Dar Manzoor Ahmad, Krishnamurty Sailaja
Department of Chemistry, Islamic University of Science and Technology, Awantipora, Jammu and Kashmir 192122, India.
Physical Chemistry Division, CSIR-National Chemical Laboratory, Pune 411008, India.
ACS Omega. 2019 Jul 25;4(7):12687-12695. doi: 10.1021/acsomega.9b01581. eCollection 2019 Jul 31.
Utilization of molecular oxygen as an oxidizing agent in industrially important reactions is the ultimate goal to design environmentally benign processes under ambient conditions. However, the high thermal stability and a large O-O dissociation barrier in O molecule pose a great challenge toward its successful application in the oxidative chemistry. To achieve this goal, different catalysts based on monometallic and bimetallic clusters have been developed over the years to promote binding and dissociation of molecular oxygen. The successful design of efficient metal cluster catalysis needs an in-depth knowledge of synergistic effects between different metal atoms and intrinsic catalytic mechanisms for O adsorption and dissociation. Here, we present a systematic theoretical investigation of reaction pathways for O adsorption and dissociation on Au, Pd, and Au Pd ( = 1-7) nanoclusters in different spin states. The density functional calculations point out that the O dissociation barriers can be significantly reduced with the help of certain bimetallic clusters along specific spin channels. Our results particularly indicate that AuPd and AuPd show very large O binding energies of 1.76 and 1.69 eV, respectively. The enhanced O binding subsequently leads to low activation barriers of 0.98 and 1.19 eV along the doublet and quartet spin channels, respectively, without the involvement of any spin flip-over for O dissociation. Furthermore, the computed O dissociation barriers are significantly low as compared to the already reported barriers (1.95-3.65 eV) on monometallic and bimetallic Au-Ag clusters. The results provide key mechanistic insights into the interaction and dissociation of molecular oxygen with Au-Pd clusters, which can prove informative for the design of efficient catalysts for oxidative chemistry involving molecular oxygen as a reactant.
在工业上重要的反应中利用分子氧作为氧化剂是在环境条件下设计环境友好型工艺的最终目标。然而,O分子的高热稳定性和较大的O - O解离能垒对其在氧化化学中的成功应用构成了巨大挑战。为了实现这一目标,多年来已经开发了基于单金属和双金属簇的不同催化剂来促进分子氧的结合和解离。高效金属簇催化的成功设计需要深入了解不同金属原子之间的协同效应以及O吸附和解离的内在催化机制。在这里,我们对不同自旋态下Au、Pd和AuPd ( = 1 - 7)纳米簇上O吸附和解离的反应途径进行了系统的理论研究。密度泛函计算指出,借助某些双金属簇沿着特定的自旋通道可以显著降低O解离能垒。我们的结果特别表明,AuPd和AuPd的O结合能非常大,分别为1.76和1.69 eV。增强的O结合随后分别导致沿双重态和四重态自旋通道的低活化能垒,分别为0.98和1.19 eV,且O解离不涉及任何自旋翻转。此外,与已经报道的单金属和双金属Au - Ag簇上的能垒(1.95 - 3.65 eV)相比,计算得到的O解离能垒显著较低。这些结果为分子氧与Au - Pd簇的相互作用和解离提供了关键的机理见解,这对于设计以分子氧为反应物的氧化化学高效催化剂可能具有指导意义。