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      Rational Phase Control in the Synthesis of Cobalt Sulfides

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          Abstract

          A library of substituted thioureas was used as sulfur reagents in the synthesis of cobalt sulfides. The substitution pattern of the thioureas controls the decomposition rate of precursors into sulfur monomers and thereby aids in the exploration of decomposition kinetics on cobalt sulfide-phase formation, including phase-pure jaipurite (CoS), cobalt pentlandite (Co 8S 9), linnaeite (Co 3S 4), and cattierite (CoS 2). We hypothesize that the available transformation pathways between phases during synthesis are dictated by the approximate ccp or hcp stacking of the sulfur lattice. Through gaining a complex understanding of the cobalt sulfide crystal system, phase-pure syntheses of all four naturally occurring crystalline structures in the cobalt sulfide system were achieved.

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          Most cited references33

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          Ultra-strength materials

          Ju Li, Ting Zhu (2010)
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            NANOMATERIALS. A tunable library of substituted thiourea precursors to metal sulfide nanocrystals.

            Controlling the size of colloidal nanocrystals is essential to optimizing their performance in optoelectronic devices, catalysis, and imaging applications. Traditional synthetic methods control size by terminating the growth, an approach that limits the reaction yield and causes batch-to-batch variability. Herein we report a library of thioureas whose substitution pattern tunes their conversion reactivity over more than five orders of magnitude and demonstrate that faster thiourea conversion kinetics increases the extent of crystal nucleation. Tunable kinetics thereby allows the nanocrystal concentration to be adjusted and a desired crystal size to be prepared at full conversion. Controlled precursor reactivity and quantitative conversion improve the batch-to-batch consistency of the final nanocrystal size at industrially relevant reaction scales.
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              Phase and composition controlled synthesis of cobalt sulfide hollow nanospheres for electrocatalytic water splitting

              This work demonstrates the controllable synthesis of cobalt sulfide hollow nanospheres and the phase-dependent catalytic properties for the OER and HER. Developing cheap, highly efficient and stable electrocatalysts for both oxygen and hydrogen evolution reactions (OER and HER) is extremely meaningful to realize large-scale implementation of water splitting technology. Herein, we report the phase and composition controlled synthesis of cobalt sulfide (CoS x ) hollow nanospheres (HNSs) and their catalytic efficiencies for hydrogen and oxygen evolution reactions in alkaline media. Three CoS x compounds, i.e. , Co 9 S 8 , Co 3 S 4 , and CoS 2 HNSs, were precisely synthesized by simply adjusting the molar ratio of carbon disulfide to cobalt acetate using a facile solution-based strategy. Electrochemical results reveal that the as-prepared CoS 2 HNSs exhibit superior OER and HER catalytic performance to Co 9 S 8 and Co 3 S 4 HNSs in 1.0 M KOH, with overpotentials of 290 mV for the OER and 193 mV for the HER at 10 mA cm −2 , and the corresponding Tafel slopes of 57 and 100 mV dec −1 , respectively. In addition, the CoS 2 HNSs exhibit remarkable long-term catalytic durability, which is even superior to precious metal catalysts of RuO 2 and Pt/C. Moreover, an alkaline electrolyzer assembled using CoS 2 HNSs as both anode and cathode materials can achieve 10 mA cm −2 at a low cell voltage of 1.54 V at 60 °C with a faradaic efficiency of 100% for overall water splitting. Further analysis demonstrates that the surface morphology, crystallographic structure and coordination environment of Co n+ active sites in combination determine the HER/OER activities in the synthesized binary CoS x series, which would provide insight into the rational design of transition metal chalcogenides for highly efficient hydrogen and oxygen-involved electrocatalysis.
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                Author and article information

                Journal
                Chem Mater
                Chem Mater
                cm
                cmatex
                Chemistry of Materials
                American Chemical Society
                0897-4756
                1520-5002
                31 July 2024
                13 August 2024
                : 36
                : 15
                : 7186-7196
                Affiliations
                []Department of Chemistry, Vanderbilt University , Nashville, Tennessee 37235, United States
                []Vanderbilt Institute of Nanoscale Science and Engineering, Vanderbilt University , Nashville, Tennessee 37235, United States
                Author notes
                Author information
                https://orcid.org/0000-0001-7571-337X
                https://orcid.org/0000-0001-6256-0706
                Article
                10.1021/acs.chemmater.4c00911
                11325534
                5c50f99e-8123-47b9-843f-7b8ba864cffa
                © 2024 The Authors. Published by American Chemical Society

                Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained ( https://creativecommons.org/licenses/by/4.0/).

                History
                : 28 March 2024
                : 01 July 2024
                : 28 June 2024
                Funding
                Funded by: Division of Chemistry, doi 10.13039/100000165;
                Award ID: CHE1905265
                Funded by: Division of Chemistry, doi 10.13039/100000165;
                Award ID: CHE2305161
                Categories
                Article
                Custom metadata
                cm4c00911
                cm4c00911

                Materials science
                Materials science

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