ABSTRACT
Catalytic materials are the greatest challenge for the commercial application of water electrolysis (WEs) and fuel cells (FCs) as clean energy technologies. There is a need to find an alternative to expensive and unavailable platinum group metal (PGM) catalysts. This study aimed to reduce the cost of PGM materials by replacing Ru with RuO2 and lowering the amount of RuO2 by adding abundant and multifunctional ZnO. A ZnO@RuO2 composite in a 10:1 molar ratio was synthesized by microwave processing of a precipitate as a green, low-cost, and fast method, and then annealed at 300°C and 600°C to improve the catalytic properties. The physicochemical properties of the ZnO@RuO2 composites were investigated by X-ray powder diffraction (XRD), Raman and Fourier transform infrared (FTIR) spectroscopy, field emission scanning electron microscopy (FESEM), UV-Vis diffuse reflectance spectroscopy (DRS), and photoluminescence (PL) spectroscopy. The electrochemical activity of the samples was investigated by linear sweep voltammetry in acidic and alkaline electrolytes. We observed good bifunctional catalytic activity of the ZnO@RuO2 composites toward HER and OER in both electrolytes. The improved bifunctional catalytic activity of the ZnO@RuO2 composite by annealing was discussed and attributed to the reduced number of bulk oxygen vacancies and the increased number of established heterojunctions.
ABSTRACT
Water pollution is a significant issue nowadays. Among the many different technologies for water purification, photocatalysis is a very promising and environment-friendly approach. In this study, the photocatalytic activity of Sr0.9La0.1TiO3 (SLTO) and Sr0.25Ca0.25Na0.25Pr0.25TiO3 (SCNPTO) nano-sized powders were evaluated by degradation of pindolol in water. Pindolol is almost entirely insoluble in water due to its lipophilic properties. The synthesis of the SCNPTO was performed using the reverse co-precipitation method using nitrate precursors, whereas the SLTO was produced by spray pyrolysis (CerPoTech, Trondheim Norway). The phase purity of the synthesized powders was validated by XRD, while HR-SEM revealed particle sizes between 50 and 70 nm. The obtained SLTO and SCNPTO powders were agglomerated but had relatively similar specific surface areas of about 27.6 m2 g-1 and 34.0 m2 g-1, respectively. The energy band gaps of the SCNPTO and SLTO were calculated (DFT) to be about 2.69 eV and 3.05 eV, respectively. The photocatalytic performances of the materials were examined by removing the pindolol from the polluted water under simulated solar irradiation (SSI), UV-LED irradiation, and UV irradiation. Ultra-fast liquid chromatography was used to monitor the kinetics of the pindolol degradation with diode array detection (UFLC-DAD). The SLTO removed 68%, 94%, and 100% of the pindolol after 240 min under SSI, UV-LED, and UV irradiation, respectively. A similar but slightly lower photocatalytic activity was obtained with the SCNPTO under identical conditions, resulting in 65%, 84%, and 93% degradation of the pindolol, respectively. Chemical oxygen demand measurements showed high mineralization of the investigated mixtures under UV-LED and UV irradiation.
ABSTRACT
Electrochemical exfoliation is an efficient and scalable method to obtain liquid-phase graphene. Graphene in solution, obtained through electrochemical exfoliation or other methods, is typically polydisperse, containing particles of various sizes, which is not optimal for applications. We employed cascade centrifugation to select specific particle sizes in solution and prepared thin films from those graphene particles using the Langmuir-Blodgett assembly. Employing centrifugation speeds of 3, 4, and 5 krpm, further diluting the solutions in different volumes of solvent, we reliably and consistently obtained films of tunable thickness. We show that there is a limit to how thin these films can be, which is imposed by the percolation threshold. The percolation threshold is quantitatively compared to results found in literature that are obtained using other, more complex graphene film fabrication methods, and is found to occur with a percolation exponent and percolative figure of merit that are of the same order as results in literature. A maximum optical transparency of 82.4% at a wavelength of 660 nm is obtained for these films, which is in agreement with earlier works on Langmuir-Blodgett assembled ultrasonic-assisted liquid-phase exfoliated graphene. Our work demonstrates that films that are in all respects on par with films of graphene obtained through other solution-based processes can be produced from inexpensive and widely available centrifugal post-processing of existing commercially available solutions of electrochemically exfoliated graphene. The demonstrated methodology will lower the entry barriers for new research and industrial uses, since it allows researchers with no exfoliation experience to make use of widely available graphene materials.
ABSTRACT
Eco-friendly and rapid microwave processing of a precipitate was used to produce Fe-doped zinc oxide (Zn1-xFexO, x = 0, 0.05, 0.1, 0.15 and 0.20; ZnO:Fe) nanoparticles, which were tested as catalysts toward the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in a moderately alkaline solution. The phase composition, crystal structure, morphology, textural properties, surface chemistry, optical properties and band structure were examined to comprehend the influence of Zn2+ partial substitution with Fe3+ on the catalytic activity of ZnO:Fe. Linear sweep voltammetry showed an improved catalytic activity of ZnO:5Fe toward the ORR, compared to pure ZnO, while with increased amounts of the Fe-dopant the activity decreased. The improvement was suggested by a more positive onset potential (0.394 V vs. RHE), current density (0.231 mA cm-2 at 0.150 V vs. RHE), and faster kinetics (Tafel slope, b = 248 mV dec-1), and it may be due to the synergistic effect of (1) a sufficient amount of surface oxygen vacancies, and (2) a certain amount of plate-like particles composed of crystallites with well developed (0001) and (0001[combining macron]) facets. Quite the contrary, the OER study showed that the introduction of Fe3+ ions into the ZnO crystal structure resulted in enhanced catalytic activity of all ZnO:Fe samples, compared to pure ZnO, probably due to the modified binding energy and an optimized band structure. With the maximal current density of 1.066 mA cm-2 at 2.216 V vs. RHE, an onset potential of 1.856 V vs. RHE, and the smallest potential difference between the OER and ORR (ΔE = 1.58 V), ZnO:10Fe may be considered a promising bifunctional catalyst toward the OER/ORR in moderately alkaline solution. This study demonstrates that the electrocatalytic activity of ZnO:Fe strongly depends on the defect chemistry and consequently the band structure. Along with providing fundamental insight into the electrocatalytic activity of ZnO:Fe, the study also indicates an optimal stoichiometry for enhanced bifunctional activity toward the OER/ORR, compared to pure ZnO.
