Theoretical Study of 4-(Hydroxymethyl)benzoic Acid Synthesis from Ethylene and 5-(Hydroxymethyl)furoic Acid Catalyzed by Sn-BEA

Li, Yi-Pei; Head-Gordon, Martin; Bell, Alexis T.

doi:10.1021/acscatal.6b01160

Theoretical Study of 4-(Hydroxymethyl)benzoic Acid Synthesis from Ethylene and 5-(Hydroxymethyl)furoic Acid Catalyzed by Sn-BEA

Journal Article · Thu Jun 23 04:00:00 UTC 2016 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.6b01160· OSTI ID:1571065

Li, Yi-Pei ^[1]; Head-Gordon, Martin ^[1]; Bell, Alexis T. ^[1]

Univ. of California, Berkeley, CA (United States)

A sustainable route has been confirmed for the production of terephthalic acid (PTA) from 5-(hydroxymethyl)furoic acid (HMFA) and ethylene, both of which can be derived from biomass. This process starts with the production of 4-(hydroxymethyl)benzoic acid (HMBA) from HMFA and ethylene catalyzed by Sn-BEA. The subsequent oxidation of HMBA leads to PTA. Our research introduces the results of a detailed computational investigation of the mechanism of HMBA synthesis from ethylene and HMFA mediated by Sn-BEA. Density functional theory calculations show that the formation of HMBA proceeds via Diels-Alder cycloaddition of HMFA and ethylene, which is rate-limiting, followed by Lewis acid-catalyzed dehydration. The solution-phase reaction and six different pathways in Sn-BEA, including one pathway on the Si site and five different pathways on the Sn site, are investigated for the Diels-Alder cycloaddition of HMFA and ethylene. Energy decomposition analysis (EDA) reflects that the Sn site stabilizes the transition state of the Diels-Alder reaction electrostatically instead of facilitating charge transfer between HMFA and ethylene. Therefore, the preferred pathway for the Diels-Alder reaction starts with binding HMFA to the Sn site by the carbonyl oxygen, which is the configuration that maximizes electrostatic interactions between substrates and the catalyst in the transition state. The effect of substituting Sn in the active site by Zr and Ti was examined and the highest reaction barriers were for the Ti sites. Using EDA, we found that though the barriers of the Sn and Zr site are comparable, the individual contributing effects are different: lower energy penalty associated with distortion of the geometry of the Zr site overcomes less favorable electrostatic and charge transfer effects compared to the Sn site.

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC); National Science Foundation (NSF)

DOE Contract Number:: AC02-05CH11231

OSTI ID:: 1571065

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 8 Vol. 6; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

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