Chang Chun-Chih, Ho Jia-Jen
Department of Chemistry, National Taiwan Normal University, No. 88, Section 4, Tingchow Road, Taipei 116, Taiwan.
Phys Chem Chem Phys. 2015 Apr 28;17(16):11028-35. doi: 10.1039/c5cp01121c.
The catalytic activity of rhodium nanoclusters (Rh13) on unzipped graphene oxide (Rh13/UGO) has been investigated for comparison with Rh13 nanoclusters and Rh(111) surfaces. The binding energy of Rh atoms on UGO is less than the cohesive energy (-5.75 eV) of bulk Rh, indicating that the Rh atoms adsorbed on UGO tend to collect into clusters. We systematically calculated the adsorption energies of CO2 on Rh13 nanoclusters in various stable shapes on unzipped graphene oxide; Rh13-Ih/UGO had the highest energy (where the Ih represents icosahedral shape), -1.18 eV, with the C-O bond being elongated from 1.17 to 1.29 Å; the barrier to dissociation of CO2 on Rh13-Ih/UGO is, accordingly, the smallest (Ea = 0.45 eV), indicating that Rh13-Ih/UGO might act as an effective material to adsorb and activate the scission of the C-O bond of CO2. The calculated data required to support all evidence of this result, including the electronic distribution and the density of states, are provided.
为了与铑纳米团簇（Rh13）和Rh(111)表面进行比较，研究了铑纳米团簇（Rh13）在解链氧化石墨烯（Rh13/UGO）上的催化活性。Rh原子在UGO上的结合能小于块状Rh的内聚能（-5.75 eV），这表明吸附在UGO上的Rh原子倾向于聚集成团簇。我们系统地计算了二氧化碳在解链氧化石墨烯上各种稳定形状的Rh13纳米团簇上的吸附能；Rh13-Ih/UGO具有最高的能量（其中Ih代表二十面体形状），为-1.18 eV，C-O键从1.17 Å拉长到1.29 Å；因此，二氧化碳在Rh13-Ih/UGO上解离的势垒最小（Ea = 0.45 eV），这表明Rh13-Ih/UGO可能是一种吸附和激活二氧化碳C-O键断裂的有效材料。提供了支持该结果所有证据所需的计算数据，包括电子分布和态密度。
