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This study investigates the structure, electrochemical behavior and hydrogen evolution reaction (HER) performance of electrodeposited Ru–Co alloy coatings. The alloys were prepared from a 0.75 M Co2+ + 0.025 M Ru3+ solution at various potentials ranging from −0.5 to −1.2 V vs. SCE. Results reveal that the Ru and Co deposition processes are interdependent. The deposition of nobler Ru from the mixed metal solution reaches pure diffusion control already at −0.7 V compared to −1.0 V from a single Ru bath. On the other hand, Co deposition is significantly facilitated in the presence of Ru in the solution. Consequently, as the deposition potential changes from −0.6 to −1.0 V, Ru–Co solid solution coatings characterized by a distinct globular morphology are formed, with their Co content increasing from 22.1/7.4 to 70.2/86.1 wt% for the Cu/Ti2AlC MAX phase substrate applied. The alloy catalysts are found to show much better HER activity and stability in alkaline than in acidic solutions. The best Ru–Co@Ti2AlC sample, electrodeposited at −0.6 V, requires an overpotential of only −95 mV to deliver a current density of −100 mA cm−2 in 1 M KOH, thus outperforming most Ru–Co-based HER electrocatalysts reported to date.

Elektroliza vode u kombinaciji sa obnovljivim izvorima energije, kao što su Sunce ili vetar, predstavlja najefektivniji put za dobijanje ultračistog zelenog vodonika kao goriva sa nultom emisijom ugljenik-dioksida. Šira komercijalizacija elektrolizera vode umnogome zavisi od cene, aktivnosti i radnog veka katalizatora za katodnu reakciju izdvajanja vodonika. Često korišćena strategija za smanjenje sadržaja i povećanje masene aktivnosti skupocenih katodnih nanokatalizatora jeste njihova imobilizacija na provodne nosače sa visokorazvijenom površinom i dobrom mehaničkom i hemijskom stabilnošću. Uređene TiO2 nanotubularne strukture pripremljene anodnom oksidacijom titana su zbog svojih jedinstvenih optičkih, poluprovodničkih i elektronskih karakteristika intenzivno ispitivane za različite primene u fotokatalizi i fotoelektrohemiji [1]. Međutim, tek odnedavno je prepoznat njihov potencijal kao nosača u elektrokatalizi reakcije izdvajanja vodonika [2], pre svega zbog dobre provodnosti u katodnom smeru, trodimenzionalne strukture velike površine, korozione stabilnosti u kiseloj i alkalnoj sredini, ekološke neškodljivosti i niske cene. Ovo predavanje daće kratki osvrt na metode sinteze, strukturna i elektrohemijska svojstva i elektrokatalitičku aktivnost za izdvajanje vodonika nedavno prijavljenih kompozitnih materijala na bazi TiO2 nanotubularnih nizova. Literatura [1] K. Lee, A. Mazare, P. Schmuki, One-dimensional titanium dioxide nanomaterials: Nanotubes, Chem. Rev. 114 (2014) 9385. [2] U.Č. Lačnjevac, V.V. Radmilović, V.R. Radmilović, N.V. Krstajić, RuOx nanoparticles deposited on TiO2 nanotube arrays by ion-exchange method as electrocatalysts for the hydrogen evolution reaction in acid solution, Electrochim. Acta 168 (2015) 178-190.

Nanocatalysts Pd/C and Pd-Cu/C were synthesized by a borohydride reduction method and characterized by thermogravimetric analysis (TGA), X-ray diffraction (XRD) and transmission electron microscopy (TEM). In addition, the Pd/C catalyst was decorated by Cuupd in an acid solution with various surface coverages (up to 0.5). The catalysts were electrochemically characterized by cyclic voltammetry (CV) and COads stripping in acid and alkaline solutions. The electrochemically active surface area (ECSA) was estimated from the charge under the CO desorption peak in the alkaline solution and used for determining specific and mass activity for the EOR.

We herein report a simple two-step procedure for fabricating tetragonal CoMn2O4 spinel nanocrystals on carbon fibers. The battery-type behavior of these composite fibers arises from the redox activity of CoMn2O4 in an alkaline aqueous solution, which, in combination with the carbon fibers, endows good electrochemical performance and long-term stability. The C"CoMn2O4 electrode exhibited high specific capacity, up to 62 mA h g(-1) at 1 A g(-1) with a capacity retention of around 90% after 4000 cycles. A symmetrical coin-cell device assembled with the composite electrodes delivered a high energy density of 7.3 W h kg(-1) at a power density of 0.1 kW kg(-1), which is around 13 times higher than that of bare carbon electrodes. The coin cell was cycled for 5000 cycles with 96.3% capacitance retention, at a voltage of up to 0.8 V, demonstrating excellent cycling stability.

Hydrated iridium oxyhydroxide (IrOx) films were electrochemically deposited from an alkaline oxalic solution at constant anodic potentials and by applying a potential cycling protocol, in both cases with variation of the electrodeposition time. From UV–vis spetroscopy of the solution for the deposition and their characterization it was concluded that a mixture of Ir(III)/Ir(IV) monomers participates in the deposition of IrOx film. X-ray photoelectron spectroscopy (XPS) of IrOx films indicated that both types of films contained hydrated Ir(IV) hydroxide as the dominant species, but in the film deposited by potential cycling the presence of the additional Ir(III) species was evident. The scanning electon microscopy (SEM) analysis of the surface morphology revealed that films deposited by potential cycling were more uniform than the films deposited at a constant potential. The amount of electrochemically active Ir-species on the surface of deposited IrOx films was estimated from the voltammetric charge of the Ir(III)/Ir(IV) transition. Depending on the film electrodeposition parameters, the values between 15 and 1080 nmol cm−2 were obtained. The electrochemically active surface area (ECSA) of IrOx films was calculated from cyclic voltammetry and electrochemical impedance spectroscopy (EIS) measurements and ranged from 3 to 131 cm2 per 1 cm2 of geometric surface area for various films. The activity and stability of IrOx films toward oxygen evolution reaction (OER) was investigated in 0.5 M H2SO4 solution under potentiostatic conditions. The intrinsic activity, stated as turnover frequency and specific current density normalized per ECSA, showed that the OER activity of IrOx films deposited by potential cycling are up to two and a half times higher than the activity of films deposited at a constant anodic potential. Potentiostatic stability test showed a decrease in OER current over time for both type of the films. Determination of ECSA, the amount of electroactive Ir sp

Two types of iridium oxide films formed at the Ti-2 AlC substrate were investigated: (1) anodically electrodeposited iridium oxide film from the solution based on IrCl(3)xH(2)O; (2) iridium oxide film prepared by cycling thin layer of electrodeposited Ir in the 0.5 M H2SO4 from - 0.25 to 1.20 V. It was shown that during anodic electrodeposition of iridium oxide film (1) coulombic efficiency decreases with increasing anodic potential, being only 3% atE = 0.7 V vs. SCE and 26% atE = 0.62 V vs. SCE. A pair of peaks corresponding to the transition Ir(III)-oxide/Ir(IV)-oxide was present on the CVs recorded in 0.5 M H2SO4. While cycling pure Ir thin layer in the solution of 0.5 M H2SO4 from - 0.25 to 1.20 V (2) up to 100 cycles, typical CV response was characterized with the prepeak and a pair of peaks corresponding to the Ir(III)/Ir(IV)-oxide transition. With the increase of cycles number to 150, additional peak at potential of 1.0 V appeared. This peak was formed on the account of pair of peaks corresponding to the Ir(III)/Ir(IV)-oxide transition. The oxygen evolution reaction (OER) was investigated at both iridium oxide films. It was shown that the Tafel slope for the OER was similar to 40 mV dec(-1)for the first polarization curve, confirming that the rds was a reaction S-OH - gt S-O-ads + H++ e(-). As the number of recorded polarization curves increased, the activity of both types of iridium oxide films decreased, due to dissolution of iridium oxide films at the potentials of the OER. It is shown that anodically electrodeposited iridium oxide film is more active for the OER than that obtained by cycling electrodeposited iridium layer. However, both iridium oxide films exhibited insufficient stability.

The growth of thin oxide coatings on the aluminum substrate in water-based sodium tungstate electrolyte by plasma electrolytic oxidation (PEO) is discussed and experimentally illustrated. The growth is carried out using a distinctive ultra-low duty cycle pulsed direct current (DC) power supply. During the PEO processing elements present in micro-discharges are identified using standard optical emission spectroscopy (OES) technique. The spectral line shape analysis of the first two hydrogen Balmer lines shows the presence of two types of micro-discharges. Obtained coatings are also characterized with respect to their morphology and chemical and phase composition. It is shown that coatings are composed of Al, O, and W, featuring low roughness and porosity. Partial crystallization of the coatings resulted in identification of WO3, W3O8, and gamma-Al2O3 crystalline phases.

In this paper, we employed plasma electrolytic oxidation (PEO) of aluminum in a water solution of sodium tungstate (Na2WO4 center dot 2H(2)O) with the addition of the pure and Ce-loaded zeolites clinoptilolite and 13 X for the preparation of oxide coatings. The obtained coatings were characterized with respect to their morphologies and chemical and phase compositions using scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy, atomic force microscopy, and X-ray diffraction. The prepared coatings contained gamma-alumina, WO3, and metallic tungsten. The surface morphologies of the obtained coatings strongly depended on the PEO processing time; the roughness of all coatings increased with PEO time, while porosity decreased with PEO processing time as a result of microdischarge coalescence and growth. All coatings contained elements originating from the substrate and from the electrolytes. Coatings containing zeolites with Ce showed higher photoactivity than those with immobilized pure zeolites. The highest photocatalytic activity levels were observed for coatings containing immobilized Ce-exchanged clinoptilolite processed for 10 min. It was observed that both clinoptilolite and 13X zeolites improved the features of the PEO coatings in a similar manner, making natural and abundant clinoptilolite an excellent candidate for various applications.

We herein report a simple two-step procedure for fabricating tetragonal CoMn2O4 spinel nanocrystals on carbon fibers. The battery-type behavior of these composite fibers arises from the redox activity of CoMn2O4 in an alkaline aqueous solution, which, in combination with the carbon fibers, endows good electrochemical performance and long-term stability. The C"CoMn2O4 electrode exhibited high specific capacity, up to 62 mA h g(-1) at 1 A g(-1) with a capacity retention of around 90% after 4000 cycles. A symmetrical coin-cell device assembled with the composite electrodes delivered a high energy density of 7.3 W h kg(-1) at a power density of 0.1 kW kg(-1), which is around 13 times higher than that of bare carbon electrodes. The coin cell was cycled for 5000 cycles with 96.3% capacitance retention, at a voltage of up to 0.8 V, demonstrating excellent cycling stability.

Pt, PtSn and PtSnO2 catalysts supported on high surface area carbon synthesized by microwave assisted polyol procedure were tested for methanol oxidation. Based on TGA, EDX and XRD analysis, PtSn/C is composed of Pt and Pt3Sn phase while the rest of Sn is present in a form of very small tin oxide particles. This paper focuses on structure-activity relationships for CO tolerance and methanol oxidation reactions after addition of Sn to Pt catalysts. Alloying of Sn with Pt improves the rate of CO oxidation despite the fact that the pure Sn does not react with CO and therefore activity for methanol oxidation increases similar to 2 times in comparison to Pt/C catalyst. PtSn/C catalyst shows small advantage in comparison with PtSnO2/C catalyst due to the alloyed Sn and its electronic effect. Long term stability tests also confirmed that PtSn/C catalyst is somewhat better in comparison to PtSnO2/C.

Hydrated iridiumoxyhydroxide (IrOx) films were electrochemically deposited from an alkaline oxalic solution at constant anodic potentials and by applying a potential cycling protocol, in both cases with variation of the electrodeposition time. FromUV-vis spetroscopy of the solution for the deposition and their characterization it was concluded that a mixture of Ir(III)/Ir(IV) monomers participates in the deposition of IrOx film. X-ray photoelectron spectroscopy (XPS) of IrOx films indicated that both types of films contained hydrated Ir(IV) hydroxide as the dominant species, but in the film deposited by potential cycling the presence of the additional Ir(III) species was evident. The scanning electon microscopy (SEM) analysis of the surface morphology revealed that films deposited by potential cycling were more uniform than the films deposited at a constant potential. The amount of electrochemically active Ir-species on the surface of deposited IrOx films was estimated from the voltammetric charge of the Ir(III)/Ir(IV) transition. Depending on the film electrodeposition parameters, the values between 15 and 1080 nmol cm-2 were obtained. The electrochemically active surface area (ECSA) of IrOx films was calculated from cyclic voltammetry and electrochemical impedance spectroscopy (EIS) measurements and ranged from 3 to 131 cm(2) per 1 cm(2) of geometric surface area for various films. The activity and stability of IrOx films toward oxygen evolution reaction (OER) was investigated in 0.5 M H2SO4 solution under potentiostatic conditions. The intrinsic activity, stated as turnover frequency and specific current density normalized per ECSA, showed that the OER activity of IrOx films deposited by potential cycling are up to two and a half times higher than the activity of films deposited at a constant anodic potential. Potentiostatic stability test showed a decrease in OER current over time for both type of the films. Determination of ECSA, the amount of electroactive Ir

Developing ultraefficient electrocatalytic materials for the hydrogen evolution reaction (HER) with low content of expensive platinum group metals (PGMs) via low-energy-input procedures is the key to the successful commercialization of green water electrolysis technologies for sustainable production of high-purity hydrogen. In this study, we report a facile room-temperature synthesis of ultrafine metallic Ir nanoparticles on conductive, proton-intercalated TiO2 nanotube (H-TNT) arrays via galvanic displacement. A series of experiments demonstrate that a controlled transformation of the H-TNT surface microstructure from neat open-top tubes to disordered nanostripe bundles (“nanograss”) is highly beneficial for providing an abundance of exposed Ir active sites. Consequently, for nanograss-engineered composites, outstanding HER activity metrics are achieved even at very low Ir(III) precursor concentrations. An optimum Ir@TNT cathode loaded with 5.7 μgIr cm−2 exhibits an overpotential of −63 mV at −100 mA cm−2 and a mass activity of 34 A mgIr−1 at −80 mV under acidic conditions, along with excellent catalytic durability and structural integrity. Density functional theory (DFT) simulations reveal that the hydrogen-rich TiO2 surface not only stabilizes the deposited Ir and weakens its H binding strength to a moderate intensity, but also actively takes part in the HER mechanism by refreshing the Ir catalytic sites near the Ir|H–TiO2 interface, thus substantially promoting H2 generation. The comprehensive characterization combined with theory provides an in-depth understanding of the electrocatalytic behavior of H-TNT supported PGM nanoparticles and demonstrates their high potential as competitive electrocatalyst systems for the HER.

We report a mesoporous composite system consisting of carbon fiber cores surrounded with Co1.5Mn1.5O4 spinel nanocrystal shells, synthesized by a simple two-step process involving single-nozzle co-electrospinning and subsequent calcination. Benefiting from the obtained core-shell structure, this composite has exhibited high specific capacitance in the two-electrode configuration, up to 384 F g(-1) at 0.28 A g(-1), with no capacitance loss after 2000 cycles at 50 mV s(-1). The incorporation of spinel nanocrystals improved the capacitive performances of composite fibers due to a synergistic effect of redox-active shells and the conductive cores, making this novel material promising for symmetrical supercapacitors.

Rising demands for renewable energy sources have led to the development of dye sensitized solar cells. It is a challenge to find a good and low cost sensitizer, which has a low environmental impact. In this work, we conducted spectroscopic and electrochemical experiments, as well as quantum-chemical calculations of the natural pigment hypericin, in order to provide insight into its sensitizing efficiency. To this end, three identical cells were made and characterized. Although this pigment exhibited good adsorption onto a semiconductor surface, a high molar absorption coefficient (43 700 L mol−1 cm−1 ) and favorable alignment of energy levels and provided a long lifetime of electrons (17.8 ms) in the TiO2 photoanode, it was found that the efficiency of hypericin-sensitized solar cells was very low, only 0.0245%. We suggest that this inefficiency originated from a low injection of electrons into the conduction band of TiO2. This conclusion is supported by the density functional theory calculations which revealed a low electron density in the anchoring groups of electronically excited hypericin. The results of this work could be valuable not only in the photovoltaic aspect, but also for application of hypericin in medicine in photodynamic therapy

Rising demands for renewable energy sources have led to the development of dye sensitized solar cells. It is a challenge to find a good and low cost sensitizer, which has a low environmental impact. In this work, we conducted spectroscopic and electrochemical experiments, as well as quantum-chemical calculations of the natural pigment hypericin, in order to provide insight into its sensitizing efficiency. To this end, three identical cells were made and characterized. Although this pigment exhibited good adsorption onto a semiconductor surface, a high molar absorption coefficient (43700 L mol(-1) cm(-1)) and favorable alignment of energy levels and provided a long lifetime of electrons (17.8 ms) in the TiO2 photoanode, it was found that the efficiency of hypericin-sensitized solar cells was very low, only 0.0245%. We suggest that this inefficiency originated from a low injection of electrons into the conduction band of TiO2. This conclusion is supported by the density functional theory calculations which revealed a low electron density in the anchoring groups of electronically excited hypericin. The results of this work could be valuable not only in the photovoltaic aspect, but also for application of hypericin in medicine in photodynamic therapy.

In our previous paper, we described in detail studies of Sn influence on electrocatalytic activity of PtSn catalyst for CO and formic acid oxidation (StevanoviAc et al., J. Phys. Chem. C, 118 (2014) 278-289). The catalyst was composed of a Pt phase, Pt3Sn alloy and very small SnO2 particles. Different electrochemical treatment enabled studies of PtSn/C having Sn both in surface and subsurface layers and skeleton structure of this catalyst with Sn only in subsurface layers. The results obtained revealed the promotional effect of surface Sn whether alloyed or as oxide above all in preventing accumulation of CO and blocking the surface Pt atoms. As a consequence, in formic acid oxidation, the currents are not entering the plateau but increasing constantly until reaching a maximum. It was concluded that at lower potentials the effect of Sn on formic acid oxidation was predominantly electronic but with increasing the potential bi-functional mechanism prevailed due to the leading role of SnO2. This role of SnO2 is restated in the present study. Therefore, CO and formic acid oxidation were examined at PtSnO2/C catalyst. The catalyst was synthesised by the same microwave-assisted polyol procedure. According to XRD analysis, the catalyst is composed of a Pt phase and SnO2 phase. The reactions were examined on PtSnO2/C catalyst treated on the same way as PtSn/C. Comparing the results obtained, the role of SnO2 is confirmed and at the same time the significance of alloyed Sn and its electronic effect is revealed.

Mesoporous TiO2 films with spherical architectures and promising performance in dye-sensitized solar cells (DSSCs) were prepared. The morphology of the films was investigated by scanning electron microscopy. Transmission electron microscopy analysis of the spheres disclosed the elongated shape of sub-20 nm primary particles, while BET analysis revealed their high surface area of 135m2/g. Anatase presence was observed in the films based on X-ray diffractometry, selected-area electron diffraction analysis and Raman spectroscopy analyses. Increased light scattering of the spheres in visible region was observed by UV-VIS-NIR spectroscopy. Photovoltaic performance of the operating N719-sensitized cells was tested using electrochemical impedance spectroscopy and current density-voltage (J-V) curves under simulated AM1.5 spectrum. The 0.25 cm2 cells exhibited photo-to-electric power efficiency of 4.9%, which is among noteworthy values for DSSCs with similar photoanodic structures

Electrodeposited NiSn alloy coatings onto Ni 40 mesh substrate were tested for application as cathodes and anodes in the cell for alkaline water electrolysis in 30 wt% KOH at 80 degrees C. The "accelerated service life test" (ASLT) was performed for the hydrogen evolution reaction (HER), as well as for the oxygen evolution reaction (OER), and compared to that recorded for the Ni coating (Ni-dep) and Ni-mesh for both reactions. The morphology and chemical compositions of the NiSn and Ni coatings were investigated by scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS), while their surface composition was investigated by X-ray photoelectron spectroscopy (XPS) before and after the ASLT for both reactions, respectively. By measuring the potential at j = 0.3 A cm (-2) it was shown that during the ASLT the NiSn alloy coating catalytic activity for the HER decreases (about 24 mV after 25 cycles), while the catalytic activity for the OER increases (about 50 mV after 25 cycles), so that the cell voltage decreases for about 26 mV. The Ni-dep and Ni-mesh electrodes catalytic activity was found to increase for the HER (for about 103 mV), as well as for the OER (for about 52 mV) during the ASLT. Hence, the cell voltage for the Ni-dep and Ni-mesh electrodes decreased from 2.402 V to 2.245 V during the ASLT, while that for the NiSn electrode decreased from 1.967 V to 1.941 V. The cell voltage saving with the NiSn electrodes amounts to about 435 mV before the ASLT and about 304 mV after the ASLT. SEM results showed that no changes in the morphology of as prepared samples could be detected after the ASLTs for both reactions. EDS analysis confirmed that some changes occurred during the ASLT, particularly for the oxygen content in the surface layer. Similar conclusions were made from the XPS analysis.

In our previous paper, we described in detail studies of Sn influence on electrocatalytic activity of PtSn catalyst for CO and formic acid oxidation (StevanoviAc et al., J. Phys. Chem. C, 118 (2014) 278-289). The catalyst was composed of a Pt phase, Pt3Sn alloy and very small SnO2 particles. Different electrochemical treatment enabled studies of PtSn/C having Sn both in surface and subsurface layers and skeleton structure of this catalyst with Sn only in subsurface layers. The results obtained revealed the promotional effect of surface Sn whether alloyed or as oxide above all in preventing accumulation of CO and blocking the surface Pt atoms. As a consequence, in formic acid oxidation, the currents are not entering the plateau but increasing constantly until reaching a maximum. It was concluded that at lower potentials the effect of Sn on formic acid oxidation was predominantly electronic but with increasing the potential bi-functional mechanism prevailed due to the leading role of SnO2. This role of SnO2 is restated in the present study. Therefore, CO and formic acid oxidation were examined at PtSnO2/C catalyst. The catalyst was synthesised by the same microwave-assisted polyol procedure. According to XRD analysis, the catalyst is composed of a Pt phase and SnO2 phase. The reactions were examined on PtSnO2/C catalyst treated on the same way as PtSn/C. Comparing the results obtained, the role of SnO2 is confirmed and at the same time the significance of alloyed Sn and its electronic effect is revealed.

The aim of this work was to investigate the possibility of preparation of the composite Cr–MoO2 coatings onto steel and titanium substrates as cathode materials with high selective properties which imply the suppression of hypochlorite reduction as a side reaction during hypochlorite commercial production. The electrodes were prepared by simultaneous deposition of chromium and suspended MoO2 particles on titanium substrate from acid chromium (VI) bath. The current efficiency for electrodeposition of the composite coatings did not vary significantly with the concentration of suspended MoO2 particles. The content of molybdenum in the deposits was relatively low (0.2–1.5 at.%) and increased with increasing the concentration of suspended MoO2 particles in the bath, in the range from 0 to 10 g dm−3. With further increase in the concentration of MoO2, the content of molybdenum in the coating varied insignificantly. X-ray photoelectron spectroscopy-XPS and EDS analysis were applied to analyze elemental composition and chemical bonding of elements on the surface and in the sub-surface region of obtained coatings. When the concentration of MoO2 particles in the bath was raised above 5 g dm−3, the appearance of the coating changed from the typical pure chromium deposit to needle-like deposit with the appearance of black inclusions on the surface. XPS analysis and corresponding Cr 2p spectra showed the presence of chromium oxide, probably Cr2O3 with Cr(3+) valence state on the surface and in the sub-surface region of Cr–MoO2 coatings. Investigation of the current efficiency for the hydrogen evolution reaction (HER) on Cr–MoO2 cathodes showed that it increased with the increase of the content of MoO2 particles in the coating, exceeding the value of 97% in the solution with the hypochlorite concentration of 0.21 mol dm−3. Under the same conditions, the current efficiency for the HER on Ti and Ti/Cr cathodes is very low (≈20%), and corresponding polarization curves confirmed the