Molecular cathode and photocathode materials for hydrogen evolution in photoelectrochemical devices

Queyriaux, Nicolas; Kaeffer, Nicolas; Morozan, Adina; Chavarot‐Kerlidou, Murielle; Artero, Vincent

doi:10.1016/j.jphotochemrev.2015.08.001

Cited by 87 publications

(72 citation statements)

References 160 publications

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“…Covalent attachment, [22][23][24][25] electropolymerization, [26][27][28][29][30] and adsorption/noncovalent attachment of metal complexes [31][32][33][34][35] are methods of heterogenizing molecular catalysts for energy-conversion applications and were reviewed elsewhere. [36][37][38]…”

Section: Molecular Electrocatalysts For Energy Conversionmentioning

confidence: 99%

Electrocatalytic Metal–Organic Frameworks for Energy Applications

2017

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With the global energy demand expected to increase drastically over the next several decades, the development of a sustainable energy system to meet this increase is paramount. Renewable energy sources can be coupled with electrochemical conversion processes to store energy in chemical bonds. To promote these difficult transformations, electrocatalysts that operate at high conversion rates and efficiency are required. Metal–organic frameworks (MOFs) have emerged as a promising class of materials; however, the insulating nature of MOFs has limited their application as electrocatalysts. The recent development of conductive MOFs has led to several electrocatalytic MOFs that display activity comparable to that of the best‐performing heterogeneous catalysts. Although many electrocatalytic MOFs exhibit low activity and stability, the few successful examples highlight the possibility of MOF electrocatalysts as replacements for noble‐metal‐based catalysts in commercial energy‐converting devices. We review herein the use of pristine MOFs as electrocatalysts to facilitate important energy‐related reactions.

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Section: Molecular Electrocatalysts For Energy Conversionmentioning

confidence: 99%

Electrocatalytic Metal–Organic Frameworks for Energy Applications

2017

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“…As well as their electronic properties, the perfectly planar nature of the aromatic dithiolene complexes has been used to prepare materials that act as cathodes in the hydrogen evolution reaction . In this context, Clough et al.…”

Section: Introductionmentioning

confidence: 99%

Proton‐Reduction Reaction Catalyzed by Homoleptic Nickel–bis‐1,2‐dithiolate Complexes: Experimental and Theoretical Mechanistic Investigations

et al. 2017

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A series of homoleptic monoanionic nickel dithiolene complexes [Ni(bdt)2](NBu4), [Ni(tdt)2](NBu4), and [Ni(mnt)2](NBu4) containing the ligands benzene‐1,2‐dithiolate (bdt2−), toluene‐3,4‐dithiolate (tdt2−), and maleonitriledithiolate (mnt2−), respectively, were employed as electrocatalysts in the hydrogen‐evolution reaction with trifluoroacetic acid as the proton source in acetonitrile. All complexes are active catalysts with TONs reaching 113, 158, and 6 for [Ni(bdt)2](NBu4), [Ni(tdt)2](NBu4), and [Ni(mnt)2](NBu4), respectively. The Faradaic yield for the hydrogen evolution reaction reaches 88 % for 2−, which also displays the minimal overpotential requirement value (467 mV) within the series. Two pathways for H2 evolution can be hypothesized that differ in the sequence of protonation and reduction steps. DFT calculations are in agreement with experimental data and indicate that protonation at sulfur follows the reduction to the dianion. Hydrogen evolves from the direduced–diprotonated form via a highly distorted nickel hydride intermediate. The effects of acid strength and concentration in the hydrogen‐evolving mechanism are also discussed.

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“…Efficient electrochemical reduction of protons to molecular hydrogen is critical for realization of more sustainable energy practices. The process is a required half reaction for conversion of solar energy into useful hydrogen fuel via water splitting devices [1][2][3]. Moreover, when driven by renewable electricity, the electrochemical hydrogen evolution reaction (HER) can supply hydrogen for fertilizer, petrochemical, and other industries [4,5], thereby serving as a clean, carbon-free alternative to steam reforming [6,7].…”

Section: Introductionmentioning

confidence: 99%

“…Moreover, when driven by renewable electricity, the electrochemical hydrogen evolution reaction (HER) can supply hydrogen for fertilizer, petrochemical, and other industries [4,5], thereby serving as a clean, carbon-free alternative to steam reforming [6,7]. However, for electrochemical HER to be efficient enough for large scale or solar-driven applications, highly active catalysts are needed to lower its activation energy barrier and to facilitate the kinetics [1][2][3]. Platinum has traditionally been the best HER catalyst, but cheaper, more earth abundant catalysts are needed to ensure scalability and economic viability [8].…”

Section: Introductionmentioning

confidence: 99%

[Mo2O2S8]2− small molecule dimer as a basis for hydrogen evolution reaction (HER) catalyst materials

et al. 2020

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Molybdenum sulfides have emerged as promising, low cost alternatives to platinum for catalysis of the electrochemical hydrogen evolution reaction (HER). A wide variety of sulfides already achieve impressive catalysis, but further development could be enabled by an understanding of the relative activities of different sulfur sites. To contribute towards a better understanding, the small molecule dimer [Mo 2 O 2 S 8 ] 2− , which is rich in terminal and unsaturated sulfur, has been investigated for HER. Homogeneous catalysis has been attempted in acidified DMF but is precluded by electrodeposition. The resulting deposit ultimately proves to be an active heterogeneous HER catalyst in aqueous acid and is compared to dropcasts of the molecular dimer which are also HER catalysts. XPS elucidates the end structures of the electrodeposits and dropcasts showing a shift away from molecular features in both cases. Investigation of HER performance reveals that the activity of both dimer-based heterogeneous catalysts lags behind that of other reported molybdenum sulfides. However, detailed performance comparisons allow for consideration of key design parameters. Density functional theory calculations are presented for the reduced molecular dimer as well as possible molecular catalytic pathways. These give insight into the cathodic structural transformations of the dimer as well as the observation of heterogeneous but not homogeneous catalysis.

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Molecular cathode and photocathode materials for hydrogen evolution in photoelectrochemical devices

Cited by 87 publications

References 160 publications

Electrocatalytic Metal–Organic Frameworks for Energy Applications

Electrocatalytic Metal–Organic Frameworks for Energy Applications

Proton‐Reduction Reaction Catalyzed by Homoleptic Nickel–bis‐1,2‐dithiolate Complexes: Experimental and Theoretical Mechanistic Investigations

[Mo2O2S8]2− small molecule dimer as a basis for hydrogen evolution reaction (HER) catalyst materials

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