Two-Dimensional Biphenylene: A Graphene Allotrope with Superior Activity toward Electrochemical Oxygen Reduction Reaction

Abstract

Developing efficient and inexpensive catalysts for the oxygen reduction reaction (ORR) is a key for sustainable development of fuel cell technologies. Herein, by means of density functional theory calculations and microkinetic modeling, we demonstrate that two-dimensional (2D) biphenylene, a recently synthesized allotrope of graphene composed of tetragonal, hexagonal, and octagonal rings, is a metal-free candidate for facilitating the electrochemical ORR. Different from semimetallic graphene, 2D biphenylene is metallic, and carbon atoms of its tetragonal rings are substantially positively charged, resulting in good ORR activity due to the enhanced binding strength with reaction intermediates. In particular, the ORR activity of 2D biphenylene is pH-dependent, and it can be significantly boosted under alkaline conditions. Moreover, 2D biphenylene possesses rather good electrochemical stability, rendering it attractive for alkaline fuel cells.

Why heterogeneous single-atom catalysts preferentially produce CO in the electrochemical CO2 reduction reaction

“…Specically, the total energy of the charged slab at the corresponding potential, E(U), was calculated by including energy corrections for it is necessary to add or remove electrons and background charge on the electronic energy obtained from self-consistent calculations. [45][46][47][48][49] Then, for each species, we can deduce the energy at a given potential by tting the ve energy-potential points in a quadratic form.…”

Biphenylene monolayer: a novel nonbenzenoid carbon allotrope with potential application as an anode material for high-performance sodium-ion batteries

“…Based on the experimental realization, Li's group conducted a theoretical study on the catalytic activity of 2D biphenylene for the oxygen reduction reaction (ORR), and revealed that biphenylene is a metal-free ORR electrocatalyst with high activity. 31 Most recently, Obeid and Sun designed a biphenylene-based 3D porous carbon allotrope, which can serve as a promising anode material for LIBs. 32 In terms of the performance of the newly synthesized biphenylene as an anode for SIBs, herein we carried out comprehensive density functional theory (DFT) calculations as implemented in the Vienna Ab initio Simulation Package (VASP).…”

“…Based on the experimental realization, Li's group conducted a theoretical study on the catalytic activity of 2D biphenylene for the oxygen reduction reaction (ORR), and revealed that biphenylene is a metal-free ORR electrocatalyst with high activity. 31 Most recently, Obeid and Sun designed a biphenylene-based 3D porous carbon allotrope, which can serve as a promising anode material for LIBs. 32…”

Doping-engineered biphenylene as a metal-free electrocatalyst for the hydrogen evolution reaction

“…BPN also has excellent stability and mechanical performance, [31][32][33] and its thermal transport is lower than graphene. 34,35 In addition, BPN can be used in optoelectronics and electronics, 36 in catalysts for the oxygen reduction reaction (ORR) 37 and in anode materials for batteries. [38][39][40] Although some preliminary explorations have been performed on BPN, a more detailed understanding is still lacking, and the effect of heteroatoms on its catalytic activity in particular has not been widely explored.…”