Mechanism of selective benzene hydroxylation catalyzed by iron-containing zeolites

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.

doi:10.1073/pnas.1813849115

Title: Mechanism of selective benzene hydroxylation catalyzed by iron-containing zeolites

Journal Article · 13 November 2018 · Proceedings of the National Academy of Sciences of the United States of America

DOI: https://doi.org/10.1073/pnas.1813849115 · OSTI ID:1482162

Snyder, Benjamin E. R.; Bols, Max L.; Rhoda, Hannah M.; Vanelderen, Pieter; Böttger, Lars H.; Braun, Augustin;

; Hadt, Ryan G.; Babicz, Jr., Jeffrey T.;

; Zhao, Jiyong; Alp, E. Ercan; Hedman, Britt; Hodgson, Keith O.; Schoonheydt, Robert A.; Sels, Bert F.;

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, 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.

View Journal Article

Cite

Export

Save

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-06CH11357; AC02-76SF00515

OSTI ID:: 1482162

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Issue: 48 Vol. 115; ISSN 0027-8424

Publisher:: National Academy of Sciences, Washington, DC (United States)Copyright Statement

Country of Publication:: United States

Language:: English

References (32)

Counterdiffusion of liquid hydrocarbons in type Y zeolite: Effect of molecular size, molecular type, and direction of diffusion Moore, Rebecca M.; Katzer, James R. AIChE Journal, Vol. 18, Issue 4 https://doi.org/10.1002/aic.690180426	journal	July 1972
Mechanism of Aromatic Hydroxylation by an Activated FeIVO Core in Tetrahydrobiopterin-Dependent Hydroxylases Bassan, Arianna; Blomberg, Margareta R. A.; Siegbahn, Per E. M. Chemistry - A European Journal, Vol. 9, Issue 17 https://doi.org/10.1002/chem.200304768	journal	September 2003
Magnetic circular dichroism spectroscopy as a probe of the geometric and electronic structure of non-heme ferrous enzymes Solomon, Edward I.; Pavel, Elizabeth G.; Loeb, Kelly E. Coordination Chemistry Reviews, Vol. 144 https://doi.org/10.1016/0010-8545(95)01150-N	journal	October 1995
The role of iron in N2O decomposition on ZSM-5 zeolite and reactivity of the surface oxygen formed Pannov, G. I.; Sobolev, V. I.; Kharitonov, A. S. Journal of Molecular Catalysis, Vol. 61, Issue 1 https://doi.org/10.1016/0304-5102(90)85197-P	journal	July 1990
Kinetics of benzene to phenol oxidation over Fe-ZSM-5 catalyst Ivanov, A. A.; Chernyavsky, V. S.; Gross, M. J. Applied Catalysis A: General, Vol. 249, Issue 2 https://doi.org/10.1016/S0926-860X(03)00224-2	journal	August 2003
Kinetic isotope effects and mechanism of biomimetic oxidation of methane and benzene on FeZSM-5 zeolite Dubkov, K. A.; Sobolev, V. I.; Talsi, E. P. Journal of Molecular Catalysis A: Chemical, Vol. 123, Issue 2-3 https://doi.org/10.1016/S1381-1169(97)00051-4	journal	August 1997
Nitrous oxide in oxidation chemistry and catalysis: application and production Parmon, V. N.; Panov, G. I.; Uriarte, A. Catalysis Today, Vol. 100, Issue 1-2 https://doi.org/10.1016/j.cattod.2004.12.012	journal	February 2005
Stability and reactivity of active sites for direct benzene oxidation to phenol in Fe/ZSM-5: A comprehensive periodic DFT study Li, Guanna; Pidko, Evgeny A.; van Santen, Rutger A. Journal of Catalysis, Vol. 284, Issue 2 https://doi.org/10.1016/j.jcat.2011.07.008	journal	December 2011
Catalytic performance of sheet-like Fe/ZSM-5 zeolites for the selective oxidation of benzene with nitrous oxide Koekkoek, A. J. J.; Kim, W.; Degirmenci, V. Journal of Catalysis, Vol. 299 https://doi.org/10.1016/j.jcat.2012.12.002	journal	March 2013
Effect of steaming on the catalytic performance of ZSM-5 zeolite in the selective oxidation of phenol by nitrous oxide Ivanov, D. P.; Pirutko, L. V.; Panov, G. I. Journal of Catalysis, Vol. 311 https://doi.org/10.1016/j.jcat.2013.12.010	journal	March 2014
Mechanistic insights into the biomimetic catalytic hydroxylation of arenes by a molecular Fe(NHC) complex Lindhorst, Anja C.; Drees, Markus; Bonrath, Werner Journal of Catalysis, Vol. 352 https://doi.org/10.1016/j.jcat.2017.06.018	journal	August 2017
Nuclear resonance vibrational spectroscopy ? NRVS Scheidt, W.; Durbin, S.; Sage, J. Journal of Inorganic Biochemistry, Vol. 99, Issue 1 https://doi.org/10.1016/j.jinorgbio.2004.11.004	journal	January 2005
Iron and Copper Active Sites in Zeolites and Their Correlation to Metalloenzymes Snyder, Benjamin E. R.; Bols, Max L.; Schoonheydt, Robert A. Chemical Reviews, Vol. 118, Issue 5 https://doi.org/10.1021/acs.chemrev.7b00344	journal	December 2017
Stable Fe/ZSM-5 Nanosheet Zeolite Catalysts for the Oxidation of Benzene to Phenol Meng, Lingqian; Zhu, Xiaochun; Hensen, Emiel J. M. ACS Catalysis, Vol. 7, Issue 4 https://doi.org/10.1021/acscatal.6b03512	journal	March 2017
High-Valent Iron(IV)–Oxo Complexes of Heme and Non-Heme Ligands in Oxygenation Reactions Nam, Wonwoo Accounts of Chemical Research, Vol. 40, Issue 7 https://doi.org/10.1021/ar700027f	journal	July 2007
Mechanism of Aromatic Amino Acid Hydroxylation ^† Fitzpatrick, Paul F. Biochemistry, Vol. 42, Issue 48 https://doi.org/10.1021/bi035656u	journal	December 2003
Geometric and Electronic Structure/Function Correlations in Non-Heme Iron Enzymes Solomon, Edward I.; Brunold, Thomas C.; Davis, Mindy I. Chemical Reviews, Vol. 100, Issue 1 https://doi.org/10.1021/cr9900275	journal	January 2000
Resonance Raman spectra of high- and low-spin ferric phenolates. Models for dioxygenases and nitrile hydratase Carrano, Carl J.; Carrano, Mary W.; Sharma, Kamala Inorganic Chemistry, Vol. 29, Issue 10 https://doi.org/10.1021/ic00335a021	journal	May 1990
Combined Experimental and Theoretical Study on Aromatic Hydroxylation by Mononuclear Nonheme Iron(IV)−Oxo Complexes de Visser, Sam P.; Oh, Kyungeun; Han, Ah-Rim Inorganic Chemistry, Vol. 46, Issue 11 https://doi.org/10.1021/ic700462h	journal	May 2007
Model studies of iron-tyrosinate proteins Pyrz, Joseph W.; Roe, A. Lawrence; Stern, Lawrence J. Journal of the American Chemical Society, Vol. 107, Issue 3 https://doi.org/10.1021/ja00289a013	journal	February 1985
Mechanistic Insight into the Aromatic Hydroxylation by High-Valent Iron(IV)-oxo Porphyrin π-Cation Radical Complexes Kang, Min-Jung; Song, Woon Ju; Han, Ah-Rim The Journal of Organic Chemistry, Vol. 72, Issue 16 https://doi.org/10.1021/jo070557y	journal	August 2007
A Density Functional Theory Study of Direct Oxidation of Benzene to Phenol by N ₂ O on a [FeO] ¹⁺ -ZSM-5 Cluster Fellah, Mehmet Ferdi; Onal, Isik; van Santen, Rutger A. The Journal of Physical Chemistry C, Vol. 114, Issue 29 https://doi.org/10.1021/jp1023247	journal	June 2010
Direct Spectroscopic Observation of Fe(III)−Phenolate Complex Formed From the Reaction of Benzene With Peroxide Species on Fe/ZSM-5 At Room Temperature Xia, Haian; Sun, Keqiang; Sun, Keju The Journal of Physical Chemistry C, Vol. 112, Issue 24 https://doi.org/10.1021/jp800455x	journal	May 2008
Direct Methane−Methanol and Benzene−Phenol Conversions on Fe−ZSM-5 Zeolite: Theoretical Predictions on the Reaction Pathways and Energetics Yoshizawa, Kazunari; Shiota, Yoshihito; Yumura, Takashi The Journal of Physical Chemistry B, Vol. 104, Issue 4 https://doi.org/10.1021/jp991844b	journal	February 2000
The AlphOx^TM process or the one‐step hydroxylation of benzene into phenol by nitrous oxide. Understanding and tuning the ZSM‐5 catalyst activities Notté, Patrick P. Topics in Catalysis, Vol. 13, Issue 4, p. 387-394 https://doi.org/10.1023/A:1009015223793	journal	September 2000
Cluster Model DFT Study of the Intermediates of Benzene to Phenol Oxidation by N₂O on FeZSM-5 Zeolites Kachurovskaya, Nelly A.; Zhidomirov, Georgii M.; Hensen, Emiel J. M. Catalysis Letters, Vol. 86, Issue 1/3, p. 25-31 https://doi.org/10.1023/A:1022642521434	journal	March 2003
The active site of low-temperature methane hydroxylation in iron-containing zeolites Snyder, Benjamin E. R.; Vanelderen, Pieter; Bols, Max L. Nature, Vol. 536, Issue 7616 https://doi.org/10.1038/nature19059	journal	August 2016
A hierarchical Fe/ZSM-5 zeolite with superior catalytic performance for benzene hydroxylation to phenol Xin, Hongchuan; Koekkoek, Arjan; Yang, Qihua Chemical Communications, Issue 48 https://doi.org/10.1039/b917038c	journal	January 2009
Spectroscopic and electronic structure studies of aromatic electrophilic attack and hydrogen-atom abstraction by non-heme iron enzymes Neidig, M. L.; Decker, A.; Choroba, O. W. Proceedings of the National Academy of Sciences, Vol. 103, Issue 35 https://doi.org/10.1073/pnas.0605067103	journal	August 2006
Structural characterization of a non-heme iron active site in zeolites that hydroxylates methane Snyder, Benjamin E. R.; Böttger, Lars H.; Bols, Max L. Proceedings of the National Academy of Sciences, Vol. 115, Issue 18 https://doi.org/10.1073/pnas.1721717115	journal	April 2018
Metalloenzymes: the entatic nature of their active sites. Vallee, B. L.; Williams, R. J. Proceedings of the National Academy of Sciences, Vol. 59, Issue 2 https://doi.org/10.1073/pnas.59.2.498	journal	February 1968
Hydroxylation-Induced Migration: The NIH Shift: Recent experiments reveal an unexpected and general result of enzymatic hydroxylation of aromatic compounds Guroff, G.; Renson, J.; Udenfriend, S. Science, Vol. 157, Issue 3796 https://doi.org/10.1126/science.157.3796.1524	journal	September 1967

Similar Records

Chemical Interactions in Multimetal/Zeolite Catalysts

Technical Report · 2004 · OSTI ID:899300

Sachtler, Wolfgang M. H.

Structural characterization of a non-heme iron active site in zeolites that hydroxylates methane

Journal Article · 2018 · Proceedings of the National Academy of Sciences of the United States of America · OSTI ID:1430783

Snyder, Benjamin E. R.; Böttger, Lars H.; Bols, Max L.; +11 more

Acidity and catalytic properties of H-Na-ZSM-8 zeolite: effect of H/sup +/ exchange, pretreatment condition, and poisoning of stronger acid sites

Journal Article · 1987 · J. Catal.; (United States) · OSTI ID:5450199

Akolekar, D B; Choudhary, V R

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
catalysis
spectroscopy
zeolites

Title: Mechanism of selective benzene hydroxylation catalyzed by iron-containing zeolites

Citation Formats

References (32)

Similar Records

Related Subjects