Adsorption of Transition-Metal Clusters on Graphene and N-Doped Graphene: A DFT Study

Chengkai Jin; Lihong Cheng; Gang Feng; Runping Ye; Zhang-Hui Lu; Rongbin Zhang; Xiaohu Yu

doi:10.1021/acs.langmuir.1c03187

Adsorption of Transition-Metal Clusters on Graphene and N-Doped Graphene: A DFT Study

Langmuir. 2022 Mar 29;38(12):3694-3710. doi: 10.1021/acs.langmuir.1c03187. Epub 2022 Mar 14.

Authors

Chengkai Jin¹, Lihong Cheng², Gang Feng¹, Runping Ye¹, Zhang-Hui Lu³, Rongbin Zhang¹, Xiaohu Yu⁴

Affiliations

¹ Key Laboratory of Jiangxi Province for Environment and Energy Catalysis, Institute of Applied Chemistry, College of Chemistry, Nanchang University, No. 999 Xuefu Road, Nanchang 330031, P. R. China.
² Key Laboratory of Surface Engineering of Jiangxi Province, Jiangxi Science & Technology Normal University, Nanchang 330031, P. R. China.
³ Institute of Advanced Materials (IAM), College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang 330022, P. R. China.
⁴ Institute of Theoretical and Computational Chemistry, Shaanxi Key Laboratory of Catalysis, School of Chemical & Environment Sciences, Shaanxi University of Technology, Hanzhong 723000, P. R. China.

PMID: 35285652
DOI: 10.1021/acs.langmuir.1c03187

Abstract

Using the dispersion-corrected density functional theory (DFT-D3) method, we systematically studied the adsorption of 15 kinds of transition-metal (TM) clusters on pristine graphene (Gr) and N-doped graphene (N-Gr). It has been found that TM_n (n = 1-4) clusters adsorbed on the N-Gr surface are much stronger than those on the pristine Gr surface, while 3d series clusters present similar geometries on Gr and N-Gr surfaces. The most preferred sites of TMs migrate from hollow to bridge to the top site on the Gr surface along the d series in the periodic table, while the preferred sites of TMs migrate in a much more complex manner on the N-Gr surface. It has also been found that charge transfer decreases along the d series for adsorbed clusters on both surfaces, but adsorbed clusters present less charge transfer on the N-Gr surface than on the Gr surface. What is more interesting is that some TM (Tc, Ru, and Re) clusters change the growth mechanism from the three-dimensional (3D) growth mode on the Gr surface to the two-dimensional (2D) growth mode on the N-Gr surface. At last, it has been found that adsorbed clusters are more dispersed on the N-Gr surface than on the pristine Gr surface due to growth and average aggregation energies.