Fe(III) grafted MoO3 nanorods for effective electrocatalytic fixation of atmospheric N2 to NH3

Electrocatalytic nitrogen reduction reaction (ENRR) offers a carbon-neutral process to fix nitrogen into ammonia, but its feasibility depends on the development of highly efficient electrocatalysts. Herein, we report that Fe ion grafted on MoO₃ nanorods synthesized by an impregnation technique can efficiently enhance the electron harvesting ability and the selectivity of H⁺ during the NRR process in neutral electrolyte. In 0.1 M Na₂SO₄ solution, the electrocatalyst exhibited a remarkable NRR activity with an NH₃ yield of 9.66 μg h^?1 mg^?1_cat and a Faradaic efficiency (FE) of 13.1%, far outperforming the ungrafted MnO₃. Density functional theory calculations revealed that the Fe sites are major activation centers along the alternating pathway.     

Electrodeposited NiMoP catalysts on carbon felt for hydrogenation of indigo during electrocatalytically splitting water

Electrochemical hydrogenation is an environmentally favorable alternative to chemical reduction of indigo because it performs under ambient conditions using water as the donor of hydrogen. The purpose of this work is to fabricate electrocatalysts with high activity and durability for electrocatalytic hydrogenation of indigo. This work compares the performances of a series of Ni based catalysts (Ni, NiMo, NiP and NiMoP) on the substrate of carbon felt (CF) for electrolyzing water. Both the overpotential and Tafel slop are decreased as a function of the components as Ni > NiMo > NiP > NiMoP. Hence, NiMoP/CF shows the excellent performance based on the thermodynamics (η₁₀ = 239 mV) and kinetics (Tafel slope = 89.7 mV·dec^?1) for splitting water. Further, the electrode of NiMoP/CF was used for the electrocatalytic hydrogenation of indigo. The conversion efficiency and Faradic efficiency can be improved as 26.2% and 10.7% respectively. Furthermore, the dyeing behavior of the electrohydrogenated indigo is similar to that of conventional reduction methods. Thus, the present work offers foundational results and paves the way for the design of new catalytic materials for the reduction of vat dyes.     

Phytic acid-assisted fabrication of superhydrophilic Ru 3D electrode for electrocatalytic hydrogenation of p-Nitrophenol

A superhydrophilic Ru-based 3D electrode, denoted as Ru-PA/NF, was fabricated under the assistance of phytic acid (PA) for electrocatalytic hydrogenation of p-Nitrophenol. PA serves as a multifunctional modulator to facilitate the dispersion of active Ru species in porous nickel foam (NF), meanwhile enhance the surface wettability as well as adjust the micromorphology. In alkaline media, the Ru-PA/NF electrode shows the PNP conversion of 94.68% and the PAP selectivity of 99% after 9 h, accompanied by the faraday efficiency (FE) of 73.15%. Over the superhydrophilic Ru-PA/NF the rate constant of PNP conversion into PAP is 2.62-times higher than that over the hydrophobic Ru/NF prepared without the aid of PA, and FE of Ru-PA/NF is 1.28-times higher than Ru/NF. This can be ascribed to intriguing features of Ru-PA/NF involving higher Ru loading, more exposed sites, superior electrolyte wetting along with faster charge transfer rate.     

Platinum nanoparticles decorated on graphitic carbon nitride-ZIF-67 composite support: An electrocatalyst for the oxidation of butanol in fuel cell applications

In the present study, we report an eco-friendly and simple route to design and synthesize novel nanocomposite catalyst based on platinum nanoparticles anchored on binary support of graphitic carbon nitride (g-C₃N₄) and cobalt-metal-organic framework (ZIF-67). For this purpose, ZIF-67 was prepared by precipitation method and g-C₃N₄ was prepared through thermal polymerization method. Later, ZIF-67 and g-C₃N₄ were hybridized through sonication to get homogeneous g–C₃N₄–ZIF-67 nanocomposite support material. Platinum nanoparticles (PtNPs) were uniformly deposited on g–C₃N₄–ZIF-67 by an electrochemical method. The as-developed nanocatalyst was characterized by morphological, structural and electrochemical techniques. The electrocatalytic activity of PtNPs@g–C₃N₄–ZIF-67 nanocatalyst towards butanol oxidation was evaluated via CV, CA, LSV and EIS in an alkaline medium. Results revealed that the proposed catalyst showed greatly enhanced electrooxidation of butanol in terms of high magnificent current density, lower oxidation potential, excellent long-term stability, large surface area, low charge transfer resistance and less toxic ability. Enhanced catalytic performance of the proposed catalyst could be ascribed to the synergistic effect of g–C₃N₄–ZIF-67 nanocomposite and PtNPs. The PtNPs@g–C₃N₄–ZIF-67 catalyst holds promising potential applications to be used as an anodic electrocatalyst for the development of high-performance alkaline fuel cells.     

Se doped nickel-molybdenum bimetal sulfide with enhanced electrochemical activity for hydrogen evolution reaction

In this work, we synthesized Se doped MoS₂@Ni₃S₂ with nanosheets coated nanorods structure supported on Ni foam (MoNiSeS). Firstly, MoS₂@Ni₃S₂ (MoNiS) nanorods was synthesized by hydrothermal method. After selenization treatment, MoSe₂ successfully formed on the edge of MoS₂ nanosheets and particle Ni₃S₂ transformed into NiSe, in which MoSe₂ and NiSe acted as new phase in MoNiSeS. The obtained MoNiSeS only needs a low overpotential of 68 mV to reach the current density of 10 mA cm^?2, and has a low Tafel plots of 72.77 mV dec^?1 and good electrochemical durability, whose electrochemical activity is much better than that of MoNiS and NiSeS, implying the introduction of Mo and Se is beneficial to improve the electrocatalytic performance of NiS for HER. In addition, the proper amount of Mo source, which has an effect on the morphology of product, has also been investigated. For MoNiSeS, the typical nanosheets coated nanarods expose more active sites and the synergic effects is good to the improvement of the catalytic activity. Meanwhile, WNiSeS has also been prepared using the same method and the corresponding results show that the electrochemical activity of WNiSeS is much better than that of NiSeS, proving the universality of this strategy.     

Hydrogen evolution during the oxidation of formaldehyde on Au:: The influence of single crystal structure and Tl-upd

Hydrogen evolution during formaldehyde oxidation in alkaline solution has been monitored by Differential Electrochemical Mass Spectrometry on Au(111) and polycrystalline gold. The current efficiency for hydrogen evolution increases with higher concentration and is in the same range on both, polycrystalline Au and Au(111) electrode. The onset potentials and half-wave potentials are higher on Au(111). Reaction orders for the faradaic current on the bare gold electrodes have been determined as 0.21 for higher and 0.76 for lower concentrations. Reaction orders for hydrogen evolution during formaldehyde oxidation are 1.4 times higher in each case. Tafel slopes in the range of 140-160 mV are found. This signifies that the first reaction step involving the formation of adsorbed hydrogen is largely determining the overall reaction rate. In the presence of thallium adlayers hydrogen evolution from formaldehyde oxidation is largely suppressed. On the thallium modified polycrystalline Au, formaldehyde oxidation is shifted for 100 mV to higher potentials where Tl is partially desorbed and hydroxide is coadsorbed on the modified surface. On thallium modified Au(111), a similar process takes place, but in the same potential region as the onset of formaldehyde oxidation on the bare surface and therefore the formaldehyde oxidation is only slightly shifted. Tafel slopes are decreased to 80 mV/dec in the presence of thallium. In the presence of adsorbed thallium, the first reaction step is in equilibrium, the coverage with adsorbed hydrogen is smaller and its recombination to H₂ is largely suppressed.     

Electrophoretic deposition of ZnCo2O4 spinel and its electrocatalytic properties for oxygen evolution reaction

In this paper, ZnCo₂O₄ was deposited on nickel substrate by electrophoretic deposition (EPD) method as electrocatalyst for the oxygen evolution reaction. The effect of electrophoresis variables including the deposition time, the applied voltages was discussed. XRD, SEM, and electrochemical measurement techniques were used to characterize the deposit and ZnCo₂O₄/Ni electrode. Compared with the ZnCo₂O₄ electrode prepared by nitrate decomposition method, the electrophoretic ZnCo₂O₄ electrodes exhibit better electrocatalytic properties and higher mechanical stability. And the electrode prepared at 10 V for 5 min has the best electrocatalytic properties with the overpotential of only 0.203 V at current density of 100 mA cm⁻².     

A sensitive hydrazine electrochemical sensor based on electrodeposition of gold nanoparticles on choline film modified glassy carbon electrode

A highly sensitive hydrazine sensor was developed based on the electrodeposition of gold nanoparticles onto the choline film modified glassy carbon electrode (GNPs/Ch/GCE). The electrochemical experiments showed that the GNPs/Ch film exhibited a distinctly higher activity for the electro-oxidation of hydrazine than GNPs with 3.4-fold enhancement of peak current. The kinetic parameters such as the electron transfer coefficient (α) and the rate of electron exchange (k) for the oxidation of hydrazine were determined. The diffusion coefficient (D) of hydrazine in solution was also calculated by chronoamperometry. The sensor exhibited two wide linear ranges of 5.0 × 10⁻⁷-5.0 × 10⁻⁴ and 5.0 × 10⁻⁴-9.3 × 10⁻³ M with the detection limit of 1.0 × 10⁻⁷ M (s/n = 3). The proposed electrode presented excellent operational and storage stability for the determination of hydrazine. Moreover, the sensor showed outstanding sensitivity, selectivity and reproducibility properties. All the results indicated a good potential application of this sensor in the detection of hydrazine.     

The electroactive species in the catalysis of cyclohexadiene to benzene by Rh2(TM4) 4 +2 (TM4=2,5-diisocyano-2,5-dimethylhexane)

Upon further investigation of the recently reported electrocatalytic oxidation of 1,4-cyclohexadiene to benzene by Rh₂(TM4) ₄ ⁺² (TM4=2,5-diisocyano-2,5-dimethylhexane), we have obtained data which strongly implicates the 2e^– oxidized d⁷-d⁷ complex as the electroactive species. This contrasts with the original report which suggested that the le^– oxidized d⁷-d⁸ radical acted as the key species via hydrogen atom abstraction from 1,4-cyclohexadiene. A possible mechanism for the catalysis is proposed.     

Cu-doped GdFeO3 perovskites as electrocatalysts for the oxygen evolution reaction in alkaline media

Development of electrocatalysts for the oxygen evolution reaction (OER) plays a critical role in electrochemical water splitting systems. In this aim, iron based perovskite oxides with composition GdFe_1-x Cu_x O₃ (0 ≤ x ≤ 0.3) have been investigated. The effect of copper doping, calcination temperature on the OER performance in alkaline media was studied. The incorporation of Cu²⁺ (0 ≤ x ≤ 0.3) decreases the activity of calcined electrodes at 800 °C from 6.33 to 2.79 mA cm⁻², while that containing 0.2 mol of copper calcined at 600 °C, exhibits the higher activity (9.66 mA cm⁻²) at 0.66 V. The stability study during 8 h indicates that the undoped electrode calcined at 800 °C, exhibits relatively a better stability of the OER performance compared to that doped with 20% of copper calcined at 600 °C. The achieved results show promising potential for cost-effective hydrogen generation using earth-abundant materials and cheap fabrication processes.