Pathways for the Photoreduction of Fumarate on ZnS

Mangiante, David; Schaller, Richard D.; Banfield, Jillian F.; Gilbert, Benjamin

doi:10.1021/acsearthspacechem.9b00169

Title: Pathways for the Photoreduction of Fumarate on ZnS

Abstract

Semiconductor mineral particles can act as photocatalysts for organic redox reactions that occur enzymatically in modern biological metabolic pathways. Semiconductor mineral-mediated photocatalysis may have contributed to the prebiotic synthesis of organic acids on the early Earth, but assessing the plausibility of this hypothesis is impeded by the lack of knowledge about the mechanisms for light-driven organic redox reactions on mineral surfaces. We selected one step in the reverse tricarboxylic acid (rTCA) cycle, the reduction of fumarate to succinate, that has been shown to be photocatalyzed by zinc sulfide (ZnS). Using static and time-resolved optical emission and absorption spectroscopy, we studied the adsorption of fumarate and the rates and pathways for charge transfer. We find that ZnS transfers photoexcited electrons to bound and dissolved fumarate on a wide range of time scales but not to succinate, supporting the concept that ZnS mediated photoreduction of fumarate could have operated in oceans of the early Earth. Optical transient absorption (TA) spectroscopy identified a signature tentatively attributed to the fumarate radical anion that is stable for at least 8 ns, providing evidence that fumarate photoreduction under solar illumination levels occurs by successive photoelectron transfer. Finally, the model for electronic excitation, relaxation, and interfacial charge-transfermore »« less

Authors:

Mangiante, David ^[1]; Schaller, Richard D. ^[2]; Banfield, Jillian F. ^[3];

^[4]

Univ. of California, Berkeley, CA (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Publication Date:: Sun Jul 21 00:00:00 EDT 2019

Research Org.:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Org.:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1581378

Grant/Contract Number:: AC02-05CH11231; 1324791; AC02-06CH11357

Resource Type:: Accepted Manuscript

Journal Name:: ACS Earth and Space Chemistry

Additional Journal Information:: Journal Volume: 3; Journal Issue: 10; Journal ID: ISSN 2472-3452

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; photochemistry; carbon cycle; carbon dioxide; mineralization; ultrafast spectroscopy

Citation Formats


                    Mangiante, David, Schaller, Richard D., Banfield, Jillian F., and Gilbert, Benjamin. Pathways for the Photoreduction of Fumarate on ZnS.  United States: N. p., 2019. 
Web.  doi:10.1021/acsearthspacechem.9b00169.

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                    Mangiante, David, Schaller, Richard D., Banfield, Jillian F., & Gilbert, Benjamin. Pathways for the Photoreduction of Fumarate on ZnS.  United States.  https://doi.org/10.1021/acsearthspacechem.9b00169

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                    Mangiante, David, Schaller, Richard D., Banfield, Jillian F., and Gilbert, Benjamin. Sun .  
"Pathways for the Photoreduction of Fumarate on ZnS".  United States.  https://doi.org/10.1021/acsearthspacechem.9b00169.  https://www.osti.gov/servlets/purl/1581378.

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@article{osti_1581378,

  title        = {Pathways for the Photoreduction of Fumarate on ZnS},

  author       = {Mangiante, David and Schaller, Richard D. and Banfield, Jillian F. and Gilbert, Benjamin},

  abstractNote = {Semiconductor mineral particles can act as photocatalysts for organic redox reactions that occur enzymatically in modern biological metabolic pathways. Semiconductor mineral-mediated photocatalysis may have contributed to the prebiotic synthesis of organic acids on the early Earth, but assessing the plausibility of this hypothesis is impeded by the lack of knowledge about the mechanisms for light-driven organic redox reactions on mineral surfaces. We selected one step in the reverse tricarboxylic acid (rTCA) cycle, the reduction of fumarate to succinate, that has been shown to be photocatalyzed by zinc sulfide (ZnS). Using static and time-resolved optical emission and absorption spectroscopy, we studied the adsorption of fumarate and the rates and pathways for charge transfer. We find that ZnS transfers photoexcited electrons to bound and dissolved fumarate on a wide range of time scales but not to succinate, supporting the concept that ZnS mediated photoreduction of fumarate could have operated in oceans of the early Earth. Optical transient absorption (TA) spectroscopy identified a signature tentatively attributed to the fumarate radical anion that is stable for at least 8 ns, providing evidence that fumarate photoreduction under solar illumination levels occurs by successive photoelectron transfer. Finally, the model for electronic excitation, relaxation, and interfacial charge-transfer processes in ZnS provided here will inform all future studies of the photochemical reactions of this mineral.},

  doi          = {10.1021/acsearthspacechem.9b00169},

  journal      = {ACS Earth and Space Chemistry},

  number       = 10,

  volume       = 3,

  place        = {United States},

  year         = {Sun Jul 21 00:00:00 EDT 2019},

  month        = {Sun Jul 21 00:00:00 EDT 2019}

}

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Scheme 1: Reduction of Fumarate to Succinate

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