Abstract
Development of highly active electrocatalysts for oxygen evolution reaction (OER) is one of the critical issues for water splitting, and most reported catalysts operate at overpotentials above 190 mV. Here we present a multiphase nickel iron sulfide (MPS) hybrid electrode with a hierarchical structure of iron doped NiS and Ni3S2, possessing a benchmark OER activity in alkaline media with a potential as low as 1.33 V (vs. reversible hydrogen electrode) to drive an OER current density of 10 mA cm−2. The Fe doped NiS, combined with highly conductive disulfide phase on porous Ni foam, is believed to be responsible for the ultrahigh activity. Further more, density functional theory simulation reveals that partially oxidized sulfur sites in Fe doped NiS could dramatically lower the energy barrier for the rate determining elementary reaction, thus contributing to the active oxygen evolution.
摘要
开发高效和低成本的析氧电极材料是工业电解水制氢技术发展道路上至关重要的技术难题. 本文利用溶剂热方法将镍铁水滑石阵列转化为具有铁掺杂的多相硫化镍(NiS和Ni3S2)阵列, 制备出一种具有高效析氧性能的电极材料. 粗糙的纳米片表面有利于高活性位点的暴露. 电化学分析表明其仅需要100 mV的过电位就可以达到10 mA cm−2的电流密度, 相对于镍铁水滑石阵列降低了130 mV. 我们进一步通过密度泛函理论计算来揭示其活性提升机理, 发现具有部分S氧化的Fe掺杂NiS可以极大地降低析氧反应中间体形成的阻力, 从而加快催化反应进行, 提高催化活性. 另一方面, (Ni,Fe)S和(Ni,Fe)3S2与三维多孔泡沫镍结构有很好的结合作用, 反应电子可以通过金属性的二硫化镍相进行高效传输, 进一步加速析氧催化进程.
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References
Turner JA. Sustainable hydrogen production. Science, 2004, 305: 972–974
Hu C, Zhang L, Gong J. Recent progress made in the mechanism comprehension and design of electrocatalysts for alkaline water splitting. Energy Environ Sci, 2019, 12: 2620–2645
Chandrasekaran S, Yao L, Deng L, et al. Recent advances in metal sulfides: From controlled fabrication to electrocatalytic, photocatalytic and photoelectrochemical water splitting and beyond. Chem Soc Rev, 2019, 48: 4178–4280
Li S, Hao X, Abudula A, et al. Nanostructured co-based bifunctional electrocatalysts for energy conversion and storage: Current status and perspectives. J Mater Chem A, 2019, 7: 18674–18707
Jiao Y, Zheng Y, Jaroniec M, et al. Design of electrocatalysts for oxygen- and hydrogen-involving energy conversion reactions. Chem Soc Rev, 2015, 44: 2060–2086
Shi Y, Zhang B. Recent advances in transition metal phosphide nanomaterials: Synthesis and applications in hydrogen evolution reaction. Chem Soc Rev, 2016, 45: 1529–1541
Li P, Duan X, Wang S, et al. Amorphous ruthenium-sulfide with isolated catalytic sites for Pt-like electrocatalytic hydrogen production over whole pH range. Small, 2019, 305: 1904043
Anantharaj S, Ede SR, Sakthikumar K, et al. Recent trends and perspectives in electrochemical water splitting with an emphasis on sulfide, selenide, and phosphide catalysts of Fe, Co, and Ni: A review. ACS Catal, 2016, 6: 8069–8097
Zheng Y, Jiao Y, Vasileff A, et al. The hydrogen evolution reaction in alkaline solution: From theory, single crystal models, to practical electrocatalysts. Angew Chem Int Ed, 2018, 57: 7568–7579
Fabbri E, Schmidt TJ. Oxygen evolution reaction—the enigma in water electrolysis. ACS Catal, 2018, 8: 9765–9774
Guo Y, Shang C, Li J, et al. Recent development of hydrogen evolution, oxygen evolution and oxygen reduction reaction. Sci Sin-Chim, 2018, 48: 926–940
Suen NT, Hung SF, Quan Q, et al. Electrocatalysis for the oxygen evolution reaction: Recent development and future perspectives. Chem Soc Rev, 2017, 46: 337–365
Reier T, Nong HN, Teschner D, et al. Electrocatalytic oxygen evolution reaction in acidic environments-reaction mechanisms and catalysts. Adv Energy Mater, 2017, 7: 1601275
Cherevko S, Geiger S, Kasian O, et al. Oxygen and hydrogen evolution reactions on Ru, RuO2, Ir, and IrO2 thin film electrodes in acidic and alkaline electrolytes: A comparative study on activity and stability. Catal Today, 2016, 262: 170–180
Yu F, Yu L, Mishra IK, et al. Recent developments in earth-abundant and non-noble electrocatalysts for water electrolysis. Mater Today Phys, 2018, 7: 121–138
Chen Y, Rui K, Zhu J, et al. Recent progress on nickel-based oxide/(oxy)hydroxide electrocatalysts for the oxygen evolution reaction. Chem Eur J, 2019, 25: 703–713
Han L, Dong S, Wang E. Transition-metal (Co, Ni, and Fe)-based electrocatalysts for the water oxidation reaction. Adv Mater, 2016, 28: 9266–9291
Zhou P, He J, Zou Y, et al. Single-crystalline layered double hydroxides with rich defects and hierarchical structure by mild reduction for enhancing the oxygen evolution reaction. Sci China Chem, 2019, 62: 1365–1370
Rossmeisl J, Qu ZW, Zhu H, et al. Electrolysis of water on oxide surfaces. J Electroanal Chem, 2007, 607: 83–89
Zhang B, Zheng X, Voznyy O, et al. Homogeneously dispersed multimetal oxygen-evolving catalysts. Science, 2016, 352: 333–337
Li P, Duan X, Kuang Y, et al. Tuning electronic structure of NiFe layered double hydroxides with vanadium doping toward high efficient electrocatalytic water oxidation. Adv Energy Mater, 2018, 8: 1703341
Wang Y, Yan D, El Hankari S, et al. Recent progress on layered double hydroxides and their derivatives for electrocatalytic water splitting. Adv Sci, 2018, 5: 1800064
Zhou L, Shao M, Wei M, et al. Advances in efficient electro-catalysts based on layered double hydroxides and their derivatives. J Energy Chem, 2017, 26: 1094–1106
Li BQ, Zhang SY, Tang C, et al. Anionic regulated NiFe (oxy)sulfide electrocatalysts for water oxidation. Small, 2017, 13: 1700610
Du Y, Cheng G, Luo W. Colloidal synthesis of urchin-like Fe doped NiSe2 for efficient oxygen evolution. Nanoscale, 2017, 9: 6821–6825
Feng LL, Yu G, Wu Y, et al. High-index faceted Ni3S2 nanosheet arrays as highly active and ultrastable electrocatalysts for water splitting. J Am Chem Soc, 2015, 137: 14023–14026
Dong B, Zhao X, Han GQ, et al. Two-step synthesis of binary Ni-Fe sulfides supported on nickel foam as highly efficient electrocatalysts for the oxygen evolution reaction. J Mater Chem A, 2016, 4: 13499–13508
Li Y, Zhang H, Jiang M, et al. 3D self-supported Fe-doped Ni2P nanosheet arrays as bifunctional catalysts for overall water splitting. Adv Funct Mater, 2017, 27: 1702513
Gao WK, Yang M, Chi JQ, et al. In situ construction of surface defects of carbon-doped ternary cobalt-nickel-iron phosphide nanocubes for efficient overall water splitting. Sci China Mater, 2019, 62: 1285–1296
Bai X, Ren Z, Du S, et al. In-situ structure reconstitution of NiCo2P for enhanced electrochemical water oxidation. Sci Bull, 2017, 62: 1510–1518
Lu Z, Xu W, Zhu W, et al. Three-dimensional NiFe layered double hydroxide film for high-efficiency oxygen evolution reaction. Chem Commun, 2014, 50: 6479–6482
Kresse G, Hafner J. Ab initio molecular dynamics for liquid metals. Phys Rev B, 1993, 47: 558–561
Kresse G, Furthmüller J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput Mater Sci, 1996, 6: 15–50
Hammer B, Hansen LB, Nørskov JK. Improved adsorption energetics within density-functional theory using revised perdewburke-ernzerhof functionals. Phys Rev B, 1999, 59: 7413–7421
Li P, Wang M, Duan X, et al. Boosting oxygen evolution of single-atomic ruthenium through electronic coupling with cobalt-iron layered double hydroxides. Nat Commun, 2019, 10: 1711
Xiong X, Cai Z, Zhou D, et al. A highly-efficient oxygen evolution electrode based on defective nickel-iron layered double hydroxide. Sci China Mater, 2018, 61: 939–947
Liao Y, Pan K, Pan Q, et al. In situ synthesis of a NiS/Ni3S2 nanorod composite array on Ni foil as a FTO-free counter electrode for dye-sensitized solar cells. Nanoscale, 2015, 7: 1623–1626
Acknowledgements
This work was supported by the National Natural Science Foundation of China, the National Key Research and Development Project (2018YFB1502401), the Royal Society and Newton Fund through Newton Advanced Fellowship award (NAFR1191294), the Program for Changjiang Scholars and Innovative Research Team in the University, and the Fundamental Research Funds for the Central Universities, and the Longterm Subsidy Mechanism from the Ministry of Finance and the Ministry of Education of China. Li P thanks the financial support from China Scholarships Council (CSC).
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Author contributions Li P, Sun X, and Kuang Y conceived the project and designed the experiments. Li P and Zhao X conducted the material synthesis and electrochemical measurements. Li P, Duan X, and Li Y carried out the theoretical calculations. Li P, Kuang Y and Sun X co-wrote the paper. All authors discussed the results and commented on the manuscript.
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Pengsong Li is now a joint training PhD student at Beijing University of Chemical Technology (BUCT) in the group of Prof. Xiaoming Sun and Yale University working with Prof. Hailiang Wang. His current research interests include the synthesis of inorganic nanostructures and their application in energy conversion and storage.
Xiuping Zhao is currently a graduate student at the State Key Laboratory of Chemical Resource Engineering, BUCT. Her research interests include the transition metal sulfide/hydroxide nanoarrays for electrocatalysis and DFT modeling studies.
Yaping Li received her BSc degree from the Department of Chemical Engineering and PhD from the Department of Chemistry, Beijing Institute of Technology in 1996 and 2005, respectively. She joined the State Key Laboratory of Chemical Resource Engineering, BUCT at 2008. Her main research interests focus on the first-principle theory and density functional study on the OER mechanism for metal/metal oxides, and the corresponding nonlinear dynamics behaviors.
Yun Kuang obtained his BE and PhD degrees from BUCT in 2010 and 2015, respectively. He then joined the faculty of BUCT. He is now an associate professor in chemistry at the College of Chemistry, BUCT and a visiting associate professor in the Department of Chemistry at Stanford University. His current research interest mainly focuses on the synthesis, structure regulation and assembly of transitional metal based nanostructures under control, as well as their application in catalysis and energy related areas.
Xiaoming Sun obtained his BSc and PhD degrees at Tsinghua University in 2000 and 2005, respectively. He worked in Stanford University as a postdoc from 2005 to 2008. Then he joined BUCT and obtained the Foundation of Outstanding Young Scholar from NSFC in 2011. His current research interest mainly focuses on the synthesis and separation of nanomaterials, to improve the energy related electrocatalysis process by tailoring the compositions, surface wettability, and micro-/nano- structures.
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Li, P., Zhao, X., Duan, X. et al. A multiphase nickel iron sulfide hybrid electrode for highly active oxygen evolution. Sci. China Mater. 63, 356–363 (2020). https://doi.org/10.1007/s40843-019-1215-9
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DOI: https://doi.org/10.1007/s40843-019-1215-9