IMDEA Nanociencia, Ciudad Universitaria de Cantoblanco, c/Faraday 9, 28049, Madrid, Spain.
Departamento de Química Inorgánica, Universidad Complutense de Madrid, 28040, Madrid, Spain.
Nat Commun. 2018 Jul 10;9(1):2671. doi: 10.1038/s41467-018-05183-8.
One of the most attractive applications of carbon nanomaterials is as catalysts, due to their extreme surface-to-volume ratio. The substitution of C with heteroatoms (typically B and N as p- and n-dopants) has been explored to enhance their catalytic activity. Here we show that encapsulation within weakly doping macrocycles can be used to modify the catalytic properties of the nanotubes towards the reduction of nitroarenes, either enhancing it (n-doping) or slowing it down (p-doping). This artificial regulation strategy presents a unique combination of features found in the natural regulation of enzymes: binding of the effectors (the macrocycles) is noncovalent, yet stable thanks to the mechanical link, and their effect is remote, but not allosteric, since it does not affect the structure of the active site. By careful design of the macrocycles' structure, we expect that this strategy will contribute to overcome the major hurdles in SWNT-based catalysts: activity, aggregation, and specificity.
碳纳米材料最吸引人的应用之一是作为催化剂，因为它们具有极高的比表面积。通过用杂原子（通常是 B 和 N 作为 p-和 n-掺杂剂）取代 C，可以提高它们的催化活性。在这里，我们表明，通过弱掺杂大环的封装可以用于修饰纳米管的催化性质，以促进硝基芳烃的还原，要么增强它（n-掺杂），要么减缓它（p-掺杂）。这种人工调控策略结合了酶的自然调控中所具有的独特特征：效应物（大环）的结合是非共价的，但由于机械连接而稳定，并且它们的作用是远程的，但不是变构的，因为它不会影响活性位点的结构。通过对大环结构的精心设计，我们期望这种策略将有助于克服基于 SWNT 的催化剂的主要障碍：活性、聚集和特异性。
