Manzoor Dar, Krishnamurty Sailaja, Pal Sourav
Theoretical Chemistry Group, Physical Chemistry Division, CSIR-National Chemical Laboratory, Pune-411 008, India.
Functional Materials Division, CSIR-Central Electrochemical Research Institute, Karaikudi-630 003, India.
Phys Chem Chem Phys. 2016 Mar 14;18(10):7068-74. doi: 10.1039/c5cp05624a.
Gold nanocages are the most attractive catalytic materials as all the atoms in the cage type clusters reside on the surface, making them available for chemisorption by reacting molecules. Due to a hollow space at the center, their chemical and catalytic properties can be tuned effectively and easily by endohedral doping. While a significant experimental and theoretical understanding is currently available on the structural and electronic properties of doped gold cages, very little information is available on their reactivity and catalytic behavior. In the present work, with the help of density functional theory calculations we demonstrate that endohedral doping leads to a notable increase in the binding energy of molecular oxygen on the gold nanocages. The enhancement in the O2 binding energy on the doped gold cages is also confirmed by a significant decrease in the Au-O and an increase in the O-O bond lengths, corroborated by a red shift (∼250 cm(-1)) in the O-O stretching frequency as compared to the pristine cage. Furthermore, interestingly, the doped gold cages show very low activation barriers for the environmentally important CO oxidation reaction as compared to the pristine gold cage. Importantly, the decrease in the barrier height is comparatively greater for the rate limiting step of O-O-C-O intermediate formation and as a result the CO oxidation is expected to be more facile on the doped gold cages. Thus, the current study highlights the role of heteroatom doping in imparting new chemical and catalytic properties to gold cages and is expected to spur further research in the design of efficient gold nanocatalysts.
金纳米笼是最具吸引力的催化材料,因为笼状簇中的所有原子都位于表面,使得它们可通过与反应分子发生化学吸附作用。由于其中心存在中空空间,通过内掺杂可以有效且轻松地调节它们的化学和催化性能。虽然目前在掺杂金笼的结构和电子性质方面已有大量实验和理论研究,但关于它们的反应性和催化行为的信息却非常少。在本工作中,借助密度泛函理论计算,我们证明内掺杂会导致分子氧在金纳米笼上的结合能显著增加。与原始笼相比,掺杂金笼上O₂结合能的增强也通过Au - O键长的显著缩短和O - O键长的增加得到证实,同时O - O伸缩频率出现红移(约250 cm⁻¹)。此外,有趣的是,与原始金笼相比,掺杂金笼对环境重要的CO氧化反应显示出非常低的活化能垒。重要的是,对于限速步骤O - O - C - O中间体形成而言,能垒高度的降低相对更大,因此预计在掺杂金笼上CO氧化会更容易。因此,当前研究突出了杂原子掺杂在赋予金笼新的化学和催化性能方面的作用,有望推动高效金纳米催化剂设计方面的进一步研究。