journal article·2022-05Open access

Electrocatalytic layers for hydrogen evolution reaction based on nickel phosphides: cost-effective fabrication and XPS characterization

Roberto Bernasconi, Mohammed Ibrahim Khalil, Dogukan Selahattin Cakmakci, Yagmur Bektas, Luca Nobili, Luca Magagnin, Cristina Lenardi

Journal of Materials Science· Volume 57· Issue 20

Abstract

Abstract The development of efficient electrocatalysts based on Pt-free materials is a crucial step for the maturation of competitive water splitting technologies able to sustain the upcoming hydrogen-based economy. In this context, the present work optimizes a codeposition/annealing methodology to produce electrocatalytic layers for the hydrogen evolution reaction (HER) based on one of the most promising alternatives to Pt-based catalysts: nickel phosphides. A nickel–phosphorus solid solution is codeposited with red phosphorus microparticles and the obtained composites are annealed to promote interdiffusion and reaction between nickel and phosphorus. The experimentation carried out demonstrates that the properties of the final phosphide layers depend on the conditions employed in both the codeposition step and the annealing step. It is fundamental to evaluate and optimize the NiP/P codeposition process, and it is also important to understand the influence of annealing time and temperature on the microstructure and HER performance of the layers obtained. X-ray photoelectron spectroscopy (XPS) is employed to evaluate the phase composition at the surface, highlighting the presence of a top layer characterized by a Ni2P/Ni12P5 ratio significantly lower than the value found in the bulk of the coating. Annealed NiP/P layers are tested for HER in 0.5 M sulphuric acid solution. The tests demonstrate a clear correlation between the Ni2P/Ni12P5 ratio on the surface and the overpotential for HER. Coherently, when the outer Ni12P5-rich layer is mechanically removed, lower overpotentials are observed (169.5 mV vs. RHE for 10 mA cm−2).
Source: crossref · Quality: baseline

Research context

OpenAlex topics: Electrocatalysts for Energy Conversion · Advanced battery technologies research · Electrochemical Analysis and Applications

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

References (70)

Show source-provided references
1. Foley A, Olabi AG (2017) Renewable energy technology developments, trends and policy implications that can underpin the drive for global climate change. Renew Sustain Energy Rev 68:1112–111410.1016/j.rser.2016.12.065 ↗
2. Amrouche SO, Rekioua D, Rekioua T, Bacha S (2016) Overview of energy storage in renewable energy systems. Int J Hydrogen Energy 41:20914–2092710.1016/j.ijhydene.2016.06.243 ↗
3. Markovic NM (2013) Interfacing electrochemistry. Nat Mater 12:101–10210.1038/nmat3554 ↗
4. van Renssen S (2020) The hydrogen solution? Nat Clim Change 10:799–80110.1038/s41558-020-0891-0 ↗
5. Brouwer J (2010) On the role of fuel cells and hydrogen in a more sustainable and renewable energy future. Curr Appl Phys 10:S9–S1710.1016/j.cap.2009.11.002 ↗
6. Züttel A, Remhof A, Borgschulte A, Friedrichs O (2010) Hydrogen: the future energy carrier. Philos Trans R Soc A Math Phys Eng Sci 368:3329–3342. https://doi.org/10.1098/rsta.2010.011310.1098/rsta.2010.0113 ↗
7. Edwards PP, Kuznetsov VL, David WIF (2007) Hydrogen energy. Philos Trans R Soc A Math Phys Eng Sci 365:1043–105610.1098/rsta.2006.1965 ↗
8. Kelly NA (2014) Hydrogen production by water electrolysis. In: Basile A and Iulianelli A (eds) Advances in hydrogen production, storage and distribution. Elsevier, Amsterdam, Netherland, pp 159–18510.1533/9780857097736.2.159 ↗
9. Ezaki H, Morinaga M, Watanabe S (1993) Hydrogen overpotential for transition metals and alloys, and its interpretation using an electronic model. Electrochim Acta 38:557–564. https://doi.org/10.1016/0013-4686(93)85012-N10.1016/0013-4686(93)85012-N ↗
10. Eftekhari A (2017) Electrocatalysts for hydrogen evolution reaction. Int J Hydrogen Energy 42:11053–1107710.1016/j.ijhydene.2017.02.125 ↗
11. Salonen LM, Petrovykh DY, Kolen’ko YV (2021) Sustainable catalysts for water electrolysis: Selected strategies for reduction and replacement of platinum-group metals. Mater Today Sustain 11:10006010.1016/j.mtsust.2021.100060 ↗
12. Zheng Y, Jiao Y, Jaroniec M, Qiao SZ (2015) Advancing the electrochemistry of the hydrogen-evolution reaction through combining experiment and theory. Angew Chem Int Ed 54:52–6510.1002/anie.201407031 ↗
13. Gong M, Wang DY, Chen CC et al (2016) A mini review on nickel-based electrocatalysts for alkaline hydrogen evolution reaction. Nano Res 9:28–46. https://doi.org/10.1007/s12274-015-0965-x10.1007/s12274-015-0965-x ↗
14. Brown DE, Mahmood MN, Man MCM, Turner AK (1984) Preparation and characterization of low overvoltage transition metal alloy electrocatalysts for hydrogen evolution in alkaline solutions. Electrochim Acta 29:1551–1556. https://doi.org/10.1016/0013-4686(84)85008-210.1016/0013-4686(84)85008-2 ↗
15. Safizadeh F, Ghali E, Houlachi G (2015) Electrocatalysis developments for hydrogen evolution reaction in alkaline solutions—a review. Int J Hydrogen Energy 40:256–274. https://doi.org/10.1016/j.ijhydene.2014.10.10910.1016/j.ijhydene.2014.10.109 ↗
16. Lv H, Xi Z, Chen Z et al (2015) A new core/shell NiAu/Au nanoparticle catalyst with Pt-like activity for hydrogen evolution reaction. J Am Chem Soc 137:5859–5862. https://doi.org/10.1021/jacs.5b0110010.1021/jacs.5b01100 ↗
17. Li L, Zhang G, Wang B et al (2020) Electrochemical formation of PtRu bimetallic nanoparticles for highly efficient and pH-universal hydrogen evolution reaction. J Mater Chem A 8:2090–209810.1039/C9TA12300H ↗
18. Faber MS, Lukowski MA, Ding Q et al (2014) Earth-abundant metal pyrites (FeS2, CoS2, NiS2, and their alloys) for highly efficient hydrogen evolution and polysulfide reduction electrocatalysis. J Phys Chem C 118:21347–21356. https://doi.org/10.1021/jp506288w10.1021/jp506288w ↗
19. Wang F, Li Y, Shifa TA et al (2016) Selenium-enriched nickel selenide nanosheets as a robust electrocatalyst for hydrogen generation. Angew Chem Int Ed 55:6919–6924. https://doi.org/10.1002/anie.20160280210.1002/anie.201602802 ↗
20. Xiao P, Chen W, Wang X (2015) A review of phosphide-based materials for electrocatalytic hydrogen evolution. Adv Energy Mater 5:1–13. https://doi.org/10.1002/aenm.20150098510.1002/aenm.201500985 ↗
21. Du H, Kong RM, Guo X et al (2018) Recent progress in transition metal phosphides with enhanced electrocatalysis for hydrogen evolution. Nanoscale 10:21617–21624. https://doi.org/10.1039/c8nr07891b10.1039/c8nr07891b ↗
22. Wang Y, Kong B, Zhao D et al (2017) Strategies for developing transition metal phosphides as heterogeneous electrocatalysts for water splitting. Nano Today 15:26–55. https://doi.org/10.1016/j.nantod.2017.06.00610.1016/j.nantod.2017.06.006 ↗
23. Yu F, Zhou H, Huang Y et al (2018) High-performance bifunctional porous non-noble metal phosphide catalyst for overall water splitting. Nat Commun 9:1–9. https://doi.org/10.1038/s41467-018-04746-z10.1038/s41467-018-04746-z ↗
24. Ray A, Sultana S, Paramanik L, Parida KM (2020) Recent advances in phase, size, and morphology-oriented nanostructured nickel phosphide for overall water splitting. J Mater Chem A 8:19196–1924510.1039/D0TA05797E ↗
25. Jin M, Zhang X, Shi R et al (2021) Hierarchical CoP@ Ni2P catalysts for pH-universal hydrogen evolution at high current density. Appl Catal B Environ 296:12035010.1016/j.apcatb.2021.120350 ↗
26. Chen W-F, Muckerman JT, Fujita E (2013) Recent developments in transition metal carbides and nitrides as hydrogen evolution electrocatalysts. Chem Commun 49:8896–890910.1039/c3cc44076a ↗
27. Owens-Baird B, Kolen’ko Y V., Kovnir K, (2018) Structure–activity relationships for Pt-free metal phosphide hydrogen evolution electrocatalysts. Chem A Eur J 24:7298–7311. https://doi.org/10.1002/chem.20170532210.1002/chem.201705322 ↗
28. Huang Z, Chen Z, Chen Z et al (2014) Ni12P5 nanoparticles as an efficient catalyst for hydrogen generation via electrolysis and photoelectrolysis. ACS Nano 8:8121–812910.1021/nn5022204 ↗
29. Kucernak ARJ, Naranammalpuram Sundaram VN (2014) Nickel phosphide: the effect of phosphorus content on hydrogen evolution activity and corrosion resistance in acidic medium. J Mater Chem A 2:17435–17445. https://doi.org/10.1039/c4ta03468f10.1039/c4ta03468f ↗
30. Wexler RB, Martirez JMP, Rappe AM (2017) Active role of phosphorus in the hydrogen evolving activity of nickel phosphide (0001) surfaces. ACS Catal 7:7718–772510.1021/acscatal.7b02761 ↗
31. Park J, Koo B, Yoon KY et al (2005) Generalized synthesis of metal phosphide nanorods via thermal decomposition of continuously delivered metal–phosphine complexes using a syringe pump. J Am Chem Soc 127:8433–8440. https://doi.org/10.1021/ja042749610.1021/ja0427496 ↗
32. Read CG, Callejas JF, Holder CF, Schaak RE (2016) General strategy for the synthesis of transition metal phosphide films for electrocatalytic hydrogen and oxygen evolution. ACS Appl Mater Interfaces 8:12798–1280310.1021/acsami.6b02352 ↗
33. Liu P, Zhang Z-X, Jun SW et al (2019) Controlled synthesis of nickel phosphide nanoparticles with pure-phase Ni2P and Ni12P5 for hydrogenation of nitrobenzene. React Kinet Mech Catal 126:453–46110.1007/s11144-018-1496-8 ↗
34. Wang X, Kolen’ko YV, Liu L (2015) Direct solvothermal phosphorization of nickel foam to fabricate integrated Ni2P-nanorods/Ni electrodes for efficient electrocatalytic hydrogen evolution. Chem Commun 51:6738–6741. https://doi.org/10.1039/c5cc00370a10.1039/c5cc00370a ↗
35. Liu Z, Huang X, Zhu Z, Dai J (2010) A simple mild hydrothermal route for the synthesis of nickel phosphide powders. Ceram Int 36:1155–1158. https://doi.org/10.1016/j.ceramint.2009.12.01510.1016/j.ceramint.2009.12.015 ↗
36. Zhang G, Xu Q, Liu Y et al (2020) Red phosphorus as self-template to hierarchical nanoporous nickel phosphides toward enhanced electrocatalytic activity for oxygen evolution reaction. Electrochim Acta. https://doi.org/10.1016/j.electacta.2019.13550010.1016/j.electacta.2019.135500 ↗
37. Xiao J, Lv Q, Zhang Y et al (2016) One-step synthesis of nickel phosphide nanowire array supported on nickel foam with enhanced electrocatalytic water splitting performance. RSC Adv 6:107859–10786410.1039/C6RA20737E ↗
38. Wang X, Kolen’ko Y V, Bao X, et al (2015) One-step synthesis of self-supported nickel phosphide nanosheet array cathodes for efficient electrocatalytic hydrogen generation. Angew Chemie Int Ed 54:8188–819210.1002/anie.201502577 ↗
39. Wang X, Li W, Xiong D et al (2016) Bifunctional nickel phosphide nanocatalysts supported on carbon fiber paper for highly efficient and stable overall water splitting. Adv Funct Mater 26:4067–407710.1002/adfm.201505509 ↗
40. Wang X, Li W, Xiong D, Liu L (2016) Fast fabrication of self-supported porous nickel phosphide foam for efficient, durable oxygen evolution and overall water splitting. J Mater Chem A 4:5639–564610.1039/C5TA10317G ↗
41. Xing J, Zou Z, Guo K, Xu C (2018) The effect of phosphating time on the electrocatalytic activity of nickel phosphide nanorod arrays grown on Ni foam. J Mater Res 33:556–56710.1557/jmr.2017.399 ↗
42. Bains W, Petkowski JJ, Sousa-Silva C, Seager S (2019) Trivalent phosphorus and phosphines as components of biochemistry in anoxic environments. Astrobiology 19:885–90210.1089/ast.2018.1958 ↗
43. Sparling DW, Day D, Klein P (1999) Acute toxicity and sublethal effects of white phosphorus in mute swans, Cygnus olor. Arch Environ Contam Toxicol 36:316–32210.1007/s002449900477 ↗
44. Bernasconi R, Khalil MI, Iaquinta C et al (2020) Nickel phosphides fabricated through a codeposition-annealing technique as low-cost electrocatalytic layers for efficient hydrogen evolution reaction. ACS Appl Energy Mater 3:6525–653510.1021/acsaem.0c00733 ↗
45. Lelevic A, Walsh FC (2019) Electrodeposition of Ni-P alloy coatings: a review. Surf Coatings Technol 369:198–220. https://doi.org/10.1016/j.surfcoat.2019.03.05510.1016/j.surfcoat.2019.03.055 ↗
46. Alleg S, Boussaha A, Tebib W et al (2016) Microstructure and magnetic properties of NiP alloys. J Supercond Nov Magn 29:1001–101110.1007/s10948-016-3397-2 ↗
47. Baer DR, Engelhard MH (2010) XPS analysis of nanostructured materials and biological surfaces. J Electron Spectros Relat Phenomena 178:415–43210.1016/j.elspec.2009.09.003 ↗
48. Okamoto Y, Nitta Y, Imanaka T, Teranishi S (1979) Surface characterisation of nickel boride and nickel phosphide catalysts by X-ray photoelectron spectroscopy. J Chem Soc Faraday Trans 1 Phys Chem Condens Phases 75:2027–2039
49. Tiwari AP, Lee K, Kim K et al (2020) Conformally coated nickel phosphide on 3D, ordered nanoporous nickel for highly active and durable hydrogen evolution. ACS Sustain Chem Eng 8:17116–1712310.1021/acssuschemeng.0c05192 ↗
50. Sun T, Dong J, Huang Y et al (2018) Highly active and stable electrocatalyst of Ni2P nanoparticles supported on 3D ordered macro-/mesoporous Co-N-doped carbon for acidic hydrogen evolution reaction. J Mater Chem A 6:12751–12758. https://doi.org/10.1039/c8ta03672a10.1039/c8ta03672a ↗
51. Xin H, Guo K, Li D et al (2016) Production of high-grade diesel from palmitic acid over activated carbon-supported nickel phosphide catalysts. Appl Catal B Environ 187:375–38510.1016/j.apcatb.2016.01.051 ↗
52. Hovestad A, Janssen LJJ (1995) Electrochemical codeposition of inert particles in a metallic matrix. J Appl Electrochem 25:519–52710.1007/BF00573209 ↗
53. Łosiewicz B (2015) Electrodeposition mechanism of composite coatings. Solid State Phenom 228:65–78. https://doi.org/10.4028/www.scientific.net/SSP.228.6510.4028/www.scientific.net/SSP.228.65 ↗
54. Guglielmi N (1971) Kinetics of the deposition of inert particles from electrolytic baths. J Electrochem Soc 1501:1009–1012
55. Berçot P, Pea-Muoz E, Pagetti J (2002) Electrolytic composite Ni-PTFE coatings: an adaptation of Guglielmi’s model for the phenomena of incorporation. Surf Coat Technol 157:282–289. https://doi.org/10.1016/S0257-8972(02)00180-910.1016/S0257-8972(02)00180-9 ↗
56. Shrestha NK, Takebe T, Saji T (2006) Effect of particle size on the co-deposition of diamond with nickel in presence of a redox-active surfactant and mechanical property of the coatings. Diam Relat Mater 15:1570–1575. https://doi.org/10.1016/j.diamond.2005.12.04010.1016/j.diamond.2005.12.040 ↗
57. Bernasconi R, Allievi F, Sadeghi H, Magagnin L (2017) Codeposition of nickel–phosphorus alloys reinforced with boron carbide microparticles: direct and pulse plating. Trans IMF 95:52–5910.1080/00202967.2017.1263477 ↗
58. Okamoto H (2010) Ni–P (nickel–phosphorus). J Phase Equilibria Diffus 31:200–20110.1007/s11669-010-9664-1 ↗
59. Biesinger MC, Payne BP, Lau LWM et al (2009) X-ray photoelectron spectroscopic chemical state quantification of mixed nickel metal, oxide and hydroxide systems. Surf Interface Anal Int J Dev Appl Tech Anal Surf Interfaces Thin Film 41:324–332
60. Elsener B, Atzei D, Krolikowski A, Rossi A (2008) Effect of phosphorus concentration on the electronic structure of nanocrystalline electrodeposited Ni–P alloys: an XPS and XAES investigation. Surf Interface Anal 40:919–926. https://doi.org/10.1002/sia.280210.1002/sia.2802 ↗
61. Shimizu M, Tsushima Y, Arai S (2017) Electrochemical Na-insertion/extraction property of Ni-coated black phosphorus prepared by an electroless deposition method. ACS Omega 2:4306–431510.1021/acsomega.7b00950 ↗
62. Sherwood PMA (2002) Introduction to studies of phosphorus-oxygen compounds by XPS. Surf Sci Spectra 9:62–6610.1116/11.20030101 ↗
63. Pan Y, Liu Y, Zhao J et al (2015) Monodispersed nickel phosphide nanocrystals with different phases: synthesis, characterization and electrocatalytic properties for hydrogen evolution. J Mater Chem A 3:1656–166510.1039/C4TA04867A ↗
64. Hu C, Lv C, Liu S et al (2020) Nickel phosphide electrocatalysts for hydrogen evolution reaction. Catalysts. https://doi.org/10.3390/catal1002018810.3390/catal10020188 ↗
65. Wasalathanthri RN, Jeffrey S, Su N et al (2017) Stoichiometric control of electrocatalytic amorphous nickel phosphide to increase hydrogen evolution reaction activity and stability in acidic medium. ChemistrySelect 2:8020–802710.1002/slct.201701755 ↗
66. Jiang N, You B, Sheng M, Sun Y (2016) Bifunctionality and mechanism of electrodeposited nickel–phosphorous films for efficient overall water splitting. ChemCatChem 8:106–11210.1002/cctc.201501150 ↗
67. Chai L, Liu S, Pei S, Wang C (2021) Electrodeposited amorphous cobalt-nickel-phosphide-derived films as catalysts for electrochemical overall water splitting. Chem Eng J 420:129686. https://doi.org/10.1016/j.cej.2021.12968610.1016/j.cej.2021.129686 ↗
68. Wu Y, He H (2019) Electrodeposited nickel–iron–carbon–molybdenum film as efficient bifunctional electrocatalyst for overall water splitting in alkaline solution. Int J Hydrogen Energy 44:1336–1344. https://doi.org/10.1016/j.ijhydene.2018.11.16810.1016/j.ijhydene.2018.11.168 ↗
69. Liu S, Hu C, Lv C et al (2019) Facile preparation of large-area self-supported porous nickel phosphide nanosheets for efficient electrocatalytic hydrogen evolution. Int J Hydrogen Energy 44:17974–17984. https://doi.org/10.1016/j.ijhydene.2019.05.10010.1016/j.ijhydene.2019.05.100 ↗
70. Hu C, Cai J, Liu S et al (2020) General strategy for preparation of porous nickel phosphide nanosheets on arbitrary substrates toward efficient hydrogen generation. ACS Appl Energy Mater 3:1036–1045. https://doi.org/10.1021/acsaem.9b0206710.1021/acsaem.9b02067 ↗