调控氧化石墨烯添加量以增强金属有机框架衍生材料的电容储能性能

doi:10.61558/2993-074X.3548

电化学（中英文） ›› 2025, Vol. 31 ›› Issue (7): 2503101-2503101. doi: 10.61558/2993-074X.3548

调控氧化石墨烯添加量以增强金属有机框架衍生材料的电容储能性能

秦永吉^a^,^*(), 杨净泉^a, 王昊^b, 练美玲^c, 贾沛沛^a^,^*(), 罗俊^a^,^*(), 刘熙俊^d, 刘军枫^e

^a 电子科技大学，电子科技大学（深圳）高等研究院，深思实验室，广东深圳518110
^b 中国中煤能源集团有限公司，北京 100120
^c 中国民航大学交通科学与工程学院，天津市民航能源环境与绿色发展工程研究中心，天津 300300
^d 广西大学资源环境与材料学院，广西有色金属及特色材料加工重点实验室，省部共建特色金属材料与组合结构全寿命安全国家重点实验室，广西南宁530004
^e 北京化工大学，化工资源有效利用国家重点实验室，北京 100029

收稿日期:2025-03-10 修回日期:2025-04-30 接受日期:2025-05-15 发布日期:2025-05-16 出版日期:2025-07-28
通讯作者: 秦永吉,贾沛沛,罗俊 E-mail:qyj@uestc.edu.cn;jiapeipei@uestc.edu.cn;jluo@uestc.edu.cn

Regulating the Amount of Graphene Oxide for Enhanced Capacitive Energy Storage of MOF Derived Materials

Yong-Ji Qin^a^,^*(), Jing-Quan Yang^a, Hao Wang^b, Mei-Ling Lian^c, Pei-Pei Jia^a^,^*(), Jun Luo^a^,^*(), Xi-Jun Liu^d, Jun-Feng Liu^e

^a ShenSi Lab, Shenzhen Institute for Advanced Study, University of Electronic Science and Technology of China, Longhua, Shenzhen 518110, China
^b China National Coal Group Corporation, Beijing 100120, China
^c Tianjin Engineering Research Center of Civil Aviation Energy Environment and Green Development, School of Transportation Science and Engineering, Civil Aviation University of China, Tianjin, 300300, China
^d State Key Laboratory of Featured Metal Materials and Life-cycle Safety for Composite Structures, Guangxi Key Laboratory of Processing for Non-ferrous Metals and Featured Materials, MOE Key Laboratory of New Processing Technology for Nonferrous Metals and Materials, School of Resources, Environment and Materials, Guangxi University, Nanning, 530004 Guangxi, China
^e State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China

Received:2025-03-10 Revised:2025-04-30 Accepted:2025-05-15 Online:2025-05-16 Published:2025-07-28
Contact: Yong-Ji Qin, Pei-Pei Jia, Jun Luo E-mail:qyj@uestc.edu.cn;jiapeipei@uestc.edu.cn;jluo@uestc.edu.cn

1. 2503101-Regulating the Amount of Graphene Oxide for Enhanced Capacitive Energy Storage of MOF Derived Materials-supporting information.pdf(1008KB)

摘要/Abstract

摘要：

为获得更高性能的电化学储能材料，兼具独特结构与优异特性的金属氧化物/氧化石墨烯复合材料体系受到广泛关注。本研究通过调控氧化石墨烯的引入量，构建金属有机框架与氧化石墨烯的复合结构，并基于一步煅烧法成功制备了氮掺杂碳骨架支撑金属氧化物与氧化石墨烯的复合体系。电化学性能测试结果表明，当氧化石墨烯引入量为7 wt%时，复合材料的比电容可达642 F·g^-1（1 A·g^-1），5000次循环后容量保持率达93%，其优异的储锂性能源于氧化石墨烯对金属氧化物纳米颗粒的导电网络优化与结构稳定作用。该研究为高稳定性金属氧化物/碳基复合电极材料的理性设计提供了新思路。

关键词: 金属有机框架, 氧化铁, 氧化石墨烯, 复合材料, 超级电容器

Abstract:

In pursuit of more efficient and stable electrochemical energy storage materials, composite materials consisting of metal oxides and graphene oxide have garnered significant attention due to their unique structures and exceptional properties. Graphene oxide (GO), a two-dimensional material with an extremely high specific surface area and excellent conductivity, offers new possibilities for enhancing the electrochemical performance of metal oxides. In this work, we synthesized metal-organic framework (MOF) and GO composites by regulating the amount of GO, and successfully prepared composites of metal oxides supported by nitrogen-doped carbon frameworks and GO through a simple one-step calcination process. Based on the electrochemical tests, the optimal amount of GO was determined. This research will provide new insights into and directions for designing and synthesizing metal oxide and graphene oxide composite materials with an ideal electrochemical performance.

Key words: Metal-organic framework, Iron oxide, Graphene oxide, Composite material, Supercapacitor

秦永吉, 杨净泉, 王昊, 练美玲, 贾沛沛, 罗俊, 刘熙俊, 刘军枫. 调控氧化石墨烯添加量以增强金属有机框架衍生材料的电容储能性能[J]. 电化学（中英文）, 2025, 31(7): 2503101-2503101.

Yong-Ji Qin, Jing-Quan Yang, Hao Wang, Mei-Ling Lian, Pei-Pei Jia, Jun Luo, Xi-Jun Liu, Jun-Feng Liu. Regulating the Amount of Graphene Oxide for Enhanced Capacitive Energy Storage of MOF Derived Materials[J]. Journal of Electrochemistry, 2025, 31(7): 2503101-2503101.

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链接本文: https://electrochem.xmu.edu.cn/CN/10.61558/2993-074X.3548

https://electrochem.xmu.edu.cn/CN/Y2025/V31/I7/2503101

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参考文献 43

[1]	Quan L, Jiang H, Mei G L, Sun Y J, You B. Bifunctional electrocatalysts for overall and hybrid water splitting[J]. Chem. Rev., 2024, 124(7): 3694-3812. https: https://doi.org/10.1021/acs.chemrev.3c00332
[2]	Yao W Q, Liao K, Lai T X, Sul H, Manthiram A. Rechargeable metal-sulfur batteries: key materials to mechanisms[J]. Chem. Rev., 2024, 124(8): 4935-5118. https://doi.org/10.1021/acs.chemrev.3c00919
[3]	Lu G L, Hou X H, Ding J Y, Qin Y J, Luo J, Liu X J. Research progress in electrocatalytic reduction of nitrate to ammonia by copper-based materials[J]. Chin. Sci. Bull., 2024, 69(25): 3728-3747. https://doi.org/10.1360/TB-2023-1349
[4]	Zhang T Y, Shi X H, Li Y, Sangaraju S, Wang F J, Yang L, Ran F. Carboxylic bacterial cellulose fiber-based hydrogel electrolyte with imidazole-type ionic liquid for dendrite-free zinc metal batteries[J]. Mater. R. Energy, 2024, 4(2): 100272. https://doi.org/10.1016/j.matre.2024.100272
[5]	Qin Y J, Luo J. Applications of single-atom catalysts in CO₂ conversion[J]. Chem. J. Chinese Universities, 2022, 43(9): 20220300. https://doi.org/10.7503/cjcu20220300
[6]	Liu X J, Chen M Y, Ma J J, Liang J Q, Li C S, Chen C J, He H B. Advances in the synthesis strategies of carbon-based single-atom catalysts and their electrochemical applications[J]. China Powder Sci. Technol., 2024, 30(5): 35-45. https://doi.org/10.13732/j.issn.1008-5548.2024.05.004
[7]	Yang J P, Zhang F Z, Chen J. Structural design and application of fiber-based electrocatalytic materials[J]. China Powder Sci. Technol., 2024, 30(4): 161-170. https://doi.org/10.13732/j.issn.1008-5548.2024.04.015
[8]	Chen X, Qin Y J, Feng X C, Yang S Q, Wang H, Lian M L, Zhang D X, Guo Q Q, Luo J, Yang J, Wang X Z. Hierarchical multi-dimensional Mn₂GeO₄ coupled with CNT for long-cycling lithium-ion battery[J]. Inorg. Chem. Commun., 2024, 164: 112467. https://doi.org/10.1016/j.inoche.2024.112467
[9]	El Aggadi S, Ennouhi M, Boutakiout A, El Hourch A. Progress towards efficient phosphate-based materials for sodium-ion batteries in electrochemical energy storage[J]. Ionics, 2023, 29(6): 2099-2113.
[10]	Alhammadi A S, Yun H J, Choi D. Investigation of LiFePO₄/MWCNT cathode-based half-cell lithium-ion batteries in subzero temperature environments[J]. Ionics, 2023, 29(6): 2163-2174. https://doi.org/10.1007/s11581-023-04953-9
[11]	Qin Y J, Cao H J, Liu Q, Yang S Q, Feng X C, Wang H, Lian M L, Zhang D X, Wang H, Luo J, Liu X J. Multi-functional layered double hydroxides supported by nanoporous gold toward overall hydrazine splitting[J]. Front. Chem. Sci. Eng., 2024, 18(1): 6. https://doi.org/10.1007/s11705-023-2373-1
[12]	Zhang H, Luo Y, Chu P K, Liu Q, Liu X J, Zhang S S, Luo J, Wang X Z, Hu G Z. Recent advances in non-noble metal-based bifunctional electrocatalysts for overall seawater splitting[J]. J. Alloys Compd., 2022, 922: 166113. https://doi.org/10.1016/j.jallcom.2022.166113
[13]	Peng X Y, Hou J R, Mi Y Y, Sun J Q, Qi G C, Qin Y J, Zhang S S, Qiu Y, Luo J, Liu X J. Bifunctional single-atomic Mn sites for energy-efficient hydrogen production[J]. Nanoscale, 2021, 13(9): 4767-4773. https://doi.org/10.1039/d0nr09104a
[14]	Liu W J, Liu W X, Hou T, Ding J Y, Wang Z G, Yin R L, San X Y, Feng L G, Luo J, Liu X J. Coupling Co-Ni phosphides for energy-saving alkaline seawater splitting[J]. Nano Res., 2024, 17(6): 4797-4806. https://doi.org/10.1007/s12274-024-6433-8
[15]	Cheng H H, Li J P, Meng T, Shu D. Advances in Mn‐based MOFs and their derivatives for high‐performance supercapacitor[J]. Small, 2024, 20(20): 2308804. https://doi.org/10.1002/smll.202308804
[16]	Han J J, Yan Q R, Chen Z W, Wang Z, Chen C. Application of Cr-metal organic framework (MOF) modified polyaniline/graphene oxide materials in supercapacitors[J]. Ionics, 2022, 28(5): 2349-2362. https://doi.org/10.1007/s11581-022-04443-4
[17]	Jayakumar A, Antony R P, Wang R, Lee J M. MOF‐derived hollow cage Ni_xCo_3-xO₄ and their synergy with graphene for outstanding supercapacitors[J]. Small, 2017, 13(11): 1603102. https://doi.org/10.1002/smll.2016031024
[18]	Zhu J, Shen X P, Kong L R, Zhu G X, Ji Z Y, Xu K Q, Li B L, Zhou H, Yue X Y. MOF derived CoP-decorated nitrogen-doped carbon polyhedrons/reduced graphene oxide composites for high performance supercapacitors[J]. Dalton T., 2019, 48(28): 10661-10668. https://doi.org/10.1039/c9dt01629e
[19]	Qin Y J, Han X, Li Y P, Han A J, Liu W X, Xu H J, Liu J F. Hollow mesoporous metal-organic frameworks with enhanced diffusion for highly efficient catalysis[J]. ACS Catal., 2020, 10(11): 5973-5978. https://dx.doi.org/10.1021/acscatal.0c01432
[20]	Yang M S, Sun J Q, Qin Y J, Yang H, Zhang S S, Liu X J, Luo J. Hollow CoFe-layered double hydroxide polyhedrons for highly efficient CO₂ electrolysis[J]. Sci. China Mater., 2021, 65(2): 536-542. https://doi.org/10.1007/s40843-021-1890-7
[21]	Qin Y L, Wang B Q, Qiu Y, Liu X J, Qi G C, Zhang S S, Han A J, Luo J, Liu J F. Multi-shelled hollow layered double hydroxides with enhanced performance for the oxygen evolution reaction[J]. Chem. Commun., 2021, 57(22): 2752-2755. https://dx.doi.org/10.1039/d0cc07643k
[22]	Yang Y, Zhang W R, Chen K W, Chen Y T, Dai X J, Gong C H, Wang P. Research progress on adsorption mechanism of radioactive iodine by metal-organic framework composites[J]. China Powder Sci. Technol., 2024, 30(4): 151-160. https://dx.doi.org/10.13732/j.issn.1008-5548.2024.04.014
[23]	Wang X G, He Z X, Ding D F, Luo X Q, Dai L, Zhang W Q, Ma Q, Huang Y, Xia F. Highly sensitive detection of strontium ions using metal-organic frameworks functionalized solid-state nanochannels[J]. J. Electrochem., 2024, 30(10): 2414003. https://doi.org/10.61558/2993-074X.3482
[24]	Shi Q Y, Zhao Y, Liu M H, Shi F Y, Chen L X, Xu X R, Gao J, Zhao H B, Lu F P, Qin Y J, Zhang Z, Lian M L. Engineering platelet membrane-coated bimetallic MOFs as biodegradable nanozymes for efficient antibacterial therapy[J]. Small, 2023, 20(23): 2309366. https://doi.org/10.1002/smll.202309366
[25]	Han X, Zhang T Y, Wang X H, Zhang Z D, Li Y P, Qin Y J, Wang B Q, Han A J, Liu J F. Hollow mesoporous atomically dispersed metal-nitrogen-carbon catalysts with enhanced diffusion for catalysis involving larger molecules[J]. Nat. Commun., 2022, 13(1): 2900. https://doi.org/10.1038/s41467-022-30520-3
[26]	Wang H F, Chen L Y, Pang H, Kaskel S, Xu Q. MOF-derived electrocatalysts for oxygen reduction, oxygen evolution and hydrogen evolution reactions[J]. Chem. Soc. Rev., 2020, 49(5): 1414-1448. https://doi.org/ 10.1039/c9cs00906j
[27]	Qin Y J, Wang F Q, Shang J, Iqbal M, Han A J, Sun X M, Xu H J, Liu J F. Ternary NiCoFe-layered double hydroxide hollow polyhedrons as highly efficient electrocatalysts for oxygen evolution reaction[J]. J. Energy Chem., 2020, 43: 104-107. https://doi.org/10.1016/j.jechem.2019.08.014
[28]	Lu Y, Yu L, Wu M H, Wang Y, Lou X W. Construction of complex Co₃O₄@Co₃V₂O₈ hollow structures from metal-organic frameworks with enhanced lithium storage properties[J]. Adv. Mater., 2017, 30(1): 1702875. https://doi.org/10.1002/adma.201702875
[29]	He P, Yu X Y, Lou X W. Carbon‐incorporated nickel-cobalt mixed metal phosphide nanoboxes with enhanced electrocatalytic activity for oxygen evolution[J]. Angew. Chem. Int. Ed., 2017, 56(14): 3897-3900. http://dx.doi.org/10.1002/anie.201612635
[30]	Hu H, Guan B Y, Lou X W. Construction of complex CoS hollow structures with enhanced electrochemical properties for hybrid supercapacitors[J]. Chem, 2016, 1(1): 102-113.http://dx.doi.org/10.1016/j.chempr.2016.06.001
[31]	He P P, Shi J H, Li X Y, Liu M J, Fang Z, He J, Li Z J, Peng X S, He Q G. A CNT intercalated Co porphyrin-based metal organic framework catalyst for oxygen reduction reaction[J]. J. Electrochem., 2025, 31(1): 2405241. https://doi.org/10.61558/2993-074X.3502
[32]	Dennyson Savariraj A, Justin Raj C, Kale A M, Kim B C. Road map for in situ grown binder‐free MOFs and their derivatives as freestanding electrodes for supercapacitors[J]. Small, 2023, 19(20): 2207713. https://doi.org/10.1002/smll.202207713
[33]	Rashi. Exploring the methods of synthesis, functionalization, and characterization of graphene and graphene oxide for supercapacitor applications[J]. Ceram. Int., 2023, 49(1): 40-47. https://doi.org/10.1016/j.ceramint.2022.10.333
[34]	Mane V A, Dake D V, Raskar N D, Sonpir R B, Gattu K P, Shirsat M D, Dole B N. Harnessing the synergistic effects of graphene oxide based Sn/Fe codoped Bi₂O₃ nanocomposites for superior supercapacitor performance[J]. J. Energy Storage, 2024, 96: 112636. https://doi.org/10.1016/j.est.2024.112636
[35]	Lin Z H, Han Z J, O'connell G E P, Wan T, Zhang D, Ma Z P, Chu D W, Lu X Y. Graphene and MOF assembly: enhanced fabrication and functional derivative via MOF amorphization[J]. Adv. Mater., 2024, 36(19): 2312797. https://doi.org/10.1002/adma.202312797
[36]	Zhao J W, Wei Z Q, Wang C, Zhou M P, Lu C G. NiCo₂S₄/rGO composite electrode material derived from Co-based MOFs for hybrid supercapacitors[J]. Ionics, 2024, 30(3): 1723-1733. https://doi.org/10.1007/s11581-024-05399-3
[37]	Liu S A, Jin M M, Sun J Q, Qin Y J, Gao S S, Chen Y, Zhang S S, Luo J, Liu X J. Coordination environment engineering to boost electrocatalytic CO₂ reduction performance by introducing boron into single-Fe-atomic catalyst[J]. Chem. Eng. J., 2022, 437: 135294. https://doi.org/10.1016/j.cej.2022.135294
[38]	Cao H J, Wei T R, Liu Q, Zhang S S, Qin Y J, Wang H, Luo J, Liu X J. Hollow carbon cages derived from polyoxometalate-encapsuled metal-organic frameworks for energy-saving hydrogen production[J]. ChemCatChem, 2023, 15(5): 202201615. https://doi.org/10.1002/cctc.202201615
[39]	Wang W X, Liu Y, Yue Y F, Wang H H, Cheng G, Gao C Y, Chen C L, Ai Y J, Chen Z, Wang X K. The confined interlayer growth of ultrathin two-dimensional Fe₃O₄ nanosheets with enriched oxygen vacancies for peroxymonosulfate activation[J]. ACS Catal., 2021, 11(17): 11256-11265. https://doi.org/10.1021/acscatal.1c03331
[40]	Wang T W, Gao S S, Wei T R, Qin Y J, Zhang S S, Ding J Y, Liu Q, Luo J, Liu X J. Co Nanoparticles confined in mesoporous Mo/N Co-doped polyhedral carbon frameworks towards high-efficiency oxygen reduction[J]. Chem. Eur. J., 2023, 29(23): 202204034. https://doi.org/10.1002/chem.202204034
[41]	Jamadar A S, Sutar R, Patil S, Khandekar R, Yadav J B. Progress in metal oxide-based electrocatalysts for sustainable water splitting[J]. Mater. R. Energy, 2024, 4(3): 100283. https://doi.org/10.1016/j.matre.2024.100283
[42]	Ge S M, Zhang L W, Hou J R, Liu S, Qin Y J, Liu Q, Cai X B, Sun Z Y, Yang M S, Luo J, Liu X J. Cu₂O-derived PtCu nanoalloy toward energy-efficient hydrogen production via hydrazine electrolysis under large current density[J]. ACS Appl. Energy Mater., 2022, 5(8): 9487-9494. https://doi.org/10.1021/acsaem.2c01006
[43]	Liu Y F, Guo Y S, Jiang Y R, Feng L Z, Sun Y, Wang Y J. Recent progress in thermodynamic and kinetics modification of magnesium hydride hydrogen storage materials[J]. Mater. R. Energy, 2024, 4(1): 100252. https://doi.org/10.1016/j.matre.2024.100252

调控氧化石墨烯添加量以增强金属有机框架衍生材料的电容储能性能

Regulating the Amount of Graphene Oxide for Enhanced Capacitive Energy Storage of MOF Derived Materials

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