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Globally, the emergence of drug-resistant bacteria has created an urgent need for an effective method to remove antibiotics from pharmaceutical wastewater. Engineering Bismuth vanadate (BiVO4) with an oxygen evolution cocatalyst (OEC) holds a promising potential for enhancing water splitting efficiency in the production of hydrogen (H2) using free solar energy. Here, we successfully developed a Zr:BiVO4/NiFeOOH heterojunction by electrodeposition and photoelectrochemical transformation. Zr:BiVO4/NiFeOOH photoanodes exhibit 5 fold superior photocurrent response at 1.23 V compared with Zr:BiVO4 electrodes, since NiFeOOH acts as an oxygen-releasing catalyst. Furthermore, the attained heterojunctioned electrode can effectively degrade TCH, riboflavin, and streptomycin in PEC. The degradation rate of TCH acquired 96% within 1 h, which is 3 times superior than the efficiency reported for pristine Zr:BiVO4 photoelectrodes. By introducing NiFeOOH into BiVO4, electron life-time was increased and electron-hole recombination was suppressed. In this study, we present a solar-driven, sustainable and effective way of treating wastewater and provide new insights into the process.

Developing highly efficient and stable electrocatalysts for urea electro-oxidation reactions (UORs) will improve wastewater treatment and energy conversion. A low-cost cobalt sulfide-anchored nickel sulfide electrode (CoS/Ni3S2@CP) was synthesized by electrodeposition in DMSO solutions and found to be highly effective and long-lasting. The morphology and composition of catalyst surfaces were examined using comprehensive physicochemical and electrochemical characterization. Specifically, CoS/Ni3S2@CP electrodes require a potential of 1.52 volts for a 50 mA/cm2 current, confirming CoS in the heterointerface CoS/Ni3S2@CP catalyst. Further, the optimized CoS/Ni3S2@CP catalyst shows a decrease of 100 mV in the onset potential (1.32 VRHE) for UORs compared to bare Ni3S2@CP catalysts (1.42 VRHE), demonstrating much greater performance of UORs. As compared to Ni3S2@CP, CoS/Ni3S2@CP exhibits twofold greater UOR efficiency as a result of a larger electroactive surface area. The results obtained indicate that the synthetic CoS/Ni3S2@CP catalyst may be a favorable electrode material for managing urea-rich wastewater and generating H2.

Using green synthetic methods, a manganese-cobalt oxyhydroxide (MnCo-OOH) nanocomposite for electrocatalysis was prepared. Electrocatalysts were examined using powder X-ray diffraction analysis (XRD), Fourier transform infrared spectroscopy (FT-IR), and field-emission scanning electron microscopy (FESEM). In an alkaline medium, cyclic voltammetry and chronoamperometric analysis were applied to assess the electrocatalytic features of the MnCo-OOH nanocomposite. A strong correlation existed between MnCo-OOH’s morphology, crystallinity, and electrochemical activity. Upon examining the electrochemical characteristics, the as-deposited MnCo-OOH catalyst demonstrated a significantly lower overpotential, achieving 75 mA·cm−2 OER current density at 370 mV, four times larger than 19.7 mA·cm−2 for CoOOH catalysts, signifying that the MnCo-OOH catalyst exhibits a higher electrocatalytic OER features. In addition, the MnCo-OOH nanocomposite demonstrated a high current density of 30 and 65 mA·cm−2 at 1.55 and 1.60 VRHE for 12 h in 1.0 M KOH aqueous electrolyte. As a result of this study, it was determined that the fabricated MnCo-OOH nanocomposite would be an appropriate electrocatalyst in water electrolysis.

This work examines the cooperative effect between Zr doping and oxygen vacancy engineering in anodized TiO2 nanotubes (TNTs) for enhanced oxygen reduction reactions (ORRs). Zr dopant and annealing conditions significantly affected the electrocatalytic characteristics of grown TNTs. Zr doping results in Zr4+ substituted for Ti4+ species, which indirectly creates oxygen vacancy donors that enhance charge transfer kinetics and reduce carrier recombination in TNT bulk. Moreover, oxygen vacancies promote the creation of unsaturated Ti3+(Zr3+) sites at the surface, which also boosts the ORR interfacial process. Annealing at reductive atmospheres (e.g., H2, vacuum) resulted in a larger increase in oxygen vacancies, which greatly enhanced the ORR activity. In comparison to bare TNTs, Zr doping and vacuum treatment (Zr:TNT–Vac) significantly improved the conductivity and activity of ORRs in alkaline media. The finding also provides selective hydrogen peroxide production by the electrochemical reduction of oxygen.

Transition metal oxides, especially perovskites, have been considered effective electrocatalysts for the oxygen evolution (OER) and oxygen reduction (ORR) reactions in an alkaline solution. Here, a series of lanthanum cobalt rhodium oxide perovskites with the chemical formula LaCo1-xRhxO3 (LCRO, 0.1 ≤ x ≤ 0.70) were prepared through the approach of solid-phase synthesis and their bifunctional electrocatalytic activity was assessed for both the OER and ORR. The crystallinity, morphology, surface, and electrocatalytic features of the LCRO were significantly correlated with the rhodium content. The LaCo0.7Rh0.3O3 electrocatalysts with x = 0.3 showed enhanced electrocatalytic bifunctional performance with a substantially lower OER/ORR onset potential of 1.38/0.73 V vs HRE, smaller Tafel slope (116/90 mV/dec), and low charge-transfer resistance, which is the most efficient catalyst among the other studied ratios and superior to the pristine lanthanum cobalt oxide benchmark electrocatalysts. The LaCo0.7Rh0.3O3 electrode exhibit good bifunctional electrocatalytic behavior and long-term durability with an OER and ORR onset potential gap (ΔE = EOER − EORR) of only 0.65 V, which could be credited to the enriched oxygen vacancies, lattice expansion and the improved electrical conductivity upon the doping of larger size of Rh ions. The LaCo1-xRhxO3 catalysts are obtained from abundant materials that have the potential of highly-active bifunctional OER and ORR electrocatalysts.

Cost-effective, efficient and stable electrocatalyst for water splitting in the acidic electrolyte medium has been developed. The acidic electrolyte could be a support for the high purity hydrogen production via water splitting. Accordingly, we have prepared the defect-rich titania nanostructure via electrochemical anodization and cathodization routes using the titanium plate, which showed highly effective and durable electrocatalyst of hydrogen evolution reaction (HER) in an acidic medium. This hybrid compound showed a low onset potential of −0.17 V for HER with a current density of −150 mA cm−2 in 1 M H2SO4. Moreover, the stability test has been performed with the defect-rich titania nanostructure as cathode for 6 h in the two electrodes system.

Organic-inorganic hybrid formamidinium lead iodide (FAPbI3) perovskite has shown tremendous attention in recently developed photovoltaics and optelectronic devices. However, it suffers from structural instability complications, particularly the spontaneous phase transition from a dark color photoactive perovskite phase (α-FAPbI3) to a yellow color photo-inactive phase (δ-FAPbI3) at room temperature. To stabilize the photoactive α-FAPbI3, several methods were employed, including compositional engineering, 2D layer deposition on the surface, and solvent engineering method. In this communication, we have proposed a facile sequential rapid annealing method to produce the photoactive α-FAPbI3 perovskite on an industrial scale, which is highly stable at room temperature. The structural, morphological, compositional, and optical properties of the perovskite were studied using X-ray diffraction (XRD), UV–visible absorption, Laser Raman, thermogravimetric analysis (TGA), and field emission electron microscopy with elemental analysis (FE-SEM & EDAX). The strong characteristic diffraction peaks of cubic structure in XRD showed the proposed additives free preparation method is more adaptable for the preparation of high quality α-FAPbI3 perovskite for optoelectronic applications.

We present exemplary fabrications of controlled Nickel phosphate (NiPi)/TiO2 nanotubes arrays (TNTs) in phosphate buffer for boosted photoelectrochemical (PEC) water splitting. The TNTs/NiPi composite electrodes revealed a considerably enhanced photocurrent density of 0.76 mA/cm2, up to 3-time enhancements than bare TNTs, mostly because of the enhanced charge separation, decreased carrier recombination, and improving kinetics of the water oxidation. Also, we demonstrated that the NiPi can assist the PEC features of TNTs over a varied region of pH values from 1 to 14. Incorporation of NiPi over the TNTs surface advances the light absorption features of the electrode, resulting in an enhanced photogenerated charge carrier; and promotes the reactive sites for water oxidation, which was proved by the double-layer capacitance. The TNTs/NiPi photoelectrode exhibited excellent photostabilization under continuous illumination for 5 h, and the photoconversion efficiencies were 0.45%, 3-fold enhancements than with bare TNTs under the illuminations. Overall, this work might offer an innovative approach to fabricating and designing efficient electrodes with superior contact interfaces among photoanodes and numerous co-catalysts.

Photoelectrochemical (PEC) solar water splitting is favourable for transforming solar energy into sustainable hydrogen fuel using semiconductor electrodes. Perovskite-type oxynitrides are attractive photocatalysts for this application due to their visible light absorption features and stability. Herein, strontium titanium oxynitride (STON) containing anion vacancies of SrTi(O,N)3−δ was prepared via solid phase synthesis and assembled as a photoelectrode by electrophoretic deposition, and their morphological and optical properties and PEC performance for alkaline water oxidation are investigated. Further, cobalt-phosphate (CoPi)-based co-catalyst was photo-deposited over the surface of the STON electrode to boost the PEC efficiency. A photocurrent density of ~138 μA/cm at 1.25 V versus RHE was achieved for CoPi/STON electrodes in presence of a sulfite hole scavenger which is approximately a four-fold enhancement compared to the pristine electrode. The observed PEC enrichment is mainly due to the improved kinetics of oxygen evolution because of the CoPi co-catalyst and the reduced surface recombination of the photogenerated carriers. Moreover, the CoPi modification over perovskite-type oxynitrides provides a new dimension for developing efficient and highly stable photoanodes in solar-assisted water-splitting reactions.

Herein, we have examined the effect of tungsten trioxide (WO3) doping in graphitic carbon nitride (g-C3N4) photocatalysts towards photodegradation of organic pollutant in aqueous medium. A sequence of visible light driven WO3/g-C3N4 composites were synthesized at various mole ratios (1, 2, 3 and 5%) of WO3 into g-C3N4 via simple and short-time wet-impregnation method. The fabricated photocatalytic materials were investigated by X-ray diffraction (XRD), Fourier transform-infrared (FT-IR) spectroscopy, UV–vis diffuse reflection spectroscopy (DRS), photoluminescence (PL) and scanning electron microscopy (SEM). The photocatalytic performance of the fabricated photocatalysts were assessed by the degradation of acid orange 7 (AO7) in visible-light illumination. The WO3/g-C3N4 composites were found to be exhibit an improved visible-light induced photocatalytic performances compared to the pure WO3 and g-C3N4. However, among the different composites, the optimized 3 wt% WO3/g-C3N4 composite has shown complete (100%) degradation efficiency of AO7 after 75 min which is superior than the pure g-C3N4. This synergistic enhancement might be credited to its increased light absorption in visible-light region and the photoexcited electron transfer from g-C3N4 to WO3 catalyst surface and enhanced charge separation efficiency. Additionally, the photo-electrochemical measurements of 3 wt% WO3/g-C3N4 composite has exhibited a quicker migration of the photo-excited charge-carriers. The radical scavenging studies inferred that the O2·− are the key species accountable for the degradation of AO7 for fabricated WO3/g-C3N4 composite materials. Hence, the higher photocatalytic activity, long-term stability and recyclability of WO3/g-C3N4 composite has displayed it is a auspicious material for the photocatlytic degradation of organic contaminant applications.

Low-loading of oxidized platinum nanoparticles (0.1–0.5 wt%) was incorporated into mesoporous titanium dioxide support (Ptx/meso-TiO2) via evaporation self-assembly (ESA) approach followed by a two-step calcination processes. The physicochemical characterizations showed that the oxidized Ptx/meso-TiO2 catalysts exhibit high surface area around 200 m2/g and Pt nanoparticles having an average size of 3.0 nm are uniformly incorporated into the mesoporous TiO2 matrix with the existence of Pt(II) and Pt(IV) oxidation states. The Ptx/meso-TiO2 electrocatalysts showed an enhanced electrocatalytic activity with hydrogen evolution onset potential at −10 mV vs. RHE, Tafel slope of −110 mV/dec, small charge transfer resistance, and mass activity that reaches up to 25.7 A/mgPt at −300 mV vs. RHE. The hydrogen evolution mass activity of Ptx/meso-TiO2 electrocatalysts is significantly more efficient than the commercial Pt/C catalysts and Pt nanoparticles supported on nanostructured carbon substrates. Moreover, the Ptx/meso-TiO2 electrocatalysts exhibit excellent durability for a 24-hour electrolysis in acid solution with a further current activation during the prolonged electrolysis. The enhanced mass activity and durability are attributed to the substrate mesoporosity, uniform distribution and strong bonding between the oxidized Pt nanoparticles and the TiO2 substrate. These results demonstrate the promise of the mesoporous TiO2 substrate modified with low loading of platinum nanoparticles for energy conversion technologies. Keywords: Oxidized Pt nanoparticles, Mesoporous TiO2, Electrocatalyst, Hydrogen evolution

A crystalline mesoporous cobalt phosphate (meso-CoPi) electrocatalyst is prepared using liquid crystal template of non-ionic surfactant of Brij®78. The physicochemical investigations of the electrocatalyst executed by surface area analyzer, XRD, transmission electron microscope submits creation of a mesoporous crystalline nanostructured of meso-CoPi with a surface area of 124 m2 g−1. This is an 10-fold greatness superior than that for bulk-CoPi particles produced without surfactant template. The meso-CoPi electrocatalyst comprises of metallic cobalt layered with a cobalt-oxo/hydroxo-phosphate layer which facilitates the electro-oxidation of methanol at modest overpotential of

Photoelectrocatalytic approaches are fascinating options for long-lasting energy storage through the transformation of solar energy into electrical energy or hydrogen fuel. Herein, we report a facile method of fabricating a composite electrode of well-aligned TiO2 nanotubes (TNTs) decorated with photodeposited silver phosphate (Ag3PO4) nanoparticles. Assessment of the optical, physiochemical and photoelectrochemical features demonstrated that the fabricated TNTs/Ag3PO4 films showed a substantially boosted photocurrent response of 0.74 mA/cm2, almost a 3-fold enrichment in comparison with the pure TNTs. Specifically, the applied bias photon-to-current efficiency of the fabricated TNTs/Ag3PO4 composite electrode was 2.4-fold superior to that of the pure TNTs electrode. In these TNTs/Ag3PO4 photoanodes, the introduction of Ag3PO4 over TNTs enhanced light absorption and improved charge transfer and surface conductivity. The developed process can be generally applied to designing and developing efficient contact interfaces between photoanodes and numerous cocatalysts.

The rising significance of the field of biopolymers has driven the rapid progress of this distinctive class of polymeric materials in the past decades. Biodegradable polymers have acquired much attention because they play an essential role in humans’ lives due to their specific tunable electrical conductivity and biodegradability characteristics, making them fascinating in many applications. Herein, we debated the recent progress in developing biodegradable polymers and their applications. Initially, we introduce the basics of conducting and biodegradable polymers, trailed by debates about the effective strategies currently used to develop biopolymers. Special importance will focus on the uses of biodegradable polymers in drug delivery and tissue engineering, as well as wound healing, demonstrating the recent findings, and uses of several biodegradable polymers in modern biological uses. In this review, we have provided comprehensive viewpoints on the latest progress of the challenges and future prospects involving biodegradable polymers’ advancement and commercial applications.

Herein, sponge-like bismuthoxychloride (BiOCl) and hematite iron oxide (α-Fe2O3) were synthesized by simple and inexpensive method via two-step process, including hydrothermal and solution combustion method. The BiOCl/α-Fe2O3 composite photocatalysts were prepared by incorporating various weight ratios of α-Fe2O3 on BiOCl by a low-cost wet chemical process. The chemical interaction, phase and crystalline nature of the samples were ascertained by Fourier transform infrared spectroscopy (FT-IR) and x-ray diffraction (XRD). Further, the surface morphology and optical properties of the fabricated materials was characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM) and UV–vis diffuse reflection spectroscopy (DRS). Photocatalytic activities of the fabricated samples towards the photocatalytic degradation of direct red 81 (DR81) was evaluated under ultraviolet light illumination. The BiOCl/α-Fe2O3 composites showed remarkably enhanced photo-induced catalytic performances. The photocatalyst with optimal content of α-Fe2O3 with the highest photocatalytic performance was observed to 1%-BiOCl/α-Fe2O3. The synergistic improvement in the photodegradation of BiOCl/α-Fe2O3 sample may be because of an expansion in the noticeable light absorption efficiency as well as fast photo-generated charge separation. A probable mechanism for the photocatalytic degradation has been proposed for the catalytic performance of BiOCl/α-Fe2O3 photocatalyst. Keywords: Bismuthoxychloride, Direct red 81, Iron oxide, Photocatalysis, Photodegradation

The search of low cost, highly competent electrode material is the hot research area for various next-gen applications. Herein, cost effective nitrogen doped carbon quantum dots (N-CQDs) anchored in cobalt oxide (Co3O4) nanocomposite was fabricated through a simple hydrothermal method. The fabricated N-CQDs/Co3O4 nanocomposite showed high specific surface area (BET) of ~880 m2 g−1 with BJH pore size and volume of ~21 nm, 0.81945 cm3 g−1 respectively. The electrochemical performance through cyclic voltammetry (CV) in 3-electrode systems exhibited an improved specific capacitance of 1782 F g−1 at 5 mV s−1 in 6 M KOH electrolyte. Additionally, galvanostatic charge–discharge (GCD) analysis showed an improved capacitive performance with a specific capacitance of 1867 F g−1 at 1 A g−1 current density. The energy density was calculated 36.9 Wh kg−1 at the power density of 480 W kg−1. The capacitance retention graph demonstrates 96% stability through 500 GCD cycles.

Perovskites of strontium cobalt oxyhalides having the chemical formulae Sr2CoO4-xHx (H = F, Cl, and Br; x = 0 and 1) were prepared using a solid-phase synthesis approach and comparatively evaluated as electrocatalysts for oxygen evolution in an alkaline solution. The perovskite electrocatalyst crystal phase, surface morphology, and composition were examined by X-ray diffraction, a scanning electron microscope, and energy-dispersive X-ray (EDX) mapping. The electrochemical investigations of the oxyhalides catalysts showed that the doping of F, Cl, or Br into the Sr2CoO4 parent oxide enhances the electrocatalytic activity for the oxygen evolution reaction (OER) with the onset potential as well as the potential required to achieve a current density of 10 mA/cm2 shifting to lower potential values in the order of Sr2CoO4 (1.64, 1.73) > Sr2CoO3Br (1.61, 1.65) > Sr2CoO3Cl (1.53, 1.60) > Sr2CoO3F (1.50, 1.56) V vs. HRE which indicates that Sr2CoO3F is the most active electrode among the studied catalysts under static and steady-state conditions. Moreover, Sr2CoO3F demonstrates long-term stability and remarkably less charge transfer resistance (Rct = 36.8 ohm) than the other oxyhalide counterparts during the OER. The doping of the perovskites with halide ions particularly the fluoride-ion enhances the surface oxygen vacancy density due to electron withdrawal away from the Co-atom which improves the ionic and electronic conductivity as well as the electrochemical activity of the oxygen evolution in alkaline solution.

Electrooxidation of urea plays a substantial role in the elimination of urea-containing wastewater and industrial urea. Here, we report the electrodeposition of nickel hydroxide catalyst on commercial carbon paper (CP) electrodes from dimethyl sulphoxide solvent (Ni(OH)2-DMSO/CP) for urea electrooxidation under alkaline conditions. The physicochemical features of Ni(OH)2-DMSO/CP catalysts using scanning electron microscopy and X-ray photoelectron spectroscopy revealed that the Ni(OH)2-DMSO/CP catalyst shows nanoparticle features, with loading of 2-DMSO/CP electrode has a urea oxidation onset potential of 0.33 V vs. Ag/AgCl and superior electrocatalytic performance, which is a more than 2-fold higher activity in comparison with the counterpart Ni(OH)2 catalyst prepared from the aqueous electrolyte. As expected, the enhancement in electrocatalytic activity towards urea was associated with the superficial enrichment in the electrochemically active surface area of the Ni(OH)2-DMSO/CP electrodes. The results might be a promising way to activate commercial carbon paper with efficient transition metal electrocatalysts, for urea electrooxidation uses in sustainable energy systems, and for relieving water contamination.

Visible-light-driven photoelectrochemical (PEC) and photocatalytic water splitting systems featuring heterogeneous semiconductor photocatalysts (oxynitrides, oxysulfides, organophotocatalysts) signify an environmentally friendly and promising approach for the manufacturing of renewable hydrogen fuel. Semiconducting electrode materials as the main constituents in the PEC water splitting system have substantial effects on the device’s solar-to-hydrogen (STH) conversion efficiency. Given the complication of the photocatalysis and photoelectrolysis methods, it is indispensable to include the different electrocatalytic materials for advancing visible-light-driven water splitting, considered a difficult challenge. Heterogeneous semiconductor-based materials with narrower bandgaps (2.5 to 1.9 eV), equivalent to the theoretical STH efficiencies ranging from 9.3% to 20.9%, are recognized as new types of photoabsorbents to engage as photoelectrodes for PEC water oxidation and have fascinated much consideration. Herein, we spotlight mainly on heterogenous semiconductor-based photoanode materials for PEC water splitting. Different heterogeneous photocatalysts based materials are emphasized in different groups, such as oxynitrides, oxysulfides, and organic solids. Lastly, the design approach and future developments regarding heterogeneous photocatalysts oxide electrodes for PEC applications and photocatalytic applications are also discussed.

The storage, utilization, and control of the greenhouse (CO2) gas is a topic of interest for researchers in academia and society. The present review article is dedicating to cover the overall role of ionic liquid-modified hybrid materials in cycloaddition reactions. Special emphasis is on the synthesis of various cyclic carbonate using ionic liquid-based modified catalysts. Catalytic activity studies have discussed with respect to process conditions and their effects on conversion and product selectivity for the reaction of cycloaddition of CO2 with styrene oxide. The reaction temperature and the partial pressure of CO2 have found to play a key role in cyclic carbonate formation. The role of other influential parameter (solvent effect) is also discussed for the conversion of cyclic/aromatic oxides to polycarbonate production. Our own research work that deals with ionic liquid-based halide-modified mesoporous catalyst (MCM-41 type) derived from rice husk waste has also been discussed. Finally, the role of carbon dioxide activation and ring-opening mechanisms involved in the cyclic carbonate product formation from CO2 have been discussed.

NiMoO4/g-C3N4 was fabricated by a hydrothermal method and used as an electrode material in a supercapacitor. The samples were characterized by XRD, FTIR, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) to study the physical and structural properties of the as-prepared NiMoO4/g-C3N4 material. The electrochemical responses of pristine NiMoO4 and the NiMoO4/g-C3N4 nanocomposite material were investigated by cyclic voltammetry (CV), galvanostatic charge-discharge (GCD) and electrochemical impedance spectroscopy (EIS). From the CD studies, the NiMoO4/g-C3N4 nanocomposite revealed a higher maximum specific capacitance (510 Fg−1) in comparison to pristine NiMoO4 (203 Fg−1). In addition, the NiMoO4/g-C3N4 composite electrode material exhibited high stability, which maintained up to 91.8% capacity even after 2000 charge-discharge cycles. Finally, NiMoO4/g-C3N4 was found to exhibit an energy density value of 11.3 Whkg−1. These findings clearly suggested that NiMoO4/g-C3N4 could be a suitable electrode material for electrochemical capacitors.

n-BiVO4 is a favorable photoelectrode candidate for a photoelectrochemical (PEC) water splitting reaction owing to its suitable energy level edge locations for an oxygen evolution reaction. On the other hand, the sluggish water oxidation kinetics of BiVO4 photoanodes when used individually make it necessary to use a hole blocking layer as well as water oxidation catalysts to overcome the high kinetic barrier for the PEC water oxidation reaction. Here, we describe a very simple synthetic strategy to fabricate nanocomposite photoanodes that synergistically address both of these critical limitations. In particular, we examine the effect of a SnO2 buffer layer over BiVO4 films and further modify the photoanode surface with a crystalline nickel tungstate (NiWO4) nanoparticle film to boost PEC water oxidation. When NiWO4 is incorporated over BiVO4/SnO2 films, the PEC performance of the resultant triple-layer NiWO4/BiVO4/SnO2 films for the oxygen evolution reaction (OER) is further improved. The enhanced performance for the PEC OER is credited to the synergetic effect of the individual layers and the introduction of a SnO2 buffer layer over the BiVO4 film. The optimized NiWO4/BiVO4/SnO2 electrode demonstrated both enriched visible light absorption and achieves charge separation and transfer efficiencies of 23% and 30%, respectively. The photoanodic current density for the OER on optimized NiWO4/BiVO4/SnO2 photoanode shows a maximum photocurrent of 0.93 mA/cm2 at 1.23 V vs. RHE in a phosphate buffer solution (pH~7.5) under an AM1.5G solar simulator, which is an incredible five-fold and two-fold enhancement compared to its parent BiVO4 photoanode and BiVO4/SnO2 photoanodes, respectively. Further, the incorporation of the NiWO4 co-catalyst over the BiVO4/SnO2 film increases the interfacial electron transfer rate across the composite/solution interface.

Hybrids of low-symmetry (disordered) mesoporous titanium dioxide modified with different weight ratios of cobalt oxide nanoparticles (Co3O4(x)/lsm-TiO2) are prepared using a one-pot self-assembly surfactant template. The physicochemical characterization of Co3O4(x)/lsm-TiO2 hybrids by scanning and transmission electron microscopy, X-ray diffraction, N2 adsorption−desorption isotherms, and X-ray photoelectron spectroscopy confirm the successful incorporation of cobalt oxide nanoparticles (2−3 nm in diameter) with preservation of the highly mesoporous structure of titanium dioxide substrate. Among these mesoporous hybrids, the ~3.0 wt.% Co3O4/lsm-TiO2 exhibits the best performance toward both the oxygen evolution (OER) and reduction (ORR) reactions in alkaline solution. For the OER, the hybrid shows oxidation overpotential of 348 mV at 10 mA cm−2, a turnover frequency (TOF) of 0.034 s−1, a Tafel slope of 54 mV dec−1, and mass activity of 42.0 A g−1 at 370 mV. While for ORR, an onset potential of 0.84 V vs. RHE and OER/ORR overpotential gap (ΔE) of 0.92 V are achieved which is significantly lower than that of commercial Pt/C, hexagonal mesoporous, and bulk titanium dioxide analogous. The Co3O4/lsm-TiO2 hybrid demonstrates significantly higher long-term durability than IrO2. Apparently, such catalytic activity performance originates from the synergetic effect between Co3O4 and TiO2 substrate, in addition to higher charge carrier density and the presence of disordered mesopores which provide short ions diffusion path during the electrocatalytic process.

Nanostructured photoanodes are attractive materials for hydrogen production via water photo-electrolysis process. This study focused on the incorporation of carbon quantum dots doped with nitrogen as a photosensitizer into mesoporous tungsten trioxide photoanodes (N-CQD/meso-WO3) using a surfactant self-assembly template approach. The crystal structure, composition, and morphology of pure and N-CQD- modified mesoporous WO3 photoanodes were investigated using scanning electron and transmission microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. Due to their high surface area, enhanced optical absorption, and charge-carrier separation and transfer, the resulting N-CQD/meso-WO3 photoanodes exhibited a significantly enhanced photocurrent density of 1.45 mA cm−2 at 1.23 V vs. RHE under AM 1.5 G illumination in 0.5 M Na2SO4 without any co-catalysts or sacrificial reagent, which was about 2.23 times greater than its corresponding pure meso-WO3. Moreover, the oxygen evolution onset potential of the N-CQD/meso-WO3 photoanodes exhibited a negative shift of 95 mV, signifying that both the charge-carrier separation and transfer processes were promoted.

Photoanodes fabricated by the electrophoretic deposition of a thermally prepared zinc tantalum oxynitride (ZnTaO2N) catalyst onto indium tin oxide (ITO) substrates show photoactivation for the oxygen evolution reaction (OER) in alkaline solutions. The photoactivity of the OER is further boosted by the photodeposition of cobalt phosphate (CoPi) layers onto the surface of the ZnTaO2N photoanodes. Structural, morphological, and photoelectrochemical (PEC) properties of the modified ZnTaO2N photoanodes are studied using X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet visible (UV−Vis) diffuse reflectance spectroscopy, and electrochemical techniques. The presence of the CoPi layer significantly improved the PEC performance of water oxidation in an alkaline sulphate solution. The photocurrent-voltage behavior of the CoPi-modified ZnTaO2N anodes was improved, with the influence being more prominent at lower oxidation potentials. A stable photocurrent density of about 2.3 mA·cm−2 at 1.23 V vs. RHE was attained upon visible light illumination. Relative to the ZnTaO2N photoanodes, an almost three-fold photocurrent increase was achieved at the CoPi/ZnTaO2N photoelectrode. Perovskite-based oxynitrides are modified using an oxygen-evolution co-catalyst of CoPi, and provide a new dimension for enhancing the photoactivity of oxygen evolution in solar-assisted water-splitting reactions.

Platinum-free counter electrodes (CE) were developed for use in efficient and cost-effective energy conversion devices, such as dye-sensitized solar cells (DSSCs). Electrochemical deposition of CoS2 on fluorine-doped tin oxide (FTO) formed a hierarchical sheet-like structured CoS2 thin film. This film was engaged as a cost-effective platinum-free and high-efficiency CE for DSSCs. High stability was achieved using a phthaloychitosan-based gel-polymer electrolyte as the redox electrolyte. The electrocatalytic performance of the sheet-like CoS2 film was analyzed by electrochemical impedance spectroscopy and cyclic voltammetry. The film displayed improved electrocatalytic behavior that can be credited to a low charge-transfer resistance at the CE/electrolyte boundary and improved exchange between triiodide and iodide ions. The fabricated DSSCs with a phthaloychitosan-based gel-polymer electrolyte and sheet-like CoS2 CE had a power conversion efficiency (PCE, η) of 7.29% with a fill factor (FF) of 0.64, Jsc of 17.51 mA/cm2, and a Voc of 0.65 V, which was analogous to that of Pt CE (η = 7.82%). The high PCE of the sheet-like CoS2 CE arises from the enhanced FF and Jsc, which can be attributed to the abundant active electrocatalytic sites and enhanced interfacial charge-transfer by the well-organized surface structure.

Low-cost and high-performance advanced electrocatalysts for direct methanol fuel cells are of key significance for the improvement of environmentally-pleasant energy technologies. Herein, we report the facile synthesis of cobalt phosphate (Co3(PO4)2) nanospheres by a microwave-assisted process and utilized as an electrocatalyst for methanol oxidation. The phase formation, morphological surface structure, elemental composition, and textural properties of the synthesized (Co3(PO4)2) nanospheres have been examined by powder X-ray diffraction (XRD), Fourier transform-infrared spectroscopy (FT-IR), field emission-scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption-desorption isotherm investigations. The performance of an electrocatalytic oxidation of methanol over a Co3(PO4)2 nanosphere-modified electrode was evaluated in an alkaline solution using cyclic voltammetry (CV) and chronopotentiometry (CP) techniques. Detailed studies were made for the methanol oxidation by varying the experimental parameters, such as catalyst loading, methanol concentration, and long-term stability for the electro-oxidation of methanol. The good electrocatalytic performances of Co3(PO4)2 should be related to its good surface morphological structure and high number of active surface sites. The present investigation illustrates the promising application of Co3(PO4)2 nanospheres as a low-cost and more abundant electrocatalyst for direct methanol fuel cells.