Splitting Water with Cobalt

Artero, Vincent; Chavarot‐Kerlidou, Murielle; Fontecave, Marc

doi:10.1002/anie.201007987

Cited by 1,294 publications

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“…It is shown that the materials containing Co and/or V (typically the oxides) are potential catalysts for OER [33]. We then studied the OER performance of the samples in 1 mol L −1 KOH.…”

Section: Electrochemical Performance For Oermentioning

confidence: 99%

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Cobalt-vanadium bimetal-based nanoplates for efficient overall water splitting

Xiao

Tian

et al. 2017

Sci. China Mater.

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The development of effective and low-cost catalysts for overall water splitting is essential for clean production of hydrogen from water. In this paper, we report the synthesis of cobalt-vanadium (Co-V) bimetal-based catalysts for the effective water splitting. The Co 2 V 2 O 7 ·xH 2 O nanoplates containing both Co and V elements were selected as the precursors. After the calcination under NH 3 atmosphere, the Co 2 VO 4 and Co/VN could be obtained just by tuning the calcination temperature. Electrochemical tests indicated that the Co-V bimetal-based materials could be used as active hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) catalyst by regulating their structure. The Co/VN showed good performance for HER with the onset potential of 68 mV and can achieve a current density of 10 mA cm −2 at an overpotential of 92 mV. Meanwhile, the Co 2 VO 4 exhibited the obvious OER performance with overpotential of 300 mV to achieve a current density of 10 mA cm −2 . When the Co 2 VO 4 and Co/VN were used as the anode and cathode in a twoelectrode system, respectively, the cell needed a voltage of 1.65 V to achieve 10 mA cm −2 together with good stability. This work would be indicative to constructing Co-V bimetalbased catalysts for the catalytic application.

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“…It is shown that the materials containing Co and/or V (typically the oxides) are potential catalysts for OER [33]. We then studied the OER performance of the samples in 1 mol L −1 KOH.…”

Section: Electrochemical Performance For Oermentioning

confidence: 99%

“…The cobalt (Co), as a typical LTM, is promising in HER due to its relatively low cost and the activity for the reduction of H + [33]. Generally, single Co metals have shown poor activity and stability for HER.…”

Section: Introductionmentioning

confidence: 99%

Cobalt-vanadium bimetal-based nanoplates for efficient overall water splitting

Xiao

Tian

et al. 2017

Sci. China Mater.

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“…This family of complexes has become of renewed interest in the past few years, following reports in 2005 [1,2] and 2007 [3,4,5] of their promising hydrogen-evolving catalytic capability. Today, cobaloximes, and the related diimine-dioxime cobalt complexes [6,7,8,9], are recognized as some of the most efficient molecular catalysts for electro-and photo-catalytic hydrogen evolution [10,11,12]. These compounds are known to be powerful nucleophiles in their reduced Co(I) state.…”

Section: Introductionmentioning

confidence: 99%

“…These compounds are known to be powerful nucleophiles in their reduced Co(I) state. It is accepted that the catalytic cycle for hydrogen evolution proceeds via protonation of the Co(I) species, yielding a Co(III)-H hydridocobaloxime intermediate that, after further reduction to the Co(II)-H state, can evolve dihydrogen through either protonation of the hydride moiety or bimolecular reductive elimination [1,2,3,4,5,10,11,6,13,14,15,16,17,18].Recent reports from the groups of Muckerman [19], and Jiang [21] have addressed aspects of the catalytic activity of these compounds using quantum chemical approaches and confirm the role of the Co(I) species. Experimentally, the spectroscopic signatures of Co(I) intermediates have been observed during the course of electro-and photo-catalytic experiments [4,5,22], and the Co(I) species [14,23,24,9], and its protonated Co(III)-H form [25,26,27] Figure 1).…”

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confidence: 99%

Theoretical Modeling of Low‐Energy Electronic Absorption Bands in Reduced Cobaloximes

Bhattacharjee¹,

Chavarot‐Kerlidou²,

Dempsey³

et al. 2014

ChemPhysChem

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The reduced Co(I) states of cobaloximes are powerful nucleophiles that play an important role in the hydrogen-evolving catalytic activity of these species. In this work we have analyzed the low energy electronic absorption bands of two cobaloxime systems experimentally and using a variety of density functional theory and molecular orbital ab initio quantum chemical approaches. Overall we find a reasonable qualitative understanding of the electronic excitation spectra of these compounds but show that obtaining quantitative results remains a challenging task. KeywordsCobaloxime complexes; H 2 evolving catalysts; theoretical electronic spectra; vitamin B 12 mimics IntroductionCobaloximes are pseudo-macrocyclic bis(dialkylglyoximato) cobalt complexes, first developed in the seventies as vitamin B 12 mimics. This family of complexes has become of * martin.field@ibs.fr. Europe PMC Funders GroupAuthor Manuscript Chemphyschem. Author manuscript; available in PMC 2015 August 10. Published in final edited form as:Chemphyschem. [3,4,5] of their promising hydrogen-evolving catalytic capability. Today, cobaloximes, and the related diimine-dioxime cobalt complexes [6,7,8,9], are recognized as some of the most efficient molecular catalysts for electro-and photo-catalytic hydrogen evolution [10,11,12]. These compounds are known to be powerful nucleophiles in their reduced Co(I) state. It is accepted that the catalytic cycle for hydrogen evolution proceeds via protonation of the Co(I) species, yielding a Co(III)-H hydridocobaloxime intermediate that, after further reduction to the Co(II)-H state, can evolve dihydrogen through either protonation of the hydride moiety or bimolecular reductive elimination [1,2,3,4,5,10,11,6,13,14,15,16,17,18].Recent reports from the groups of Muckerman [19], and Jiang [21] have addressed aspects of the catalytic activity of these compounds using quantum chemical approaches and confirm the role of the Co(I) species. Experimentally, the spectroscopic signatures of Co(I) intermediates have been observed during the course of electro-and photo-catalytic experiments [4,5,22], and the Co(I) species [14,23,24,9], and its protonated Co(III)-H form [25,26,27] Figure 1). We have employed both time-dependent density functional theory (TDDFT) and correlated molecular orbital methods to characterize the electronic excitation spectra of these compounds and show that a reasonable qualitative description of them can be obtained. Methods CalculationsThe ORCA [28] program (version 2.9) was employed for all DFT and TDDFT calculations. Geometry optimizations were performed at the DFT level using the BP86 [29,30] and B3LYP [31,32] functionals. Test calculations were also carried out with the addition of empirical van der Waals corrections [33] on compound 2 but the effects were found to be small and so will not be considered further here. To be precise, the relative ordering of the energies of the different isomers remained unchanged and the RMS heavy atom coordinate differences between equivalent optimized st...

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“…The FeFe hydrogenase is the most active catalyst for H 2 evolution, with a fascinating turnover frequency (TOF) up to 6000À9000 s À1 . 16,17 Since the structure of FeFe hydrogenase was resolved in 1998 (as shown in Figure 4), 35,36 45,46 For its high activity and relatively low working potential, this type of complex has been recognized as a functional hydrogenase mimic. 47,48 To achieve lightdriven H 2 evolution, hydrogenase mimics were combined with light harvesters.…”

Section: Hybrid Photocatalysts For H 2 Evolutionmentioning

confidence: 99%

Hybrid Artificial Photosynthetic Systems Comprising Semiconductors as Light Harvesters and Biomimetic Complexes as Molecular Cocatalysts

2013

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S olar fuel production through artificial photosynthesis may be a key to generating abundant and clean energy, thus addressing the high energy needs of the world's expanding population. As the crucial components of photosynthesis, the artificial photosynthetic system should be composed of a light harvester (e.g., semiconductor or molecular dye), a reduction cocatalyst (e.g., hydrogenase mimic, noble metal), and an oxidation cocatalyst (e.g., photosystem II mimic for oxygen evolution from water oxidation). Solar fuel production catalyzed by an artificial photosynthetic system starts from the absorption of sunlight by the light harvester, where charge separation takes place, followed by a charge transfer to the reduction and oxidation cocatalysts, where redox reaction processes occur. One of the most challenging problems is to develop an artificial photosynthetic solar fuel production system that is both highly efficient and stable. The assembly of cocatalysts on the semiconductor (light harvester) not only can facilitate the charge separation, but also can lower the activation energy or overpotential for the reactions. An efficient light harvester loaded with suitable reduction and oxidation cocatalysts is the key for high efficiency of artificial photosynthetic systems.In this Account, we describe our strategy of hybrid photocatalysts using semiconductors as light harvesters with biomimetic complexes as molecular cocatalysts to construct efficient and stable artificial photosynthetic systems. We chose semiconductor nanoparticles as light harvesters because of their broad spectral absorption and relatively robust properties compared with a natural photosynthesis system. Using biomimetic complexes as cocatalysts can significantly facilitate charge separation via fast charge transfer from the semiconductor to the molecular cocatalysts and also catalyze the chemical reactions of solar fuel production. The hybrid photocatalysts supply us with a platform to study the photocatalytic mechanisms of H 2 /O 2 evolution and CO 2 reduction at the molecular level and to bridge natural and artificial photosynthesis. We demonstrate the feasibility of the hybrid photocatalyst, biomimetic molecular cocatalysts, and semiconductor light harvester for artificial photosynthesis and therefore provide a promising approach for rational design and construction of highly efficient and stable artificial photosynthetic systems.

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Splitting Water with Cobalt

Cited by 1,294 publications

References 232 publications

Cobalt-vanadium bimetal-based nanoplates for efficient overall water splitting

Cobalt-vanadium bimetal-based nanoplates for efficient overall water splitting

Theoretical Modeling of Low‐Energy Electronic Absorption Bands in Reduced Cobaloximes

Hybrid Artificial Photosynthetic Systems Comprising Semiconductors as Light Harvesters and Biomimetic Complexes as Molecular Cocatalysts

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