Chemically Activating Tungsten Disulfide via Structural and Electronic Engineering Strategy for Upgrading the Hydrogen Evolution Reaction

Abstract

Both improving the intrinsic activity and activating basal plane sites of the layered metal dichalcogenides are desirable to enhance their electrocatalytic performance for energy storage and conversion. Herein, we present palladium (Pd)-doped tungsten disulfide (WS 2 ) epitaxially sheathed around linear tungsten oxide for the hydrogen evolution reaction (HER). The Pd doping is evidenced to tune the electronic structure of WS 2 for activating basal sites of WS 2 , while the unique core−shell structure facilitates charge transfer. The asprepared Pd-WS 2 /W 3 O with 5.65 wt % Pd content exhibits a small overpotential of only 54 mV at −10 mA cm −2 and superior stability in the acidic electrolyte, which are superior to that of the 5 wt % Pt/C benchmark and are unprecedented in the reported WS 2 -based electrocatalysts. Theoretical results have revealed that Pd substituting for W in coordination with four S atoms is thermodynamically stable, and the in-plane S atoms adjacent to the doped Pd represent new catalytic active centers for promoting hydrogen adsorption. This work provides a new multiscale structural and electronic engineering strategy for improving the catalytic performance of transition-metal dichalcogenides.

Theoretical Screening of Transition Metal-Embedded Ti2N for High-Efficiency Hydrogen Evolution Reaction

“…However, Pt and Pd are of low natural abundance and are expensive. 7,8 Therefore, a great deal of experimental and theoretical work has been carried out to search for Pt/Pd alternative catalysts. 9−11 Recently, single-atom catalysts (SACs), which provide excellent catalytic activity, are considered to be effective to reduce the cost of traditional pure Pt/Pd catalysts.…”

“…Hydrogen is the most potential renewable source to alternative fossil fuels and is viably produced in an environmentally friendly manner by electroreduction of H 2 O to high purity H 2 . − As an uphill hydrogen evolution reaction (HER) requires high voltage (1.8–2.0 V), the sluggish kinetics makes practical application difficult. , In this regard, Pt/Pd-based metal catalysts are regarded as unrivaled catalysts in minimizing overpotential and increasing reaction rates. However, Pt and Pd are of low natural abundance and are expensive. , Therefore, a great deal of experimental and theoretical work has been carried out to search for Pt/Pd alternative catalysts. − Recently, single-atom catalysts (SACs), which provide excellent catalytic activity, are considered to be effective to reduce the cost of traditional pure Pt/Pd catalysts . The biggest challenge of SACs is that the dispersed single atoms with high activity are more likely to aggregate on the supports .…”

Defect‐engineered two‐dimensional transition metal dichalcogenides towards electrocatalytic hydrogen evolution reaction

“…In recent years, introducing metal atoms into TMDs has become a well‐accepted method to regulate the catalytic activity owing to the highly exposed active centres and maximized atom utilization of these metal sites. Several metal elements (including V, 99 Zn, 41 Fe, 93 Co, 100 Mn, 101 Ni, 102 Pt, 103 Pd, 104 etc.) have been successfully employed as dopants to modify the performance of TMD‐based catalysts.…”

Bio-inspired design of NiFeP nanoparticles embedded in (N,P) co-doped carbon for boosting overall water splitting

“…1,2 Highly efficient and low-cost catalysts for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are therefore greatly pursued. [3][4][5][6][7][8][9][10] Transition metal phosphides (TMPs), especially multi-TMPs, have been widely considered as promising candidates due to the improved electrical conductivity by P atoms and the adsorption activity of the active center for key species by the synergistic effect of different metals. [11][12][13][14][15][16] However, the lower electrical conductivity derived from less conductive support could induce the unsatisfactory HER and OER performances.…”