A DFT study of the interaction between olefins and Cu²⁺ on silica and MCM-41 model surfaces

Abstract

The interaction between ethylene and Cu(2+) on a silica model surface was studied by density functional theory (DFT) with nine popular functionals. It is found that B3LYP with BSSE correction is the best method by comparing the calculated results with reported experimental data. This method was also used to study the interactions of Cu(2+) with β-carotene, 1,3,5,7,9,11,13-tetradecaheptaene and ethylene on a MCM-41 model surface. The relationship between the reorganization energy of an olefin and its conjugation length was studied, and the roles of the electrostatic interaction between the olefin and the Cu(2+) were investigated. It is also found that the different environments of Cu(2+) affect the Cu(2+)-olefin interaction significantly.

Selective Gas Adsorption of Alkane/Alkene in a Single-Crystal and Powder Bimetallic Metal–Organic Framework Compound Cu2.97Zn0.03(btc)2 Studied by Electron Paramagnetic Resonance

“…16 Likewise, comparable coordination geometries have been experimentally found by electron spin echo envelope modulation spectroscopy for Cu 2+ −C 2 H 4 adsorbate complexes in copper-exchanged A zeolites, 46 SAPO-17 molecular sieves, 47 and on silica surfaces. 48 More recent theoretical investigations using DFT computations for ethylene adsorption over Cu(110) 49 and of Cu 2+ −C 2 H 4 adsorbate complexes on a silica surface 50 provided a specific interaction between Cu 2+ and C 2 H 4 . A similar orientation of the sp 2 -hybridized carbon atom fragments and their π-bond with respect to the Cu 2+ ion is observed for the adsorbate complex models DFT-C 4 H 8 syn (Figure 6a) and DFT-C 4 H 8 skew (Figure S9a in the Supporting Information) of two 1-butene conformers.…”

Hydrogen Bond Formation between the Carotenoid Canthaxanthin and the Silanol Group on MCM-41 Surface

“…In this study, the two-fragment BSSE correction is used. Details about the BSSE correction were described in a previous study …”

“…The calculated IE is −2.58 kcal/mol, which is also similar to that of the CAR-Cu 2+ complex. 37 The calculations suggest that CAN should also form a CAN-Cu 2+ complex when CAN is imbedded in Cu-MCM-41. The only difference between the structure of CAR and that of CAN is that CAN has one oxygen atom at each of the two cyclohexene rings.…”

Cluster modeling and coordination structures of Cu+ ions in Al-incorporated Cu-MEL catalysts – a density functional theory study

“…Transition-metal ions (TMIs) incorporated into zeolitic frameworks are known as active heterogeneous catalysts for numerous applications [1][2][3]. There has been fairly extensive research into copper ions impregnated over different supports [1,[4][5][6][7][8][9][10][11][12][13][14][15][16][17], which serve as efficient catalysts for a wide range of reactions, such as, methanol synthesis, oxidation of hydrocarbons, carbonylation of methanol, pollutant abatement, and hydrogenation reactions [4][5][6]18]. Among different metal exchanged zeolites, e.g., Cu-ZSM-5 proved to be the most active catalyst for direct decomposition of NO [8].…”

“…There exist several reports on the experimental identification as well as theoretical modeling of copper ions in porous materials [2,4,[6][7]. Meanwhile, the monovalent copper ion has received substantial interest.…”