期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 28, 期 49, 页码 -出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202201136
关键词
doping effects; methane activation; size effects; Ti-Si-O cluster
资金
- National Natural Science Foundation of China [21878265]
The size and doping effects in methane activation by Ti-Si-O clusters were investigated using gas-phase experiments and quantum chemical calculations. It was found that Ti-Si-O clusters with a low Ti : Si ratio are beneficial for methane adsorption and hydrogen atom transfer, while clusters with a high Ti : Si ratio favor the generation of oxygen radicals. The study also recommended a cluster size of m+n=12 for improving the reaction efficiency.
The size and doping effects in methane activation by Ti-Si-O clusters have been explored by using a combination of gas-phase experiments and quantum chemical calculations. All [TimSinO2(m+n)](.+) (m+n=2, 3, 8, 10, 12, 14) clusters can extract a hydrogen from methane. The associated energies and structures have been revealed in detail. Moreover, the doping and size effects have been discussed involving generalized Kohn-Sham energy decomposition analysis, natural population analysis, Wiberg bond indexes (WBI), molecular polarity index (MPI) and ionization potential (IP). It suggested that Ti-Si-O clusters with a low Ti : Si ratio is beneficial to adsorbing methane and inclination to the hydrogen atom transfer (HAT) process, while the clusters with a high Ti : Si ratio favors the generation of a terminal oxygen radical and results in high reactivity and turnover frequency. On the other hand, a cluster size of m+n=12 is recommended considering both the ionization potential and the turnover frequency of the reaction. Hopefully, these finding will be instructive for the design of high-performance Ti-Si-O catalyst toward methane conversion.
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