Visible-Light-Driven Photoproduction of Hydrogen Using Rhodium Catalysts and Platinum Nanoparticles with Formate

Soojin Kim, Ga Ye Lee, Jin Ook Baeg, Youngmee Kim, Sung Jin Kim, Jinheung Kim

Research output: Contribution to journalArticlepeer-review

14 Scopus citations

Abstract

Photochemical hydrogen production is carried out using molecular Rh complexes and sodium formate in the presence of platinum nanoparticles (PtNPs) in aqueous buffer solution. Visible-light-driven photocatalytic reactions for hydrogen production with and without nicotinamide adenine dinucleotide (NAD+) follow two different pathways. Complex [Cp Rh(bpy)(OH2)]2+ selectively reduces NAD+ to generate NADH using formate as a proton and electron donor and the chemically generated NADH is sequentially used by PtNPs upon photoactivation of eosin Y to produce hydrogen. However, hydrogen is also produced in photoreactions of the Rh catalyst and PtNPs with formate in the absence of NAD+ and eosin Y. The second pathway for hydrogen production was performed under the conditions without NAD+ and eosin Y and derived from a direct electron transfer from in situ generated rhodium(III)-hydride species to photoexcited PtNPs. The direct electron transfer from the rhodium-hydride species to visible-light-driven PtNPs was first observed in this study. These two pathways for hydrogen production showed different rate-limiting steps based on a Hammett plot using Rh catalysts containing electron-donating and electron-withdrawing groups. Kinetic isotope effects as well as Hammett plot supported the rate-limiting step of the NADH generation for the first pathway of hydrogen production and the Rh-H formation for the second pathway.

Original languageEnglish
Pages (from-to)25844-25852
Number of pages9
JournalJournal of Physical Chemistry C
Volume118
Issue number45
DOIs
StatePublished - 13 Nov 2014

Bibliographical note

Publisher Copyright:
© 2014 American Chemical Society.

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