Self‐Assembly Approach Towards MoS₂‐Embedded Hierarchical Porous Carbons for Enhanced Electrocatalytic Hydrogen Evolution

Abstract

Transition metal‐based nanoparticle‐embedded carbon materials have received increasing attention for constructing next‐generation electrochemical catalysts for energy storage and conversion. However, designing hybrid carbon materials with controllable hierarchical micro/mesoporous structures, excellent dispersion of metal nanoparticles, and multiple heteroatom‐doping remains challenging. Here, a novel pyridinium‐containing ionic hypercrosslinked micellar frameworks (IHMFs) prepared from the core–shell unimicelle of s‐poly(tert‐butyl acrylate)‐b‐poly(4‐bromomethyl) styrene (s‐PtBA‐b‐PBMS) and linear poly(4‐vinylpyridine) were used as self‐sacrificial templates for confined growth of molybdenum disulfide (MoS2) inside cationic IHMFs through electrostatic interaction. After pyrolysis, MoS2‐anchored nitrogen‐doped porous carbons possessing tunable hierarchical micro/mesoporous structures and favorable distributions of MoS2 nanoparticles exhibited excellent electrocatalytic activity for hydrogen evolution reaction as well as small Tafel slope of 66.7 mV dec−1, low onset potential, and excellent cycling stability under acidic condition. Crucially, hierarchical micro/mesoporous structure and high surface area could boost their catalytic hydrogen evolution performance. This approach provides a novel route for preparation of micro/mesoporous hybrid carbon materials with confined transition metal nanoparticles for electrochemical energy conversion.

Asymmetric Push–Pull Type Co(II) Porphyrin for Enhanced Electrocatalytic CO2 Reduction Activity

“…In Figure 6a, the as-PorCo-OMe shows the Tafel value of 145 mV dec −1 , which is smaller than that of cs-PorCo-OMe (200 mV dec −1 ), indicating that as-PorCo-OMe has the higher catalytic activity of *COOH formation in CO 2 reduction reaction via electron/proton transfer [52,53]. To evaluate the electrochemical behavior of as-prepared complexes in electrocatalytic CO 2 RR, electrochemical impedance spectroscopy (EIS) was carried out [54]. The charge transfer resistance (R ct ) derived from the Nyquist plot exhibits that the resistance of 33.25 Ω for as-PorCo-OMe is lower than that of cs-PorCo-OMe (38.69 Ω) (Figure 6b), demonstrating the superior electron transfer ability of as-PorCo-OMe.…”

Structural Engineering of Nitrogen‐Doped MoS2 Anchored on Nitrogen‐Doped Carbon Nanotubes towards Enhanced Hydrogen Evolution Reaction

“…[14] Recently, interface coupling of MoS 2 with carbonaceous materials, such as porous carbon, graphene and multi-walled carbon nanotubes (CNTs), has been made concentrating on overcoming the above limitations. [15][16][17] Considering its large surface area, good charge mobility and strong mechanical strength, one dimensional (1D)-CNTs has been regarded as a versatile substrate for MoS 2 growing to enable improved properties. [18,19] In addition, CNTs can be easily functionalized under mild conditions without damaging their own structure, insuring the abundant anchoring sites.…”

“…However, the in‐depth enhancement of HER activity is still greatly impeded by the inherently easy agglomeration and poor electronic conductivity of nano or doped MoS 2 [14] . Recently, interface coupling of MoS 2 with carbonaceous materials, such as porous carbon, graphene and multi‐walled carbon nanotubes (CNTs), has been made concentrating on overcoming the above limitations [15–17] . Considering its large surface area, good charge mobility and strong mechanical strength, one dimensional (1D)‐CNTs has been regarded as a versatile substrate for MoS 2 growing to enable improved properties [18,19] .…”