Design of Phosphorene for Hydrogen Evolution Performance Comparable to Platinum

Abstract

Phosphorene, a monolayer of bulk black phosphorus, is promising for light harvest owing to its high charge mobility and tunable direct band gap covering a broad spectral range of light. Here, via atomic-scale first-principles simulations, we report a ultrahigh activity of hydrogen evolution reaction (HER) of phosphorene originated from defective activation. Quantitative evaluation of the Gibbs free energy of the ad/desorption of hydrogen (H*) to/from phosphorene (∆GH*) reveals that atomic vacancies and edges play a dominant role in activating the reaction. We find that the defective states, empty and well-localized around the defect core, are compensated by H* species. This induces a proper hydrogen interaction complying with the thermoneutral condition of the free energy (∆GH*≈0) comparable to platinum. Our findings of the highly activating defective states suggest the design of non-metal HER catalysts with structural engineering of earth-abundant phosphorus structures.

Phosphorus‐Based Electrocatalysts: Black Phosphorus, Metal Phosphides, and Phosphates

“…Cai and co‐workers first attempted to reveal the catalytic mechanism of phosphorene from the atomic standpoint, and they believed that the perfect phosphorene could be catalytically inert for HER. [ 54 ] Indeed, the inert HER activity of perfect phosphorene is mainly ascribed to the high H* adsorption energy associated with the packed lone‐pair p electrons of phosphorus atoms. Therefore, modulation in the electronic structure of phosphorene is desired.…”

“…Despite atomic sites at di‐vacancies are catalytically inert, a proper tensile strain caused by the locally distorted lattice sites in the defect cores can make it catalytically active. [ 54 ] In addition to the vacancies and strains, the edges and metal doping were considered in the DFT calculation and showed to potentially boost the HER activity. Lu and co‐workers indicated that the exposed edges could introduce more active sites and present higher electrochemical activity compared to the basal plane due to the metallic character of edges.…”

Up-scalable emerging energy conversion technologies enabled by 2D materials: from miniature power harvesters towards grid-connected energy systems

“…274 Phosphorene based on its inherent properties displays a wide light absorption range from ultraviolet to near-infrared View Article Online making it very appealing for solar photocatalysis applications. [275][276][277][278][279] However, it is considerably less stable than graphene, with a tendency to oxidize towards P x O y . The oxidative degradation of the material in ambient conditions is still a puzzling obstacle towards practical applications.…”

Recent Advances on Black Phosphorus Based Electrocatalysts for Water‐Splitting

“…[60] A very recently research via DFT calculations reported that the HER activity of BP originated from defects and the reaction could be activated by atomic vacancies and edges based on the quantitative evaluation of the Gibbs free energy of the ad/desorption of hydrogen (H*) to/ from phosphorene (ΔG H* ). [61] The corresponding electrocatalysts mentioned in the whole section 2 have been tabulated and are listed in Table 1. The Pt/C catalyst is presented as a reference.…”

“…Theoretical calculations showed that both heteroatoms doping and functional groups introducing could effectively enhance the HER catalytic performance of the plane and zigzag edge of BP, but degrade the catalytic activity of armchair edge slightly . A very recently research via DFT calculations reported that the HER activity of BP originated from defects and the reaction could be activated by atomic vacancies and edges based on the quantitative evaluation of the Gibbs free energy of the ad/desorption of hydrogen (H*) to/from phosphorene (ΔG H* ) . The corresponding electrocatalysts mentioned in the whole section 2 have been tabulated and are listed in Table .…”