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Title: Multimetallic Systems for the Photocatalytic Production of Fuels from Abundant Sources

Abstract

The reported findings herein are a result of a collaboration between the groups of Claudia Turro at The Ohio State University (DE-SC0010542) and Kim R. Dunbar at Texas A&M University (DE-SC0010721). The Turro and Dunbar groups jointly discovered that cationic d 7–d 7 Rh 2(II,II) complexes bridged by electron-donating formamidinate (form) ligands possess redox-active excited states that are relatively long-lived and can engage in charge transfer reactions. As part of the present grant we designed new complexes that exhibit strong absorption from the UV to ~800 nm. The Rh 2(II,II) complexes under investigation are poised to undergo catalytic reduction of substrates because they are robust to changes in metal oxidation state, the two metals and the two diimine ligands, together with the non-innocent bridges, can be used to store redox equivalents, making these complexes capable of coupling one-electron events with multi-electron transformations. We discovered the electrocatalytic reduction of H + and CO 2 by complexes that are able to electrocatalytically reduce H + to H 2 with high turnover frequencies (TOFs) and overpotentials, η, of ~0.5 V,8 as well as to reduce CO 2 to HCOOH. We now have experimental evidence that both the production of H 2 from Hmore » + and HCOOH. The molecular catalysts are stable after the acid and/or CO 2 is consumed since electrocatalysis is restored at the same rate upon the addition of substrate to the cell.8,9 Moreover, we showed that the catalysis is not a result of a decomposition product deposited on the electrode, since placing an electrode from an active electrocatalytic solution into one that does not contain catalyst completely shuts down the reactivity. We are currently exploring the reactivity of these complexes in hydride transfer reactions with other substrates and in the presence of CO 2 and reducing agents, as well as attempting to grow single crystals for x-ray diffraction.« less

Authors:
 [1];  [2]
  1. Texas A & M Univ., College Station, TX (United States)
  2. The Ohio State Univ., Columbus, OH (United States)
Publication Date:
Research Org.:
Texas A & M Univ., College Station, TX (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Contributing Org.:
Texas A&M University and The Oho State University
OSTI Identifier:
1430648
Report Number(s):
DOE_TexasA&M0010721
DOE Contract Number:  
SC0010721
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
14 SOLAR ENERGY; Solar energy; carbon dioxide reduction; hydrogen production; electrocatalytic reduction of H+ and CO2

Citation Formats

Dunbar, Kim R., and Turro, Claudia. Multimetallic Systems for the Photocatalytic Production of Fuels from Abundant Sources. United States: N. p., 2018. Web. doi:10.2172/1430648.
Dunbar, Kim R., & Turro, Claudia. Multimetallic Systems for the Photocatalytic Production of Fuels from Abundant Sources. United States. doi:10.2172/1430648.
Dunbar, Kim R., and Turro, Claudia. Sun . "Multimetallic Systems for the Photocatalytic Production of Fuels from Abundant Sources". United States. doi:10.2172/1430648. https://www.osti.gov/servlets/purl/1430648.
@article{osti_1430648,
title = {Multimetallic Systems for the Photocatalytic Production of Fuels from Abundant Sources},
author = {Dunbar, Kim R. and Turro, Claudia},
abstractNote = {The reported findings herein are a result of a collaboration between the groups of Claudia Turro at The Ohio State University (DE-SC0010542) and Kim R. Dunbar at Texas A&M University (DE-SC0010721). The Turro and Dunbar groups jointly discovered that cationic d7–d7 Rh2(II,II) complexes bridged by electron-donating formamidinate (form) ligands possess redox-active excited states that are relatively long-lived and can engage in charge transfer reactions. As part of the present grant we designed new complexes that exhibit strong absorption from the UV to ~800 nm. The Rh2(II,II) complexes under investigation are poised to undergo catalytic reduction of substrates because they are robust to changes in metal oxidation state, the two metals and the two diimine ligands, together with the non-innocent bridges, can be used to store redox equivalents, making these complexes capable of coupling one-electron events with multi-electron transformations. We discovered the electrocatalytic reduction of H+ and CO2 by complexes that are able to electrocatalytically reduce H+ to H2 with high turnover frequencies (TOFs) and overpotentials, η, of ~0.5 V,8 as well as to reduce CO2 to HCOOH. We now have experimental evidence that both the production of H2 from H+ and HCOOH. The molecular catalysts are stable after the acid and/or CO2 is consumed since electrocatalysis is restored at the same rate upon the addition of substrate to the cell.8,9 Moreover, we showed that the catalysis is not a result of a decomposition product deposited on the electrode, since placing an electrode from an active electrocatalytic solution into one that does not contain catalyst completely shuts down the reactivity. We are currently exploring the reactivity of these complexes in hydride transfer reactions with other substrates and in the presence of CO2 and reducing agents, as well as attempting to grow single crystals for x-ray diffraction.},
doi = {10.2172/1430648},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Sun Apr 01 00:00:00 EDT 2018},
month = {Sun Apr 01 00:00:00 EDT 2018}
}

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