从塑料废弃物到能源催化剂：塑料衍生碳@CoMoO4复合材料在电解水析氢反应中的应用

doi:10.11949/0438-1157.20241525

化工学报 ›› 2025, Vol. 76 ›› Issue (8): 4081-4094.DOI: 10.11949/0438-1157.20241525

• 催化、动力学与反应器 • 上一篇下一篇

从塑料废弃物到能源催化剂：塑料衍生碳@CoMoO₄复合材料在电解水析氢反应中的应用

杨宁¹^,²(), 李皓男¹, LIN Xiao³(), GEORGIADOU Stella², LIN Wen-Feng²^,⁴^,⁵

^1.东北电力大学能源与动力工程学院，吉林吉林 132012
^2.拉夫堡大学化学工程系，英国莱斯特郡LE11 3TU
^3.剑桥大学化学工程与生物技术系，英国剑桥郡CB3 0AS
^4.浙江白马湖实验室有限公司，浙江杭州 311121
^5.浙江工业大学能源与碳中和科教融合学院，浙江杭州 310014

收稿日期:2024-12-30 修回日期:2025-04-17 出版日期:2025-08-25 发布日期:2025-09-17
通讯作者: LIN Xiao
作者简介:杨宁 (1989—)，男，博士，副教授，1020219438@qq.com
基金资助:
吉林省科技发展计划项目(20250205047GH);国家自然科学基金项目(52006029);吉林省青年科技人才托举工程项目(QT202113);吉林省产业技术研发专项(2019C056-2)

Application of plastic-derived carbon@CoMoO₄composites as an efficient electrocatalyst for hydrogen evolution reaction in water electrolysis

Ning YANG¹^,²(), Haonan LI¹, Xiao LIN³(), Stella GEORGIADOU², Wen-Feng LIN²^,⁴^,⁵

^1.College of Energy Resource and Power Engineering, Northeast Electric Power University, Jilin 132012, Jilin, China
^2.Department of Chemical Engineering, Loughborough University, Loughborough, Leicestershire LE11 3TU, United Kingdom
^3.Department of Chemical Engineering and Biotechnology, University of Cambridge, Cambridge CB3 0AS, United Kingdom
^4.Zhejiang Baima Lake Laboratory Co. , Ltd. , Hangzhou 311121, Zhejiang, China
^5.Science and Education Integration College of Energy and Carbon Neutralization, Zhejiang University of Technology, Hangzhou 310014, Zhejiang, China

Received:2024-12-30 Revised:2025-04-17 Online:2025-08-25 Published:2025-09-17
Contact: Xiao LIN

摘要/Abstract

摘要：

采用模板碳化和水热法将塑料矿泉水瓶转化为氮掺杂多孔碳材料（PNAC），然后在此基础上利用水热法和退火法成功制备了负载在塑料衍生氮掺杂碳上的CoMoO₄纳米颗粒（CoMoO₄@PNAC）复合材料，并用于电解水析氢催化剂。合成的CoMoO₄@PNAC复合材料在1 mol/L KOH的碱性电解液中表现出良好的析氢催化活性，仅需要162 mV的过电位就可以达到10 mA/cm²的电流密度，并表现出良好的稳定性。PNAC提供了良好的电子转移通道，其卷曲的纳米片形状可以对CoMoO₄纳米颗粒附近的电解液产生扰动，加快电解液与活性位点之间的质量交换，促进气泡产物的快速脱离。DFT计算表明，与CoMoO₄相比，CoMoO₄@PNAC具有更低的ΔG_H*，DOS曲线显示，PNAC的引入填充了纯CoMoO₄之中的态密度间隙，重新调整了电子分布，费米能级附近的态密度增加，提高了可用电子数量，释放出CoMoO₄的析氢催化潜力，进而使得CoMoO₄@PNAC具有良好的析氢催化性能。

关键词: CoMoO₄, 塑料衍生碳, 制氢, 电解水, 电化学, 催化剂

Abstract:

Waste plastic mineral-water bottles were converted into nitrogen-doped porous carbon materials using template carbonization and hydrothermal methods, then CoMoO₄ nanoparticles were loaded on the plastic-derived nitrogen-doped carbon (PNAC) to prepare the composite (CoMoO₄@PNAC) materials using hydrothermal and annealing methods, the latter were tested as catalysts for the electrocatalytic hydrogen evolution reaction (HER) in water electrolysis. The synthesized CoMoO₄@PNAC material exhibits good hydrogen evolution catalytic activity in 1 mol/L KOH alkaline electrolyte, requiring only 162 mV overpotential to reach a current density of 10 mA/cm², and exhibits good stability. PNAC provides an efficient electron transfer channel, and its curled nanosheet shape can perturb the electrolyte near the CoMoO₄ nanoparticles, accelerating the mass transport between the electrolyte and the active site and promoting the rapid detachment of the bubble products. DFT calculations show that CoMoO₄@PNAC has a lower ΔG_H* compared to CoMoO₄, and the DOS curves show that the introduction of PNAC fills the density-of-states gap among pure CoMoO₄, realigns the electron distribution, increases the density of states near the Fermi energy level, improves the number of available electrons, and releases the catalytic potential of CoMoO₄ towards HER, all of these leads to a high catalytic performance of CoMoO₄@PNAC.

Key words: CoMoO₄, waste plastic derived carbon, hydrogen production, water electrolysis, electrochemistry, catalyst

中图分类号:

O 646

杨宁, 李皓男, LIN Xiao, GEORGIADOU Stella, LIN Wen-Feng. 从塑料废弃物到能源催化剂：塑料衍生碳@CoMoO₄复合材料在电解水析氢反应中的应用[J]. 化工学报, 2025, 76(8): 4081-4094.

Ning YANG, Haonan LI, Xiao LIN, Stella GEORGIADOU, Wen-Feng LIN. Application of plastic-derived carbon@CoMoO₄composites as an efficient electrocatalyst for hydrogen evolution reaction in water electrolysis[J]. CIESC Journal, 2025, 76(8): 4081-4094.

图/表 14

图1 CoMoO4@PNAC的制备过程示意图

Fig.1 Schematic illustration of the preparation process for CoMoO4@PNAC

图2 PNAC的XRD谱图(a); PNAC的拉曼光谱图(b)

Fig.2 XRD pattens (a) and Raman spectrum (b) of PNAC sample

图3 PNAC的SEM图像[(a)、(b)]; PNAC的EDS图像[(c)~(f)]

Fig.3 SEM images of PNAC [(a),(b)]; EDS images of PNAC [(c)-(f)]

图4 CoMoO4@PNAC的XRD谱图(a); CoMoO4@PNAC的拉曼光谱图[(b)、(c)]

Fig.4 XRD pattens of CoMoO4@PNAC (a); Raman spectra of CoMoO4@PNAC sample [(b),(c)]

图5 CoMoO4@PNAC的SEM图像[(a)、(b)]; CoMoO4@PNAC的TEM图像[(c)、(d)]

Fig.5 SEM images of CoMoO4@PNAC[(a)，(b)]; TEM images of CoMoO4@PNAC [(c)，(d)]

图6 CoMoO4@PNAC的EDS图像

Fig.6 EDS images of CoMoO4@PNAC

图7 CoMoO4@PNAC的XPS全谱(a)和C 1s、N 1s、O 1s、Co 2p、Mo 3d的XPS精细谱[(b)~(f)]

Fig.7 Survey XPS spectra (a) and high-resolution XPS spectra of C 1s,N 1s,O 1s,Co 2p,Mo 3d [(b)—(f)] of CoMoO4@PNAC

图8 CoMoO4@PNAC的氮气吸附-脱附等温线(a)和孔径分布曲线(b)

Fig.8 Nitrogen adsorption-desorption isotherm (a) and the corresponding pore size distribution curve (b) obtained on CoMoO4@PNAC

图9 制备的样品在1 mol/L KOH 的碱性电解液中进行电化学测试：(a)样品的极化曲线; (b)过电位; (c)EIS曲线; (d)Tafel斜率

Fig.9 Electrochemical measurements of the as-prepared samples for hydrogen evolution reaction in 1 mol/L KOH aqueous solution: (a) polarization curves; (b) overpotential; (c) EIS curves; (d) Tafel plots

表1 CoMoO4基催化剂的部分研究

Table 1 Partial studies on CoMoO4-based catalysts

催化剂	电解液	η₁₀/mV	Tafel斜率/(mV/dec)	文献
CMO _x CNT	1 mol/L KOH	171	69.9	[35]
CoP@CoMoO₄ HNTs	1 mol/L KOH	120	34	[36]
CoMoO₄/N, S co-doped carbon	1 mol/L KOH	89	32	[40]
Co_0.5Zn_0.5MoO₄	1 mol/L KOH	204	162.7	[41]
N,S-NCO@CMO	1 mol/L KOH	100	64	[42]
CoMoO₄@PNAC	1 mol/L KOH	162	130.66	本工作

图10 CoMoO4@PNAC的CV曲线(a); 样品的Cdl(b); CoMoO4、PNAC与CoMoO4@PNAC的ECSA(c); 归一化HER极化曲线(d)

Fig.10 CV curve obtained on CoMoO4@PNAC (a); Cdl of the sample (b); ECSA of CoMoO4, PNAC and CoMoO4@PNAC (c); Normalized HER polarization curve (d)

图11 CoMoO4@PNAC在1 mol/L KOH中的i-t曲线(a); CoMoO4@PNAC经过1000次循环前后的极化曲线(b)

Fig.11 The i-t curves obtained on CoMoO4@PNAC in 1 mol/L KOH (a) and polarization curves obtained before and after 1000 CV cycles (b)

图12 样品表面的吸附模型(a);氢吸附自由能(b); DOS曲线(c)

Fig.12 Models of the structures for the adsorption on the sample surface (a); hydrogen adsorption free energy (b); DOS curve (c)

图13 CoMoO4@PNAC的HER增强机制示意图

Fig.13 Schematic diagram of the HER enhancement mechanism on CoMoO4@PNAC

参考文献 46

[1]	Truong H B, Tran N T, Do H H. Recent advancements and perspectives of hydrogen evolution reaction electrocatalysts based on molybdenum phosphides[J]. International Journal of Hydrogen Energy, 2024, 80: 696-711.
[2]	张正, 宋凌珺. 电解水制氢技术: 进展、挑战与未来展望[J]. 工程科学学报, 2025, 47(2): 282-295.
	Zhang Z, Song L J. Hydrogen production by water electrolysis: advances, challenges and future prospects[J]. Chinese Journal of Engineering, 2025, 47(2): 282-295.
[3]	Zhao G Q, Rui K, Dou S X, et al. Heterostructures for electrochemical hydrogen evolution reaction: a review[J]. Advanced Functional Materials, 2018, 28(43): 1803291.
[4]	Strmcnik D, Lopes P P, Genorio B, et al. Design principles for hydrogen evolution reaction catalyst materials[J]. Nano Energy, 2016, 29: 29-36.
[5]	Gao G L, Zhao G Z, Zhu G, et al. Recent advancements in noble-metal electrocatalysts for alkaline hydrogen evolution reaction[J]. Chinese Chemical Letters, 2025, 36(1): 109557.
[6]	Chen J Y C, Miller J T, Gerken J B, et al. Inverse spinel NiFeAlO₄ as a highly active oxygen evolution electrocatalyst: promotion of activity by a redox-inert metal ion[J]. Energy & Environmental Science, 2014, 7(4): 1382-1386.
[7]	Upadhyay S, Ahmad Mir R, Kumar N, et al. Reusing waste plastic bottle to reduce MoO₃ into carbon-supported MoO₂ nanoparticles for efficient water electrolysis[J]. Surfaces and Interfaces, 2023, 42: 103297.
[8]	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): 3785-3790.
[9]	Zhang C, Liu Y, Wang J M, et al. A well-designed fencelike Co₃O₄@MoO₃ derived from Co foam for enhanced electrocatalytic HER[J]. Applied Surface Science, 2022, 595: 153532.
[10]	Jiang M H, Hu Z C, Zou Y J, et al. NiSe-modified CoMoO₄ nanosheets as bifunctional electrocatalysts for hydrogen and oxygen evolution reactions[J]. Journal of Alloys and Compounds, 2024, 978: 173495.
[11]	Dashtian K, Ganjali M R, Albo J, et al. CoMoO₄ nano-architecture-based supercapacitors: tunable properties, performance optimization, and prospective applications[J]. Journal of Energy Storage, 2024, 102: 114063.
[12]	Li W X, Wang X W, Hu Y C, et al. Hydrothermal synthesized of CoMoO₄ microspheres as excellent electrode material for supercapacitor[J]. Nanoscale Research Letters, 2018, 13(1): 120.
[13]	You N, Cao S, Huang M Q, et al. Constructing P-CoMoO₄@NiCoP heterostructure nanoarrays on Ni foam as efficient bifunctional electrocatalysts for overall water splitting[J]. Nano Materials Science, 2023, 5(3): 278-286.
[14]	Ray S K, Bastakoti B P. Improved supercapacitor and oxygen evolution reaction performances of morphology-controlled cobalt molybdate[J]. International Journal of Hydrogen Energy, 2024, 51: 1109-1118.
[15]	Li T Z, Dong Y Y, Zhang J J, et al. Carbon dots-based composites electrocatalysts in hydrogen evolution reaction and oxygen evolution reaction: a mini review[J]. International Journal of Hydrogen Energy, 2024, 77: 359-372.
[16]	Keivanimehr F, Habibzadeh S, Baghban A, et al. Electrocatalytic hydrogen evolution on the noble metal-free MoS₂/carbon nanotube heterostructure: a theoretical study[J]. Scientific Reports, 2021, 11(1): 3958.
[17]	Reddy S, Song L, Kang L X, et al. Preparation of Mo₂C-carbon nanomaterials for hydrogen evolution reaction[J]. Carbon Letters, 2019, 29(3): 225-232.
[18]	杨妮娜, 左剑恶, 张艳艳, 等. 塑料老化过程及其环境危害研究进展[J]. 环境科学, 2025, 46(3): 1850-1860.
	Yang N N, Zuo J E, Zhang Y Y, et al. Research progress on plastic aging processes and their environmental hazards[J]. Environmental Science, 2025, 46(3): 1850-1860.
[19]	Lian Y M, Ni M, Huang Z H, et al. Polyethylene waste carbons with a mesoporous network towards highly efficient supercapacitors[J]. Chemical Engineering Journal, 2019, 366: 313-320.
[20]	Yu W L, Chen Z, Yu S T, et al. Highly dispersed Pt catalyst supported on nanoporous carbon derived from waste PET bottles for reductive alkylation[J]. RSC Advances, 2019, 9(53): 31092-31101.
[21]	Ahmad Mir R, Kaur G, Pandey O P. Facile process to utilize carbonaceous waste as a carbon source for the synthesis of low cost electrocatalyst for hydrogen production[J]. International Journal of Hydrogen Energy, 2020, 45(44): 23908-23919.
[22]	Yang Y X, An X Q, Wang D X, et al. Selenium-inducing activates molybdenum phosphide/nitrogen-doped porous carbon nanoparticles for boosting hydrogen generation[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2023, 666: 131307.
[23]	Sui D, Luo R S, Xie S M, et al. Atomic ruthenium doping in collaboration with oxygen vacancy engineering boosts the hydrogen evolution reaction by optimizing H absorption[J]. Chemical Engineering Journal, 2024, 480: 148007.
[24]	Pi C R, Huang C, Yang Y X, et al. In situ formation of N-doped carbon-coated porous MoP nanowires: a highly efficient electrocatalyst for hydrogen evolution reaction in a wide pH range[J]. Applied Catalysis B: Environmental, 2020, 263: 118358.
[25]	Wu A P, Xie Y, Ma H, et al. Integrating the active OER and HER components as the heterostructures for the efficient overall water splitting[J]. Nano Energy, 2018, 44: 353-363.
[26]	Homayounfard A M, Maleki M, Ghanbari H, et al. Growth of few-layer flower-like MoS₂ on heteroatom-doped activated carbon as a hydrogen evolution reaction electrode[J]. International Journal of Hydrogen Energy, 2024, 55: 1360-1370.
[27]	Tao Y H, Wang X G, Yue S N, et al. Molybdenum carbide nanoparticles supported on nitrogen-doped carbon as efficient electrocatalysts for hydrogen evolution reaction[J]. Journal of Electroanalytical Chemistry, 2019, 842: 89-97.
[28]	He X, Zeng K, Xie Y P, et al. The effects of temperature and molten salt on solar pyrolysis of lignite[J]. Energy, 2019, 181: 407-416.
[29]	Nti F, Anang D A, Han J I. Facilely synthesized NiMoO₄/CoMoO₄ nanorods as electrode material for high performance supercapacitor[J]. Journal of Alloys and Compounds, 2018, 742: 342-350.
[30]	Lv J L, Yang M, Suzuki K, et al. Synthesis of CoMoO₄@RGO nanocomposites as high-performance supercapacitor electrodes[J]. Microporous and Mesoporous Materials, 2017, 242: 264-270.
[31]	Fioravanti F, Martínez S, Delgado S, et al. Effect of MoS₂ in doped-reduced graphene oxide composites. Enhanced electrocatalysis for HER[J]. Electrochimica Acta, 2023, 441: 141781.
[32]	Zhang B, Liu G J, Jin B, et al. CoMoO₄/rGO hybrid structure embellished with Cu nanoparticles: an electrocatalyst rich in oxygen vacancies towards enhanced oxygen evolution reaction[J]. Materials Letters, 2021, 293: 129741.
[33]	Yan D G, Feng D X, Khan D S U, et al. Polyoxometalate and resin-derived P-doped Mo₂C@N-doped carbon as a highly efficient hydrogen-evolution reaction catalyst at all pH values[J]. Chemistry - An Asian Journal, 2018, 13(2): 158-163.
[34]	Zuo P, Liu Y F, Liu X L, et al. N, P-codoped molybdenum carbide nanoparticles loaded into N, P-codoped graphene for the enhanced electrocatalytic hydrogen evolution[J]. International Journal of Hydrogen Energy, 2022, 47(69): 29730-29740.
[35]	Chen C, Xin X, Cheng T, et al. The synergistic benefits of hydrate CoMoO₄ and carbon nanotubes culminate in the creation of highly efficient electrocatalysts for hydrogen evolution[J]. Alexandria Engineering Journal, 2024, 87: 93-106.
[36]	Gao Z F, Zeng Z F, Xu X W, et al. Hollow nanotube arrays of CoP@CoMoO₄ as advanced electrocatalyst for overall water splitting[J]. International Journal of Hydrogen Energy, 2024, 49: 260-271.
[37]	Zhang Z F, Ran J X, Fan E Z, et al. Mesoporous CoMoO₄ hollow tubes derived from POMOFs as efficient electrocatalyst for overall water splitting[J]. Journal of Alloys and Compounds, 2023, 968: 172169.
[38]	Li J S, Zhao C X, Yang Y X, et al. Synthesis of monodispersed CoMoO₄ nanoclusters on the ordered mesoporous carbons for environment-friendly supercapacitors[J]. Journal of Alloys and Compounds, 2019, 810: 151841.
[39]	Meng L X, Liu W W, Lu Y, et al. Lamellar-stacked cobalt-based nanopiles integrated with nitrogen/sulfur Co-doped graphene as a bifunctional electrocatalyst for ultralong-term zinc-air batteries[J]. Journal of Energy Chemistry, 2023, 81: 633-641.
[40]	Asen P. Cobalt molybdenum oxide/sponge-like nitrogen and sulfur Co-doped carbon composite as a bifunctional electrocatalyst for overall water splitting in alkaline media[J]. International Journal of Hydrogen Energy, 2025, 115: 1-9.
[41]	Chamani S, Sadeghi E, Unal U, et al. Tuning electrochemical hydrogen-evolution activity of CoMoO₄ through Zn incorporation[J]. Catalysts, 2023, 13(5): 798.
[42]	Wang J, Xuan H C, Meng L X, et al. N, S Co-doped NiCo₂O₄@CoMoO₄/NF hierarchical heterostructure as an efficient bifunctional electrocatalyst for overall water splitting[J]. International Journal of Hydrogen Energy, 2023, 48(22): 8144-8155.
[43]	Gao X C, Lu K X, Chen J J, et al. NiCoP–CoP heterostructural nanowires grown on hierarchical Ni foam as a novel electrocatalyst for efficient hydrogen evolution reaction[J]. International Journal of Hydrogen Energy, 2021, 46(45): 23205-23213.
[44]	Yang X, Qiu R, Lan M J, et al. Direct synthesis of binder-free Ni-Fe-S on Ni foam as superior electrocatalysts for hydrogen evolution reaction[J]. International Journal of Hydrogen Energy, 2022, 47(86): 36556-36565.
[45]	Zhang L, Hu Z H, Huang J T, et al. Experimental and DFT studies of flower-like Ni-doped Mo₂C on carbon fiber paper: a highly efficient and robust HER electrocatalyst modulated by Ni(NO₃)₂ concentration[J]. Journal of Advanced Ceramics, 2022, 11(8): 1294-1306.
[46]	Liu H C, Tan Z X, Niu Y X, et al. Ir-decorated MoS₂ monolayer as a promising candidate to detect dissolved gas in transformer oil: a DFT study[J]. Chemical Physics Letters, 2023, 818: 140410.

从塑料废弃物到能源催化剂：塑料衍生碳@CoMoO₄复合材料在电解水析氢反应中的应用

Application of plastic-derived carbon@CoMoO₄composites as an efficient electrocatalyst for hydrogen evolution reaction in water electrolysis

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