炭黑表面CoMoSSe异质结构合金的制备及其高效析氢研究

doi:10.15541/jim20240487

摘要/Abstract

摘要： 过渡金属二硫属化物(TMD)在电催化分解水制氢方面具有较好的应用前景, 引起了人们的广泛关注, 然而, 它们的电催化制氢性能与金属铂还有较大差距。构建异质结合金被认为是提高析氢活性的有效方法。本研究采用简单的溶胶-凝胶工艺在炭黑颗粒表面合成了一种新型的四元CoMoSSe复合材料(CoMoSSe@CB)。与CoSe@CB以及MoS₂@CB相比, CoMoSSe@CB表现出更加优异的析氢活性, 在–10 mA·cm^–2阴极电流密度下的过电位仅为190 mV, Tafel斜率为62 mV·dec^–1。这主要归因于复合材料的异质结构以及Co、Mo、S和Se原子之间的合金效应, 调节了电子结构和氢原子吸附的自由能, 从而增加了催化剂的活性位点数量、增强了催化剂电荷转移能力。这项工作可为设计新型高效TMD电催化剂提供指导。

关键词: 过渡金属硫族化合物, 合金, 异质结构, 析氢反应

Abstract: Transition metal dichalcogenides (TMDs) recently attracted widespread attention due to their potential application to the electrocatalysis of the hydrogen evolution reaction (HER). However, their HER performance is far inferior to that of platinum (Pt) metal. Preparation of multi-elemental alloy and construction of heterostructure are considered as highly effective methods to enhance hydrogen production activity. Herein, a novel quaternary CoMoSSe alloy with hetero-structure was synthesized on the surface of carbon black particles (CoMoSSe@CB) by a simple Sol–Gel process and served as HER catalyst. Compared to CoSe@CB and MoS₂@CB electrocatalysts, CoMoSSe@CB exhibits superior HER activity with a low overpotential of 190 mV at –10 mA·cm^-2 and a Tafel slope of 62 mV·dec^-1. This improvement is attributed to the alloying effects among Co, Mo, S and Se, as well as the heterogeneous structure in the composite material, which regulate the electronic structure and intermediate free energy, thereby increase the number of active sites and enhance charge-transfer ability. This work can provide new ideas and concepts for designing novel and efficient TMD electrocatalysts.

Key words: transition metal dichalcogenides, alloy, heterostructure, hydrogen evolution reaction

中图分类号:

任先培, 李超, 凌芳, 胡启威, 于俊玲, 向晖, 彭跃红. 炭黑表面CoMoSSe异质结构合金的制备及其高效析氢研究[J]. 无机材料学报, DOI: 10.15541/jim20240487.

REN Xianpei, LI Chao, LING Fang, HU Qiwei, YU Junling, XIANG Hui, PENG Yuehong. CoMoSSe Alloy with Heterostructure on Carbon Black for Enhanced Electro-catalytic H₂ Evolution[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20240487.

参考文献

[1] XU B, LIANG J, SUN X P,et al. Designing electrocatalysts for seawater splitting: surface/interface engineering toward enhanced electrocatalytic performance. Green Chemistry, 2023, 25: 3767.
[2] ZHANG W, GUO R, YUE Q,et al. High-entropy phosphide bifunctional catalyst: preparation and performance of efficient water splitting. Journal of Inorganic Materials, 2024, 39(11): 1265.
[3] REN P Y, WANG R, TENG Z H, et al. Effect and mechanism of hydrogen annealing temperature on the HER performance of RuO₂-based catalysts in acid media. International Journal of Hydrogen Energy, 2024, 72: 1049.
[4] ZHANG X Y, LIU T Y, GUO T, et al. High-performance MoC electrocatalyst for hydrogen evolution reaction enabled by surface sulfur substitution. ACS Applied Materials & Interfaces, 2021, 13(34): 40705.
[5] XIONG W, YIN H H, WU T X, et al. Challenges and opportunities of transition metal oxides as electrocatalysts. Chemistry-A European Journal. 2023, 29(5): e202202872.
[6] YAN X S, DENG D J, WU S Q, et al. Development of transition metal nitrides as oxygen and hydrogen electrocatalysts. Chinese Journal of Structural Chemistry, 2022, 41: 2207004.
[7] WANG Q W, HE R Z, YANG F L,et al. An overview of heteroatom doped cobalt phosphide for efficient electrochemical water splitting, Chemical Engineering Journal, 2023, 456: 141056.
[8] GE Z Q, LI J W, ZHANG H J, et al. p-d orbitals coupling heterosites of Ni₂P/NiFe-LDH interface enable O-H cleavage for water splitting. Advanced Functional Materials, 2024, 34(40): 2411024.
[9] FENG Y, CHEN L, YUAN Z Y.Recent advances in transition metal layered double hydroxide basedmaterials as efficient electrocatalysts.Journal of Industrial and Engineering Chemistry, 2023, 120: 27.
[10] LI R Z, LIANG J, LI T S,et al. Recent advances in MoS₂-based materials for electrocatalysis. Chemical Communications, 2022, 58: 2259.
[11] REN X P, HU Q W, LING F,et al. Mott-Schottky heterojunction formation between Co and MoSe₂ on carbon nanotubes towards superior hydrogen evolution. New Carbon Materials, 2023, 38(6): 1059.
[12] XUE Y Q, XU Y Y , YAN Q , et al. Coupling of Ru nanoclusters decorated mixed-phase (1T and 2H) MoSe₂ on biomass-derived carbon substrate for advanced hydrogen evolution reaction. Journal of Colloid and Interface Science, 2022, 617: 594
[13] LIU F, WANG F Q, SUN X Y,et al. Plasma-induced vacancies in CoS₂ electrocatalysts to activate sulfur sites for hydrogen evolution reaction. International Journal of Hydrogen Energy, 2024, 48: 941.
[14] ZHANG Y T, LI B B, ZHOU A H, et al. Fe-Ni-doped metal-organic framework derived CoSe₂ as an efficient and stable electrocatalyst for hydrogen evolution reaction. International Journal of Hydrogen Energy, 2024, 65: 186.
[15] HUA W, SUN H H, XU F,et al. A review and perspective on molybdenum-based electrocatalysts for hydrogen evolution reaction. Rare Metals, 2020, 39: 335.
[16] ZHANG L L, LEI Y T, ZHOU D N,et al. Interfacial engineering of 3D hollow CoSe₂@ultrathin MoSe₂ core@shell heterostructure for efficient pH-universal hydrogen evolution reaction. Nano Research, 2022, 15(4): 2895.
[17] GONG Q F, CHENG L, LIU C H, et al. Ultrathin MoS₂₍₁-_x)Se₂_x alloy nanoflakes for electrocatalytic hydrogen evolution reaction. ACS Catalysis, 2015, 5: 2213.
[18] KIRAN V, MUKHERJEE D, JENJETI R,et al. Active guests in the MoS₂/MoSe₂ host lattice: efficient hydrogen evolution using few-layer alloys of MoS₂₍₁-_x)Se₂_x. Nanoscale, 2014, 6: 12856.
[19] WANG H, OUYANG L Y, ZOU G F,et al. Optimizing MoS₂ edges by alloying isovalent W for robust hydrogen evolution activity. ACS Catalysis, 2018, 8: 9529.
[20] ZHAO G Q, RUI K, DOU S X,et al. Heterostructures for electrochemical hydrogen evolution reaction: a review. Advanced Functional Materials, 2018, 28(43): 1803291.
[21] SONG A L, SONG S L, DUANMU M, et al. Recent progress of non-noble metallic heterostructures for the electrocatalytic hydrogen evolution. Small Science, 2023, 3(9): 2300036.
[22] SUN Z M, LIN L, YUAN M W,et al. Mott-Schottky heterostructure induce the interfacial electron redistribution of MoS₂ for boosting pH-universal hydrogen evolution with Pt-like activity, Nano Energy, 2022, 101: 107563.
[23] WU M H, HUANG Y Y, CHENG X L,et al. Arrays of ZnSe/MoSe₂ nanotubes with electronic modulation as efficient electrocatalysts for hydrogen evolution reaction. Advanced Materials Interfaces, 2017, 4(23): 1700948.
[24] REN X P, LI Q, LING F,et al. Construction of MoO₂/MoS₂ heterojunction on carbon nanotubes as high-efficiency electrocatalysts for H₂ production. CrystEngComm, 2023, 25: 5238.
[25] WANG P C, WAN L, LIN Y Q,et al. MoS₂ supported CoS₂ on carbon cloth as a high-performance electrode for hydrogen evolution reaction. International Journal of Hydrogen Energy, 2019, 44(31): 16566.
[26] LI S, ZANG W, LIU X, et al. Heterojunction engineering of MoSe₂/MoS₂ with electronic modulation towards synergetic hydrogen evolution reaction and supercapacitance performance. Chemical Engineering Journal, 2019, 359: 1419.
[27] HU Z X, JIANG L J, LI R C,et al. Interface engineering of MoS₂-CoS₂ heteronanosheets for enhanced electrochemical hydrogen evolution reaction. International Journal of Hydrogen Energy, 2024, 71: 701.
[28] LI Y J, WANG W Y, HUANG B J,et al. Abundant heterointerfaces in MOF-derived hollow CoS₂-MoS₂ nanosheet array electrocatalysts for overall water splitting. Journal of Energy Chemistry, 2021, 57: 99.
[29] LIANG J, YANG Y C, ZHANG J,et al. Ultrasmall CoSe₂ nanoparticles grown on MoS₂ nanofilms: a new catalyst for hydrogen evolution reaction. Physica Status Solidi (RRL), 2023, 18(7): 2300169.
[30] LIU Z L, WANG T, CHANG P,et al. MOF-derived MoS₂@o-CoSe₂ hetero-catalysts accompanied by structural phase transition for efficient electrochemical hydrogen production. International Journal of Hydrogen Energy, 2024, 51: 119.
[31] TANG X L, ZHANG J Y, MEI B B,et al. Synthesis of hollow CoSe₂/MoSe₂ nanospheres for efficient hydrazineassisted hydrogen evolution. Chemical Engineering Journal, 2021, 404: 126529.
[32] LI R, ZHOU X, SHEN H,et al. Conductive holey MoO₂-Mo₃N₂ hetero-junctions as job-synergistic cathode host with low surface area for high-loading Li-S batteries. ACS Nano, 2019, 13(9): 10049.
[33] LIU M, ZHANG C, SU J,et al. Propelling polysulfide conversion by defect-rich MoS₂ nanosheets for high-performance lithium-sulfur batteries. ACS Applied Materials & Interfaces, 2019, 11: 20788.
[34] GE H C, WANG J Q, LUO Y C,et al. Enhancing heterojunction interface charge transport efficiency in NiCo-LDHs@Co/CoO-CNFs for high-performance asymmetric and zinc-ion hybrid supercapacitors. Carbon, 2024, 229: 119482.
[35] HOU M, QIU Y, YAN G,et al. Aging mechanism of MoS₂ nanosheets confined in N-doped mesoporous carbon spheres for sodium-ion batteries. Nano Energy, 2019, 62: 299.
[36] YANG L, FU Q, WANG W H,et al. Large-area synthesis of monolayered MoS₂₍₁-_x)Se₂_x with a tunable band gap and its enhanced electrochemical catalytic activity. Nanoscale, 2015, 7: 10490.
[37] LI Y, WANG H, XIE L,et al. MoS₂ nanoparticles grown on graphene: an advanced catalyst for the hydrogen evolution reaction. Journal of the American Chemical Society, 2011, 133: 7296.