Stabilized Photocatalytic Hydrogen Generation using a Molecular Ru(II) Sensitizer, a Molecular Cobalt Catalyst and an Amine Derivative as an Electron Donor

Stabilized Photocatalytic Hydrogen Generation using a Molecular Ru(II) Sensitizer, a Molecular Cobalt Catalyst and an Amine Derivative as an Electron Donor

Bibliographic Details
Main Author: Olaiya, Babatunde Samuel
Language:English
Published: Bowling Green State University / OhioLINK 2013
Subjects:
Chemistry
Inorganic Chemistry
Physical Chemistry
photocatalysis
transient absorbtion
spectro-electrochemistry
reductive quenching
n,n-dimethyl-p-toluidine
Online Access:http://rave.ohiolink.edu/etdc/view?acc_num=bgsu1371066177
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spelling ndltd-OhioLink-oai-etd.ohiolink.edu-bgsu13710661772021-08-03T05:24:02Z Stabilized Photocatalytic Hydrogen Generation using a Molecular Ru(II) Sensitizer, a Molecular Cobalt Catalyst and an Amine Derivative as an Electron Donor Olaiya, Babatunde Samuel Chemistry Inorganic Chemistry Physical Chemistry photocatalysis transient absorbtion spectro-electrochemistry reductive quenching n,n-dimethyl-p-toluidine Transient absorption and photoluminescence studies were carried out on a homogeneous photocatalytic proton reduction composition using tris(4,7-diphenyl-1,10-phenanthroline)-ruthenium(II) ([Ru(dpp)<sub>3</sub>]<sup>2+</sup>) as photosensitizer, a cobalt glyoxime ([Co<sup>III</sup>(dmgH)<sub>2</sub>pyCl]) water reduction catalyst and N,N-dimethyl-p-toluidine (DMT) as the sacrificial donor in water:acetonitrile solvent mixtures. Dynamic photoluminescence studies revealed that DMT reductively quenched the excited state of *Ru(dpp)<sub>3</sub><sup>2+</sup> with a bimolecular rate constant of k <sub>q</sub> = 4.9 × 10<sup>9</sup> M<sup>-1</sup> s<sup>-1</sup>. Similarly time resolved spectroscopy was used to determine the rate of electron transfer from the reduced sensitizer to the [Co<sup>III</sup>(dmgH)<sub>2</sub>pyCl] to be k <sub>Co</sub> = 2.4 ×10<sup>9</sup> M<sup>-1</sup> s<sup>-1</sup>. H2 production photocatalysis independently monitored using pressure, GC, and mass spectroscopy illustrated that the composition yields high TONs with respect to sensitizer TON ~ 10,000 (H<sub>2</sub>/Ru) while deuteration studies showed that 90% of the reduced protons comes from water. The rationale behind the large photostability imparted by the use of the DMT reductive quencher was postulated to be its ability to form stable dimer in solution following electron donation. 2013-08-22 English text Bowling Green State University / OhioLINK http://rave.ohiolink.edu/etdc/view?acc_num=bgsu1371066177 http://rave.ohiolink.edu/etdc/view?acc_num=bgsu1371066177 unrestricted This thesis or dissertation is protected by copyright: all rights reserved. It may not be copied or redistributed beyond the terms of applicable copyright laws.
collection NDLTD
language English
sources NDLTD
topic Chemistry
Inorganic Chemistry
Physical Chemistry
photocatalysis
transient absorbtion
spectro-electrochemistry
reductive quenching
n,n-dimethyl-p-toluidine
spellingShingle Chemistry
Inorganic Chemistry
Physical Chemistry
photocatalysis
transient absorbtion
spectro-electrochemistry
reductive quenching
n,n-dimethyl-p-toluidine
Olaiya, Babatunde Samuel
Stabilized Photocatalytic Hydrogen Generation using a Molecular Ru(II) Sensitizer, a Molecular Cobalt Catalyst and an Amine Derivative as an Electron Donor
author Olaiya, Babatunde Samuel
author_facet Olaiya, Babatunde Samuel
author_sort Olaiya, Babatunde Samuel
title Stabilized Photocatalytic Hydrogen Generation using a Molecular Ru(II) Sensitizer, a Molecular Cobalt Catalyst and an Amine Derivative as an Electron Donor
title_short Stabilized Photocatalytic Hydrogen Generation using a Molecular Ru(II) Sensitizer, a Molecular Cobalt Catalyst and an Amine Derivative as an Electron Donor
title_full Stabilized Photocatalytic Hydrogen Generation using a Molecular Ru(II) Sensitizer, a Molecular Cobalt Catalyst and an Amine Derivative as an Electron Donor
title_fullStr Stabilized Photocatalytic Hydrogen Generation using a Molecular Ru(II) Sensitizer, a Molecular Cobalt Catalyst and an Amine Derivative as an Electron Donor
title_full_unstemmed Stabilized Photocatalytic Hydrogen Generation using a Molecular Ru(II) Sensitizer, a Molecular Cobalt Catalyst and an Amine Derivative as an Electron Donor
title_sort stabilized photocatalytic hydrogen generation using a molecular ru(ii) sensitizer, a molecular cobalt catalyst and an amine derivative as an electron donor
publisher Bowling Green State University / OhioLINK
publishDate 2013
url http://rave.ohiolink.edu/etdc/view?acc_num=bgsu1371066177
work_keys_str_mv AT olaiyababatundesamuel stabilizedphotocatalytichydrogengenerationusingamolecularruiisensitizeramolecularcobaltcatalystandanaminederivativeasanelectrondonor
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