- Physical Review Journals
All JournalsPhysics Magazine

Physical Review Materials

Reuse & Permissions

It is not necessary to obtain permission to reuse this article or its components as it is available under the terms of the Creative Commons Attribution 4.0 International license. This license permits unrestricted use, distribution, and reproduction in any medium, provided attribution to the author(s) and the published article's title, journal citation, and DOI are maintained. Please note that some figures may have been included with permission from other third parties. It is your responsibility to obtain the proper permission from the rights holder directly for these figures.

Export citation

Export citation

Choose format for download:

Download Citation
  • Open Access

Effect of intrinsic point defects on the catalytic and electronic properties of Cu2WS4 single layer: Ab initio calculations

Tarik Ouahrani* and Reda M. Boufatah

Mohammed Benaissa

Ángel Morales-García

Michael Badawi

Daniel Errandonea†

  • Laboratoire de Physique Théorique, Université de Tlemcen, Tlemcen 13000, Algeria

  • Laboratory of Materials Discovery, Unit of Research Materials and Renewable Energies, LEPM-URMER, Université de Tlemcen, Tlemcen 13000, Algeria

  • Departament de Ciéncia de Materials i Química Física and Institut de Química Teórica i Computacional, Universitat de Barcelona, c/Martí i Franquès 1-11, 08028 Barcelona, Spain

  • Université de Lorraine, LPCT, UMR 7019, 54506 Vandoeuvre-lès-Nancy, France

  • Instituto de Ciencia de Materiales, Matter at High Pressure (MALTA) Consolider Team, Departamento de Física Aplicada, Universidad de Valencia, Edificio de Investigación, C/Dr. Moliner 50, Burjassot, 46100 Valencia, Spain

  • *Also at École supérieure en sciences appliquées, Boîte Postale. 165, Tlemcen 13000, Algeria; tarik.ouahrani@univ-tlemcen.dz
  • †daniel.errandonea@uv.es
PDF

Phys. Rev. Materials 7, 025403 – Published 17 February, 2023

DOI: https://doi.org/10.1103/PhysRevMaterials.7.025403

Abstract

The challenges imposed by climate change require the continued improvement and identification of materials for the development of green technologies. Point defect engineering is a promising technology for producing green hydrogen by taking advantage of catalytic hydrogen evolution reactions. In this work, we investigate the role of anionic and cationic vacancy point defects, as well as the nature of the active sites, in the catalytic activation of Cu2WS4 single layers. The stability of the pristine and defective structures of Cu2WS4 has been thoroughly investigated using density-functional theory calculations. A deep analysis of the formation enthalpy indicates that the Cu vacancy is the chemically most favorable vacancy. However, the calculated adsorption energy indicates that the presence of such vacancies slightly enhances the hydrogen evolution reaction. In contrast, the formation of an S vacancy considerably magnifies the same reaction in Cu2WS4 single layers.

View figure in article

Physics Subject Headings (PhySH)

Article Text

Supplemental Material

References (60)

  1. D. Er, H. Ye, N. C. Frey, H. Kumar, J. Lou, and V. B. Shenoy, Prediction of enhanced catalytic activity for hydrogen evolution reaction in Janus transition metal dichalcogenides, Nano Lett. 18, 3943 (2018).
  2. H. Wu, X. Li, R. Zhang, and J. Yang, Proposal of a stable B3S nanosheet as an efficient hydrogen evolution, J. Mater. Chem. A 7, 3752 (2019).
  3. S. Sun, G. Wang, Y. Zhou, F. Wang, and X. Xia, High-performance Ru@C4N electrocatalyst for hydrogen evolution reaction in both acidic and alkaline solutions, ACS Appl. Mater. Interfaces 11, 19176 (2019).
  4. Y. Zheng, Y. Jiao, M. Jaroniec, and S. Z. Qiao, Advancing the electrochemistry of the hydrogen-evolution reaction through combining experiment and theory, Angew. Chem., Int. Ed. 54, 52 (2015).
  5. L. Shi, C. Ling, Y. Ouyang, and J. Wang, High intrinsic catalytic activity of two-dimensional boron monolayers for the hydrogen evolution reaction, Nanoscale 9, 533 (2017).
  6. L. Luo, B. Wang, J. Jiang, M. Fitzgerald, Q. Huang, Z. Yu, H. Li, J. Zhang, J. Wei, C. Yang, H. Zhang, L. Dong, and S Chen, Heavy metal contaminations in herbal medicines: Determination, comprehensive risk assessments and solutions, Front. Pharmacol. 11, 595335 (2020).
  7. H. Li, C. Tsai, A. L. Koh, L. Cai, A. W. Contryman, A. H. Fragapane, J. Zhao, H. S. Han, H. C. Manoharan, F. A. Pedersen, J. K. Nørskov, and X. Zheng, Activating and optimizing MoS2 basal planes for hydrogen evolution through the formation of strained sulphur vacancies, Nat. Mater. 15, 48 (2016).
  8. Y. R. An, X. L. Fan, Z. F. Luo, and W. M. Lau, Nanopolygons of monolayer MS2: Best morphology and size for HER catalysis, Nano Lett. 17, 368 (2017).
  9. B. Guo, K. Yu, H. Li, R. Qi, Y. Zhang, H. Song, Z. Tang, Z. Zhu, and M. Chen, Coral-shaped MoS2 decorated with graphene quantum dots performing as a highly active electrocatalyst for hydrogen evolution reaction, ACS Appl. Mater. Inter. 9, 3653 (2017).
  10. R. Luo, M. Luo, Z. Wang, P. Liu, S. Song, X. Wang, and M. Chen, The atomic origin of nickel-doping-induced catalytic enhancement in MoS2 for electrochemical hydrogen production, Nanoscale 11, 7123 (2019).
  11. X. C. Yan, Y. Jia, and X. D. Yao, Defects on carbons for electrocatalytic oxygen reduction, Chem. Soc. Rev. 47, 7628 (2018).
  12. Y. Jia, K. Jiang, H. Wang, and X. Yao, The role of defect sites in nanomaterials for electrocatalytic energy conversion, Chem 5, 1371 (2019).
  13. Q. Wu, Y. Ma, R. Peng, B. Huang, and Y. Dai, Single-layer Cu2WS4 with promising electrocatalytic activity towards hydrogen evolution reaction, ACS Appl. Mater. Interfaces 11, 45818 (2019).
  14. Q. Wu, W. Wei, X. Lu, B. Huang, and Y. Dai, Computational screening of defective group IVA monochalcogenides as efficient catalysts for hydrogen evolution reaction, J. Phys. Chem. C 123, 11791 (2019).
  15. D. Deng, L. Yu, X. Pan, S. Wang, X. Chen, P. Hu, L. Sun, and X. Bao, Size effect of graphene on electrocatalytic activation of oxygen, Chem. Commun. 47, 10016 (2011).
  16. S. Dou, L. Tao, R. L. Wang, S. El Hankari, R. Chen, and S. Y. Wang, Plasma-assisted synthesis and surface modification of electrode materials for renewable energy, Adv. Mater. 30, 1705850 (2018).
  17. X. Wang, L. Z. Zhuang, Y. Jia, H. L. Liu, X. C. Yan, L. Z. Zhang, D. J. Yang, Z. H. Zhu, and X. D. Yao, Plasma-triggered synergy of exfoliation, phase transformation and surface engineering in cobalt diselenide for enhanced water oxidation, Angew. Chem., Int. Ed. 57, 16421 (2018).
  18. M. Niaounakis, Surface treatment, in Biopolymers: Processing and Products (Elsevier, Amsterdam, 2014), p. 303.
  19. Y. Yan, L.-C. Xu, E. A. Vogler, and C. A. Siedlecki, Contact activation by the intrinsic pathway of blood plasma coagulation hemocompatibility of biomaterials for clinical applications, in Blood-Biomaterials Interactions (Elsevier, Amsterdam, 2018), pp. 3–28.
  20. E. A. Pruss, B. S. Snyder, and A. M. Stacy, A new layered ternary sulfide: Formation of Cu2WS4 by reaction of WS42− and Cu+ ions, Angew. Chem., Int. Ed. 32, 256 (1993).
  21. C. J. Crossland, P. J. Hickey, and J. S. O. Evans, The synthesis and characterization of Cu2MX4 (M = W or Mo; X = S, Se or S/Se) materials prepared by a solvothermal method, J. Mater. Chem. 15, 3452 (2005).
  22. B. Polyakov, A. Kuzmin, S. Vlassov, E. Butanovs, J. Zideluns, J. Butikova, R. Kalendarev, and M. Zubkins, A comparative study of heterostructured CuO/CuWO4 nanowires and thin films, J. Cryst. Growth 480, 78 (2017).
  23. J. Y. Zheng, G. Song, C. W. Kim, and Y. S. Kang, Facile preparation of p-CuO and p-CuO/n-CuWO4 junction thin films and their photoelectrochemical properties, Electrochim. Acta 69, 340 (2012).
  24. N. F. Andrade Neto, Y. G. Oliveira, J. H. O. Nascimento, M. R. D. Bomio, and F. V. Motta, Influence of pH variation on CuWO4, CuWO4/WO3 and CuWO4/CuO structures stabilization: Study of the photocatalytic properties under sunlight, J. Mater. Sci. Mater. Electron. 31, 18221 (2020).
  25. A. P. Tiwari, A. Azam, T. G. Novak, O. Prakash, and S. Jeon, Chemical strain formation through anion substitution in Cu2WS4 for efficient electrocatalysis to water dissociation, J. Mater. Chem. A 6, 7786 (2018).
  26. C. Freysoldt, B. Grabowski, T. Hickel, J. Neugebauer, G. Kresse, A. Janotti, and C. G. Van de Walle, First-principles calculations for point defects in solids, Rev. Mod. Phys. 86, 253 (2014).
  27. D. Broberg, B. Medasani, N. E. R. Zimmermann, G. Yu, A. Canning, M. Haranczyk, M. Asta, and G. Hautier, PyCDT: A Python toolkit for modeling point defects in semiconductors and insulators, Comput. Phys. Commun. 226, 165 (2018).
  28. X. Hu, W. Shao, X. Hang, X. Zhang, W. Zhu, and Y. Xie, Superior electrical conductivity in hydrogenated layered ternary chalcogenide nanosheets for flexible all-solid-state supercapacitors, Angew. Chem., Int. Ed. 55, 5733 (2016).
  29. G. Kresse and J. Furthmüller, Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set, Comput. Mater. Sci. 6, 15 (1996).
  30. G. Kresse and J. Hafner, Ab initio molecular dynamics for liquid metals, Phys. Rev. B 47, 558 (1993).
  31. H. Z. Guedda, T. Ouahrani, A. Morales-García, R. Franco, M. A. Salvadó, P. Pertierra, and J. M. Recio, Computer simulations of 3C-SiC under hydrostatic and non-hydrostatic stresses, Phys. Chem. Chem. Phys. 18, 8132 (2016).
  32. P. E. Blöchl, Projector augmented-wave method, Phys. Rev. B 50, 17953 (1994).
  33. J. P. Perdew, K. Burke, and M. Ernzerhof, Generalized Gradient Approximation Made Simple, Phys. Rev. Lett. 77, 3865 (1996).
  34. H. J. Monkhorst and J. D. Pack, Special points for Brillouin-zone integrations, Phys. Rev. B 13, 5188 (1976).
  35. S. Grimme, J. Antony, S. Ehrlich, and H. Krieg, A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT−D) for the 94 elements H−Pu, J. Chem. Phys. 132, 154104 (2010).
  36. S. Grimme, S. Ehrlich, and L. Goerigk, Effect of the damping function in dispersion corrected density functional theory, J. Comput. Chem. 32, 1456 (2011).
  37. G. J. Martyna, M. L. Klein, and M. Tuckerman, Nose-Hoover chains: The canonical ensemble via continuous dynamics, J. Chem. Phys. 97, 2635 (1992).
  38. S. Nosé, A molecular dynamics method for simulations in the canonical ensemble, Mol. Phys. 52, 255 (1984).
  39. S. Nosé, A unified formulation of the constant temperature molecular dynamics methods, J. Chem. Phys. 81, 511 (1984).
  40. A. Togo and I. Tanaka, First-principles phonon calculations in materials science, Scr. Mater. 108, 1 (2015).
  41. X. Gonze and C. Lee, Dynamical matrices, born effective charges, dielectric permittivity tensors, and interatomic force constants from density-functional perturbation theory, Phys. Rev. B 55, 10355 (1997).
  42. J. K. Nørskov, J. Rossmeisl, A. Logadottir, L. Lindqvist, J. R. Kitchin, T. Bligaard, and H. Jonsson, Origin of the overpotential for oxygen reduction at a fuel-cell cathode, J. Phys. Chem. B 108, 17886 (2004).
  43. J. Greeley, T. F. Jaramillo, J. Bonde, I. Chorkendorff, and J. K. Nørskov, Computational high-throughput screening of electrocatalytic materials for hydrogen evolution, Nat. Mater. 5, 909 (2006).
  44. M. Huang, S.-S. Wang, Y.-N. Wu, and S. Chen, Defect Physics of Ternary Semiconductor ZnGeP2 With a High Density of Anion-Cation Antisites: A First-Principles Study, Phys. Rev. Appl. 15, 024035 (2021).
  45. J. Heyd, G. E. Scuseria, and M. Ernzerhof, Hybrid functionals based on a screened Coulomb potential, J. Chem. Phys. 118, 8207 (2003).
  46. L. Wang, K. Zhang, J. Luo, J.-Y. Ma, W. Ji, Q. Hong, H. Xu, W. Huang, N. Yan, and Z. Qu, Metastable facet-controlled Cu2WS4 single crystals with enhanced adsorption activity for gaseous elemental mercury, Environ. Sci. Technol. 55, 5347 (2021).
  47. L. Qin, Z. Wen, X. Zhang, K. Zhang, Y. Lin, L. Song, X. J. Wu, and X. Qiu, Multiphonon raman scattering and strong electron-phonon coupling in 2D ternary Cu2MoS4 nanoflakes, J. Phys. Chem. Lett. 11, 8483 (2020).
  48. V. Wang, N. Xu, J. C. Liu, G. Tang, and W. T. Geng, VASPKIT: A user-friendly interface facilitating high-throughput computing and analysis using VASP code, Comput. Phys. Commun. 267, 108033 (2021).
  49. See Supplemental Material at http://link.aps.org/supplemental/10.1103/PhysRevMaterials.7.025403 for additional information on calculated elastic constants, convergence tests, constraints used for determining stability conditions, calculated ΔGH for the active sites, chemical potential phase diagrams, and calculated electronic densities and band structure.
  50. M. Born and H. Huang, Dynamical Theory of Crystal Lattices (Clarendon, Oxford. 1954).
  51. F. Mouhat and F. X. Coudert, Necessary and sufficient elastic stability conditions in various crystal systems, Phys. Rev. B 90, 224104 (2014).
  52. Y. Yin, Y. Wu, G. Chen, and W.-J. Yin, Double perovskite Ba2BiTaO6 as a promising p-type transparent conductive oxide: A first-principles defect study, J. Appl. Phys. 127, 175703 (2020).
  53. J. Dabrowski and G. Kissinger, Supercell-size convergence of formation energies and gap levels of vacancy complexes in crystalline silicon in density functional theory calculations, Phys. Rev. B 92, 144104 (2015).
  54. C. Freysoldt and J. Neugebauer, First-principles calculations for charged defects at surfaces, interfaces, and two-dimensional materials in the presence of electric fields, Phys. Rev. B 97, 205425 (2018).
  55. J. Buckeridge, D. O. Scanlon, A. Walsh, and C. R. A. Catlow, Automated procedure to determine the thermodynamic stability of a material and the range of chemical potentials necessary for its formation relative to competing phases and compounds, Comput. Phys. Commun. 185, 330 (2014).
  56. Y. Huang, C. Wang, X. Chen, D. Zhou, J. Du, S. Wang, and L. Ning, First-principles study on intrinsic defects of SnSe, RSC Adv. 7, 27612 (2017).
  57. T. Ouahrani, A. B. Garg, R. Rao, P. Rodríguez-Hernández, A. Muñoz, M. Badawi, and D. Errandonea, High-Pressure properties of wolframite-type ScNbO4, J. Phys. Chem. C 126, 4664 (2022).
  58. J. K. Nørskov, T. Bligaard, A. Logadottir, J. R. Kitchin, J. G. Chen, S. Pandelov, and U. Stimming, Trends in the exchange current for hydrogen evolution, J. Electrochem. Soc. 152, J23 (2005).
  59. T. Ouahrani, A. Daouli, M. Badawi, L. Bendaoudi, A. Morales-Garcia, and D. Errandonea, Understanding the thermodynamic, dynamic, bonding, and electrocatalytic properties of low dimensional MgPSe3, Dalton Trans. 51, 9689 (2022).
  60. K. Y. Kim, J. Lee, S. Kang, Y.-W. Son, H. W. Jang, Y. Kang, and S. Han, Role of hyper-reduced states in hydrogen evolution reaction at sulfur vacancy in MoS2, ACS Catal. 8, 4508 (2018).

Outline

Information

Phys. Rev. Materials 7, 025403– Published 17 February, 2023
  • Received 22 September 2022
  • Revised 30 December 2022
  • Accepted 8 February 2023
Crossmark - Check for updates button
Creative Commons Logo

Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license. Further distribution of this work must maintain attribution to the author(s) and the published article's title, journal "citation, and DOI.

©2023 American Physical Society

Sign In to Your Journals Account

Filter

Filter

Article Lookup

Enter a citation