Chemically modified phosphorene as efficient catalyst for hydrogen evolution reaction

Abstract

Hydrogen gas produced by electrolysis has been considered as an excellent alternative to fossil fuels. Developing non-noble metal catalysts with high electrocatalytic activities is an effective way to reduce the cost of hydrogen production. Recently, black phosphorus (BP) based materials have been reported to have good potential as electrocatalysts for hydrogen evolution reaction (HER). Herein, we systematically study the catalytic performance of monolayer BP (phosphorene) and several chemically modified phosphorenes (N/S/C/O doping and adsorbed NH 2 /OH functional groups) for HER on the basis of first-principles calculations. For pristine phosphorene, the armchair edge shows much better catalytic activity than the plane site and zigzag edge. The electronic states of phosphorene near the Fermi level are strongly influenced by chemical modifications. Both of doping heteroatoms into the lattice and introducing NH 2 / OH functional groups can effectively improve the catalytic performance of the plane site and zigzag edge site, but slightly degrade the armchair edge. These theoretical results shed light on the microscopic understanding of the active sites in BP based electrocatalysts for HER and pave the way for further improving their catalytic performance.

2D Metal‐Free Nanomaterials Beyond Graphene and Its Analogues toward Electrocatalysis Applications

“…Feng et al uncovered that the armchair edge exhibited much better catalytic activity than the plane sites and zigzag edges by means of DFT calculations (Figure 4b). [96] Nevertheless, phosphorene suffers from chemical degradation under water-and oxygen-containing conditions, causing a major obstacle to produce phosphorene from bulk BP by liquid exfoliation. Therefore, to keep BP away from chemical degradation, some surface modification routes, including coupling with organic or inorganic ligands, as well as encapsulating carbon layer on the surface of BP, have been developed.…”

“…Reproduced with permission. [96] Copyright 2019, IOP. c) LSVs for HER of bulk BP, milled BP, NH 2 -BP nanosheets, GC and Pt at 5 mV s −1 in 1 m KOH.…”

“…b) Free-energy diagram for HER on pristine phosphorene plane and zigzag/armchair edges. Reproduced with permission [96]. Copyright 2019, IOP.…”

Recent Advances on Black Phosphorus Based Electrocatalysts for Water‐Splitting

“…In addition, chemical modified BP by surface adsorbing NH 2 /OH functional groups and doping N/S/C/O atoms into the lattice also have been demonstrated based on the first‐principles simulations. 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* ) .…”

Single-Step Synthesis of Platinoid-Decorated Phosphorene: Perspectives for Catalysis, Gas Sensing, and Energy Storage

“…Despite this fact, the interest in phosphorene remains enormous because of its semiconductor properties and anisotropic structural features . Furthermore, strong intralayer bonding, weak van der Waals interlayer interaction, tunable band gaps, high charge transport, and optical response properties, as well as chemical reactivity, make phosphorene an appropriate candidate for optoelectronics, energy storage, , sensing, and catalysis. , …”