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.     

Electrodeposition of the manganese-doped nickel-phosphorus catalyst with enhanced hydrogen evolution reaction activity and durability

Hydrogen technology is widely considered a novel clean energy source, and electrolysis is an effective method for hydrogen evolution. Therefore, efficient hydrogen evolution reaction (HER) catalysts are urgently needed to replace precious metal catalysts and meet ecological and environmental protection standards. Herein, Ni–Mn–P electrocatalysts are synthesized using facile electrodeposition technology. The influence of the Mn addition on the catalytic behavior is studied by the comprehensive analysis of catalytic performance and morphology of the catalysts. Among them, the Ni–Mn–P0.01 catalyst exhibits small coral-like structures, greatly improving the adsorption and desorption of hydrogen ions and reducing the overpotential hydrogen evolution. Consequently, overpotential at 10 mA cm^?2 electric current density is 113 mV, and the value of the Tafel slope achieves 74 mV/dec. Furthermore, the Ni–Mn–P catalyst shows long-time (20 h) stability at current densities of 10 and 60 mA/cm². The results confirm that the synergistic effect of Ni, Mn, and P accelerates the electrochemical reaction. Meanwhile, the addition of manganese element can change the micromorphology of the catalyst, thereby exposing more active sites to participate in the reaction, enhancing water ionization, improving the catalytic performance. This study opens a new way toward improving the activity of the catalyst by adjusting Mn concentration during the electrodeposition process.     

Annealing temperature dependent structural and optical properties of electrodeposited CdSe thin films

Cadmium selenide films were synthesized using simple electrodeposition method on indium tin oxide coated glass substrates. The synthesized films were post annealed at 200 °C, 300 °C and 400 °C. X-ray diffraction of the films showed the hexagonal structure with crystallite size <3 nm for as deposited films and 3–25 nm for annealed films. The surface morphology of films using field emission scanning electron microscopy showed granular surface. The high resolution transmission electron microscopy of a crystallite of the film revealed lattice fringes which measured lattice spacing of 3.13 Å corresponding to (002) plane, indicating the lattice contraction effect, due to small size of CdSe nanocrystallite. The calculation of optical band gap using UV–visible absorption spectrum showed strong red-shift with increase in crystallite size, indicating to the charge confinement in CdSe nanocrystallite.     

Thickness dependent barrier performance of permeation barriers made from atomic layer deposited alumina for organic devices

Organic devices like organic light emitting diodes (OLEDs) or organic solar cells degrade fast when exposed to ambient air. Hence, thin-films acting as permeation barriers are needed for their protection. Atomic layer deposition (ALD) is known to be one of the best technologies to reach barriers with a low defect density at gentle process conditions. As well, ALD is reported to be one of the thinnest barrier layers, with a critical thickness – defining a continuous barrier film – as low as 5–10 nm for ALD processed Al₂O₃. In this work, we investigate the barrier performance of Al₂O₃ films processed by ALD at 80 °C with trimethylaluminum and ozone as precursors. The coverage of defects in such films is investigated on a 5 nm thick Al₂O₃ film, i.e. below the critical thickness, on calcium using atomic force microscopy (AFM). We find for this sub-critical thickness regime that all spots giving raise to water ingress on the 20 × 20 μm² scan range are positioned on nearly flat surface sites without the presence of particles or large substrate features. Hence below the critical thickness, ALD leaves open or at least weakly covered spots even on feature-free surface sites. The thickness dependent performance of these barrier films is investigated for thicknesses ranging from 15 to 100 nm, i.e. above the assumed critical film thickness of this system. To measure the barrier performance, electrical calcium corrosion tests are used in order to measure the water vapor transmission rate (WVTR), electrodeposition is used in order to decorate and count defects, and dark spot growth on OLEDs is used in order to confirm the results for real devices. For 15–25 nm barrier thickness, we observe an exponential decrease in defect density with barrier thickness which explains the likewise observed exponential decrease in WVTR and OLED degradation rate. Above 25 nm, a further increase in barrier thickness leads to a further exponential decrease in defect density, but an only sub-exponential decrease in WVTR and OLED degradation rate. In conclusion, the performance of the thin Al₂O₃ permeation barrier is dominated by its defect density. This defect density is reduced exponentially with increasing barrier thickness for alumina thicknesses of up to at least 25 nm.     

Influence of deposition parameters on surface morphology and application of CuInS2 thin films in solar cell and photocatalysis

Copper indium disulfide (CuInS₂) thin films as an absorption layer for solar cell and photocatalytic degradation of organic pollutants, were successfully electrodeposited on the FTO coated glass substrate using the simple and inexpensive electrodeposition method and a sulfurization process. The effects of the Cu/In molar ratio, annealing temperature and kind of Cu²⁺ precursor (Cu(salen) and Cu(acac)₂ as novel Cu²⁺ precursors) on the structural and morphological properties of samples were examined. The XRD diffraction patterns and energy dispersive spectroscopy measurements exhibit that high-quality film with superior crystalline structure was formed in the presence of Cu(salen) as Cu²⁺ precursor. Also, we found that a suitable heat treatment temperature could suppress the CuS phases and form well-crystallized CIS. As we know, this is the first reported efficiency for any CuInS₂ superstrate solar cell to date that fabricated using Cu(salen) as Cu²⁺ precursor. In addition, the photocatalytic degradation of organic dye in the presence of as-synthesized CuInS₂ thin films was studied. The as-prepared semiconductor photocatalysts have a good reusability; it can be successfully reused for 5 times recycling photoactivity tests.     

Improved formic acid oxidation using electrodeposited Pd–Cd electrocatalysts in sulfuric acid solution

In the present research, nanostructured Pd–Cd alloy electrocatalysts with different compositions were produced using the electrodeposition process. The morphology of the samples was studied by scanning electron microscopy analysis. Also, the elemental composition of the samples was determined by energy-dispersive X-ray spectroscopy and elemental mapping tests. Tafel polarization and electrochemical impedance spectroscopy methods were employed to determine the electrochemical corrosion properties of the synthesized samples in a solution containing 0.5 M sulfuric acid and 0.1 M formic acid. The linear sweep voltammetry, cyclic voltammetry, and chronoamperometry techniques were also employed to evaluate the electrocatalytic activity of prepared samples toward the oxidation of formic acid. In this respect, the influence of some factors such as formic acid and sulfuric acid concentrations and also potential scan rate was investigated. Compared to the pure Pd sample, the Pd–Cd samples were more reactive for the oxidation of formic acid. Besides, the sample with a lower amount of Pd (Pd_1·3Cd) demonstrated much higher electrocatalytic activity than the Pd_7·1Cd and Pd_2·1Cd samples. The observed high mass activity of 15.06 A mg^?1_Pd for the Pd_1·3Cd sample which is 21.1 times higher than Pd/C is an interesting result of this study.     

A novel utilized method of tar derived from biomass gasification for fabricating binder-free all-solid-state hybrid supercapacitors

As an industrial pollutant, tar derived from biomass gasification is used as the precursor for fabricating a novel carbon-metal hydroxides composite electrode. A slurry (the mixture of tar, KOH and melamine) is daubed uniformly onto the nickel foam, which is directly carbonized to form NPC@LDH electrode material. This electrode is further coated with NiCo-LDH nanosheets using an electrodeposition method to form NF@NPC@LDH. The newly made NF@NPC@LDH electrode exhibits a high specific capacity of 9.6 F cm⁻² at a current density of 2 mA cm⁻² and good rate performance (55.3% retention). Furthermore, a hybrid NF@NPC@LDH//NF@PC all-solid-state supercapacitor is fabricated, and the device exhibits high energy density of 1.28 mWh cm⁻³ at a power density of 8.04 mW cm⁻³, low resistance and good cycling stability.     

Effect of organic dopants on electrodeposition and characteristics of polyaniline under the varying influence of H2SO4 and HClO4 electrolyte media

Electrodeposition of conducting polyaniline (Pani) was made under potentiostatic condition at pH 1.0 in different electrolyte media (H₂SO₄ and HClO₄) in the absence and presence of two organic dopants, disodium salts of naphthalene-1,5-disulphonic acid (NSA) and of catechol-3,5-disulphonic acid (CSA). The rate and yield of Pani deposition were dependent on the acid medium and the dopant employed. NSA in H₂SO₄ caused an increase in rate and yield but CSA decrease when compared to the rate and yield of H₂SO₄ alone. In HClO₄ medium, both the dopants showed a decrease. With regard to DC electrical conductivity, both the dopants exhibited an enhancement in H₂SO₄ medium but NSA a decline in HClO₄. Characterisation of the electrosynthesised polymer samples by various instrumental techniques (cyclic voltammetric: CV, FTIR, UV-Visible: UV-Vis, EPR, XRD, TGA and DTG methods) revealed that between the two acid media, H₂SO₄ was the better one. Further, it enlightened the role of two organic dopants in relation to the acid media. The advantageous role of NSA in H₂SO₄ had origin on its molecular characteristics such as non-polarity, larger π-electron cloud etc., while CSA could not perform such a role because of its easily oxidisable hydroxyl groups. In HClO₄, however, both the dopants could play only an unfavourable role owing to its greater polarity and oxidizing power than H₂SO₄.