ABSTRACT
The development of highly efficient noble-metal-free electrocatalysts for the hydrogen evolution reaction (HER) is still a challenge nowadays. In this work, we prepared a highly active electrocatalyst containing phosphorus-doped NiCo2S4 nanocrystals grown on carbon nanotube embedded carbon nanofibers (P-NiCo2S4@CNT/CNF). The CNTs are involved in enhancing the electrical conductivity of the three-dimensional CNF network through a facile co-electrospinning method, which can facilitate electron transfer to the attached HER active material. Templated by this nanofiber network, the electroactive NiCo2S4 is confined to grow perpendicularly onto the CNT/CNF template via a hydrothermal reaction, thus exposing more catalytic active sites. Doping of P into the hybrid via a phosphidation reaction improves the electronic structure of the electroactive NiCo2S4, thus decreasing the energy barrier during the HER process. Owing to the synergistic effects from electrical enhancement and the nanostructured morphology, along with P-doping-induced optimization of the electronic structure, the P-NiCo2S4@CNT/CNF hybrid exhibits excellent HER performance, with an ultra-low onset overpotential (η) of 27 mV, a remarkable current density of 10 mA cm-2 at η as low as 74 mV, an impressive exchange current density of 0.79 mA cm-2 and excellent long-term durability. Furthermore, its electroactivity exceeds that of most reported noble-metal-free electrocatalysts and is comparable to that of Pt, suggesting its great potential as a highly efficient HER catalyst.
ABSTRACT
Exploration of high-efficiency Pt-free electrochemical catalysts for hydrogen evolution reaction (HER) is considered as a great challenge for the development of sustainable and carbon dioxide free energy conversion systems. In this work, a unique hierarchical nanostructure of few-layered MoSe2 nanosheets perpendicularly grown on carbon nanotubes (CNTs) is synthesized through a one-step solvothermal reaction. This rationally designed architecture based on a highly conductive CNT substrate possesses fully exposed active edges and open structures for fast ion/electron transfer, thus leading to remarkable HER activity with a low onset potential of -0.07 V vs. RHE (reversible hydrogen electrode), a small Tafel slope of 58 mV per decade and excellent long-cycle stability. Therefore, this noble-metal-free and highly efficient catalyst enables prospective applications for industrial, renewable hydrogen production.
ABSTRACT
The practical applications of transition metal oxides and hydroxides for supercapacitors are restricted by their intrinsic poor conductivity, large volumetric expansion, and rapid capacitance fading upon cycling, which can be solved by optimizing these materials to nanostructures and confining them within conductive carbonaceous frameworks. In this work, flexible hybrid membranes with ultrathin Ni(OH)2 nanoplatelets vertically and uniformly anchored on the electrospun carbon nanofibers (CNF) have been facilely prepared as electrode materials for supercapacitors. The Ni(OH)2/CNF hybrid membranes with three-dimensional macroporous architectures as well as hierarchical nanostructures can provide open and continuous channels for rapid diffusion of electrolyte to access the electrochemically active Ni(OH)2 nanoplatelets. Moreover, the carbon nanofiber can act both as a conductive core to provide efficient transport of electrons for fast Faradaic redox reactions of the Ni(OH)2 sheath, and as a buffering matrix to mitigate the local volumetric expansion/contraction upon long-term cycling. As a consequence, the optimized Ni(OH)2/CNF hybrid membrane exhibits a high specific capacitance of 2523 F g(-1) (based on the mass of Ni(OH)2, that is 701 F g(-1) based on the total mass) at a scan rate of 5 mV s(-1). The Ni(OH)2/CNF hybrid membranes with high mechanical flexibility, superior electrical conductivity, and remarkably improved electrochemical capacitance are condsidered as promising flexible electrode materials for high-performance supercapacitors.
