氧化石墨烯<strong>/</strong>铈基金属有机框架构筑高稳定长耐蚀防护涂层

doi:10.11902/1005.4537.2025.315

中国腐蚀与防护学报

2026, Vol. 46

Issue (4): 1095-1106 CSTR: 32134.14.1005.4537.2025.315 DOI: 10.11902/1005.4537.2025.315

研究报告

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氧化石墨烯/铈基金属有机框架构筑高稳定长耐蚀防护涂层

柯定芳¹^,², 吴芳芳¹^,², 朱兆彬¹^,²(

), 谢声益¹^,², 洪静¹^,², 陈悦¹^,², 李亮¹^,², 李昊³, 曹发和³

^1.浙江华电器材检测研究院有限公司杭州 310007
^2.国家电网公司电力器材安全性能检测技术实验室杭州 310007
^3.中山大学材料学院深圳 518107

Composite of Graphene Oxide/Cerium-based Metal Organic Frameworks for Preparing Protective Coatings with High Stability and Long-term Corrosion Resistance

KE Dingfang¹^,², WU Fangfang¹^,², ZHU Zhaobin¹^,²(

), XIE Shengyi¹^,², HONG Jing¹^,², CHEN Yue¹^,², LI Liang¹^,², LI Hao³, CAO Fahe³

^1.Zhejiang Huadian Equipment Testing and Research Institute Co. Ltd., Hangzhou 310007, China
^2.SGCC-Testing Technology Laboratory of Electrical Equipment Safety Performance, Hangzhou 310007, China
^3.School of Materials, Sun Yat-sen University, Shenzhen 518107, China

引用本文:

柯定芳, 吴芳芳, 朱兆彬, 谢声益, 洪静, 陈悦, 李亮, 李昊, 曹发和. 氧化石墨烯/铈基金属有机框架构筑高稳定长耐蚀防护涂层[J]. 中国腐蚀与防护学报, 2026, 46(4): 1095-1106.
Dingfang KE, Fangfang WU, Zhaobin ZHU, Shengyi XIE, Jing HONG, Yue CHEN, Liang LI, Hao LI, Fahe CAO. Composite of Graphene Oxide/Cerium-based Metal Organic Frameworks for Preparing Protective Coatings with High Stability and Long-term Corrosion Resistance[J]. Journal of Chinese Society for Corrosion and protection, 2026, 46(4): 1095-1106.

全文: PDF(15067 KB) HTML

摘要:

功能化的氧化石墨烯(GO)复合材料作为填料，有助于提升有机涂层在海洋环境中的服役寿命。但这些材料的合成方法往往都涉及到有毒试剂使用和高能量消耗，既增加了成本又限制了其实际应用性。对此，通过在室温水溶液中实现铈基金属有机框架(CeMOF)在GO表面的原位生长，制得了GO-CeMOF复合材料，并将其作为填料，制备了GO-CeMOF-EP复合涂层。结果表明，CeMOF在GO纳米片上分布均匀，能显著抑制GO纳米片的团聚与堆叠。GO-CeMOF-EP涂层截面形貌分布均一、涂层致密，展现出最高的界面结合力(4.56 MPa)和最低的吸水率(0.73%)。在模拟海水溶液中浸泡60 d后，GO-CeMOF-EP涂层的Z_{f = 0.01 Hz}值为1.0 × 10⁹ Ω·cm²，分别较EP (4.8 × 10⁷ Ω·cm²)和GO-EP (1.0 × 10⁸ Ω·cm²)涂层高出20.8倍和10.0倍。剥离涂层后，Q235钢基体表面无明显腐蚀，进一步验证了复合涂层长效、可靠的腐蚀防护性能。可以预测，这种高效、简单的涂料设计策略有望提高涂料的防护性能，延长金属装备在恶劣海洋环境中的使用寿命。

关键词 ：氧化石墨烯, 金属有机框架, 海洋涂层, 腐蚀防护, 电化学

Abstract：

Incorporating functionalized graphene oxide (GO) composites as fillers can enhance the service life of organic coatings in marine environments. However, their synthesis methods typically involve the use of toxic reagents and high energy consumption, which increase production costs and restrict practical applicability. To address this, a novel composite of GO-CeMOF were prepared via in situ growth of cerium-based metal-organic frameworks (CeMOFs) on GO surface in aqueous solution at ambient temperature. Then particulates of the composite as fillers were blended with epoxy paint to prepare the GO-CeMOF-EP composite coating on carbon steel Q235. It follows that the CeMOFs were uniformly distributed on GO nanosheets, thus of which the agglomeration and stacking could be effectively suppressed. Cross-sectional analysis revealed that the GO-CeMOF particulates were uniformly distributed within the formed GO-CeMOF-EP coating and the coating is compact with optimal interfacial adhesion strength (4.56 MPa) and minimal water adsorption (0.73%). After immersion test in simulated seawater for 60 d, the Z_{f = 0.01 Hz} value of GO-CeMOF-EP coating (1.0 × 10⁹ Ω·cm²) represented 20.8-fold and 10.0-fold improvements corresponding over the plain EP (4.8 × 10⁷ Ω·cm²) and GO-EP (1.0 × 10⁸ Ω·cm²) coatings, respectively. After peeling off the GO-CeMOF-EP coating, no apparent corrosion was observed on the Q235 steel substrate, further verifying the long-term and reliable corrosion protection performance of the coating. Therefore, this innovative, efficient, and simple design strategy is expected to improve the protective performance of coatings and prolong the service life of metallic equipment in harsh marine environments.

Key words： graphene oxide metal-organic framework marine coating corrosion protection electrochemistry

收稿日期: 2025-10-12 32134.14.1005.4537.2025.315

ZTFLH:

TG172

基金资助:杭州市科技发展计划项目(20241203A22)

通讯作者: 朱兆彬，E-mail：3515636807@qq.com，研究方向为户外电力设备防护

Corresponding author: ZHU Zhaobin, E-mail: 3515636807@qq.com

作者简介: 柯定芳，男，1980年生，硕士生

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https://www.jcscp.org/CN/10.11902/1005.4537.2025.315 或 https://www.jcscp.org/CN/Y2026/V46/I4/1095

图1 GO-CeMOF复合材料的制备示意图

图2 GO和GO-CeMOF的SEM图，TEM图及元素分布

图3 GO和GO-CeMOF的XRD、FT-IR和TGA谱图

图4 GO-CeMOF的全谱及C 1s、O 1s和Ce 3d高分辨谱图

图5 不同涂层的截面形貌

图6 EP，GO-EP和GO-CeMOF-EP涂层的吸水率和结合力

图7 EP、GO-EP和GO-CeMOF-EP涂层浸泡在3.5%NaCl溶液中60 d的Nyquist和Bode图

图8 用于拟合所有电化学数据的等效电路

图9 不同涂层的低频阻抗模值lg|Zf = 0.01 Hz|，电容值lgCc和电荷转移电阻值Rct

图10 不同涂层保护下金属基体的腐蚀形貌和元素分布

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