Electronic Structure Engineering of Pt Species over Pt/WO₃ toward Highly Efficient Electrocatalytic Hydrogen Evolution

Abstract

Pt‐based supported materials, a widely used electrocatalyst for hydrogen evolution reaction (HER), often experience unavoidable electron loss, resulting in a mismatching of electronic structure and HER behavior. Here, a Pt/WO3 catalyst consisting of Pt species strongly coupled with defective WO3 polycrystalline nanorods is rationally designed. The electronic structure engineering of Pt sites on WO3 can be systematically regulated, and so that the optimal electron‐rich Pt sites on Pt/WO3‐600 present an excellent HER activity with only 8 mV overpotential at 10 mA cm−2. Particularly, the mass activity reaches 7015 mA mg−1 at the overpotential of 50 mV, up to 26‐fold higher than that of the commercial Pt/C. The combination of experimental and theoretical results demonstrates that the O vacancies of WO3 effectively mitigate the tendency of electron transfer from Pt sites to WO3, so that the d‐band center could reach an appropriate level relative to Fermi level, endowing it with a suitable . This work identifies the influence of the electronic structure on catalytic activity.

Synergistic electronic structure modulation of Pt using V2O3 and V8C7 for enhanced deuterium evolution performance

“…54,55,67 The peaks at higher binding energies of 285.6, 286.7, and 288.8 eV belong to C–O, CO, and O–CO species, respectively, which originate from incomplete graphitization of glucose pyrolysis products and are commonly observed with porous carbon materials. 56 For the Pt/V 8 C 7 and Pt/V 2 O 3 /V 8 C 7 catalysts, another peak at 282.9 eV exists, reflecting the presence of metal carbide species consistent with the identification of V 8 C 7 by XRD. 55,67…”

“…1e have a spacing of 2.26 Å, corresponding to the (111) plane of face-centered cubic Pt. 55–57 Fig. 1f shows lattice fringes extending throughout the individual particles of the support material, indicating them to be single crystals.…”

PtCu nanoalloy loaded on sulfur-doped porous g-C3N4 for electrocatalytic hydrogen evolution

“…6 Platinum (Pt)-based noble metal catalysts are considered the most ideal catalysts for the HER. 7–9 However, the high cost and scarcity limit the large-scale and widespread application of Pt. 10,11 To reduce costs and improve the electrocatalytic activity of Pt, the following three methods are mainly used: (1) preparing Pt in the form of nanoparticles to increase its specific surface area and augment reactive sites; (2) depositing monolayer Pt onto carriers with excellent conductivity and stability to improve utilization efficiency; and (3) alloying Pt with other non-precious metals to increase active sites and thereby reduce costs.…”

Ultra-low loading Pt atomic cluster electrode with Pt–O bond as an active site with high hydrogen evolution reaction performance

“…Loading Pt nanoparticles onto carbon-based materials has greatly improved the MA of Pt, for example, hollow mesoporous carbon spheres, 11 defective graphene, 12,13 and nitrogen-doped carbon materials. 14,15 Metal oxides, metal sulfides, metal carbides, and metal selenides are also used as functional carriers, such as MnO 2 , 16 WO 3− x , 17,18 F-doped SnO 2 , 19 TiO 2 –O V , 20 TiB x O y , 21 MoS 3 , 22 VS 2 , 23 WC x , 24,25 Mo 2 C, 26 MXene, 27–29 and CdSe, 30 which further enhance the activity and stability of HER. In addition, the trace Pt combined with other transition metals has also exhibited definite HER activity, such as CoPt–Pt SA , 31 Pt/Ni–Mo–N–O, 32 PtNi, 33 PtRu, 34,35 PtW, 36 Pt@Pd 3 Pb, 37 PtPd, 38 PtPdRuTe, 39 and PtSe 2 .…”