DFT calculations for the heterojunction effect between metal clusters and the stabilizer molecules

Abstract

Lately, liquid phase catalytic reactions over quasi heterogeneous catalysts, whose active site are stabilized by polymers, dendorimers, and soforth, are reported. It is well known that the heterojunction between the metal clusters and the metal oxide supports is important factor for the generation of catalytic activities of the heterogeneous catalysts, such as the metal oxide-supported Au catalysts. However, there is no metal oxide supports in the quasi heterogeneous catalysts. Therefore, we investigate the difference between the bare cluster and the polymer stabilized clusters using hybrid density functional theory. From the calculation results, it was found that the charge transfer interaction between the stabilizing molecules and the cluster plays an important role to exhibit the catalytic activities of the quasi heterogeneous catalysts. V

Mechanism of the Aerobic Homocoupling of Phenylboronic Acid on Au20−: A DFT Study

“…For the theoretical model of Au NC:PVP system, we chose the anionic Au 20 NC, in accord with previous studies on the methanol oxidation reaction . and the effects of the surrounding PVP molecules, on the energetics, in particular for the activation of the oxidative addition on the NC . All the calculations were carried out by using the Gaussian 09 suite of programs (Revision B.01) .…”

Symmetry Breaking Induced by Growth Kinetics: One‐Pot Synthesis of Janus Au−AgBr Nanoparticles

“…It originates from the PVP chains adsorbed on the surface of the Janus NPs. [47] As depicted in Figure 5a, the PVP chains are initially coordinated to Ag + before photoirradiation; however, the newly formed Au NP displace the Ag + ions, and the carbonyl groups of PVP become strongly adsorbed onto the surface of the Au NP, [49][50][51] thus protecting it (Figure 5b). This ligand displacement reaction might be enhanced by the chelating effect to the Au NP which is attributed to the large number of carbonyl groups as adsorption sites in a single PVP chain.…”

The Impact of the Polymer Chain Length on the Catalytic Activity of Poly(N-vinyl-2-pyrrolidone)-supported Gold Nanoclusters

“…However, weakly adsorbing stabilizers such as PVP represent an ideal stabilizing polymer system for AuNCs. In addition to its stabilizing function, PVP may also act as an electron donor, and the coordination of PVP to the gold surface has already been investigated 7 – 10 .…”

“…The increased electron density on the AuNC surface leads to an enhanced catalytic activity via the formation of catalytically active superoxo species, which are generated by an electron transfer from the high-lying LUMO of the anionic AuNC to the π*-orbital of the adsorbed dioxygen molecule 2 .

Figure 1 The Interaction between AuNCs and PVP 2 , 7 , 8 . Mesomeric resonance structures resulting in an electron donation from PVP to the Au surface via the C = O group are shown.

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“… The Interaction between AuNCs and PVP 2 , 7 , 8 . Mesomeric resonance structures resulting in an electron donation from PVP to the Au surface via the C = O group are shown.…”