High‐Performance Hydrogen Evolution from MoS_2(1–x)P_x Solid Solution

Abstract

Thermally annealing mixtures of MoS2 and red phosphorus from 1:0.5 to 1:8 w:w ratio at 750 °C for 1 h under argon/hydrogen leads to the formation of a MoS2(1−x)Px solid solution (x = 0 to 1). At x = 0.53, the solid solution possesses one of the highest hydrogen evolution reaction (HER) activities of non-precious-metal-based electrocatalysts. The effective and stable electrocatalyst for hydrogen evolution in acidic solution developed here holds promise for substitution of scarce and expensive platinum. The high performance originates from the increased surface area and roughness of the solid solution, as well as the activation of the previously non-active sites as suggested by first–principles calculations. The enhanced HER activity via formation of a hetero-anion solid solution may open a new avenue for improving performance of HER and related electrocatalysts.

Molybdenum Sulphoselenophosphide Spheroids as an Effective Catalyst for Hydrogen Evolution Reaction

“…From experimental and theoretical calculations, it has been reported that the synchronized active sites possessed by P bonding with transition metal ions relatively enhance the HER catalytic activity. [4a,30] When compared to previous reported works (Figure B, and Table S1 in the Supporting Information) on molybdenum phosphides (MoP/Ti—117 mV[4a]; MoP‐CA2/GC—125 mV; MoP/GC—150 mV[4b]; MoS 0.94 P 0.53 —150 mV; MoP particles—246 mV; MoP/Carbon black—141mV) and chalcogenides (MoS x /N‐CNT—110 mV; MoSSe—164 mV[14b]), our proposed material P/Se‐MoS 2 has thus far revealed a much lower catalytic overpotential of 93 mV. In addition, to demonstrate the HER activity in neutral (pH = 7) and alkaline (pH = 14) medium, experiments were carried out with the same operating parameters as followed in acidic medium (discussion with respect to pH variant and corresponding polarization curves were detailed in Figure S5, Supporting Information).…”

Two-Dimensional Material Molybdenum Disulfides as Electrocatalysts for Hydrogen Evolution

“…Another efficient way to enhance the HER performance of MoS2 is to form MoS2-based alloys [69][70][71][72][73]. Our group synthesized monolayer MoS2(1−x)Se2x alloys and MoS2(1−x)Se2x nanobelt alloys via a CVD method by using MoO3, S powder, and Se powder as reactants [69,73].…”

Recent Advances in Controlling Syntheses and Energy Related Applications of MX2 and MX2/Graphene Heterostructures

“…For example, Tour et al, reported that, by annealing particulate MoS 2 with different amounts of red phosphorus at ≈750 °C in argon/hydrogen flow, MoS 2 gradually transformed into MoS 2(1-x) P x with x varying from 0 to 1. [147] A synergistic effect of alloyed MoS 2 and MoP was observed in subsequent HER measurements, showing an optimal performance at x = 0.53. An overpotential of only ≈150 mV was needed to deliver a current density of 10 mA cm −2 (Figure 11d).…”

“…[147] Reproduced with permission. [147] Copyright 2016, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. e) Schematic process for producing MoS 2 /RGO hybrids.…”

“…Corresponding theoretical calculations revealed that the incorporation of phosphorous into the MoS 2 lattice could dramatically reduce the ΔG H on neighboring sulfur atoms, thus contributing a remarkable catalytic activity to the otherwise HER-inert basal planes. [147] Additionally, hybridization of MoS 2 with other cocatalysts provides a new vision for advanced HER performance. Dai et al, reported that, through a one-step solvothermal reaction of (NH 4 ) 2 MoS 4 and hydrazine in an N,N-dimethylformamide (DMF) solution containing mildly oxidized graphene oxide (GO), highly dispersed MoS 2 nanoparticles could be synthesized selectively on reduced graphene oxide (RGO) nanosheets (Figure 11e), forming an advanced HER catalyst that featured with an extra low overpotential of ≈140 mV at 10 mA cm −2 , and a strikingly low Tafel slope of ≈41 mV dec −1 (Figure 11f,g).…”