NDLI: Towards a comprehensive understanding of visible-light photogeneration of hydrogen from water using cobalt(ii) polypyridyl catalysts

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Towards a comprehensive understanding of visible-light photogeneration of hydrogen from water using cobalt(ii) polypyridyl catalysts

Content Provider	Royal Society of Chemistry (RSC)
Author	King, A. E. Jurss, J. W. Thoi, V. S. Roz, K. A. El Long, J. R. Castellano, F. N. Nippe, M. Chang, C. J. Khnayzer, R. S.
Copyright Year	2014
Abstract	Homogeneous aqueous solutions of photocatalytic ensembles, consisting of [Ru(bpy)3]2+ as a photosensitizer, ascorbic acid/ascorbate as the electron source, and 10 distinct Co2+-based molecular catalysts, were evaluated for visible-light induced hydrogen evolution using high-throughput screening. The combined results demonstrate that Co2+ complexes bearing tetradentate ligands yield more active photocatalytic compositions than their congeners with pentadentate ligands while operating with high catalyst stability. Additionally, molecular Co2+ catalysts with cis open coordination sites appear to be significantly more active for hydrogen evolution than those with trans open sites. As evidenced by mass spectrometric analysis of the reactor headspace and associated deuteration experiments, the H2 gas generated in all instances was derived from aqueous protons. One of the most promising cis-disposed Co2+ species, [Co(bpyPY2Me)(CH3CN)(CF3SO3)](CF3SO3) (1), engages in highly efficient hydrogen evolving photocatalysis, achieving a turnover number of 4200 (H2/Co) and a turnover frequency of 3200 (H2/Co per h) at pH 4 under simulated sunlight (AM 1.5G, 100 mW cm−2) at room temperature. At equimolar concentrations of photosensitizer and 1, the total hydrogen produced appears to be exclusively limited by the photostability of [Ru(bpy)3]2+, which was observed to decompose into an Ru(bpy)2–ascorbate adduct, as evidenced by HPLC and ESI-MS experiments. Lowering the operating temperature from 27 to 5 °C significantly attenuates bpy dissociation from the sensitizer, resulting in a net ∼two-fold increase in hydrogen production from this composition. The primary electron transfer steps of this photocatalytic ensemble were investigated by nanosecond transient absorption spectroscopy. Photoexcited [Ru(bpy)3]2+ undergoes reductive quenching by ascorbic acid/ascorbate (kq = 2.6 × 107 M−1 s−1), releasing [Ru(bpy)3]+ from the encounter solvent cage with an efficiency of 55 ± 5%. In the presence of catalyst 1, [Ru(bpy)3]+ generated in the initial flash-quench experiment transfers an electron (ket = 2 × 109 M−1 s−1) at an efficiency of 85 ± 10% to the catalyst, which is believed to enter the hydrogen evolution cycle subsequently. Using a combinatorial approach, all ten Co2+ catalysts were evaluated for their potential to operate under neutral pH 7.0 conditions. Catalyst 7, [Co(PY4MeH2)(CH3CN)(CF3SO3)](CF3SO3), was revealed to be most promising, as its performance metrics were only marginally affected by pH and turnover numbers greater than 1000 were easily obtained in photocatalytic hydrogen generation. These comprehensive findings provide guidelines for the development of molecular compositions capable of evolving hydrogen from purely aqueous media.
Starting Page	1477
Ending Page	1488
Page Count	12
File Format	HTM / HTML PDF
ISSN	17545692
Volume Number	7
Issue Number	4
Journal	Energy & Environmental Science
DOI	10.1039/c3ee43982h
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	HPLC Photosensitizer Acid Hydrogen High-throughput screening Acetonitrile Photocatalysis Turnover number PH Amplitude modulation Adduct High-performance liquid chromatography Operating temperature Dissociative Nanosecond Spectroscopy Solvent Combinatorics
Content Type	Text
Resource Type	Article
Subject	Environmental Chemistry Pollution Renewable Energy, Sustainability and the Environment Nuclear Energy and Engineering

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