钼基复合材料催化剂因其与Pt族元素的最外层电子结构类似,且在宽pH范围内仍能保持较高的活性和具有稳定性的特点,有望取代Pt基催化剂,近年来引起了越来越多研究者的关注。详细介绍了基于钼基复合材料的析氢反应电催化材料的最新进展,主要包括钼基合金、磷化钼、硫化钼、硒化钼、碳化钼、氮化钼、氧化钼、硼化钼等。着重论述了钼基复合材料的制备方法、构效关系、产氢机理与提升材料析氢性能的策略。最后,总结了钼基复合材料催化在应用时可能遇到的问题与挑战,并合理展望了此类催化剂未来的发展趋势。
Molybdenum-based composite catalysts is similar to the outermost electronic structure of the Pt group element.Moreover,it can still maintain high activity and stability in wide pH range,and expected to replace the precious metal Pt-based catalysts.In recent years,it has attracted more and more researchers' attention and in-depth researches.The latest developments in hydrogen evolution reaction (HER) electrocatalytic materials based on Mo-based composite materials was presented in detail,including Mo-based alloys,MoP,MoS2,MoSe2,Mo2C,MoN,MoO3,MoB and so on.The synthetic method of Mo-based composite,structure-activity relationship,hydrogen production mechanism and strategies to improve the hydrogen evolution performance of the material were emphatically discussed.Finally,the problems and challenges that may be encountered in the application of Mo-based composite were summarized,and reasonably prospected the future development trend of the catalysts.
[1] Chu S,Majumdar A.Opportunities and challenges for a sustainable energy future[J].Nature,2012,488(7411):294-303.
[2] Bockris J O M,Potter E C.The mechanism of the cathodic hydrogen evolution reaction[J].Journal of the Electrochemical Society,1952,99(4):169-186.
[3] Greeley J P,Jaramillo T,Bonde J,et al.Computational high-throughput screening of electrocatalytic materials for hydrogen evolution[J].Nature Materials,2006,5(11):909-913.
[4] Ren B,Li D,Jin Q,et al.In-situ tailoring cobalt nickel molybdenum oxide components for overall water splitting at high current densities[J].ChemElectroChem,2019,6:413-420.
[5] Ren B,Li D,Jin Q,et al.Integrated 3D selfsupposed Ni decorated MoO2 nanowires as highly efficient electrocatalysts for ultra highly stable and large current density hydrogen evolution[J].Journal of Materials Chemistry A,2017,5:24453-24461.
[6] Ou Y Q,Tian W Q,Liu L,et al.Co2Mo3O8 suboxides coupled with conductive cobalt nanowires for efficient and durable hydrogen evolution in alkaline electrolyte[J].Journal of Materials Chemistry A,2018,6:5217-5228.
[7] An L,Feng J,Zhang Y,et al.Epitaxial heterogeneous interfaces on N-NiMoO4/NiS2 nanowires/nanosheets to boost hydrogen and oxygen production for overall water splitting[J].Advanced Functional Materials,2019,29(1):1-11.
[8] Yu Z Y,Lang C C,Gao D J,et al.Ni-Mo-O nanorod-derived composite catalysts for efficient alkaline water-to-hydrogen conversion:via urea electrolysis[J].Energy & Environmental Science,2018,11:1890-1897.
[9] Tian J Q,Cheng N Y,Liu Q,et al.Self-supported NiMo hollow nanorod array:an efficient 3D bifunctional catalytic electrode for overall water splitting[J].Journal of Materials Chemistry A,2015,3:20056-20059.
[10] Fang M,Gao W,Dong G,et al.Hierarchical NiMo-based 3D electrocatalysts for highly-efficient hydrogen evolution in alkaline conditions[J].Nano Energy,2016,27:247-254.
[11] Wang M Y,Wang Z,Yu X T,et al.Facile one-step electrodeposition preparation of porous NiMo film as electrocatalyst for hydrogen evolution reaction[J].Interntional Journal of Hydrogen Energy,2015,40(5):2173-2181.
[12] Wang X Q,Su R,Aslan H,et al.Tweaking the composition of NiMoZn alloy electrocatalyst for enhanced hydrogen evolution reaction performance[J].Nano Energy,2015,12:9-18.
[13] Brown D E,Mahmood M N,Man M C M,et al.Preparation and characterization of low overvoltage transition metal alloy electrocatalysts for hydrogen evolution in alkaline solutions[J].Electrochim Acta,1984,29(11):1551-1556.
[14] McKone J R,Sadtler B F,Werlang C A,et al.Ni-Mo nanopowders for efficient electrochemical hydrogen evolution[J].ACS Catalysis,2013,3(2):166-169.
[15] Zhang J,Wang T,Liu P,et al.Efficient hydrogen produciton on MoNi4 electrocatalysts with fast water dissociation kinetics[J].Nature Communications,2017,8(1):15437-15445.
[16] Xing Z C,Liu Q,Asiri A M,et al.Closely interconnected network of molybdenum phosphide nanoparticles:a highly efficient electrocatalyst for generating hydrogen from water[J].Advanced Materials,2014,26(32):5702-5707.
[17] Xiao P,Sk M A,Thia L,et al.Molybdenum phosphide as an efficient electrocatalyst for the hydrogen evolution reaction[J].Energy & Environmental Science,2014,7(8):2624-2629.
[18] Liang K,Pakhira S,Yang Z,et al.S-Doped MoP nanoporous layer toward high-efficiency hydrogen evolution in pH-universal electrolyte[J].ACS Catalysis,2018,9(1):651-659.
[19] Tributsch H,Bennett J C.Electrochemistry and photochemistry of MoS2 layer crystals[J].Journal of Electroanalytical Chemistry,1977,81(1):97-111.
[20] Hinnemann B,Moses P G,Bonde J,et al.Biomimetic hydrogen evolution:MoS2 nanoparticles as catalyst for hydrogen evolution[J].Journal of the American Chemical Society,2015,127(15):5308-5309.
[21] Jaramillo T,Jorgensen K P,Bonde J,et al.Identification of active edge sites for electrochemical H2 evolution from MoS2 nanocatalysts[J].Science,2007,317(5834):100-102.
[22] Lin S H,Kuo J L.Activating and tuning basal planes of MoO2,MoS2,and MoSe2 for hydrogen evolution reaction[J].Physical Chemistry,2015,17(43):29305-29310.
[23] Li H,Tsai C,Koh A L,et al.Activating and optimizing MoS2 basal planes for hydrogen evolution through the formation of strained sulphur vacancies[J].Nature Materials,2016,15(1):48-53.
[24] Wei C B,Liu C,Gao L N,et al.MoS2 nanosheets decorated Ni(OH)2 nanorod array for active overall water splitting[J].Journal of Alloys and Compounds,2019,796:86-92.
[25] Zhang J,Wang T,Liu P,et al.Engineering water dissociation sites in MoS2 nanosheets for accelerated electrocatalytic hydrogen production[J].Energy & Environmental science,2016,9:2789-2793.
[26] Zhang K L,Li Y H,Deng S J.Molybdenum selenide electrocatalysts for electrochemical hydrogen evolution reaction[J].ChemElectroChem,2019,6:3530-3548.
[27] Gao D Q,Xia B R,Zhu C R,et al.Activation of the MoSe2 basal plane and Se-edge by B doping for enhanced hydrogen evolution[J].Journal of Materials Chemistry A,2018,6:510-515.
[28] Ren X P,Ma Q,Ren P Y,et al.Synthesis of nitrogen-doped MoSe2 nanosheets with enhanced electrocatalytic activity for hydrogen evolution reaction[J].International Journal of Hydrogen Energy,2018,43:15275-15280.
[29] Xu C,Peng S J,Tan C L,et al.Ultrathin S-doped MoSe2 nanosheets for efficient hydrogen evolution[J].Journal of Materials Chemistry A,2014,2:5597-5601.
[30] Deng S J,Yang F,Zhang Q H,et al.Phase modulation of (1T-2H)-MoSe2/TiC-C shell/core arrays via nitrogen doping for highly efficient hydrogen evolution reaction[J].Advanced Materials,2018,30:1802223-1802227.
[31] Deng S J,Ai C Z,Luo M,et al.Coupled biphase (1T-2H)-MoSe2 on mold spore carbon for advanced hydrogen evolution reaction[J].Small,2019,15:1901796-1901781.
[32] Wan C,Regmi Y,Leonard B.Multiple phases of molybdenum carbide as electrocatalysts for the hydrogen evolution recation[J].Angewandte Internation Edition Chemie,2014,53(25):6407-6410.
[33] Wang X,Xia B Y,Yan Y,et al.Molybdenum carbide based electrocatalysis for hydrogen evolution recation[J].Chemistry A European Journal,2017,23(46):10947-10961.
[34] Wang P,Qi J,Li C,et al.N-doped carbon nanotubes encapsulation Ni/MoN heterostrutures grown on carbon colth for overall water splitting[J].Chemelectrochem,2020,7(3):745-752.
[35] Xiong J,Cai W W,Shi W J,et al.Salt-templated synthesis of defect-rich MoN nano-sheet for boosted hydrogen evolution reaction[J].Journal of Materials Chemistry,2017,5(46):24193-24198.
[36] Li X,Jiang Y M,Jia L P,et al.MoO2 nanoparticles on reduced graphene oxide/polyimide-carbon nanotube film as efficient hydrogen evolution electrocatalyst[J].Journal of Power Sources,2016,304:146-154.
[37] Wu L F,Wang X S,Sun Y P,et al.Flawed MoO2 belts on graphene template transformed from MoO3 towards hydrogen evolution reaction[J].Nanoscale,2015,7:7040-7044.
[38] Jin Y S,Shen P K.Nanoflower-like metallic conductive MoO2 as a high-performance non-precious metal electrocatalyst for hydrogen evolution reaction[J].Journal of Material Chemistry A,2015,3L 20080-20085.
[39] Jin Y S,Wang H T,Li J J,et al.Porous MoO2 nanosheets as non-noble bifunctional electrocatalysts for overall water splitting[J].Advanced Materials,2016,28(19):3785-90.
[40] Ren B,Li D Q,Jin Q Y,et al.Integrated 3D self-supported Ni decorated MoO2 nanowires as highly efficient electrocatalysts for ultra-highly stable and large-current-density hydrogen evolution[J].Journal of Materials Chenistry A,2017,5:24453-24461.
[41] Deng S F,Liu X P,Huang T,et al.MoO2 modulated electrocatalytic properties of Ni:investigate from hydrogen oxidation reaction to hydrogen evolution reaction[J].Electrochimica Acta,2019,324:134892-134896.
[42] Wang B Z,Huang H X,Sun T T,et al.Dissolution reconstruction of electron-transfer enhanced hierarchical NiSx-MoO2 nanosponges as a promising industrialized hydrogen evolution catalyst beyond Pt/C[J].Journal of Colloid and Interface Science,2020,567:339-346.
[43] Hu X L,Vrubel H.Molybdenum boride and carbide catalyze hydrogen evolution in both acidic and basic solution[J].Angewandte Chemie International Edition,2012,51(51):12703-12706.
[44] Park H,Encinas A,Scheifers J P,et al.Boron-dependency of molybdenum boride electrocatalysts for the hydrogen evolution reaction[J].Angewndate Chemie,2017,129(20):5667-5670.
基金资助
国家自然科学基金面上项目(21671092);辽宁省“兴辽英才”创新领军人才项目(XLYC1802057);辽宁省-沈阳材料科学国家研究中心联合研发基金项目(2019010280-JH3/301)
PDF
