Liu Naigui, Gao Delu, Wang Dunyou
Qingdao Huanghai University, 266400, Qingdao, Shandong, China.
College of Physics and Electronics, Shandong Normal University, 250014, Jinan, Shandong, China.
Chemphyschem. 2024 Mar 15;25(6):e202300861. doi: 10.1002/cphc.202300861. Epub 2024 Feb 13.
Recent studies have shown that graphene-supported metal clusters can enhance catalytic reactivity compared with corresponding metal clusters. In this study, the adsorptions of NH , H S, and HCN on Cu and defective graphene-supported Cu clusters are investigated using plane-wave density functional theory. The results reveal the three gas molecules can be adsorbed on three types of top sites of Cu atoms, respectively. The adsorption energies of the corresponding adsorption sites on the defective graphene-supported Cu clusters are all increased compared with those on the Cu clusters. The orbital-resolved, crystal orbital Hamilton population analysis demonstrates that the larger the integrated crystal orbital Hamilton population, the stronger the adsorption between the gas molecule and the bonded Cu atom. The center of antibonding states on the defective graphene-supported Cu is shifted upward relative to Fermi level compared to the corresponding one on pure Cu , which explains the enhanced adsorption energy on defective graphene-supported Cu In addition, the closer d-band center to the Fermi level on the defective graphene-supported Cu indicates a stronger adsorption capacity than on pure Cu .
最近的研究表明，与相应的金属簇相比，石墨烯负载的金属簇可以提高催化反应活性。在本研究中，使用平面波密度泛函理论研究了NH、H₂S和HCN在Cu以及缺陷石墨烯负载的Cu簇上的吸附情况。结果表明，这三种气体分子可以分别吸附在Cu原子的三种类型的顶位上。与Cu簇上相应吸附位点相比，缺陷石墨烯负载的Cu簇上相应吸附位点的吸附能均有所增加。轨道分辨的晶体轨道哈密顿布居分析表明，晶体轨道哈密顿布居积分越大，气体分子与键合Cu原子之间的吸附越强。与纯Cu上的相应态相比，缺陷石墨烯负载的Cu上反键态的中心相对于费米能级向上移动，这解释了缺陷石墨烯负载的Cu上吸附能增强的原因。此外，缺陷石墨烯负载的Cu上d带中心更接近费米能级，表明其吸附能力比纯Cu更强。
