Modification of carbon surfaces by electrografting is a relevant topic due to its potential applications in different fields of science, which has motivated the publication of many works focused on different methodologies to get covalently attached films or to study their properties. Diverse organic molecules have been found to be able to produce grafted films on carbon-based electrodes and their reduction or oxidation involve free radicals that participate in complex reaction mechanisms, from the incipient radical attack of the electrode surface until the film growth. Once the grafted film is generated, electron conduction as well as mass transport through this film are processes that depend on many experimental factors, which are still susceptible of further studies. Hence, the knowledge of the grafting mechanisms is always useful for designing grafted films with more specific and controlled properties. Therefore, this critical review is focused to the main mechanistic aspects of different electrochemical methodologies to get grafted films on carbon surfaces. The use of cyclic voltammetry as tool of modification and characterization of electrochemically active films is summarized. Information about the use of reversible redox probes as indirect method to infer structural information of grafted films is also discussed. Structural reorganization, permeation processes, supporting electrolyte effects and rectification of voltametric responses of redox probes on grafted electrodes were also considered.

由于其在不同科学领域的潜在应用，通过电接枝对碳表面进行改性是一个相关主题，这促使发表了许多专注于不同方法以获得共价附着薄膜或研究其性质的作品。已发现多种有机分子能够在碳基电极上产生接枝薄膜，它们的还原或氧化涉及参与复杂反应机制的自由基，从电极表面的初始自由基攻击直到薄膜生长。一旦产生接枝膜，通过该膜的电子传导和质量传输是取决于许多实验因素的过程，这些因素仍然易于进一步研究。因此，接枝机制的知识对于设计具有更具体和可控性能的接枝薄膜总是有用的。因此，这篇批判性评论集中在不同电化学方法的主要机械方面，以在碳表面上获得接枝薄膜。总结了循环伏安法作为电化学活性薄膜修饰和表征工具的用途。还讨论了有关使用可逆氧化还原探针作为间接方法推断接枝薄膜结构信息的信息。还考虑了结构重组、渗透过程、支持电解质效应和氧化还原探针在接枝电极上的伏安响应的校正。这篇批判性评论集中在不同电化学方法的主要机械方面，以在碳表面上获得接枝薄膜。总结了循环伏安法作为电化学活性薄膜修饰和表征工具的用途。还讨论了有关使用可逆氧化还原探针作为间接方法推断接枝薄膜结构信息的信息。还考虑了结构重组、渗透过程、支持电解质效应和氧化还原探针在接枝电极上的伏安响应的校正。这篇批判性评论集中在不同电化学方法的主要机械方面，以在碳表面上获得接枝薄膜。总结了循环伏安法作为电化学活性薄膜修饰和表征工具的用途。还讨论了有关使用可逆氧化还原探针作为间接方法推断接枝薄膜结构信息的信息。还考虑了结构重组、渗透过程、支持电解质效应和氧化还原探针在接枝电极上的伏安响应的校正。还讨论了有关使用可逆氧化还原探针作为间接方法推断接枝薄膜结构信息的信息。还考虑了结构重组、渗透过程、支持电解质效应和氧化还原探针在接枝电极上的伏安响应的校正。还讨论了有关使用可逆氧化还原探针作为间接方法推断接枝薄膜结构信息的信息。还考虑了结构重组、渗透过程、支持电解质效应和氧化还原探针在接枝电极上的伏安响应的校正。