Laboratory of Chemical Biology, Division of Biological Inorganic Chemistry, Changchun Institute of Applied Chemistry, Graduate School of the Chinese Academy of Sciences, Chinese Academy of Sciences, Changchun, Jilin 130022, China.
ACS Appl Mater Interfaces. 2012 Sep 26;4(9):5001-9. doi: 10.1021/am301376m. Epub 2012 Sep 13.
Natural DNA has been considered as a building block for developing novel functional materials. It is abundant, renewable, and biodegradable and has a well-defined structure and conformation with many unique features, which are difficult to find in other polymers. Herein, calf thymus DNA modified graphene/Pd nanoparticle (DNA-G-Pd) hybrid materials are constructed for the first time using DNA as a mediator, and the prepared DNA-G-Pd hybrid shows high catalytic activity for fuel cell formic acid electro-oxidation and for organic Suzuki reaction. The main advantages of using DNA are not only because the aromatic nucleobases in DNA can interact through π-π stacking with graphene basal surface but also because they can chelate Pd via dative bonding in such defined sites along the DNA lattice. Our results indicate that isolated, homogeneous, and ultrafine spherical Pd nanoparticles are densely in situ decorated on DNA-modified graphene surfaces with high stability and dispersibility. The prepared DNA-G-Pd hybrid has much greater activity and durability for formic acid electro-oxidation than the commercial Pd/C catalyst and polyvinylpyrrolidone-mediated graphene/Pd nanoparticle (PVP-G-Pd) hybrid used for direct formic acid fuel cells (DFAFCs). Besides, the DNA-G-Pd hybrid can also be an efficient and recyclable catalyst for the organic Suzuki reaction in aqueous solution under aerobic conditions without any preactivation. Since DNA can chelate various transition metal cations, this proof-of-concept protocol provides the possibility for the tailored design of other novel catalytic materials based on graphene with full exploitation of their properties.
天然 DNA 一直被视为开发新型功能材料的基础。它丰富、可再生、可生物降解，具有明确的结构和构象，具有许多独特的性质，这在其他聚合物中很难找到。本文首次使用 DNA 作为介导物构建小牛胸腺 DNA 修饰的石墨烯/Pd 纳米粒子（DNA-G-Pd）杂化材料，所制备的 DNA-G-Pd 杂化材料对燃料电池甲酸电氧化和有机铃木反应具有高催化活性。使用 DNA 的主要优点不仅在于 DNA 中的芳族碱基可以通过π-π 堆积与石墨烯基面相互作用，而且在于它们可以通过 DNA 晶格上的特定位置的配位键螯合 Pd。我们的结果表明，孤立、均匀和超精细的球形 Pd 纳米粒子在 DNA 修饰的石墨烯表面上以高稳定性和分散性进行原位高密度装饰。与商业 Pd/C 催化剂和用于直接甲酸燃料电池（DFAFC）的聚乙烯吡咯烷酮介导的石墨烯/Pd 纳米粒子（PVP-G-Pd）杂化物相比，制备的 DNA-G-Pd 杂化物对甲酸电氧化具有更大的活性和耐久性。此外，在有氧条件下的水溶液中，DNA-G-Pd 杂化物也可以作为有机铃木反应的高效和可回收催化剂，无需任何预激活。由于 DNA 可以螯合各种过渡金属阳离子，因此该概念验证方案为基于石墨烯的其他新型催化材料的定制设计提供了可能性，可以充分利用它们的性质。
