Synthesis of High Entropy and Entropy-Stabilized Metal Sulfides and Their Evaluation as Hydrogen Evolution Electrocatalysts

Weichen Xiao; Yi Li; Amr Elgendy; Ercin C. Duran; Mark A. Buckingham; Ben F. Spencer; Bing Han; Firoz Alam; Xiangli Zhong; Sarah H. Cartmell; Robert J. Cernik; Alexander S. Eggeman; Robert A.W. Dryfe; David J. Lewis

doi:10.1021/acs.chemmater.3c00363

Synthesis of High Entropy and Entropy-Stabilized Metal Sulfides and Their Evaluation as Hydrogen Evolution Electrocatalysts

Weichen Xiao, Yi Li, Amr Elgendy, Ercin C. Duran, Mark A. Buckingham, Ben F. Spencer, Bing Han, Firoz Alam, Xiangli Zhong, Sarah H. Cartmell, Robert J. Cernik, Alexander S. Eggeman, Robert A.W. Dryfe, David J. Lewis^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

19 Citations (Scopus)

Abstract

High entropy metal chalcogenides are materials containing five or more elements within a disordered sublattice. These materials exploit a high configurational entropy to stabilize their crystal structure and have recently become an area of significant interest for renewable energy applications such as electrocatalysis and thermoelectrics. Herein, we report the synthesis of bulk particulate HE zinc sulfide analogues containing four, five, and seven metals. This was achieved using a molecular precursor cocktail approach with both transition and main group metal dithiocarbamate complexes which are decomposed simultaneously in a rapid (1 h) and low-temperature (500 °C) thermolysis reaction to yield high entropy and entropy-stabilized metal sulfides. The resulting materials were characterized by powder XRD, SEM, and TEM, alongside EDX spectroscopy at both the micro- and nano-scales. The entropy-stabilized (CuAgZnCoMnInGa)S material was demonstrated to be an excellent electrocatalyst for the hydrogen evolution reaction when combined with conducting carbon black, achieving a low onset overpotential of (∼80 mV) and η₁₀ of (∼255 mV).

Original language	English
Pages (from-to)	7904-7914
Number of pages	11
Journal	Chemistry of Materials
Volume	35
Issue number	19
DOIs	https://doi.org/10.1021/acs.chemmater.3c00363
Publication status	Published - 10 Oct 2023
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2023 The Authors. Published by American Chemical Society.

Funding

A.E. (Amr Ahmed Sadek) would like to thank the Newton-Mosharafa Fund (a partnership between the British Council and the Ministry of Higher Education─Missions Sector, Egypt) for supporting him in the form of a full PhD scholarship. E.C.D. acknowledges financial support from the Republic of Turkey Ministry of National Education. M.A.B., D.J.L., and R.A.W.D. acknowledge support from the EPSRC (EP/W033348/1). B. S. acknowledges support for the XPS at UoM by the Henry Royce Institute for Advanced Materials, funded through EPSRC grants EP/R00661 X/1, EP/S019367/1, EP/P025021/1, and EP/P025498/1. A.E. acknowledges support by the Henry Royce Institute for Advanced Materials, funded through EPSRC grants EP/R00661 X/1, EP/S019367/1, EP/P025021/1, EP/S021531/1, and EP/P025498/1. R.A.W.D. gratefully acknowledges further support from the EPSRC (EP/T01816 X/1). D.J.L. thanks the EPSRC (EP/R022518/1) for funding. a

Funders	Funder number
Henry Royce Institute	EP/R00661 X/1, EP/S021531/1, EP/S019367/1, EP/R022518/1, EP/T01816 X/1, EP/P025021/1, EP/P025498/1
Engineering and Physical Sciences Research Council	EP/W033348/1
British Council
Ministry of Higher Education

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Xiao, W., Li, Y., Elgendy, A., Duran, E. C., Buckingham, M. A., Spencer, B. F., Han, B., Alam, F., Zhong, X., Cartmell, S. H., Cernik, R. J., Eggeman, A. S., Dryfe, R. A. W., & Lewis, D. J. (2023). Synthesis of High Entropy and Entropy-Stabilized Metal Sulfides and Their Evaluation as Hydrogen Evolution Electrocatalysts. Chemistry of Materials, 35(19), 7904-7914. https://doi.org/10.1021/acs.chemmater.3c00363

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title = "Synthesis of High Entropy and Entropy-Stabilized Metal Sulfides and Their Evaluation as Hydrogen Evolution Electrocatalysts",

abstract = "High entropy metal chalcogenides are materials containing five or more elements within a disordered sublattice. These materials exploit a high configurational entropy to stabilize their crystal structure and have recently become an area of significant interest for renewable energy applications such as electrocatalysis and thermoelectrics. Herein, we report the synthesis of bulk particulate HE zinc sulfide analogues containing four, five, and seven metals. This was achieved using a molecular precursor cocktail approach with both transition and main group metal dithiocarbamate complexes which are decomposed simultaneously in a rapid (1 h) and low-temperature (500 °C) thermolysis reaction to yield high entropy and entropy-stabilized metal sulfides. The resulting materials were characterized by powder XRD, SEM, and TEM, alongside EDX spectroscopy at both the micro- and nano-scales. The entropy-stabilized (CuAgZnCoMnInGa)S material was demonstrated to be an excellent electrocatalyst for the hydrogen evolution reaction when combined with conducting carbon black, achieving a low onset overpotential of (∼80 mV) and η10 of (∼255 mV).",

author = "Weichen Xiao and Yi Li and Amr Elgendy and Duran, {Ercin C.} and Buckingham, {Mark A.} and Spencer, {Ben F.} and Bing Han and Firoz Alam and Xiangli Zhong and Cartmell, {Sarah H.} and Cernik, {Robert J.} and Eggeman, {Alexander S.} and Dryfe, {Robert A.W.} and Lewis, {David J.}",

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Xiao, W, Li, Y, Elgendy, A, Duran, EC, Buckingham, MA, Spencer, BF, Han, B, Alam, F, Zhong, X, Cartmell, SH, Cernik, RJ, Eggeman, AS, Dryfe, RAW & Lewis, DJ 2023, 'Synthesis of High Entropy and Entropy-Stabilized Metal Sulfides and Their Evaluation as Hydrogen Evolution Electrocatalysts', Chemistry of Materials, vol. 35, no. 19, pp. 7904-7914. https://doi.org/10.1021/acs.chemmater.3c00363

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AU - Xiao, Weichen

AU - Li, Yi

AU - Elgendy, Amr

AU - Duran, Ercin C.

AU - Buckingham, Mark A.

AU - Spencer, Ben F.

AU - Han, Bing

AU - Alam, Firoz

AU - Zhong, Xiangli

AU - Cartmell, Sarah H.

AU - Cernik, Robert J.

AU - Eggeman, Alexander S.

AU - Dryfe, Robert A.W.

AU - Lewis, David J.

PY - 2023/10/10

Y1 - 2023/10/10

N2 - High entropy metal chalcogenides are materials containing five or more elements within a disordered sublattice. These materials exploit a high configurational entropy to stabilize their crystal structure and have recently become an area of significant interest for renewable energy applications such as electrocatalysis and thermoelectrics. Herein, we report the synthesis of bulk particulate HE zinc sulfide analogues containing four, five, and seven metals. This was achieved using a molecular precursor cocktail approach with both transition and main group metal dithiocarbamate complexes which are decomposed simultaneously in a rapid (1 h) and low-temperature (500 °C) thermolysis reaction to yield high entropy and entropy-stabilized metal sulfides. The resulting materials were characterized by powder XRD, SEM, and TEM, alongside EDX spectroscopy at both the micro- and nano-scales. The entropy-stabilized (CuAgZnCoMnInGa)S material was demonstrated to be an excellent electrocatalyst for the hydrogen evolution reaction when combined with conducting carbon black, achieving a low onset overpotential of (∼80 mV) and η10 of (∼255 mV).

AB - High entropy metal chalcogenides are materials containing five or more elements within a disordered sublattice. These materials exploit a high configurational entropy to stabilize their crystal structure and have recently become an area of significant interest for renewable energy applications such as electrocatalysis and thermoelectrics. Herein, we report the synthesis of bulk particulate HE zinc sulfide analogues containing four, five, and seven metals. This was achieved using a molecular precursor cocktail approach with both transition and main group metal dithiocarbamate complexes which are decomposed simultaneously in a rapid (1 h) and low-temperature (500 °C) thermolysis reaction to yield high entropy and entropy-stabilized metal sulfides. The resulting materials were characterized by powder XRD, SEM, and TEM, alongside EDX spectroscopy at both the micro- and nano-scales. The entropy-stabilized (CuAgZnCoMnInGa)S material was demonstrated to be an excellent electrocatalyst for the hydrogen evolution reaction when combined with conducting carbon black, achieving a low onset overpotential of (∼80 mV) and η10 of (∼255 mV).

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Synthesis of High Entropy and Entropy-Stabilized Metal Sulfides and Their Evaluation as Hydrogen Evolution Electrocatalysts

Abstract

Bibliographical note

Funding

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