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 · Wed Nov 14 00:00:00 EST 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 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.

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

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

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

OSTI ID:: 1482162

Alternate ID(s):: OSTI ID: 1490261; OSTI ID: 1490638

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 Vol. 115 Journal Issue: 48; ISSN 0027-8424

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

Country of Publication:: United States

Language:: English

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Cited by: 10 works

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