Blanco Matías, Mosconi Dario, Otyepka Michal, Medveď Miroslav, Bakandritsos Aristides, Agnoli Stefano, Granozzi Gaetano
Department of Chemical Sciences , INSTM Unit , University of Padova , Via F. Marzolo 1 , 35131 , Padova , Italy . Email:
Regional Centre for Advanced Technologies and Materials , Faculty of Science , Palacký University Olomouc , Šlechtitelů 27 , 771 46 Olomouc , Czech Republic.
Chem Sci. 2019 Sep 6;10(41):9438-9445. doi: 10.1039/c9sc02954k. eCollection 2019 Nov 7.
Graphene oxide, the most prominent carbocatalyst for several oxidation reactions, has severe limitations due to the overstoichiometric amounts required to achieve practical conversions. Graphene acid, a well-defined graphene derivative selectively and homogeneously covered by carboxylic groups but maintaining the high electronic conductivity of pristine graphene, sets new activity limits in the selective and general oxidation of a large gamut of alcohols, even working at 5 wt% loading for at least 10 reaction cycles without any influence from metal impurities. According to experimental data and first principles calculations, the selective and dense functionalization with carboxyl groups, combined with excellent electron transfer properties, accounts for the unprecedented catalytic activity of this graphene derivative. Moreover, the controlled structure of graphene acid allows shedding light upon the critical steps of the reaction and regulating precisely its selectivity toward different oxidation products.
氧化石墨烯是几种氧化反应中最突出的碳催化剂，但由于实现实际转化所需的化学计量过量，它存在严重局限性。石墨烯酸是一种定义明确的石墨烯衍生物，被羧基选择性且均匀地覆盖，同时保持了原始石墨烯的高电子导电性，在多种醇类的选择性和一般氧化反应中设定了新的活性极限，甚至在5 wt%的负载量下至少能进行10个反应循环，且不受金属杂质的任何影响。根据实验数据和第一性原理计算，羧基的选择性和密集功能化与优异的电子转移性能相结合，解释了这种石墨烯衍生物前所未有的催化活性。此外，石墨烯酸的可控结构有助于揭示反应的关键步骤，并精确调节其对不同氧化产物的选择性。
