目的 为明确纳米材料表面基团对其缓蚀性能的调控规律及其作用机理,本文以表面基团易于修饰的碳点为研究对象,在控制其粒径与碳核结构基本一致的前提下,构建仅表面基团类型不同的单一变量碳点体系,揭示不同基团（羧基、巯基和氨基）对碳点缓蚀性能的影响及其内在机理,从而为高效纳米缓蚀剂开发提供直接实验依据与理论指导。方法 采用后修饰策略制备出三种表面分别富含羧基、巯基和氨基的碳点（OCDs、SCDs和NCDs）。采用失重法和电化学法,评价三类碳点在1 mol/L HCl溶液中对Q235碳钢的缓蚀性能;通过电化学测试、微观形貌分析以及分子动力学模拟多尺度揭示了不同表面基团影响缓蚀性能的内在机理。结果 失重法与电化学测试一致表明,在1 mol/L HCl介质中,三类碳点对碳钢的缓蚀性能存在显著差异。在100 mg/L浓度下,由动电位极化曲线计算所得的三类碳点缓蚀效率分别为：NCDs最优（91.2%）,其次为SCDs（86.6%）,OCDs最低（79.0%）。结论 不同表面基团影响碳点缓蚀性能的机理为：碳点通过吸附成膜和诱导形成氧化膜发挥保护作用,其中NCDs因平行构型稳定吸附、结合能最强而形成最致密保护膜并促进致密氧化膜生成,缓蚀效果最佳;SCDs同样呈平行吸附,但吸附与成膜能力略弱;OCDs难以实现平行吸附,结合能最低,形成的吸附膜与诱导形成的氧化膜最不致密,保护效果最差。
Abstract
Surface functional groups are one of the key factors determining the corrosion inhibition performance of nanomaterials. However, the effects and mechanisms of different functional groups remain unclear. This is mainly because it is difficult to modify the surface groups of nanomaterials while keeping other structural parameters such as particle size and crystallinity constant, thus making it impossible to isolate the single-variable effect of surface functional groups. To address this issue, carbon dots (CDs), which are easily surface-modifiable, are used as a model system in this work. A post-modification strategy is employed to prepare three types of CDs with nearly identical particle size and carbon core structure but distinctly different surface functional groups: carboxyl-rich (OCDs), thiol-rich (SCDs), and amino-rich (NCDs). Transmission electron microscopy, Raman spectroscopy, and Fourier transform infrared spectroscopy collectively confirm that the three types of CDs are essentially identical in particle size and carbon core structure, including lattice spacing and graphitization degree, while their surface functional groups are significantly different, being rich in —COOH, —NH2, and —SH, respectively. In addition, qualitative observation combined with quantitative spectroscopic data demonstrates that regardless of which type of surface groups the as-prepared CDs are rich in, they all possess excellent long-term dispersion stability in HCl corrosive medium and are therefore suitable as corrosion inhibitors for acidic solutions. Weight loss measurements, electrochemical impedance spectroscopy (EIS), and potentiodynamic polarization (PDP) are systematically used to evaluate the corrosion inhibition performance of the three types of CDs on Q235 carbon steel in 1 mol/L HCl solution at a concentration of 100 mg/L. All test data show highly consistent trends, collectively confirming a core conclusion: under the condition that particle size, carbon core structure and other parameters are kept essentially constant, the corrosion inhibition performance of CDs significantly depends on their surface functional groups, with the inhibition efficiency following the order of NCDs > SCDs > OCDs. The inhibition efficiencies calculated from PDP are as follows: NCDs are the highest at 91.2%, followed by SCDs at 86.6%, and OCDs are the lowest at 79.0%. By comprehensively employing electrochemical tests, microscopic morphology analysis, and molecular dynamics simulations, the mechanism by which different surface functional groups affect the inhibition performance is revealed at multiple scales. Specifically, CDs exert a protective effect by forming an adsorbed film and inducing the formation of an oxide film. Among them, NCDs exhibit stable parallel adsorption and the strongest binding energy, thereby forming the most compact protective film and promoting the generation of a dense oxide film, resulting in the best inhibition efficiency. SCDs also adopt parallel adsorption but with slightly weaker adsorption and film-forming ability. In contrast, OCDs cannot achieve parallel adsorption and have the lowest binding energy, forming the least compact adsorbed film and the least dense induced oxide film, thus giving the poorest protection. This work not only provides evidence for clarifying the relationship between the surface functional groups of CDs and their corrosion inhibition performance, but also offers a theoretical basis for the design and development of high-performance, tailor-made nanoscale corrosion inhibitors based on surface functional groups.
关键词
表面基团 /
碳点 /
缓蚀性能 /
机理 /
碳钢
Key words
surface functional groups /
carbon dots /
corrosion inhibition performance /
mechanism /
carbon steel
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基金
浙江省尖兵领雁计划项目（2026C02A1052）;浙江省自然科学基金项目联合基金资助项目（LGEZ26E090004）;台州市科学技术局项目（25gya13）;国家自然科学基金青年科学基金项目（A类）（52525804）
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