CeO2电子调控FeNi纳米片大电流密度电解水催化剂

doi:10.13208/j.electrochem.2208121

摘要/Abstract

摘要：

开发高活性的大电流密度非贵金属双功能催化剂对于电解水制氢的发展意义重大。本文通过水热法和高温退火处理制备了自生长在泡沫镍上的CeO₂电子调控的FeNi双金属复合物多孔纳米片(NiFe₂O₄-Fe₂₄N₁₀-CeO₂/NF)。电化学测试结果表明,NiFe₂O₄:-Fe₂₄N₁₀-CeO₂/NF 在1.0 mol·L^-1KOH电解液中具有出色的析氧和析氢反应（OER和HER)活性，在±1000 mA cm^-2电流密度下所需的过电位分别为352 mV和429 mV。将其组装成电解水（OWS）两电极体系，只需1.81V的电池电压就能达到100 mA ·cm^-2的电流密度。对于OER、HER和OWS，可以在+500 mA cm^-2的电流密度下稳定运行30小时，其优异的大电流密度催化性能可以归功于CeO₂对于FeNi复合物的电子结构调控增强了催化剂的本征活性和反应中间体的吸附。原位生长在泡沫镍(NF)上的多孔纳米片可以增强活性位点与电解质的接触，并利于气体产物的释放，从而提高其化学稳定性和机械稳定性。本工作为制备双功能非贵金属电解水催化剂提供了一种新思路。

关键词: FeNi复合物, 析氢反应, 析氧反应, 催化剂

Abstract:

Exploiting highly active and non-noble metal bifunctional catalysts at large current density is significant for the advancement of water electrolysis. In this work, CeO₂ electronically structure modulated FeNi bimetallic composite porous nanosheets in-situ grown on nickel foam (NiFe₂O₄-Fe₂₄N₁₀-CeO₂/NF) is synthesized. Electrochemical experiments show that the NiFe₂O₄-Fe₂₄N₁₀-CeO₂/NF exhibited the outstanding activities toward both oxygen and hydrogen evolution reactions (OER and HER) (η₁₀₀₀ = 352 mV and η₁₀₀₀ = 429 mV, respectively). When assembled into a two-electrode system for overall water splitting (OWS), it only needs a low cell voltage of 1.81 V to drive 100 mA·cm^-2. And it can operate stably at ±500 mA·cm^-2 over 30 h toward OER, HER and OWS without significant activity changes. The reason could be assigned to the electronic modulating of CeO₂ on FeNi composite, which can boost the intrinsic activity and optimize the adsorption of reaction intermediates. Moreover, the porous nanosheets in-situ grown on NF could enhance the contact of active site with electrolyte and facilitate the gas release, thus improving its chemical and mechanical stabilities. This study highlights a novel approach to design bifunctional non-noble metal catalysts for water splitting at large current density.

Key words: FeNi composite, hydrogen evolution reaction, oxygen evolution reaction, catalyst

丁明宇, 蒋文杰, 余天琦, 卓小燕, 覃晓静, 尹诗斌. CeO₂电子调控FeNi纳米片大电流密度电解水催化剂[J]. 电化学（中英文）, 2023, 29(5): 2208121.

Ming-Yu Ding, Wen-Jie Jiang, Tian-Qi Yu, Xiao-Yan Zhuo, Xiao-Jing Qin, Shi-Bin Yin. Electronically Modulated FeNi Composite by CeO₂ Porous Nanosheets for Water Splitting at Large Current Density[J]. Journal of Electrochemistry, 2023, 29(5): 2208121.

图/表 6

参考文献 41

[1]	Lu H S, He X B, Yin F X, Li G R. Preparations of nickel-iron hydroxide/sulfide and their electrocatalytic performances for overall water splitting[J]. J. Electrochem., 2020, 26(1): 136-147.
[2]	Song M, Zhao Y, Wu Z X, Liu X E. MoS₂/CoB with Se doping on carbon cloth to drive overall water-splitting in an alkaline electrolyte[J]. Sustain. Energ. Fuels, 2020, 4(10): 5036-5041. doi: 10.1039/D0SE00864H URL
[3]	Ma D D, Shi J W, Sun L W, Sun Y X, Mao S M, Pu Z X, He C, Zhang Y J, He D, Wang H K, Cheng Y H. Knack behind the high performance CdS/ZnS-NiS nanocomposites: Optimizing synergistic effect between cocatalyst and heterostructure for boosting hydrogen evolution[J]. Chem. Eng. J., 2022, 431: 133446. doi: 10.1016/j.cej.2021.133446 URL
[4]	Li Y, Luo Z Y, Ge J J, Liu C P, Xing W. Research progress in hydrogen evolution low noble/non-precious metal catalysts of water electrolysis[J]. J. Electrochem., 2018, 24(6): 572-588. doi: 10.13208/j.electrochem.180855 URL
[5]	Chen S S, Hisatomi T, Ma G J, Wang Z, Pan Z H, Takata T, Domen K. Metal selenides for photocatalytic Z-scheme pure water splitting mediated by reduced graphene oxide[J]. Chin. J. Catal., 2019, 40(11): 1668-1672. doi: 10.1016/S1872-2067(19)63326-7
[6]	Niu S, Jiang W J, Tang T, Yuan L P, Luo H, Hu J S. Autogenous growth of hierarchical NiFe(OH)_x/FeS nanosheet-on-microsheet arrays for synergistically enhanced high-output water oxidation[J]. Adv. Funct. Mater., 2019, 29(36): 1902180. doi: 10.1002/adfm.v29.36 URL
[7]	Shi Y M, Yu Y, Liang Y, Du Y H, Zhang B. In situ electrochemical conversion of an ultrathin tannin nickel iron complex film as an efficient oxygen evolution reaction electrocatalyst[J]. Angew. Chem. Int. Ed., 2019, 58(12): 3769-3773. doi: 10.1002/anie.v58.12 URL
[8]	Yu L, Yang J F, Guan B Y, Lu Y, Lou X W. Hierarchical hollow nanoprisms based on ultrathin Ni-Fe layered double hydroxide nanosheets with enhanced electrocatalytic activity towards oxygen evolution[J]. Angew. Chem., Int. Ed., 2018, 57(1): 172-176. doi: 10.1002/anie.201710877 pmid: 29178355
[9]	Cui X J, Ren P J, Deng D H, Deng J, Bao X H. Single layer graphene encapsulating non-precious metals as high-performance electrocatalysts for water oxidation[J]. Energy Environ. Sci., 2016, 9(1): 123-129. doi: 10.1039/C5EE03316K URL
[10]	Tao J Y, Zhang Y J, Wang S P, Wang G, Hu F, Yan X J, Hao L F, Zuo Z J, Yang X W. Activating three-dimensional networks of Fe@Ni nanofibers via fast surface modification for efficient overall water splitting[J]. ACS Appl. Mater. Inter., 2019, 11(20): 18342-18348. doi: 10.1021/acsami.9b01431 URL
[11]	Ma E H, Liu X P, Shen T, Wang D L. Constructing carbon-encapsulated NiFeV-based electrocatalysts by alkoxide-based self-template method for oxygen evolution reaction[J]. J. Electrochem., DOI: 10.13208/j.electrochem.211103. doi: 10.13208/j.electrochem.211103
[12]	Zou Y J, Xiao B, Shi J W, Hao H, Ma D D, Lv Y X, Sun G T, Li J, Cheng Y H. 3D hierarchical heterostructure assembled by NiFe LDH/(NiFe)S_x on biomass-derived hollow carbon microtubes as bifunctional electrocatalysts for overall water splitting[J]. Electrochim. Acta, 2020, 348: 136339. doi: 10.1016/j.electacta.2020.136339 URL
[13]	Wang M, Zhang L, Pan J L, Huang M R, Zhu H W. A highly efficient Fe-doped Ni₃S₂ electrocatalyst for overall water splitting[J]. Nano Res., 2021, 14(12): 4740-4747. doi: 10.1007/s12274-021-3416-5
[14]	Friebel D, Louie M W, Bajdich M, Sanwald K E, Cai Y, Wise A M, Cheng M J, Sokaras D, Weng T C, Alonso M R, Davis R C, Bargar J R, Norskov J K, Nilsson A, Bell A T. Identification of highly active Fe sites in (Ni, Fe)OOH for electrocatalytic water splitting[J]. J. Am. Chem. Soc., 2015, 137(3): 1305-1313. doi: 10.1021/ja511559d pmid: 25562406
[15]	Subbaraman R, Tripkovic D, Chang K C, Strmcnik D, Paulikas A P, Hirunsit P, Chan M, Greeley J, Stamenkovic V, Markovic N M. Trends in activity for the water electrolyser reactions on 3d M (Ni, Co, Fe, Mn) hydr(oxy)oxide catalysts[J]. Nat. Mater., 2012, 11(6): 550-557. doi: 10.1038/nmat3313 pmid: 22561903
[16]	Shah J H, Xie Q X, Kuang Z C, Ge R L, Zhou W H, Liu D R, Rykov A I, Li X N, Luo J S, Wang J H. In-situ/operando ⁵⁷Fe Mössbauer spectroscopic technique and its applications in NiFe-based electrocatalysts for oxygen evolution reaction[J]. J. Electrochem., 2022, 28(3): 2108541.
[17]	Chen H Y, Hu M H, Jing P, Liu B C, Gao R, Zhang J. Constructing heterostructure of CeO₂/WS₂ to enhance catalytic activity and stability toward hydrogen generation[J]. J. Power Sources, 2022, 521: 230948. doi: 10.1016/j.jpowsour.2021.230948 URL
[18]	Zheng Z, Li N, Wang C Q, Li D Y, Zhu Y M, Wu G. Ni-CeO₂ composite cathode material for hydrogen evolution reaction in alkaline electrolyte[J]. Int. J. Hydrogen Energy, 2012, 37(19): 13921-13932. doi: 10.1016/j.ijhydene.2012.07.102 URL
[19]	Lu M J, Chen D, Wang B, Li R Q, Cai D, Tu H R, Yang H, Zhang Y P, Han W. Boosting alkaline hydrogen evolution performance of Co₄N porous nanowires by interface engineering of CeO₂ tuning[J]. J. Mater. Chem. A, 2021, 9(3): 1655-1662. doi: 10.1039/D0TA08347J URL
[20]	Zhang R, Ren X, Hao S, Ge R X, Liu Z A, Asiri A M, Chen L, Zhang Q J, Sun X P. Selective phosphidation: An effective strategy toward CoP/CeO₂ interface engineering for superior alkaline hydrogen evolution electrocatalysis[J]. J. Mater. Chem. A, 2018, 6(5): 1985-1990. doi: 10.1039/C7TA10237B URL
[21]	Chen Z H, Ma Z P, Song J J, Wang L X, Shao G J. A novel approach for the preparation of Ni-CeO₂ composite cathodes with enhanced electrocatalytic activity[J]. RSC Adv., 2016, 6(65): 60806-60814. doi: 10.1039/C6RA14667H URL
[22]	Sivanantham A, Ganesan P, Shanmugam S. A synergistic effect of Co and CeO₂ in nitrogen-doped carbon nanostructure for the enhanced oxygen electrode activity and stability[J]. Appl. Catal., B, 2018, 237: 1148-1159. doi: 10.1016/j.apcatb.2017.08.063 URL
[23]	Gao W, Wen D, Ho J C, Qu Y. Incorporation of rare earth elements with transition metal-based materials for electrocatalysis: A review for recent progress[J]. Mater. Today Chem., 2019, 12: 266-281. doi: 10.1016/j.mtchem.2019.02.002
[24]	Feng J X, Ye S H, Xu H, Tong Y X, Li G R. Design and synthesis of FeOOH/CeO₂ heterolayered nanotube electrocatalysts for the oxygen evolution reaction[J]. Adv. Mater., 2016, 28(23): 4698-4703. doi: 10.1002/adma.v28.23 URL
[25]	Zhou H Q, Yu F, Zhu Q, Sun J Y, Qin F, Yu L, Bao J M, Yu Y, Chen S, Ren Z F. Water splitting by electrolysis at high current densities under 1.6 volts[J]. Energy Environ. Sci., 2018, 11(10): 2858-2864. doi: 10.1039/C8EE00927A URL
[26]	Yu X T, Wang M Y, Gong X Z, Guo Z C, Wang Z, Jiao S Q. Self-supporting porous CoP-based films with phase-separation structure for ultrastable overall water electrolysis at large current density[J]. Adv. Energy Mater., 2018, 8(34): 1802445. doi: 10.1002/aenm.201802445 URL
[27]	Mao L Q, Ba Q Q, Jia X J, Liu S, Liu H, Zhang J, Li X J, Chen W. Ultrathin Ni(OH)₂ nanosheets: A new strategy for cocatalyst design on CdS surfaces for photocatalytic hydrogen generation[J]. RSC Adv., 2019, 9(3): 1260-1269. doi: 10.1039/C8RA07307D URL
[28]	Li G L, Zhang X B, Zhang H. Ultrathin 2D Nanosheet based 3D hierarchical hollow polyhedral CoM/C (M = Ni, Cu, Mn) phosphide nanocages as superior electrocatalysts toward oxygen evolution reaction[J]. Chem. Eng. J., 2020, 398: 125467. doi: 10.1016/j.cej.2020.125467 URL
[29]	Wang J Y, Zhu R L, Cheng J L, Song Y Y, Mao M, Chen F F, Cheng Y L. Co, Mo₂C encapsulated in N-doped carbon nanofiber as self-supported electrocatalyst for hydrogen evolution reaction[J]. Chem. Eng. J., 2020, 397: 125481. doi: 10.1016/j.cej.2020.125481 URL
[30]	Yu T Q, Xu Q L, Luo L, Liu C R, Yin S B. Interface engineering of NiO/RuO₂ heterojunction nano-sheets for robust overall water splitting at large current density[J]. Chem. Eng. J., 2022, 430: 133117. doi: 10.1016/j.cej.2021.133117 URL
[31]	Ji R Y, Chan D S, Jow J J, Wu M S. Formation of open-ended nickel hydroxide nanotubes on three-dimensional nickel framework for enhanced urea electrolysis[J]. Electrochem. Commun., 2013, 29: 21-24. doi: 10.1016/j.elecom.2013.01.006 URL
[32]	Wang Y M, Qian G F, Xu Q L, Zhang H, Shen F, Luo L, Yin S B. Industrially promising IrNi-FeNi₃ hybrid nanosheets for overall water splitting catalysis at large current density[J]. Appl. Catal., B, 2021, 286: 119881. doi: 10.1016/j.apcatb.2021.119881 URL
[33]	Sun Z H, Cao X C, Gonzalez M I G, Rümmeli M H, Yang R Z. Enhanced electrocatalytic activity of FeCo₂O₄ interfacing with CeO₂ for oxygen reduction and evolution reactions[J]. Electrochem. Commun., 2018, 93: 35-38. doi: 10.1016/j.elecom.2018.06.001 URL
[34]	Trotochaud L, Young S L, Ranney J K, Boettcher S W. Nickel-iron oxyhydroxide oxygen-evolution electrocatalysts: The role of intentional and incidental iron incorporation[J]. J. Am. Chem. Soc., 2014, 136(18): 6744-6753. doi: 10.1021/ja502379c pmid: 24779732
[35]	Feng Z H, Pu J Y, Liu M S, Zhang W X, Zhang X Y, Cui L, Liu J Q. Facile construction of hierarchical Co₃S₄/CeO₂ heterogeneous nanorod array on cobalt foam for electrocatalytic overall water splitting[J]. J. Colloid Interface Sci., 2022, 613: 806-813. doi: 10.1016/j.jcis.2022.01.081 URL
[36]	Chen L L, Jang H, Kim M G, Qin Q, Liu X, Cho J. Fe_xNi_y/CeO₂ loaded on N-doped nanocarbon as an advanced bifunctional electrocatalyst for the overall water splitting[J]. Inorg. Chem. Front., 2020, 7(2): 470-476. doi: 10.1039/C9QI01251F URL
[37]	Park K R, Tran D T, Nguyen T T, Kim N H, Lee J H. Copper-incorporated heterostructures of amorphous NiSe_x/Crystalline NiSe₂ as an efficient electrocatalyst for overall water splitting[J]. Chem. Eng. J., 2021, 422: 130048. doi: 10.1016/j.cej.2021.130048 URL
[38]	Zhang J, Wang T, Rellinghaus D P B, Dong R H, Liu S H, Zhuang X D, Feng X L. Interface engineering of MoS₂/Ni₃S₂ heterostructures for highly enhanced electrochemical overall-water-splitting activity[J]. Angew. Chem., Int. Ed., 2016, 55(23): 6702-6707. doi: 10.1002/anie.201602237 pmid: 27100374
[39]	Qian G F, Chen J L, Luo L, Zhang H, Chen W, Gao Z J, Yin S B, Tsiakaras P. Novel bifunctional V₂O₃ nanosheets coupled with N-doped-carbon encapsulated Ni heterostructure for enhanced electrocatalytic oxidation of urea-rich wastewater[J]. ACS Appl. Mater. Inter., 2020, 12(34): 38061-38069. doi: 10.1021/acsami.0c09319 URL
[40]	Wu M X, Zhang G X, Qiao J L, Chen N, Chen W F, Sun S H. Ultra-long life rechargeable zinc-air battery based on high-performance trimetallic nitride and NCNT hybrid bifunctional electrocatalysts[J]. Nano Energy, 2019, 61: 86-95. doi: 10.1016/j.nanoen.2019.04.031 URL
[41]	Watkins M B, Foster A S, Shluger A L. Hydrogen cycle on CeO₂(111) surfaces: Density functional theory calculations[J]. J. Phys. Chem. C, 2007, 111(42): 15337-15341. doi: 10.1021/jp071715s URL

CeO₂电子调控FeNi纳米片大电流密度电解水催化剂

Electronically Modulated FeNi Composite by CeO₂ Porous Nanosheets for Water Splitting at Large Current Density

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