Nitrogen-doped carbons are promising materials for a broad range of applications. However, their rational design is greatly hampered by the lack of efficient methods to control the nitrogen speciation, which not only causes controversy about the roles of specific nitrogen functionalities but also hinders investigations into other physicochemical characteristics of these materials. We herein present a cutting-edge strategy that allows a systematic tuning of the electrical conductivity of polyaniline-derived N-doped carbons at a defined nitrogen speciation and content, and similar porous properties. By application of these model systems in acetylene hydrochlorination, a major industrial technology for the production of polyvinyl chloride, we provide insights into the active sites and the reaction mechanism and disclose two key catalytic descriptors for N-doped carbons in this reaction: (i) a high content of pyrrolic-N functionalities, promoting the adsorption of the reactants, and (ii) good electrical conductivity, likely influencing the surface diffusion of adsorbed species. Since increasing the electrical conductivity leads to a reduced nitrogen content, the interplay between these two properties must be carefully controlled to maximize catalytic performance. This understanding enabled the design of the first N-doped carbon catalyst that rivals the unprecedented activity of benchmark gold-based systems in acetylene hydrochlorination.

中文翻译：

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乙炔氯化氢中高性能氮掺杂碳催化剂的描述子

氮掺杂碳是广泛应用领域中很有希望的材料。但是，缺乏合理的控制氮形态的方法极大地阻碍了它们的合理设计，这不仅引起对特定氮功能的作用的争论，而且还阻碍了对这些材料其他理化特性的研究。我们在此提出了一种先进的策略，该策略允许在规定的氮形态和含量以及相似的多孔性下，对聚苯胺衍生的N掺杂碳的电导率进行系统调节。通过将这些模型系统应用于乙炔氢氯化，这是生产聚氯乙烯的一项主要工业技术，我们提供了有关活性位点和反应机理的见解，并公开了该反应中N掺杂碳的两个关键催化描述符：（i）高含量的吡咯N功能性，促进了反应物的吸附，以及（ii）良好的导电性，可能影响吸附物质的表面扩散。由于增加电导率会导致氮含量降低，因此必须仔细控制这两种性能之间的相互作用，以最大限度地提高催化性能。这种理解使我们设计出了首款与氮基乙炔氢氯化工艺中的基准金基体系前所未有的活性相媲美的N掺杂碳催化剂。（ii）良好的导电性，可能影响被吸附物质的表面扩散。由于增加电导率会导致氮含量降低，因此必须仔细控制这两种性能之间的相互作用，以最大限度地提高催化性能。这种理解使我们设计出了首款与氮基乙炔氢氯化工艺中的基准金基体系前所未有的活性相媲美的N掺杂碳催化剂。（ii）良好的导电性，可能会影响被吸附物质的表面扩散。由于增加电导率会导致氮含量降低，因此必须仔细控制这两种性能之间的相互作用，以最大限度地提高催化性能。这种理解使我们设计出了首款与氮基乙炔氢氯化工艺中的基准金基体系前所未有的活性相媲美的N掺杂碳催化剂。