Growth of iron diselenide nanorods on graphene oxide nanosheets as advanced electrocatalyst for hydrogen evolution reaction

Advanced electrocatalysts for the fabrication of sustainable hydrogen from water splitting are innermost to energy research. Herein, we report the growth of iron diselenide (FeSe₂) nanorods on graphene oxide (GO) sheets using two-step process viz., simple hydrothermal reduction and followed by wet chemical process. The orthorhombic phase of FeSe₂ incorporated GO nanosheet was developed as a low-cost and efficient electrocatalyst for hydrogen evolution reaction (HER) by water splitting. The phase purity, crystalline structure, surface morphology and elemental composition of the synthesized samples have been investigated by UV–visible absorption spectroscopy (UV–vis), fourier transform-infrared spectroscopy (FT-IR), X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and energy dispersive X-ray analysis (EDS). Voltammetry and Tafel polarization methods have been utilized to assess the performance of various weight ratio of GO nanosheet in FeSe₂ nanorods towards H₂ evolution. Detailed electrochemical investigations revealed that the 30% FeSe₂/GO composite showed a tremendous electrocatalytic HER activity in acidic medium with high cathodic current density of 9.68 mA/cm² at η = 250 mV overpotential and with a Tafel slope of 64 mV/dec. The 30% FeSe₂/GO composite offers a high synergistic effect towards HER activity, which is mainly due to high electrochemical active catalytic sites, low charge-transfer resistance and enhanced electrocatalytic performances of H₂ production. The present analysis revealed the possible application of FeSe₂/GO composite as a promising low-cost alternative to platinum based electrocatalysts for H₂ production.     

Defective-MoS2/rGO heterostructures with conductive 1T phase MoS2 for efficient hydrogen evolution reaction

As a two-dimensional material, molybdenum disulfide (MoS₂) exhibits great potential to replace metal platinum-based catalysts for hydrogen evolution reaction (HER). However, poor electrical conductivity and low intrinsic activity of MoS₂ limit its application in electrocatalysis. Herein, we prepare a defective-MoS₂/rGO heterostructures material containing 1T phase MoS₂ and evaluate its HER performance. The experimental results shown that defective-MoS₂/rGO heterostructures exhibits outstanding HER performance with a low overpotential at 154.77 mV affording the current density of 10 mA cm^?2 and small Tafel slope of 56.17 mV dec^?1. The unique HER performance of as-prepared catalyst can be attributed to the presence of 1T phase MoS₂, which has more active sites and higher intrinsic conductivity. While the defects of as-prepared catalyst fully expose the active sites and further improve catalytic activity. Furthermore, the interaction between MoS₂ and rGO heterostructures can accelerate electron transfer kinetics, and effectively ensure that the obtained catalyst displays excellent conductivity and structural stability, so the as-prepared catalyst also exhibits outstanding electrochemical cycling stability. This work provides a feasible and effective method for preparation of defective-MoS₂/rGO heterostructures, which also supplies a new strategy for designing of highly active and conductive catalysts for HER.     

A platinum modulated tungsten oxide on Ag nanowires network as an indicator for in-situ visualized evaluation of the hydrogen evolution performance

The development of the real-time evaluation for the catalytic hydrogen evolution performance under a simple and convinient condiction is urgently needed, but still a great challenge. Herein, a platinum modulated WO_x on Ag nanowires (Pt-WO_x@Ag NWs) is developed as an optical-electrochemical catalyst to realize an in-situ intuitive evaluation for the hydrogen evolution performance, in which the color of as-prepared Pt-WO_x@Ag NWs catalyst changes from the transparent to the deep blue with the increase of the applied potential. The real-time H₂ evolution with an H₂ turnover frequency (from 0 to 2.26 s^?1 per site), optical transmittance (from 80.3% to 48.7% at the wavelength of 630 nm) and energy consumption (from 0 to 0.74 W h in 1 h) is established. The charge transfer and mass transport are greatly promoted by the three demensional Ag NWs conductive network and abundant active sites, which are provided by the platinum modulated WO₃ on the Ag substrate. Density functional theory (DFT) calculations indicate that the modified WO_x shows the preferred adsorption affinity toward H₂O (ΔG_H2O, ?0.17 eV), which reach a high coloration efficiency and optical modulation range for the electrochromic reaction. The Pt sites on WO_x with a suitable H binding energy (ΔG_H1, 0.38 eV) efficiently promote the H1 conversion and H₂ release of water splitting. This work propose an intelligent hydrogen evolution indicator by real-time color change to boost the high-quality development of green hydrogen energy.     

Tungsten-molybdenum oxide nanowires/reduced graphene oxide nanocomposite with enhanced and durable performance for electrocatalytic hydrogen evolution reaction

Hydrogen has attracted huge interest globally as a durable, environmentally safe and renewable fuel. Electrocatalytic hydrogen evolution reaction (HER) is one of the most promising methods for large scale hydrogen production, but the high cost of Pt-based materials which exhibit the highest activity for HER forced researchers to find alternative electro-catalyst. In this study, we report noble metal free a 3D hybrid composite of tungsten-molybdenum oxide and reduced graphene oxide (GO) prepared by a simple one step hydrothermal method for HER. Benefitting from the synergistic effect between tungsten-molybdenum oxide nanowires and reduced graphene oxide, the obtained W-Mo-O/rGO nanocomposite showed excellent electro-catalytic activity for HER with onset potential 50 mV, a Tafel slope of 46 mV decade^?1 and a large cathodic current, while the tungsten-molybdenum oxide nanowires itself is not as efficient HER catalyst. Additionally, W-Mo-O/rGO composite also demonstrated good durability up to 2000 cycles in acidic medium. The enhanced and durable hydrogen evolution reaction activity stemmed from the synergistic effect broadens noble metal free catalysts for HER and provides an insight into the design and synthesis of low-cost and environment friendly catalysts in electrochemical hydrogen production.     

NiMo/Cu-nanosheets/Ni-foam composite as a high performance electrocatalyst for hydrogen evolution over a wide pH range

We designed and fabricated non-precious and highly efficient electrocatalysts of nickelmolybdenum/copper-nanosheets/nickel-foam composites (NiMo/Cu-NS/NF) by step electrodepositions, combining with chemical oxidation method. The catalysts were charaterized by means of SEM, XRD and XPS spectra. Their electrocatalytic activities were assessed by hydrogen evolution reactions (HER) over a wide pH range, where acidic, neutral and alkaline electrolytes were used, respectively. Benefiting from the unique midlayer Cu nanosheets (NS) architecture and optimum Mo–Ni composition at the surface layer which led to high electronic conductivity and large electrochemically active surface area (ECSA), the NiMo/Cu-NS/NF-2 catalyst displayed superior electrocatalytic activities with low overpotentials of η₁₀ = 43, 86 and 89 mV in 0.5 M H₂SO₄, 1.0 M PBS and 1.0 M KOH electrolyte, respectively. Especially in the acidic condition, it exhibited the best electrocatalytic activity with smaller Tafel slope of 54 mV dec^?1 and higher exchange current density of 1.93 mA cm^?2.     

Ni–Zn nanosheet anchored on rGO as bifunctional electrocatalyst for efficient alkaline water-to-hydrogen conversion via hydrazine electrolysis

Bifunctional Ni-15 at.% Zn/rGO catalyst was fabricated by a two-step electrodeposition to be used for efficient alkaline water-to-hydrogen conversion via hydrazine electrolysis. Experiments show that the as-deposited Ni-15 at.% Zn/rGO nanosheet arrays with porous structure possesses excellent catalytic activity and stability towards both hydrogen evolution reaction (HER) and hydrazine oxidation reaction (HzOR). A small overpotential of 49 mV at 10 mA cm⁻² with a low Tafel slope of 26.3 mV dec⁻¹, and a retention rate of 91.4% after 12 h at 10 mA cm⁻² are observed for Ni-15 at.% Zn/rGO towards HER. Moreover, Ni-15 at.% Zn/rGO also shows an extra-high current density of 1097 mA cm⁻² at 0.6 V vs RHE with a low Tafel slope of 33.5 mV dec⁻¹, and a high durability of 90.5% after 5000 s towards HzOR. Moreover, two-electrode cell was constructed using Ni-15 at.% Zn/rGO as both cathode and anode for HER and HzOR, achieving 100 mA cm⁻² at an ultralow cell voltage of 0.418 V. The above outstanding bifunctional catalytic performance should be attributed to its large ECSA, high electrical conductivity and most importantly, its superaerophobic surface induced by the porous structure with nanosheet arrays.     

Multi-walled carbon nanotubes supported porous nickel oxide as noble metal-free electrocatalysts for efficient water oxidation

Herein we report for the first time to use multi-walled carbon nanotubes (MWCNTs) supported porous nickel oxide (NiO_x) as non-precious electrocatalysts for oxidation of water at low overpotentials. The nickel oxide catalyst was facilely electrodeposited on MWCNTs in a 0.1 M KBi buffered solution at pH 9.2 containing 0.1 mM Ni²⁺ with an applied anodic potential. The current density of bulk electrolysis is 2.2 mA/cm² at +1.1 V (vs Ag/AgCl) using NiO_x-MWCNTs as the working electrode at pH 9.2, which is much higher than that in a system containing no MWCNTs. Tafel plot indicates that the present NiO_x-MWCNTs catalyst requires the overpotential of only 200 mV to catalyze the water oxidation reaction at pH 9.2. The Faradaic efficiency of >95% has been achieved at +1.1 V. The highly porous character of the NiO_x catalyst materials were further studied by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray analysis (EDX).     

Nanostructural Co–MoS2/NiCoS supported on reduced Graphene oxide as a high activity electrocatalyst for hydrogen evolution in alkaline media

There are many tremendous challenges to enhance the hydrogen evolution reaction (HER) activity of MoS₂. In this study, nanoflower-like Co–MoS₂/NiCoS structure supported on reduced Graphene Oxide (rGO) was rationally developed via a simple hydrothermal route, where the synergistic regulations of both interface structural and electronic conductivity were successfully presented by using controllable interface engineering and Co metal ions doped into MoS₂ nanosheets. Ascribed to the 3D flower-like nanostructure with massive active sites, the interface coupling effect between MoS₂ and Ni–Co–S phase, and Co-doped MoS₂ can modulate its surface electronic density. The optimal Co–MoS₂/NiCoS/rGO hybrid exhibits excellent HER activity in 1.0 M KOH, with a small overpotential (η₁₀, 84 mV) at 10 mA cm^?2 and a low Tafel slope (46 mV dec^?1), accompanied by good stability. This work provides an effective route to produce other electrocatalysts based on interface structure and electronic conductivity engineering for HER in the future.