The development of highly active, universal, and stable inexpensive electrocatalysts/cocatalysts for hydrogen evolution reaction (HER) by morphology and structure modulations remains a great challenge. Herein, a simple self-template strategy was developed to synthesize hollow Co-based bimetallic sulfide (MxCo3-xS4, M = Zn, Ni, and Cu) polyhedra with superior HER activity and stability. Homogenous bimetallic metal-organic frameworks are transformed to hollow bimetallic sulfides by solvothermal sulfidation and thermal annealing. Electrochemical measurements and density functional theory computations show that the combination of hollow structure and homoincorporation of a second metal significantly enhances the HER activity of Co3S4. Specifically, the homogeneous doping in Co3S4 lattice optimizes the Gibbs free energy for H* adsorption and improves the electrical conductivity. Impressively, hollow Zn0.30Co2.70S4 exhibits electrocatalytic HER activity better than most of the reported nobel-metal-free electrocatalysts over a wide pH range, with overpotentials of 80, 90, and 85 mV at 10 mA cm(-2) and 129, 144, and 136 mV at 100 mA cm(-2) in 0.5 M H2SO4, 0.1 M phosphate buffer, and 1 M KOH, respectively. It also exhibits photocatalytic HER activity comparable to that of Pt cocatalyst when working with organic photosensitizer (Eosin Y) or semiconductors (TiO2 and C3N4). Furthermore, this catalyst shows excellent stability in the electrochemical and photocatalytic reactions. The strategy developed here, i.e., homogeneous doping and self-templated hollow structure, provides a way to synthesize transition metal sulfides for catalysis and energy conversion.
We have developed a facile, scale up, and efficient method for the preparation of graphitic-C3N4 nanofibers (GCNNFs) as electrodes for supercapacitors and photocatalysts. The as-synthesized GCNNFs have 1D structure with higher concentration of nitrogen that is favorable for higher conductivity and electrochemical performance. Secondly, the high surface area of GCNNF provides a large electrode-electrolyte contact area, sufficient light harvesting and mass transfer, as well as increased redox potential. Thus, the GCNNF supercapacitor electrode shows high capacitance of 263.75 F g(-1) and excellent cyclic stability in 0.1 M Na2SO4 aqueous electrolyte with the capacitance retention of 93.6% after 2000 cycles at 1 A g(-1) current density. GCNNFs exhibit high capacitance of 208 F g(-1) even at 10 A g(-1), with the appreciable capacitance retention of 89.5%, which proves its better rate capability. Moreover, the GCNNF shows enhanced photocatalytic activity in the photodegradation of RhB in comparison to the bulk graphitic-C3N4 (GCN). The degradation rate constant of GCNNF photocatalyst is almost 4 times higher than GCN. The enhanced photocatalytic activity of GCNNF is mainly due to the higher surface area, appropriate bandgap, and fewer defects in GCNNF as compared to GCN. As an economical precursor (melamine) and harmless, facile, and template-free synthesis method with excellent performance both in supercapacitors and in photodegradation, GCNNF is a strong candidate for energy storage and environment protection applications.
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