catalyst deactivation. Density-functional theory calculations provide further insight into the experimentally defined mechanism. The extreme reactivity of α-O significantly tunes down (eliminates) the rate-limiting barrier for aromatic hydroxylation, leading to a diffusion-limited reaction coordinate. This favors hydroxylation of the rapidly diffusing benzene substrate over the slowly diffusing (but more reactive) oxygenated product, thereby enhancing selectivity. This defines a mechanism to simultaneously attain high activity (conversion) and selectivity, enabling the efficient oxidative upgrading of inert hydrocarbon substrates.},
doi = {10.1073/pnas.1813849115},
url = {https://www.osti.gov/biblio/1482162},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
issn = {0027-8424},
number = 48,
volume = 115,
place = {United States},
year = {Wed Nov 14 00:00:00 EST 2018},
month = {Wed Nov 14 00:00:00 EST 2018}
}
Web of Science
Works referenced in this record:
Kinetic isotope effects and mechanism of biomimetic oxidation of methane and benzene on FeZSM-5 zeolite
journal, August 1997
- Dubkov, K. A.; Sobolev, V. I.; Talsi, E. P.
- Journal of Molecular Catalysis A: Chemical, Vol. 123, Issue 2-3
The role of iron in N2O decomposition on ZSM-5 zeolite and reactivity of the surface oxygen formed
journal, July 1990
- Pannov, G. I.; Sobolev, V. I.; Kharitonov, A. S.
- Journal of Molecular Catalysis, Vol. 61, Issue 1
Combined Experimental and Theoretical Study on Aromatic Hydroxylation by Mononuclear Nonheme Iron(IV)−Oxo Complexes
journal, May 2007
- de Visser, Sam P.; Oh, Kyungeun; Han, Ah-Rim
- Inorganic Chemistry, Vol. 46, Issue 11
Direct Methane−Methanol and Benzene−Phenol Conversions on Fe−ZSM-5 Zeolite: Theoretical Predictions on the Reaction Pathways and Energetics
journal, February 2000
- Yoshizawa, Kazunari; Shiota, Yoshihito; Yumura, Takashi
- The Journal of Physical Chemistry B, Vol. 104, Issue 4
Effect of steaming on the catalytic performance of ZSM-5 zeolite in the selective oxidation of phenol by nitrous oxide
journal, March 2014
- Ivanov, D. P.; Pirutko, L. V.; Panov, G. I.
- Journal of Catalysis, Vol. 311
Stability and reactivity of active sites for direct benzene oxidation to phenol in Fe/ZSM-5: A comprehensive periodic DFT study
journal, December 2011
- Li, Guanna; Pidko, Evgeny A.; van Santen, Rutger A.
- Journal of Catalysis, Vol. 284, Issue 2
Metalloenzymes: the entatic nature of their active sites.
journal, February 1968
- Vallee, B. L.; Williams, R. J.
- Proceedings of the National Academy of Sciences, Vol. 59, Issue 2
The active site of low-temperature methane hydroxylation in iron-containing zeolites
journal, August 2016
- Snyder, Benjamin E. R.; Vanelderen, Pieter; Bols, Max L.
- Nature, Vol. 536, Issue 7616
Iron and Copper Active Sites in Zeolites and Their Correlation to Metalloenzymes
journal, December 2017
- Snyder, Benjamin E. R.; Bols, Max L.; Schoonheydt, Robert A.
- Chemical Reviews, Vol. 118, Issue 5
Nitrous oxide in oxidation chemistry and catalysis: application and production
journal, February 2005
- Parmon, V. N.; Panov, G. I.; Uriarte, A.
- Catalysis Today, Vol. 100, Issue 1-2
Resonance Raman spectra of high- and low-spin ferric phenolates. Models for dioxygenases and nitrile hydratase
journal, May 1990
- Carrano, Carl J.; Carrano, Mary W.; Sharma, Kamala
- Inorganic Chemistry, Vol. 29, Issue 10
Geometric and Electronic Structure/Function Correlations in Non-Heme Iron Enzymes
journal, January 2000
- Solomon, Edward I.; Brunold, Thomas C.; Davis, Mindy I.
- Chemical Reviews, Vol. 100, Issue 1
Mechanism of Aromatic Hydroxylation by an Activated FeIVO Core in Tetrahydrobiopterin-Dependent Hydroxylases
journal, September 2003
- Bassan, Arianna; Blomberg, Margareta R. A.; Siegbahn, Per E. M.
- Chemistry - A European Journal, Vol. 9, Issue 17
Direct Spectroscopic Observation of Fe(III)−Phenolate Complex Formed From the Reaction of Benzene With Peroxide Species on Fe/ZSM-5 At Room Temperature
journal, May 2008
- Xia, Haian; Sun, Keqiang; Sun, Keju
- The Journal of Physical Chemistry C, Vol. 112, Issue 24
Kinetics of benzene to phenol oxidation over Fe-ZSM-5 catalyst
journal, August 2003
- Ivanov, A. A.; Chernyavsky, V. S.; Gross, M. J.
- Applied Catalysis A: General, Vol. 249, Issue 2
Mechanism of Aromatic Amino Acid Hydroxylation †
journal, December 2003
- Fitzpatrick, Paul F.
- Biochemistry, Vol. 42, Issue 48
Counterdiffusion of liquid hydrocarbons in type Y zeolite: Effect of molecular size, molecular type, and direction of diffusion
journal, July 1972
- Moore, Rebecca M.; Katzer, James R.
- AIChE Journal, Vol. 18, Issue 4
High-Valent Iron(IV)–Oxo Complexes of Heme and Non-Heme Ligands in Oxygenation Reactions
journal, July 2007
- Nam, Wonwoo
- Accounts of Chemical Research, Vol. 40, Issue 7
Model studies of iron-tyrosinate proteins
journal, February 1985
- Pyrz, Joseph W.; Roe, A. Lawrence; Stern, Lawrence J.
- Journal of the American Chemical Society, Vol. 107, Issue 3
Mechanistic Insight into the Aromatic Hydroxylation by High-Valent Iron(IV)-oxo Porphyrin π-Cation Radical Complexes
journal, August 2007
- Kang, Min-Jung; Song, Woon Ju; Han, Ah-Rim
- The Journal of Organic Chemistry, Vol. 72, Issue 16
Spectroscopic and electronic structure studies of aromatic electrophilic attack and hydrogen-atom abstraction by non-heme iron enzymes
journal, August 2006
- Neidig, M. L.; Decker, A.; Choroba, O. W.
- Proceedings of the National Academy of Sciences, Vol. 103, Issue 35
A Density Functional Theory Study of Direct Oxidation of Benzene to Phenol by N 2 O on a [FeO] 1+ -ZSM-5 Cluster
journal, June 2010
- Fellah, Mehmet Ferdi; Onal, Isik; van Santen, Rutger A.
- The Journal of Physical Chemistry C, Vol. 114, Issue 29
Catalytic performance of sheet-like Fe/ZSM-5 zeolites for the selective oxidation of benzene with nitrous oxide
journal, March 2013
- Koekkoek, A. J. J.; Kim, W.; Degirmenci, V.
- Journal of Catalysis, Vol. 299
A hierarchical Fe/ZSM-5 zeolite with superior catalytic performance for benzene hydroxylation to phenol
journal, January 2009
- Xin, Hongchuan; Koekkoek, Arjan; Yang, Qihua
- Chemical Communications, Issue 48
Structural characterization of a non-heme iron active site in zeolites that hydroxylates methane
journal, April 2018
- Snyder, Benjamin E. R.; Böttger, Lars H.; Bols, Max L.
- Proceedings of the National Academy of Sciences, Vol. 115, Issue 18
Stable Fe/ZSM-5 Nanosheet Zeolite Catalysts for the Oxidation of Benzene to Phenol
journal, March 2017
- Meng, Lingqian; Zhu, Xiaochun; Hensen, Emiel J. M.
- ACS Catalysis, Vol. 7, Issue 4
Magnetic circular dichroism spectroscopy as a probe of the geometric and electronic structure of non-heme ferrous enzymes
journal, October 1995
- Solomon, Edward I.; Pavel, Elizabeth G.; Loeb, Kelly E.
- Coordination Chemistry Reviews, Vol. 144
Nuclear resonance vibrational spectroscopy ? NRVS
journal, January 2005
- Scheidt, W.; Durbin, S.; Sage, J.
- Journal of Inorganic Biochemistry, Vol. 99, Issue 1
Hydroxylation-Induced Migration: The NIH Shift: Recent experiments reveal an unexpected and general result of enzymatic hydroxylation of aromatic compounds
journal, September 1967
- Guroff, G.; Renson, J.; Udenfriend, S.
- Science, Vol. 157, Issue 3796
Mechanistic insights into the biomimetic catalytic hydroxylation of arenes by a molecular Fe(NHC) complex
journal, August 2017
- Lindhorst, Anja C.; Drees, Markus; Bonrath, Werner
- Journal of Catalysis, Vol. 352