Comparative DFT and catalytic evaluation of modified graphene supported nano oriented metals for electrochemical oxygen reduction and C-C coupling reactions
Project ID: PN-III-P1-1.1-TE2016-2191

Project objectives

GraphDopSupCat proposal is build up on 3 scientific and one managerial objectives which confer it a balanced structure between experimental and theoretical evidence.

Objective 1:
The GraphDuSuCat proposes to calculate the adsorption energies of aryl-halides and aryl boronic acid derivatives, dissociation and activation energies of C-X bond of aryl-halides and the formation and activation energies C-C bond of bifenyls derivatives on different sizes and shapes (ranging from few atoms to tens of atoms –i.e 7,13,55,147) of AuCL/AuNP on simple and modified G. The aim is to establish a trend/linear correlations for how the size, atomic coordination of CL/NP, the support control the adsorption and activation of the investigated molecules. Another aim is to shape the complete mechanism of aryl halide and homocoupling at theoretical level such as to perform activity comparisons inbetween all studied systems.
Because these type of catalysts showed promising activity at experimental level, GrapDoSuCat proposes synthesize and characterize size selected gold nanoparticles with narrow size distribution supported on G substrate and than to test and establish their catalytic activity towards S-M C-C coupling reaction with the size distribution domain.

Objective 2:
GraphDoSuCat proposes to focus on N modified G and Fe-N modified G, namelly the type and the amount of N, Fe-N4 coordination sites in G will be investigated to establish their effect on the activity for ORR. This aspect was less watched into. Progressivelly new models that describe the active sites as revealed by the experimental evidences will be build such as FeN4C12 and iron(II) phthalocyanine (C32H16FeN8) deposited on the graphene layer (simple and with vacancies), small Fe/Fe3C nanoclusters embbeded in a graphene matrix and small Fe nanoclusters encapsulated in a layer of N-doped carbon, etc. All the results will be integrated in the volcano plot using the model the applicant developed in her previous work mentioned in B2.

Objective 3:
GraphDoSuCat aim to support the catalytic results obtained experimentally by means of theoretical calculations as much as possible for both Suzuki-Miyaura cross coupling reaction and oxygen reduction reaction in PMFC.

Objective 4:
Management and dissemination of the results GraphDoSuCat will be developed by Dr. I.C. Man’s (presently Traistaru) research group. The project offers a good opportunity for consolidation of the applicant group with new members/ knowledge/experience giving an original heterogeneous aspect in term on multi-disciplinarily. Indeed, proposed research activity will be developed at the border between several domains, such as Organic Chemistry, Catalysis, Computational Chemistry, Surface science, Physical Chemistry.