Interfacial electronic structure engineering on molybdenum sulfide for robust dual-pH hydrogen evolution

Abstract

Molybdenum disulfide, as an electronic highly-adjustable catalysts material, tuning its electronic structure is crucial to enhance its intrinsic hydrogen evolution reaction (HER) activity. Nevertheless, there are yet huge challenges to the understanding and regulation of the surface electronic structure of molybdenum disulfide-based catalysts. Here we address these challenges by tuning its electronic structure of phase modulation synergistic with interfacial chemistry and defects from phosphorus or sulfur implantation, and we then successfully design and synthesize electrocatalysts with the multi-heterojunction interfaces (e.g., 1T0.81-MoS2@Ni2P), demonstrating superior HER activities and good stabilities with a small overpotentials of 38.9 and 95 mV at 10 mA/cm2, a low Tafel slopes of 41 and 42 mV/dec in acidic as well as alkaline surroundings, outperforming commercial Pt/C catalyst and other reported Mo-based catalysts. Theoretical calculation verified that the incorporation of metallic-phase and intrinsic HER-active Ni-based materials into molybdenum disulfide could effectively regulate its electronic structure for making the bandgap narrower. Additionally, X-ray absorption spectroscopy indicate that reduced nickel possesses empty orbitals, which is helpful for additional H binding ability. All these factors can decrease Mo-H bond strength, greatly improving the HER catalytic activity of these materials.

Enhancing the Low/Middle‐Frequency Electromagnetic Wave Absorption of Metal Sulfides through F− Regulation Engineering

“…This definitely would induce lattice disorder, new phase formation, and a high concentration of defect levels, which are beneficial for increasing dielectric loss abilities. [ 54,55 ] In this regard, enhanced dielectric loss would be provided in F‐12 and F‐20, followed by F‐2, compared with F‐0.…”

Recent advances in MoS2-based materials for electrocatalysis

“…In addition, higher conductivity and more exposed active sites simultaneously made great contributions to the enhancement of the catalytic performance for HER activity. This strategy has also been utilized by Liu et al , 149 although they used sulfur vapor to take place of Ar vapor.…”

Rational Design of Better Hydrogen Evolution Electrocatalysts for Water Splitting: A Review

“…In addition, catalysts with all key factors synergistically combined were obtained according to the catalyst design principles for further optimizing both intrinsic catalytic activity and overall catalytic performance, such as phase modulation, interfacial chemistry and heteroatomic injection defects working cooperatively to tune the catalyst electronic structure. [15] Although numerous outstanding reviews relevant to HER are available, [16][17][18][19][20][21][22][23][24][25][26] a comprehensive review which covers intrinsic and extrinsic effects, such as alloy effect, strain effect, support effect, and so on for HER is still not available. Herein, recent developments in intrinsic effect and extrinsic effect of advanced electrocatalysts including noble metals and transition metal based toward HER are summarized.…”

“…In addition, catalysts with all key factors synergistically combined were obtained according to the catalyst design principles for further optimizing both intrinsic catalytic activity and overall catalytic performance, such as phase modulation, interfacial chemistry and heteroatomic injection defects working cooperatively to tune the catalyst electronic structure. [ 15 ]…”