Two-Dimensional π-Conjugated Metal Bis(dithiolene) Complex Nanosheets as Selective Catalysts for Oxygen Reduction Reaction

Abstract

Developing high activity and low price catalysts for the oxygen reduction reaction (ORR) is of critical importance for the commercial application of polymer electrolyte membrane fuel cells. On the basis of density functional theory, the catalytic activity of π-conjugated metal bis­(dithiolene) complex nanosheets (MC4S4, where M denotes Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, and Pt) for the ORR has been investigated systematically. It is found that the ORR activity of MC4S4 is sensitive to the selection of the central metal atom. The adsorption energies of ORR intermediates on MC4S4 decrease as the central atom varies from group 8 to group 10. The free energy change of the rate-determining step in the ORR increases in the order of IrC4S4 < CoC4S4 ≈ RhC4S4 < FeC4S4 < PdC4S4 ≈ PtC4S4 < NiC4S4 < RuC4S4 < OsC4S4. Due to the optimal adsorption properties, the IrC4S4 nanosheet shows the best ORR catalytic activity among the nine studied MC4S4 nanosheets. The free energy change of the rate-determining step in the ORR at high electrode potential follows an inverted volcano curve as a function of the adsorption strength of OH. This work may open new avenues for the development of high-performance ORR catalysts.

Two‐Dimensional Organometallic TM3–C12S12 Monolayers for Electrocatalytic Reduction of CO2

“…It is found that the ORR activity of MC 4 S 4 is sensitive to the selection of the central metal atom. Due to the optimal adsorption properties, the IrC 4 S 4 nanosheet shows the best ORR catalytic activity among the nine studied MC 4 S 4 nanosheets, [ ] which may open new avenues for the development of high‐performance ORR catalysts. Zhou's group studied the addition reaction of Ni 3 (C 12 S 12 ) catalyzed ethylene.…”

A bifunctional two dimensional TM3(HHTP)2 monolayer and its variations for oxygen electrode reactions

“…Some previous results have shown that this implicit solvation model is an effective method to describe solvation. 15,26 The 15Å-thick vacuum is added to avoid the articial interactions between the nanosheet and its images.…”

“…The thermodynamic CHE model has been applied to interpret the experimental data and design the novel electrocatalysts for metal, oxides as well as carbon-based materials. 10,15,[27][28][29][30][31][32] Besides, the present computational method has been applied to illustrate the ORR mechanism of the TM 3 (HITP) 2 (HITP ¼ hexaiminotriphenylene) monolayer. Therein, the 2e À mechanism is predicted to be prevalent for Ni 3 (HITP) 2 system owing to the insufficient O 2 activation, which is in accordance with the experimental data established by E. M. Miner.…”

“…The metal-organic framework (MOF) provide the abundant active sites due to the structural exibility where the high level of individually coordinated metal and the wide selection of building block. 11,12 Besides the TM coordinated with N ligand, other combinations within MOF have been experimentally synthesized, [13][14][15][16] such as the uniform distribution of TMS 4 and TMO 4 motifs, 14,16 which could offer the prototype for the investigation of the TM/ligand effect. On the other hand, inspired by the attractive bifunctional electrocatalysis exhibited by the TM dichalcogenides, 17-20 the active centers consisted by the TM coordinated to the O/S/Se atoms have raised our attention as the ORR/OER electrode.…”

Synthesis of 2D Nitrogen-Doped Mesoporous Carbon Catalyst for Oxygen Reduction Reaction

“…Among them, 2D nitrogen-doped carbon is an ideal candidate as an electrocatalyst for the ORR due to its unique features [24,25,26,27]. Feng et al [28] synthesized 2D graphene-based carbon nitride nanosheets, the high specific surface area of which favors a dense assembly of the active sites.…”