II. Physikalisches Institut, Universität zu Köln, Zülpicher Straße 77, D-50937 Köln, Germany.
Nanoscale. 2017 Sep 21;9(36):13618-13629. doi: 10.1039/c7nr04491g.
Metal nanoclusters, supported on inert substrates, exhibiting well-defined shapes and sizes in a broad range of temperatures are a major object of desire in nanotechnology. Here, a technique is presented that improves the thermal stability of monodisperse and crystalline transition metal nanoclusters grown in a regular array on metal-supported graphene. To stabilize the clusters after growth under ultrahigh vacuum the system composed of the aggregates and the graphene/metal interface is exposed to radicals resulting from the dissociation of diatomic gases. As a model system we have used Pt as the metal element for cluster growth and the template consisting of the moiré pattern resulting from the lattice mismatch between graphene and the Ir(111) surface. The study has been performed for deuterium and oxygen radicals, which interact very differently with graphene. Our results reveal that after radical exposure the thermally activated motion of Pt nanoclusters to adjacent moiré cells and the subsequent sintering of neighbor aggregates are avoided, most pronounced for the case of atomic O. For the case of D the limits of the improvement are given by radical desorption, whereas for the case of O they are defined by an interplay between coalescence and graphene etching followed by Pt intercalation, which can be controlled by the amount of exposure. Finally, we determined the mechanism of how radical adsorption improves the thermal stability of the aggregates.
在惰性衬底上支持的金属纳米团簇,在很宽的温度范围内表现出明确的形状和尺寸,是纳米技术的主要目标。在这里,提出了一种技术,该技术可以提高在金属支撑的石墨烯上以规则阵列生长的单分散和结晶过渡金属纳米团簇的热稳定性。为了在超真空下生长后稳定团簇,由聚集体和石墨烯/金属界面组成的系统会暴露于双原子气体分解产生的自由基中。我们以 Pt 作为用于团簇生长的金属元素和由石墨烯与 Ir(111)表面之间的晶格失配产生的摩尔纹图案组成的模板作为模型系统。该研究针对与石墨烯相互作用非常不同的氘和氧自由基进行了研究。我们的结果表明,暴露于自由基后,Pt 纳米团簇向相邻摩尔纹单元的热激活运动以及随后相邻聚集体的烧结得到了避免,在原子 O 的情况下最为明显。对于 D 的情况,改进的限制由自由基脱附决定,而对于 O 的情况,限制由聚结和随后的石墨烯蚀刻以及 Pt 插层之间的相互作用决定,这可以通过暴露量来控制。最后,我们确定了自由基吸附如何提高聚集体热稳定性的机制。