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Steric effects of CO2 binding to transition metal-benzene complexes: A first-principles study

2016/06/02 by Hyeonhu Bae, Bing Huang, Hoonkyung Lee · 8 citations
Chemical Engineering · Chemistry · Energy · Engineering · Physics and Astronomy · #Adsorption #Atomic physics #Benzene #Binding energy #CO2 Reduction Techniques and Catalysts #Carbon Dioxide Capture Technologies #Carbon dioxide utilization in catalysis #Catalysis #Chemical physics #Chemistry #Computational chemistry #Crystallography #Density functional theory #Metal #Molecule #Organic chemistry #Physical chemistry #Physics #Stereochemistry #Steric effects #Transition metal #physics.chem-ph

paper · pdf · doi:10.1016/j.cap.2016.06.021

published in Current Applied Physics 16(9), 1124-1129 (Elsevier BV) · 17 pages, 4 figures, 1 table

arxiv created 2016/06/02 · openalex created_date 2016/06/24 · openalex publication_date 2016/06/29 · arxiv updated 2016/08/24 · openalex updated_date 2026/08/05

Abstract

Using density functional theory (DFT) calculations, we investigated the adsorption of CO2 molecules on 3d transition metal (TM)-benzene complexes. Our calculations show that the maximum number of CO2 molecules adsorbable on Sc or Ti atoms is three, but the 18-electron rule predicts it should be four. The 18-electron rule is generally successful in predicting the maximum H2 adsorption number for TM atoms including Sc or Ti atoms. We found that the 18-electron rule fails to correctly predict CO2 binding on Sc- or Ti-benzene complexes because CO2 binding, in contrast to H2 binding, requires additional consideration for steric hindrance due to the large bond length of CO2. We calculated the occupation function for CO2 using the Tolman cone angle, which shows that three CO2 molecules fully occupy the available space around Sc- and Ti-benzene complexes. This estimation is the same maximum CO2 adsorption number predicted by DFT calculations. Therefore, we propose that the occupation function for CO2 using the Tolman cone angle is an efficient model for evaluating steric hindrance of CO2 adsorption on a surface.

Citations