A new inorganic solid state electrocatalyst for the hydrogen evolution reaction (HER) is reported. Highly crystalline layered ternary sulfide copper-molybdenum-sulfide (Cu2MoS4) was prepared by a simple precipitation method from CuI and [MoS4]2− precursors. In aqueous solution and over a wide pH range (pH 0 to 7), this Cu2MoS4 showed very good catalytic activity for HER with an overvoltage requirement of only ca. 135 mV and an apparent exchange current density of 0.040 mA cm−2 (Tafel slope of ca. 95 mV per decade was found irrespective of the pH value). This Cu2MoS4 catalyst was found to be stable during electrocatalytic hydrogen generation. Therefore, it represents an attractive alternative to platinum.
Photocorrosion, that causes rapid deactivation of Cu2O photocatalysts, was addressed by incorporating this oxide in a composite with reduced graphene oxide which acts as an electron acceptor to extract photogenerated electrons from Cu2O. Cu2O–rGO composite engineering also allows enhancing significantly photocatalytic activities of Cu2O for H2 generation.
Nanowebs consisting of interwoven ZnFe2O4 nanofibers are synthesized by a simple electrospinning technique, to be employed as an environmentally friendly anode in lithium ion batteries. Effect of precursor viscosity on the growth mechanism of electrospun ZnFe2O4 nanofibers (ZFO-NF) and ZnFe2O4 nanorods (ZFO-NR) is studied by microscopy and diffraction techniques. Structural characterization by powder X-ray diffraction, FESEM and HRTEM studies evaluates the single phase nature of ZnFe2O4, which consists of 11(3) nm nanocrystals that self-agglomerate to form nanofibers after thermal treatment. FESEM micrographs depict the self-assembly of electrospun ZnFe2O4 nanofibers into intertwined porous nanowebs with a continuous framework. Benefitting from the one-dimensional functional nanostructured architecture, the application of electrospun nanowebs with ZnFe2O4 nanofiber (ZFO-NF) anodes in lithium ion batteries exhibits excellent cyclability and retains a reversible capacity of 733(10) mAh g−1 up to 30 cycles at 60 mA g−1 as compared to ZnFe2O4 nanorods (ZFO-NR) with a capacity of ∼200 mAh g−1. In addition, the importance of providing electronic wiring during lithiation/delithiation, especially in prolonged cycling, is emphasized.
The potential of water (photo)electrolysis technology to provide hydrogen as a fuel on a large scale depends on how viable electrocatalysts for the water oxidation reaction (WOR) and the hydrogen evolution reaction (HER) are and whether they can be constructed from elements which are abundant in the Earth's crust. Here we show that ternary sulfides of cobalt–tungsten and nickel–tungsten (MWSx where M is Co or Ni) are efficient and robust electrocatalysts for the HER in water over a wide pH range. These novel ternary sulfides were readily grown on a conducting electrode surface by employing a scalable electrodeposition process from aqueous solutions of [M(WS4)2]2−. In terms of HER activity, the MWSx catalysts represent attractive alternatives to platinum. Moreover, we show that the HER activity is governed by the nature of the metal M within M–S–W heterobimetallic sulfide centres, located in the WS2-like layered structure of MWSx. Our work provides structural and mechanistic keys to understand how HER activity is promoted in previously described nickel and cobalt-doped molybdenum and tungsten sulfide materials.