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Cobalt

About: Cobalt is a research topic. Over the lifetime, 69899 publications have been published within this topic receiving 1242058 citations. The topic is also known as: Co & Element 27.


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Journal ArticleDOI
01 Nov 2019-Nature
TL;DR: Improved molecule-based electrocatalyst converts CO2 to methanol with considerable activity and selectivity and with stable performance over at least 12 hours.
Abstract: Electrochemical carbon dioxide (CO2) reduction can in principle convert carbon emissions to fuels and value-added chemicals, such as hydrocarbons and alcohols, using renewable energy, but the efficiency of the process is limited by its sluggish kinetics1,2. Molecular catalysts have well defined active sites and accurately tailorable structures that allow mechanism-based performance optimization, and transition-metal complexes have been extensively explored in this regard. However, these catalysts generally lack the ability to promote CO2 reduction beyond the two-electron process to generate more valuable products1,3. Here we show that when immobilized on carbon nanotubes, cobalt phthalocyanine—used previously to reduce CO2 to primarily CO—catalyses the six-electron reduction of CO2 to methanol with appreciable activity and selectivity. We find that the conversion, which proceeds via a distinct domino process with CO as an intermediate, generates methanol with a Faradaic efficiency higher than 40 per cent and a partial current density greater than 10 milliamperes per square centimetre at −0.94 volts with respect to the reversible hydrogen electrode in a near-neutral electrolyte. The catalytic activity decreases over time owing to the detrimental reduction of the phthalocyanine ligand, which can be suppressed by appending electron-donating amino substituents to the phthalocyanine ring. The improved molecule-based electrocatalyst converts CO2 to methanol with considerable activity and selectivity and with stable performance over at least 12 hours. Individual cobalt phthalocyanine derivative molecules immobilized on carbon nanotubes effectively catalyse the electroreduction of CO2 to methanol via a domino process with high activity and selectivity and stable performance.

550 citations

Journal ArticleDOI
TL;DR: In this article, a simple approach to the preparation of cobalt sulfide nanoparticles in situ grown on a nitrogen and sulfur codoped graphene oxide surface was presented, where the particle size and phase were controlled by changing the treatment temperature.
Abstract: Electrochemical oxygen evolution and reduction reactions have received great attention due to their importance in several key technologies such as fuel cells, electrolyzers, and metal–air batteries. Here, we present a simple approach to the preparation of cobalt sulfide nanoparticles in situ grown on a nitrogen and sulfur codoped graphene oxide surface. The particle size and phase were controlled by changing the treatment temperature. Cobalt sulfide nanoparticles dispersed on graphene oxide hybrids were successfully prepared by a solid-state thermolysis approach at different temperatures (400, 500, and 600 °C) using cobalt thiourea and graphene oxide. X-ray diffraction studies revealed that hybrids prepared at 400 and 500 °C result in pure CoS2 phase, whereas the hybrid prepared at 600 °C exhibits Co9S8 phase. X-ray photoelectron spectroscopy studies revealed that nitrogen and sulfur simultaneously codoped on the graphene oxide surface, and these sites act to anchor the CoS2 nanoparticles strongly on the ...

547 citations

Journal ArticleDOI
TL;DR: The best mediator, based on tris(4,4'-di-tert-butyl-2,2'-dipyridyl)cobalt(II/III) perchlorate, resulted in DSSCs exhibiting efficiencies within 80% of that of a comparable iodide/triiodide-mediated DSSC, representing a nonvolatile, noncorrosive, and practical alternative as an efficient electron-transfer mediator in D SSCs.
Abstract: A number of cobalt complexes of substituted polypyridine ligands were synthesized and investigated as possible alternatives to the volatile and corrosive iodide/triiodide redox couple commonly used as an electron-transfer mediator in dye-sensitized solar cells (DSSCs). The extinction coefficients in the visible spectrum are on the order of 10(2) M(-1) cm(-1) for the majority of these complexes, diminishing competition with the light-harvesting dye. Cyclic voltammetric studies revealed a dramatic surface dependence of the heterogeneous electron-transfer rate, which is surprisingly different for gold, carbon, and platinum electrodes. DSSCs were assembled using a mediator that consisted of a mixture of Co(II) and Co(III) complexes in a 10:1 ratio. DSSCs containing these mediators were used to characterize incident photon-to-current conversion efficiency and photoelectrochemical responses. The best performing of these mediators were identified and subjected to further study. As suggested by electrochemical results, gold and carbon are superior cathode materials to platinum, and no evidence of corrosion on any cathode material was observed. Addition of lithium salts to the mediator solution resulted in a dramatic improvement in cell performance. The observed Li(+) effect is explained in terms of the recombination of injected electrons in the photoanode with the oxidized mediator. The best mediator, based on tris(4,4'-di-tert-butyl-2,2'-dipyridyl)cobalt(II/III) perchlorate, resulted in DSSCs exhibiting efficiencies within 80% of that of a comparable iodide/triiodide-mediated DSSC. Due to the commercial availability of the ligand and the simplicity with which the complex can be made, this new mediator represents a nonvolatile, noncorrosive, and practical alternative as an efficient electron-transfer mediator in DSSCs.

542 citations

Journal ArticleDOI
01 Feb 2019
TL;DR: Wei et al. as discussed by the authors used operando X-ray absorption spectroscopy on a uniform cobalt single-site catalyst to identify the dynamic structure of catalytically active sites under alkaline hydrogen evolution reaction (HER).
Abstract: Monitoring atomic and electronic structure changes on active sites under realistic working conditions is crucial for the rational design of efficient electrocatalysts. Identification of the active structure during the alkaline hydrogen evolution reaction (HER), which is critical to industrial water–alkali electrolysers, remains elusive and is a field of intense research. Here, by virtue of operando X-ray absorption spectroscopy on a uniform cobalt single-site catalyst, we report the atomic-level identification of the dynamic structure of catalytically active sites under alkaline HER. Our results reveal the formation of a high-valence HO–Co1–N2 moiety by the binding between isolated Co1–N4 sites with electrolyte hydroxide, and further unravel the preferred water adsorption reaction intermediate H2O–(HO–Co1–N2). Theoretical simulations rationalize this structural evolution and demonstrate that the highly oxidized Co sites are responsible for the catalytic performance. These findings suggest the electrochemical susceptibility of active sites, providing a coordination-engineered strategy for the advance of single-site catalysis. Carbon-based single-atom catalysts usually rely on nitrogen co-doping to stabilize the single metal atoms as metal–N4 moieties. Now, Wei, Yao and colleagues make use of operando techniques to show that under alkaline hydrogen evolution reaction conditions the Co–N4 active site undergoes structural distortion to a HO–Co–N2 configuration.

538 citations

Journal ArticleDOI
TL;DR: The coupled oxidation method, when applied to the histochemical demonstration of HRP in combination with cobalt method 1, was found to give excellent electron microscopical pictures of the electron dense reaction product.

537 citations


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Performance
Metrics
No. of papers in the topic in previous years
YearPapers
20232,622
20225,202
20212,220
20202,950
20193,215
20183,007