Morphology Effects on Electro- and Photo-Catalytic Properties of Zinc Oxide Nanostructures.

Environmental problems are among the most pressing issues in the modern world, including the shortage of clean drinking water partially caused by contamination from various industries and the excessive emission of CO2 primarily from the massive use of fossil fuels. Consequently, it is crucial to develop inexpensive, effective, and environmentally friendly methods for wastewater treatment and CO2 reduction, turning them into useful feedstocks. This study explores a unique method that addresses both challenges by utilizing ZnO, which is recognized as one of the most active semiconductors for photocatalysis, as well as a cost-effective electrocatalyst for the CO2 reduction reaction (CO2RR). Specifically, we investigate the influence of the morphology of various ZnO nanostructures synthesized via different low-cost routes on their photocatalytic properties for degrading the rhodamine-B dye (RhB) and on their electrocatalytic performance for the CO2RR. Our results show that the ZnO lamella morphology achieves the best performance compared to the nanorod and nanoparticle structures. This outcome is likely attributed to the lamella's higher aspect ratio, which plays a critical role in determining the structural, optical, and electrical properties of ZnO.

Effect of Hydrogen Plasma Treatment on the Sensitivity of ZnO Based Electrochemical Non-Enzymatic Biosensor.

Information on vitamin C-ascorbic acid (AA)-content is important as it facilitates the provision of dietary advice and strategies for the prevention and treatment of conditions associated with AA deficiency or excess. The methods of determining AA content include chromatographic techniques, spectrophotometry, and electrochemical methods of analysis. In the present work, an electrochemical enzyme-free ascorbic acid sensor for a neutral medium has been developed. The sensor is based on zinc oxide nanowire (ZnO NW) arrays synthesized via low-temperature chemical deposition (Chemical Bath Deposition) on the surface of an ITO substrate. The sensitivity of the electrochemical enzyme-free sensor was found to be dependent on the process treatments. The AA sensitivity values measured in a neutral PBS electrolyte were found to be 73, 44, and 92 µA mM-1 cm-2 for the ZnO NW-based sensors of the pristine, air-annealed (AT), and air-annealed followed by hydrogen plasma treatment (AT+PT), respectively. The simple H-plasma treatment of ZnO nanowire arrays synthesized via low-temperature chemical deposition has been shown to be an effective process step to produce an enzyme-free sensor for biological molecules in a neutral electrolyte for applications in health care and biomedical safety.

Construction of a ZnO Heterogeneous Structure Using Co3O4 as a Co-Catalyst to Enhance Photoelectrochemical Performance.

Recently, heterostructured photocatalysts have gained significant attention in the field of photocatalysis due to their superior properties compared to single photocatalysts. One of the key advantages of heterostructured photocatalysts is their ability to enhance charge separation and broaden the absorption spectrum, thereby improving photocatalytic efficiency. Zinc oxide is a widely used n-type semiconductor with a proper photoelectrochemical activity. In this study, zinc oxide nanorod arrays were synthesized, and then the surfaces of ZnO nanorods were modified with the p-type semiconductor Co3O4 to create a p-n junction heterostructure. A significant increase in the photocurrent for the ZnO/Co3O4 composite, of 4.3 times, was found compared to pure ZnO. The dependence of the photocurrent on the morphology of the ZnO/Co3O4 composite allows for optimization of the morphology of the ZnO nanorod array to achieve improved photoelectrochemical performance. The results showed that the ZnO/Co3O4 heterostructure exhibited a photocurrent density of 3.46 mA/cm2, while bare ZnO demonstrated a photocurrent density of 0.8 mA/cm2 at 1.23 V. The results of this study provide a better understanding of the mechanism of charge separation and transfer in the heterostructural ZnO/Co3O4 photocatalytic system. Furthermore, the results will be useful for the design and optimization of photocatalytic systems for water splitting and other applications.

Efficient Recovery Annealing of the Pseudocapacitive Electrode with a High Loading of Cobalt Oxide Nanoparticles for Hybrid Supercapacitor Applications.

Electrochemical pseudocapacitors, along with batteries, are the essential components of today's highly efficient energy storage systems. Cobalt oxide is widely developing for hybrid supercapacitor pseudocapacitance electrode applications due to its wide range of redox reactions, high theoretical capacitance, low cost, and presence of electrical conductivity. In this work, a recovery annealing approach is proposed to modify the electrochemical properties of Co3O4 pseudocapacitive electrodes. Cyclic voltammetry measurements indicate a predominance of surface-controlled redox reactions as a result of recovery annealing. X-ray diffraction, Raman spectra, and XPES results showed that due to the small size of cobalt oxide particles, low-temperature recovery causes the transformation of the Co3O4 nanocrystalline phase into the CoO phase. For the same reason, a rapid reverse transformation of CoO into Co3O4 occurs during in situ oxidation. This recrystallization enhances the electrochemical activity of the surface of nanoparticles, where a high concentration of oxygen vacancies is observed in the resulting Co3O4 phase. Thus, a simple method of modifying nanocrystalline Co3O4 electrodes provides much-improved pseudocapacitance characteristics.

Stabilization of the Surface of ZnO Films and Elimination of the Aging Effect.

Zinc oxide is a promising multifunctional material. The practical use of nano- and polycrystalline ZnO devices faces a serious problem of instability of electrical and luminescent characteristics, due to the adsorption of oxygen by the surface during aging. In this paper, the aging effect in ZnO films and nanorod arrays was studied. It was found that ZnO samples demonstrate different behavior of the degradation process, which corresponds to at least two different types of adsorbing surface sites for O2, where O2 adsorption is of a different nature. The first type of surface sites is rapidly depassivated after hydrogen passivation and the aging effect takes place due to these centers. The second type of surface sites has a stable structure after hydrogen passivation and corresponds to HO-ZnO sites. The XPS components of these sites include the Zn2p3/2 peak at 1022.2 ± 0.2 eV and Zn2p1/2 peak at 1045.2 ± 0.2 eV, with a part of the XPS O1s peak at 531.5 ± 0.3 eV. The annealing transforms the first type of site into the second one, and the subsequent short-term plasma treatment in hydrogen results in steady passivation, where the degradation of characteristics is practically reduced to zero.

Designing of WO3@Co3O4 Heterostructures to Enhance Photoelectrochemical Performances.

Heterostructured photocatalysts are superior to single photocatalysts because they offer better charge separation and broaden light harnessing abilities. Although WO3 is considered an oxygen-evolving photocatalyst with decent stability and proper band gap, its lower photocatalytic efficiency is ascribed to high charge recombination. In this research, a WO3@Co3O4 heterostructure reduced the recombination of photocatalytic charges and extended light absorption abilities, resulting in improved photocatalytic activity. The presence of Co3O4 nanoparticles improved light absorption and charge transfer of tungsten oxide films for photoelectrochemical reactions. For photoelectrochemical water oxidation, WO3@Co3O4 nanostructures generated a photocurrent 20 times higher than that of pure WO3. Both electrodeposition and sol gel techniques were utilized to synthesize the WO3@Co3O4 photoelectrode. Scanning electron microscopy and X-ray diffraction were used to characterize the formation of the above photocatalyst. A photocurrent study was done to investigate the charge separation mechanism to explain the enhanced photocatalytic activity.