Kai HE , Xuyan SU , Zhuang QU , Ye YANG , Yucai QIN , Lijuan SONG
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Abstract
This study systematically investigates the CO adsorption behavior and electron transfer mechanisms on Ptn/γ-Al2O3 catalysts using density functional theory (DFT) calculations. By combining infrared vibrational spectroscopy, electron difference density, and charge decomposition analysis, this work reveals how Pt cluster size regulates CO adsorption configurations, electron transfer, and C−O bond vibrational frequencies. The results show that small Pt4 sub-nanometric clusters, owing to the presence of highly undercoordinated Pt atoms, exhibit strong d-electron back-donation, leading to enhanced population of the CO π* antibonding orbitals, pronounced C−O bond weakening, and a redshift in the IR frequency. In contrast, large Pt13 sub-nanometric clusters, due to their dense structure, experience electron delocalization, weakened back-donation, enhanced C−O bonding, and a blueshift in the IR frequency. The intensity of electron transfer increases in linear, bridge, and multi-terminal adsorption, respectively. Bridge adsorption is most sensitive to size, with an IR blueshift of 81 cm−1 observed when the number of Pt atoms increases from 4 to 13. Multi-terminal adsorption exhibits a stable frequency due to a “saturation effect.” This study establishes a comprehensive correlation between Pt size, electronic structure, adsorption properties, and infrared response, elucidating the CO adsorption mechanism on Pt-based catalysts and providing atomic-scale theoretical guidance for the design of efficient catalysts.
期刊介绍：
Journal of Fuel Chemistry and Technology (Ranliao Huaxue Xuebao) is a Chinese Academy of Sciences(CAS) journal started in 1956, sponsored by the Chinese Chemical Society and the Institute of Coal Chemistry, Chinese Academy of Sciences(CAS). The journal is published bimonthly by Science Press in China and widely distributed in about 20 countries. Journal of Fuel Chemistry and Technology publishes reports of both basic and applied research in the chemistry and chemical engineering of many energy sources, including that involved in the nature, processing and utilization of coal, petroleum, oil shale, natural gas, biomass and synfuels, as well as related subjects of increasing interest such as C1 chemistry, pollutions control and new catalytic materials. Types of publications include original research articles, short communications, research notes and reviews. Both domestic and international contributors are welcome. Manuscripts written in Chinese or English will be accepted. Additional English titles, abstracts and key words should be included in Chinese manuscripts. All manuscripts are subject to critical review by the editorial committee, which is composed of about 10 foreign and 50 Chinese experts in fuel science. Journal of Fuel Chemistry and Technology has been a source of primary research work in fuel chemistry as a Chinese core scientific periodical.
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