Photocatalytic generation of hydrogen from water using a cobalt pentapyridine complex in combination with molecular and semiconductor nanowire photosensitizers

Sun, Yujie; Sun, Jianwei; Long, Jeffrey R.; Yang, Peidong; Chang, Christopher J.

doi:10.1039/c2sc21163g

Cited by 180 publications

(150 citation statements)

References 56 publications

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“…Some of these homogeneous photocatalytic systems can operate very efficiently (in terms of number of catalytic cycles or turnover number (TON)) in organic or mixed aqueous-organic solvents. Those reaching a turnover number versus catalyst (TON Cat ) above 100 in fully aqueous solution were rare and limited to rhodium [36][37][38][39] and platinum [40] but, since two years, several examples with cobalt [41][42][43][44][45][46][47][48][49][50][51][52][53][54], iron [55][56][57][58] nickel [59] were reported. Developing H 2 -evolving photocatalytic systems functioning in pure water is essential for their coupling with water oxidation systems in photoelectrochemical water-splitting devices.…”

Section: Introductionmentioning

confidence: 98%

Photo-induced redox catalysis for proton reduction to hydrogen with homogeneous molecular systems using rhodium-based catalysts

Stoll

Castillo

Kayanuma

et al. 2015

Coordination Chemistry Reviews

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Section: Introductionmentioning

confidence: 98%

Photo-induced redox catalysis for proton reduction to hydrogen with homogeneous molecular systems using rhodium-based catalysts

Stoll

Castillo

Kayanuma

et al. 2015

Coordination Chemistry Reviews

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“…Introduction of an electron-donating dimethylamino substituent (6, Figure 2) 2+ as a molecular photosensitizer, and ascorbic acid as a sacrificial reductant (Figure 8). 41 Likewise, 5 enhanced the hydrogen photolysis yield of GaP nanowires in water, demonstrating that this molecular catalyst platform can be interfaced with heterogeneous photosensitizers. 41 Taken together, these results suggest that judicious modifications of the ancillary ligand can furnish catalysts active in water, utilizing either sustainable solar or electrical input.…”

Section: ■ [(Py5me 2 )Co(h 2 O)] 2+ As a Tunable Platform For Water Rmentioning

confidence: 99%

“…The prevalence of molecular cobalt-based proton reduction catalysts, 9,39,40,42−63 including contributions from our 11,16,36,37,41,64,65 has attracted many experimental and computational mechanistic investigations. Although the operative mechanism for these catalysts can vary widely, formation of a cobalt-hydride is commonly invoked.…”

Section: ■ Redox-active Ligands For Redox-leveling and Facilitating Mmentioning

confidence: 99%

Metal–Polypyridyl Catalysts for Electro- and Photochemical Reduction of Water to Hydrogen

et al. 2015

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CONSPECTUS: Climate change, rising global energy demand, and energy security concerns motivate research into alternative, sustainable energy sources. In principle, solar energy can meet the world's energy needs, but the intermittent nature of solar illumination means that it is temporally and spatially separated from its consumption. Developing systems that promote solar-to-fuel conversion, such as via reduction of protons to hydrogen, could bridge this production−consumption gap, but this effort requires invention of catalysts that are cheap, robust, and efficient and that use earth-abundant elements. In this context, catalysts that utilize water as both an earthabundant, environmentally benign substrate and a solvent for proton reduction are highly desirable. This Account summarizes our studies of molecular metal−polypyridyl catalysts for electrochemical and photochemical reduction of protons to hydrogen. Inspired by concept transfer from biological and materials catalysts, these scaffolds are remarkably resistant to decomposition in water, with fast and selective electrocatalytic and photocatalytic conversions that are sustainable for several days. Their modular nature offers a broad range of opportunities for tuning reactivity by molecular design, including altering ancillary ligand electronics, denticity, and/or incorporating redox-active elements. Our first-generation complex, [(PY4)Co(CH 3 CN) 2 ] 2+, catalyzes the reduction of protons from a strong organic acid to hydrogen in 50% water. Subsequent investigations with the pentapyridyl ligand PY5Me 2 furnished molybdenum and cobalt complexes capable of catalyzing the reduction of water in fully aqueous electrolyte with 100% Faradaic efficiency. Of particular note, the complex [(PY5Me 2 )MoO] 2+ possesses extremely high activity and durability in neutral water, with turnover frequencies at least 8500 mol of H 2 per mole of catalyst per hour and turnover numbers over 600 000 mol of H 2 per mole of catalyst over 3 days at an overpotential of 1.0 V, without apparent loss in activity. Replacing the oxo moiety with a disulfide affords [(PY5Me 2 )MoS 2 ] 2+ , which bears a molecular MoS 2 triangle that structurally and functionally mimics bulk molybdenum disulfide, improving the catalytic activity for water reduction. In water buffered to pH 3, catalysis by [(PY5Me 2 )MoS 2 ] 2+ onsets at 400 mV of overpotential, whereas [(PY5Me 2 )MoO] 2+ requires an additional 300 mV of driving force to operate at the same current density. Metalation of the PY5Me 2 ligand with an appropriate Co(II) source also furnishes electrocatalysts that are active in water. Importantly, the onset of catalysis by the [(PY5Me 2 )Co(H 2 O)] 2+ series is anodically shifted by introducing electron-withdrawing functional groups on the ligand. With the [(bpy2PYMe)Co(CF 3 SO 3 )] 1+ system, we showed that introducing a redox-active moiety can facilitate the electro-and photochemical reduction of protons from weak acids such as acetic acid or water. Using a high-throughput photochemical reactor, we...

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“…There have been significant advances in such complex reaction mixtures in the pursuit of outstanding hydrogen production efficiency. [3,4] However,t he optimization of the active components remains am ajor obstacle toward improved catalytic efficiency, mainly because the key parameter is governed by ad iffusioncontrolled process and critically depends on the efficiencyo f intermolecular collisions between the species involved. [5] Indeed, the solar-to-energy conversion in nature is realized through energy and electron transfer in ad elicate supramolecular organization.…”

mentioning

confidence: 99%

Energy Transfer in a Hybrid Ir^III Carbene–Pt^II Acetylide Assembly for Efficient Hydrogen Production

Yuan

Chen

et al. 2015

Chemistry A European J

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A new heterometallic supramolecular complex, consisting of an iridium carbene-based unit appended to a platinum terpyridine acetylide unit, representing a new Ir(III) -Pt(II) structural motif, was designed and developed to act as an active species for photocatalytic hydrogen production. The results also suggested that a light-harvesting process is essential to realize the solar-to-fuel conversion in an artificial system as illustrated in the natural photosynthetic system.

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Photocatalytic generation of hydrogen from water using a cobalt pentapyridine complex in combination with molecular and semiconductor nanowire photosensitizers

Abstract: Title"Photocatalytic generation of hydrogen from water using a cobalt pentapyridine complex in combination with molecular and semiconductor nanowire photosensitizers"

Cited by 180 publications

References 56 publications

Photo-induced redox catalysis for proton reduction to hydrogen with homogeneous molecular systems using rhodium-based catalysts

Photo-induced redox catalysis for proton reduction to hydrogen with homogeneous molecular systems using rhodium-based catalysts

Metal–Polypyridyl Catalysts for Electro- and Photochemical Reduction of Water to Hydrogen

Energy Transfer in a Hybrid Ir^III Carbene–Pt^II Acetylide Assembly for Efficient Hydrogen Production

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Photocatalytic generation of hydrogen from water using a cobalt pentapyridine complex in combination with molecular and semiconductor nanowire photosensitizers

Abstract: Title"Photocatalytic generation of hydrogen from water using a cobalt pentapyridine complex in combination with molecular and semiconductor nanowire photosensitizers"

Cited by 180 publications

References 56 publications

Photo-induced redox catalysis for proton reduction to hydrogen with homogeneous molecular systems using rhodium-based catalysts

Photo-induced redox catalysis for proton reduction to hydrogen with homogeneous molecular systems using rhodium-based catalysts

Metal–Polypyridyl Catalysts for Electro- and Photochemical Reduction of Water to Hydrogen

Energy Transfer in a Hybrid IrIII Carbene–PtII Acetylide Assembly for Efficient Hydrogen Production

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Energy Transfer in a Hybrid Ir^III Carbene–Pt^II Acetylide Assembly for Efficient Hydrogen Production