Self-supporting and hierarchically porous Ni _xFe—S/NiFe₂O₄ heterostructure as a bifunctional electrocatalyst for fluctuating overall water splitting

Abstract

Stable non-noble metal bifunctional electrocatalysts are one of the challenges to the fluctuating overall water splitting driven by renewable energy. Herein, a novel self-supporting hierarchically porous Ni _xFe—S/NiFe₂O₄ heterostructure as bifunctional electrocatalyst was constructed based on porous Ni—Fe electrodeposition on three-dimensional (3D) carbon fiber cloth, in situ oxidation, and chemical sulfuration. Results showed that the Ni _xFe—S/NiFe₂O₄ heterostructure with a large specific surface area exhibits good bifunctional activity and stability for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) because of the abundance of active sites, synergistic effect of the heterostructure, superhydrophilic surface, and stable, self-supporting structure. The results further confirmed that the Ni _xFe—S phase in the heterostructure is transformed into metal oxides/hydroxides and Ni₃S₂ during OER. Compared with the commercial 20wt% Pt/C∥IrO₂—Ta₂O₅ electrolyzer, the self-supporting Ni_1/5Fe—S/NiFe₂O₄∥Ni_1/2Fe—S/NiFe₂O₄ electrolyzer exhibits better stability and lower cell voltage in the fluctuating current density range of 10–500 mA/cm². Particularly, the cell voltage of Ni_1/5Fe—S/NiFe₂O₄∥Ni_1/2Fe—S/NiFe₂O₄ is only approximately 3.91 V at an industrial current density of 500 mA/cm², which is lower than that of the 20wt% Pt/C∥IrO₂—Ta₂O₅ electrolyzer (i.e., approximately 4.79 V). This work provides a promising strategy to develop excellent bifunctional electrocatalysts for fluctuating overall water splitting.

Keywords

self-supporting / hierarchically porous structure / heterostructure / bifunctional catalyst / overall water splitting

References

[1] Wang XS, Zheng Y, Sheng WC, Xu ZJ, Jaroniec M, Qiao SZ. Strategies for design of electrocatalysts for hydrogen evolution under alkaline conditions. Mater. Today, 2020, 36, 125.

[2] Tang J, Chu MS, Li F, Feng C, Liu ZG, Zhou YS. Development and progress on hydrogen metallurgy. Int. J. Miner. Metall. Mater., 2020, 27(6): 713.

[3] Suen NT, Hung SF, Quan Q, Zhang N, Xu YJ, Chen HM. Electrocatalysis for the oxygen evolution reaction: Recent development and future perspectives. Chem. Soc. Rev., 2017, 46(2): 337.

[4] Wang M, Zhang L, He YJ, Zhu HW. Recent advances in transition-metal-sulfide-based bifunctional electrocatalysts for overall water splitting. J. Mater. Chem. A, 2021, 9(9): 5320.

[5] Srinivas K, Chen YF, Wang B, Yu B, Lu YJ, Su Z, Zhang WL, Yang DX. Metal-organic framework-derived Fe-doped Ni₃Fe/NiFe₂O₄ heteronanoparticle-decorated carbon nanotube network as a highly efficient and durable bifunctional electrocatalyst. ACS Appl. Mater. Interfaces, 2020, 12(50): 55782.

[6] Chen ZL, Qing HL, Wang RR, Wu RB. Charge pumping enabling Co—NC to outperform benchmark Pt catalyst for pH-universal hydrogen evolution reaction. Energy Environ. Sci., 2021, 14(5): 3160.

[7] Liu B, Wang S, Wang CY, Ma BZ, Chen YQ. Electrochemical behavior and corrosion resistance of IrO₂—ZrO₂ binary oxide coatings for promoting oxygen evolution in sulfuric acid solution. Int. J. Miner. Metall. Mater., 2020, 27(2): 264.

[8] Srinivas K, Lu YJ, Chen YF, Zhang WL, Yang DX. FeNi₃—Fe₃O₄ heterogeneous nanoparticles anchored on 2D MOF nanosheets/1D CNT matrix as highly efficient bifunctional electrocatalysts for water splitting. ACS Sustainable Chem. Eng., 2020, 8(9): 3820.

[9] Z.F. Huang, S.B. Xi, J.J. Song, S. Dou, X.G. Li, Y.H. Du, C.Z. Diao, Z.C.J. Xu, and X. Wang, Tuning of lattice oxygen reactivity and scaling relation to construct better oxygen evolution electrocatalyst, Nat. Commun., 12(2021), art. No. 3992.

[10] Liu LH, Li N, Han JR, Yao KL, Liang HY. Multicomponent transition metal phosphide for oxygen evolution. Int. J. Miner. Metall. Mater., 2022, 29(3): 503.

[11] Karpuraranjith M, Chen YF, Wang B, Ramkumar J, Yang DX, Srinivas K, Wang W, Zhang WL, Manigandan R. Hierarchical ultrathin layered MoS₂@NiFe₂O₄ nanohybrids as a bifunctional catalyst for highly efficient oxygen evolution and organic pollutant degradation. J. Colloid Interface Sci., 2021, 592, 385.

[12] Srinivas K, Chen YF, Wang XQ, Wang B, Karpuraranjith M, Wang W, Su Z, Zhang WL, Yang DX. Constructing Ni/NiS heteronanoparticle-embedded metal-organic framework-derived nanosheets for enhanced water-splitting catalysis. ACS Sustain. Chem. Eng., 2021, 9(4): 1920.

[13] Chen X, Wang XQ, Zhang XJ, Srinivas K, Liu DW, Zhao XC, Yu HS, Wang B, Zhang WL, Chen YF. Vertical Fe(OH)₃/Ni₉S₈ nanoarrays electrodeposited on stainless steel as binder-free electrocatalyst for highly efficient and stable oxygen evolution reaction. J. Mater. Sci., 2021, 56(34): 19144.

[14] Wang B, Chen YF, Wang XQ, Ramkumar J, Zhang XJ, Yu B, Yang DX, Karpuraranjith M, Zhang WL. rGO wrapped trimetallic sulfide nanowires as an efficient bifunctional catalyst for electrocatalytic oxygen evolution and photocatalytic organic degradation. J. Mater. Chem. A, 2020, 8(27): 13558.

[15] Yu F, Zhou HQ, Huang YF, Sun JY, Qin F, Bao JM, Goddard WA, Chen S, Ren ZF. High-performance bifunctional porous non-noble metal phosphide catalyst for overall water splitting. Nat. Commun., 2018, 9, 2551.

[16] Y. Xiao, Y. Pei, Y.F. Hu, R.G. Ma, D.Y. Wang, and J.C. Wang, Co₂P@P-doped 3D porous carbon for bifunctional oxygen electrocatalysis, Acta Phys. Chim. Sin., 37(2021), No. 7, art. No. 2009051.

[17] Huang JZ, Han JC, Wu T, Feng K, Yao T, Wang XJ, Liu SW, Zhong J, Zhang ZH, Zhang YM, Song B. Boosting hydrogen transfer during Volmer reaction at oxides/metal nanocomposites for efficient alkaline hydrogen evolution. ACS Energy Lett., 2019, 4(12): 3002.

[18] Anantharaj S, Kundu S, Noda S. “The Fe Effect”: A review unveiling the critical roles of Fe in enhancing OER activity of Ni and Co based catalysts. Nano Energy, 2021, 80, 105514.

[19] Zhang XJ, Chen YF, Chen ML, Yu B, Wang B, Wang XQ, Zhang WL, Yang DX. MOF derived multi-metal oxides anchored N, P-doped carbon matrix as efficient and durable electrocatalyst for oxygen evolution reaction. J. Colloid Interface Sci., 2021, 581, 608.

[20] Sun K, Zhao YQ, Yin J, Jin J, Liu HW, Xi PX. Surface modification of NiCo₂O₄ nanowires using organic ligands for overall water splitting. Acta Phys. Chim. Sin., 2022, 38(6): 2107005-2107005.

[21] Zhang JF, Jiang Y, Wang Y, Yu CP, Cui JW, Wu JJ, Shu X, Qin YQ, Sun J, Yan J, Zheng HM, Zhang Y, Wu YC. Ultrathin carbon coated mesoporous Ni—NiFe₂O₄ nanosheet arrays for efficient overall water splitting. Electrochim. Acta, 2019, 321, 134652.

[22] Wang M, Zhang L, Pan JL, Huang MR, Zhu HW. A highly efficient Fe-doped Ni₃S₂ electrocatalyst for overall water splitting. Nano Res., 2021, 14(12): 4740.

[23] H. Su, S.J. Song, S.S. Li, Y.Q. Gao, L. Ge, W.Y. Song, T.Y. Ma, and J. Liu, High-valent bimetal Ni₃S₂/Co₃S₄ induced by Cu doping for bifunctional electrocatalytic water splitting, Appl. Catal. B Environ., 293(2021), art. No. 120225.

[24] Zhang RZ, Zhu ZQ, Lin JH, Zhang KF, Li N, Zhao CJ. Hydrolysis assisted in situ growth of 3D hierarchical FeS/NiS/nickel foam electrode for overall water splitting. Electrochim. Acta, 2020, 332, 135534.

[25] Sun HM, Yan ZH, Liu FM, Xu WC, Cheng FY, Chen J. Self-supported transition-metal-based electrocatalysts for hydrogen and oxygen evolution. Adv. Mater., 2020, 32(3): 1806326.

[26] Nong HN, Falling LJ, Bergmann A, Klingenhof M, Tran HP, Spöri C, Mom R, Timoshenko J, Zichittella G, Knop-Gericke A, Piccinin S, Pérez-Ramírez J, Cuenya BR, Schlögl R, Strasser P, Teschner D, Jones TE. Key role of chemistry versus bias in electrocatalytic oxygen evolution. Nature, 2021, 589, 408.

[27] Li JT, Chu D, Dong H, Baker DR, Jiang RZ. Boosted oxygen evolution reactivity by igniting double exchange interaction in spinel oxides. J. Am. Chem. Soc., 2020, 142(1): 50.

[28] Lv L, Chang YX, Ao X, Li ZS, Li JG, Wu Y, Xue XY, Cao YL, Hong G, Wang CD. Interfacial electron transfer on heterostructured Ni₃Se₄/FeOOH endows highly efficient water oxidation in alkaline solutions. Mater. Today Energy, 2020, 17, 100462.

[29] Yu XT, Wang MY, Gong XZ, Guo ZC, Wang Z, Jiao SQ. Self-supporting porous CoP-based films with phase-separation structure for ultrastable overall water electrolysis at large current density. Adv. Energy Mater., 2018, 8(34): 1802445.

[30] Andronescu C, Barwe S, Ventosa E, Masa J, Vasile E, Konkena B, Möller S, Schuhmann W. Powder catalyst fixation for post-electrolysis structural characterization of NiFe layered double hydroxide based oxygen evolution reaction electrocatalysts. Angew. Chem. Int. Ed., 2017, 56(37): 11258.

[31] Wu TZ, Ren X, Sun YM, Sun SN, Xian GY, Scherer GG, Fisher AC, Mandler D, Ager JW, Grimaud A, Wang JL, Shen CM, Yang HT, Gracia J, Gao HJ, Xu ZJ. Spin pinning effect to reconstructed oxyhydroxide layer on ferromagnetic oxides for enhanced water oxidation. Nat. Commun., 2021, 12(1): 3634.

[32] Zhao YF, Zhou H, Zhu XR, Qu YT, Xiong C, Xue ZG, Zhang QW, Liu XK, Zhou FY, Mou XM, Wang WY, Chen M, Xiong Y, Lin XG, Lin Y, Chen WX, Wang HJ, Jiang Z, Zheng LR, Yao T, Dong JC, Wei SQ, Huang WX, Gu L, Luo J, Li YF, Wu YE. Simultaneous oxidative and reductive reactions in one system by atomic design. Nat. Catal., 2021, 4(2): 134.

[33] Park S, Jin K, Lim HK, Kim J, Cho KH, Choi S, Seo H, Lee MY, Lee YH, Yoon S, Kim M, Kim H, Kim SH, Nam KT. Spectroscopic capture of a low-spin Mn(IV)-oxo species in Ni—Mn₃O₄ nanoparticles during water oxidation catalysis. Nat. Commun., 2020, 11(1): 5230.

[34] S.F. Zai, X.Y. Gao, C.C. Yang, and Q. Jiang, Ce-modified Ni(OH)₂ nanoflowers supported on NiSe₂ octahedra nanoparticles as high-efficient oxygen evolution electrocatalyst, Adv. Energy Mater., 11(2021), No. 28, art. No. 2101266.

[35] Trotochaud L, Young SL, Ranney JK, Boettcher SW. Nickel—iron oxyhydroxide oxygen-evolution electrocatalysts: The role of intentional and incidental iron incorporation. J. Am. Chem. Soc., 2014, 136(18): 6744.

[36] Park BH, Kim M, Park NK, Ryu HJ, Baek JI, Kang M. Single layered hollow NiO—NiS catalyst with large specific surface area and highly efficient visible-light-driven carbon dioxide conversion. Chemosphere, 2021, 280, 130759.

[37] Zhou GY, Chen Y, Dong H, Xu L, Liu XE, Ge CW, Sun DM, Tang YW. Ultrafine monodisperse NiS/NiS₂ heteronanoparticles in situ grown on N-doped graphene nanosheets with enhanced electrocatalytic activity for hydrogen evolution reaction. Int. J. Hydrog. Energy, 2019, 44(48): 26338.

[38] L.A. Marusak and L.N. Mulay, Mössbauer and magnetic study of the antiferro to ferrimagnetic phase transition in Fe₉S₁₀ and the magnetokinetics of the diffusion of iron atoms during the transition, J. Appl. Phys., 50(1979), No. B3, p. 1865.

[39] Wang ZY, Li JT, Tian XC, Wang XP, Yu Y, Owusu KA, He L, Mai LQ. Porous nickel—iron selenide nanosheets as highly efficient electrocatalysts for oxygen evolution reaction. ACS Appl. Mater. Interfaces, 2016, 8(30): 19386.

[40] Nesbitt HW, Legrand D, Bancroft GM. Interpretation of Ni₂p XPS spectra of Ni conductors and Ni insulators. Phys. Chem. Miner., 2000, 27(5): 357.

[41] Zheng XR, Han XP, Zhang YQ, Wang JH, Zhong C, Deng YD, Hu WB. Controllable synthesis of nickel sulfide nanocatalysts and their phase-dependent performance for overall water splitting. Nanoscale, 2019, 11(12): 5646.

[42] Y.J. Li, H.C. Zhang, M. Jiang, Q. Zhang, P.L. He, and X.M. Sun, 3D self-supported Fe-doped Ni₂P nanosheet arrays as bifunctional catalysts for overall water splitting, Adv. Funct. Mater., 27(2017), No. 37, art. No. 1702513.

[43] Uhlig I, Szargan R, Nesbitt HW, Laajalehto K. Surface states and reactivity of pyrite and marcasite. Appl. Surf. Sci., 2001, 179(1–4): 222.

[44] Dickinson T, Povey AF, Sherwood PMA. Dissolution and passivation of nickel. an X-ray photoelectron spectroscopic study. J. Chem. Soc., Faraday Trans. 1, 1977, 73, 327.

[45] Zhao SQ, Guo SJ, Zhu C, Gao J, Li H, Huang H, Liu Y, Kang ZH. Achieving electroreduction of CO₂ to CH₃OH with high selectivity using a pyrite—nickel sulfide nanocomposite. RSC Adv., 2017, 7(3): 1376.

[46] Tang Y, Yang CH, Yang YW, Yin XT, Que WX, Zhu JF. Three dimensional hierarchical network structure of S—NiFe₂O₄ modified few-layer titanium carbides (MXene) flakes on nickel foam as a high efficient electrocatalyst for oxygen evolution. Electrochim. Acta, 2019, 296, 762.

[47] Zhuang GX, Chen YW, Zhuang ZY, Yu Y, Yu JG. Oxygen vacancies in metal oxides: Recent progress towards advanced catalyst design. Sci. China Mater., 2020, 63(11): 2089.

[48] D.X. Yang, Z. Su, Y.F. Chen, K. Srinivas, X.J. Zhang, W.L. Zhang, and H.P. Lin, Self-reconstruction of a MOF-derived chromium-doped nickel disulfide in electrocatalytic water oxidation, Chem. Eng. J., 430(2022), art. No. 133046.

[49] Song K, Li WT, Yang R, Zheng YJ, Chen XS, Wang X, Chen GL, Lv WC. Controlled preparation of Ni(OH)₂/NiS nanosheet heterostructure as hybrid supercapacitor electrodes for high electrochemical performance. Electrochim. Acta, 2021, 388, 138663.

[50] Yang DX, Su Z, Chen YF, Lu YJ, Yu B, Srinivas K, Wang B, Zhang WL. Double-shelled hollow bimetallic phosphide nanospheres anchored on nitrogen-doped graphene for boosting water electrolysis. J. Mater. Chem. A, 2020, 8(42): 22222.

[51] Diaz-Morales O, Ledezma-Yanez I, Koper MTM, Calle-Vallejo F. Guidelines for the rational design of Ni-based double hydroxide electrocatalysts for the oxygen evolution reaction. ACS Catal., 2015, 5(9): 5380.

[52] Wang MY, Yu XT, Wang Z, Gong XZ, Guo ZC, Dai L. Hierarchically 3D porous films electrochemically constructed on gas—liquid—solid three-phase interface for energy application. J. Mater. Chem. A, 2017, 5(20): 9488.

[53] Intikhab S, Snyder JD, Tang MH. Adsorbed hydroxide does not participate in the Volmer step of alkaline hydrogen electrocatalysis. ACS Catal., 2017, 7(12): 8314.

[54] Dong B, Zhao X, Han GQ, Li X, Shang X, Liu YR, Hu WH, Chai YM, Zhao H, Liu CG. Two-step synthesis of binary Ni—e sulfides supported on nickel foam as highly efficient electrocatalysts for the oxygen evolution reaction. J. Mater. Chem. A, 2016, 4(35): 13499.

[55] Liu G, Wang KF, Gao XS, He DY, Li JP. Fabrication of mesoporous NiFe₂O₄ nanorods as efficient oxygen evolution catalyst for water splitting. Electrochim. Acta, 2016, 211, 871.

[56] Shi X, Li YF, Bernasek SL, Selloni A. Structure of the NiFe₂O₄(001) surface in contact with gaseous O₂ and water vapor. Surf. Sci., 2015, 640, 73.

[57] Ahn SH, Choi I, Park HY, Hwang SJ, Yoo SJ, Cho E, Kim HJ, Henkensmeier D, Nam SW, Kim SK, Jang JH. Effect of morphology of electrodeposited Ni catalysts on the behavior of bubbles generated during the oxygen evolution reaction in alkaline water electrolysis. Chem. Commun., 2013, 49(81): 9323.

[58] Mahmood N, Yao YD, Zhang JW, Pan L, Zhang XW, Zou JJ. Electrocatalysts for hydrogen evolution in alkaline electrolytes: Mechanisms, challenges, and prospective solutions. Adv. Sci., 2018, 5(2): 1700464.

[59] Zheng Y, Jiao Y, Vasileff A, Qiao SZ. The hydrogen evolution reaction in alkaline solution: From theory, single crystal models, to practical electrocatalysts. Angew. Chem. Int. Ed., 2018, 57(26): 7568.