Common Photo-oxidative Decarboxylation Mechanism in Iron Hydroxy Carboxylate Complexes

Joe-Wong, Claresta; Schaller, Richard D.; Gilbert, Benjamin

doi:10.1021/acs.jpca.3c02656

Common Photo-oxidative Decarboxylation Mechanism in Iron Hydroxy Carboxylate Complexes

Journal Article · Thu Jul 20 00:00:00 EDT 2023 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.3c02656· OSTI ID:2328091

^[1]; Schaller, Richard D. ^[2]; ^[1]

Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States). Center for Nanoscale Materials (CNM)

Photochemical oxidation of dissolved organic matter is a crucial component of carbon cycling in surface waters. Photo-oxidation of iron(III)-carboxylate complexes is of particular interest because complexation with iron(III) can sensitize this functional group to photodecarboxylation. Further, the photo-oxidation mechanism of ferrioxalate has been extensively characterized, but it is unclear whether the mechanism or timing is similar for other more complex carboxylates. In this study, we use time-resolved infrared spectroscopy to demonstrate that Fe(III)-citrate, an aliphatic carboxylate, and Fe(III)-salicylate, an aromatic carboxylate, follow the same photo-oxidation kinetics as ferrioxalate. Hence the data suggest a common mechanism for decarboxylation of iron hydroxy carbonates. Differences in the CO₂ yield within 50 ps are qualitatively similar to the long-time-scale quantum yield for Fe(II) production.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Argonne National Laboratory (ANL), Argonne, IL (United States). Center for Nanoscale Materials (CNM)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC02-05CH11231; AC02-06CH11357

OSTI ID:: 2328091

Alternate ID(s):: OSTI ID: 2404910

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 30 Vol. 127; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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