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

• Published in: Chemistry : a European journal 2021-01, Vol.27 (6), p.2155-2164
• Main Authors: Liu, Yuping, Wang, Hongxing, Liu, Fengru, Kang, Jialing, Qiu, Feng, Ke, Changchun, Huang, Yu, Han, Sheng, Zhang, Fan, Zhuang, Xiaodong
• Format: Article
• Language: English
• Subjects: Carbon; Catalysts; Chemistry; electrocatalysis; Electrochemistry; Electrostatic properties; Energy conversion; Energy storage; Evolution; Hydrogen; Hydrogen evolution reactions; hypercrosslinked framework; micelle; Molybdenum; Molybdenum disulfide; Nanoparticles; porous carbon; Pyridinium; Pyrolysis; Structural hierarchy; Styrene; Transition metals
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.202004371

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. Reactive micelles: Due to its high stability and unique core–shell structure, unimicelle could be hypercrosslinked into ionic hypercrosslinked micellar frameworks, which were used as a soft template to prepare tunable hierarchical porous carbons with confined MoS2 growth for enhanced hydrogen evolution reaction.