ZnO Surface Research Articles

Electrical spiking activity of proteinoids-ZnO colloids

We are studying the remarkable electrical properties of Proteinoids-ZnO microspheres with the aim of exploring their potential for a new form of computing. Our research has revealed that these microspheres exhibit behavior similar to neurons, generating electrical spikes that resemble action potentials. Through our investigations, we have studied the underlying mechanism behind this electrical activity and proposed that the spikes arise from oscillations between the degradation and reorganization of proteinoid molecules on the surface of ZnO. These findings offer valuable insights into the potential use of Proteinoids-ZnO colloids in unconventional computing and the development of novel neuromorphic liquid circuits.

Formation of oxygen vacancy at surfaces of ZnO by trimethylaluminum

The two-dimensional electron gas (2DEG) is a group of electrons that can move freely in horizontal dimensions but are confined in the third direction. It has been reported that atomic layer deposition (ALD) of Al2O3 on various reducible n-type oxides can lead to the formation of 2DEG at the heterojunction interfaces, among which ZnO is known to provide promising properties. In this study, we have performed a theoretical analysis using density functional theory calculations combined with experimental investigations to elucidate the surface reactions of Al2O3 ALD on low-index nonpolar ZnO surfaces, specifically focusing on the formation of oxygen vacancies (VO). The trimethylaluminum precursor was observed to undergo sequential dissociation of CH3 ligands, leading to the removal of surface oxygen of ZnO in the form of dimethyl ether. In addition, by examining the electronic structure after the removal of oxygen, the localization of the charge density at the surface was confirmed. Experimentally, the carrier density of the 2DEG at the Al2O3/ZnO interface showed a strong dependence on the ALD process temperature of Al2O3, confirming the endothermic nature of the formation of the 2DEG. By examining the characteristics of the 2DEG induced by VO, insights into the fundamental comprehension of oxide-based 2DEG systems are provided.

Surface ZnOx on zirconia is highly active for high temperature methanol synthesis

Zinc containing mixed metal oxides and supported zinc oxide are stable and selective methanol synthesis catalysts at temperatures where a subsequent methanol to hydrocarbons reaction can occur directly. This work provides fundamental insights into ZnO-based high temperature methanol synthesis catalysts. A pronounced support effect was observed, where ZrO2 provided a beneficial effect while SiO2 exerted a detrimental effect compared to bulk ZnO. Preparing co-precipitated ZnO-ZrO2 catalysts showed that the initial activity correlated with the amount of amorphous ZnO on the surface of the support and that the catalytic activity increased with time on stream as zinc oxide migrated out of a solid solution with ZrO2 and onto the support surface. Hence the active phase appeared to be ZnO surface species and not zinc oxide in a solid solution with ZrO2. Operando XAS coupled with modulation excitation spectroscopy unravelled that the surface ZnO was partly reduced under operating conditions, as surface ZnOx, with x approximately equal to 0.98. In-situ DRIFTS further uncovered that the surface ZnOx activated CO2 and formed methanol via carbonate, formate and methoxide species. XPS finally showed that ZrO2 withdrew electrons from ZnO, facilitating oxygen abstraction to form the partly reduced ZnOx, which in turn facilitated the activation of CO2.

Sustainable Development of ZnO Nanostructure Doping with Water Hyacinth-Derived Activated Carbon for Visible-Light Photocatalysis.

Water hyacinth (Wh) is an aquatic weed considered a nuisance in agricultural and fishing activities. Therefore, this study proposed repurposing this plant into activated carbon (AC). First, the ZnO-AC was precipitated and applied as a photocatalyst for degrading methylene blue. The preliminary photocatalytic test under UV irradiation identified the optimum ZnO-AC photocatalyst to degrade methylene blue (MB). The ZnO-AC photocatalyst recorded the highest degradation rate constant of 11.49 × 10-3 min-1, which was almost two-fold higher than that of ZnO (5.55 × 10-3 min-1). Furthermore, photocatalytic degradation of MB and carbaryl under sunlight irradiation by ZnO-AC demonstrated degradation rate constants of 74.46 × 10-3 min-1 and 8.43 × 10-3 min-1, respectively. To investigate the properties of ZnO-AC, several techniques were performed. ZnO-AC and ZnO exhibited similar results in morphology, crystalline structure, and Raman characteristics. However, ZnO-AC presented smaller pore diameters than those of ZnO, which enlarged pore surface area, and the presence of carbon-related groups implied the presence of AC on ZnO-AC surfaces. This can be attributed to the presence of AC on the ZnO surface, increasing the capture of surrounding toxic molecules and elevating the reaction density. This mechanism is attributed to promoting the degradation of toxic molecules. Therefore, using Wh as a carbon source for the transformation of AC can alternatively solve the problems of aquatic weed management and carbon storage strategies, and the application of AC in ZnO-AC photocatalysts can enhance photocatalysis.

Monitoring Charge Transfer Dynamics of Surface Trapped Holes in ZnO Surface Utilized for Ethanol Oxidation Using Heterodyne Transient Grating Spectroscopic Techniques

Monitoring Charge Transfer Dynamics of Surface Trapped Holes in ZnO Surface Utilized for Ethanol Oxidation Using Heterodyne Transient Grating Spectroscopic Techniques

Exploring Functional Polymers in the Synthesis of Luminescent ZnO Quantum Dots for the Detection of Cr6+, Fe2+, and Cu2.

The main aim of this work is to demonstrate that well-defined methacrylate-based copolymers with oligoethylene glycol side chains and functional groups such as thiol and glycidyl, obtained by photo-initiated reversible addition-fragmentation chain transfer (RAFT) in ethanol, are highly suitable as templates in the synthesis and protection of ZnO quantum dots (ZnO QDs) with remarkable photoluminescent properties. While the affinity of thiol groups to metallic surfaces is well established, their interaction with metal oxides has received less scrutiny. Furthermore, under basic conditions, glycidyl groups could react with hydroxyl groups on the surface of ZnO, representing another strategy for hybrid synthesis. The size and crystalline morphology of the resulting hybrids were assessed using DLS, TEM, and XRD, indicating that both polymers, even with a low proportion of functional groups (5% mol) are appropriate as templates and ligands for ZnO QDs synthesis. Notably, thiol-containing polymers yield hybrids with ZnO featuring excellent quantum yield (up to 52%), while polymers with glycidyl groups require combination with the organosilane aminopropyl triethoxysilane (APTES) to achieve optimal results. In both cases, these hybrids exhibited robust stability in both ethanol and aqueous environments. Beyond fundamental research, due to the remarkable photoluminescent properties and affordability, these hybrid ZnO QDs are expected to have potential applications in biotechnology and green science; in particular, in this study, we examined their use in the detection of environmental contaminants like Fe2+, Cr6+, and Cu2+. Specifically, the limit of detection achieved at 1.13 µM for the highly toxic Cr6+ underscores the significant sensing capabilities of the hybrids.

Zinc oxide–chitosan matrix for efficient electrochemical sensing of acetaminophen

The acetaminophen is an antipyretic and nonopioid analgesic that is prescribed for the management of fever and mild to moderate pain. The detection of acetaminophen by ZnO and ZnO@Chitosan-modified electrodes made of glassy carbon was compared. Acetaminophen was detected using surfaces of ZnO and ZnO@Chitosan over a 10–50 µM concentration range. The detection limits for ZnO and ZnO@Chitosan were anticipated to be 0.94 and 0.71 μmol L−1, respectively. In a wide range of acidic, neutral, and basic mediums with varying pH values, the impact of a change in solution pH on acetaminophen sensitivity was investigated. Electrokinetic studies were used to evaluate the acetaminophen detection efficiency. The charge transfer resistance (Rc) for various surfaces was measured using electrochemical impedance spectroscopy (EIS). Using DFT studies, the synergistic effect of chitosan on zinc oxide was also shown. The Forcite model was used to calculate the surface interactions between chitosan and zinc oxide. Acetaminophen adsorption on the chitosan surface was also studied using the B3LYP density functional method.Graphical abstract

Basic Properties of ZnO, Ga2O3, and MgO—Quantitative IR Studies

In our previous study, we elaborated a method of determination of concentrations of the basic sites O2− and OH− in a quantitative IR study of CO2 adsorption. Previous adsorption studies or TPD experiments only provided the total basicity without distinguishing between O2− and OH−. In this study, we determined the concentration of O2− and OH− on ZnO, Ga2O3, and MgO surfaces. The basicity of ZnO and MgO was found to be significantly higher than that of Ga2O3. The surface of ZnO was rich in O2−, the contribution of OH− was very small, and the Ga2O3 surface contained mainly OH−. For MgO, the contribution of O2− and OH− was comparable. According to the IR results, only a small fraction of all surface hydroxyls were sufficiently basic to react with CO2. The partial dehydroxylation changed the proportion of the concentrations of O2− and OH− on the oxides. We also elaborated upon a new method to determine the total concentration of basic sites via CO2 desorption monitored using IR. For all the oxides, we studied the sum of the concentrations of O2− and OH−, as determined in our quantitative IR studies, to find whether they were comparable with the total basicity determined in the desorption experiments.

Employing zinc oxide nanoparticle coating as a corrosion inhibitor for magnesium alloys in distinct aqueous electrolyte

In this investigation, zinc oxide nanoparticles were synthesised using a straightforward microwave-assisted technique. Results showed that the synthesised nanoparticles were hexagonal wurtzite ZnO-nanoparticles with a crystallite size of 6.76 nm, as determined by physio-chemical methods. It reveals, at varying magnifications, the irregularly aggregated, spherically shaped sponge-like structure. Using Fourier transform infrared spectroscopy, corresponding functional groups on ZnO surfaces have been observed. According to absorption measurements, the direct optical bandgap is around 3.29 eV. The photoluminescence spectra may be used to detect crystal defects in the ZnO lattice by looking for red emission and blue band edge emission. An investigation into the anticorrosion capabilities of zinc oxide nanoparticles was conducted, which revealed that the particles have beneficial characteristics when coated with magnesium (Mg) substrates. These materials are evaluated for corrosive resistance with and without a protective coating. Results show that coating significantly increased the protection rate under different electrolyte conditions. Compared to bare Mg plate, the charge transfer resistance Rct was increased when ZnO nanoparticles were coated.
 KEY WORDS: Zinc oxide nanoparticle, Microwave irradiation, Corrosion resistance, magnesium alloy
 Bull. Chem. Soc. Ethiop. 2024, 38(2), 417-430. 
 DOI: https://dx.doi.org/10.4314/bcse.v38i2.10

Biosynthesis of CoCr2O4/ZnO nanocomposites using Basella alba L. leaves extracts with enhanced photocatalytic degradation of malachite green in aqueous media

The use of chemical materials to tackle environmental concerns has undergone significant evolution, particularly in the pursuit of strategies for removing pollutants from wastewater as part of environmental remediation an increasingly crucial research topic. Employing green photocatalysts stands out as an efficient and cost-effective approach, playing a key role in promoting sustainable environmental remediation. This study introduces the modification of zinc oxide with cobalt chromite (CoCr2O4/ZnO) through a green synthesis method employing Basella alba L. leaves extract (BALE). Utilizing various characterization techniques, including FT–IR, UV–Vis DRS, XRD, SEM-EDS, and TEM, key features of ZnO, CoCr2O4, and CoCr2O4/ZnO nanocomposites were identified. The optical band gaps for ZnO, CoCr2O4, and CoCr2O4/ZnO nanocomposites were determined as 3.16, 1.71, and 2.80 eV, respectively, where it was shown that the band gap of the ZnO was reduced significantly. CoCr2O4/ZnO nanocomposites displayed a cubic shape of CoCr2O4 on the surface of ZnO, with a particle size of 23.84 ± 8.08 nm. The photocatalytic activity was assessed through the degradation of malachite green under visible light irradiation, where the CoCr2O4/ZnO nanocomposites exhibited superior photodegradation efficiency at 90.91%, surpassing ZnO alone (57.09%). This improvement in photocatalytic activity is attributed to a reduced band gap energy and a high rate constant value of 9.57 × 10−3 min−1, demonstrating pseudo-first-order reaction kinetics. In summary, this research presents the development of a ZnO-based photocatalyst with exceptional performance, especially in the visible light spectrum, making it a promising candidate for applications in wastewater removal.

Visualization of the Active Sites of Zinc-Chromium Oxides and the CO/H2 Activation Mechanism in Direct Syngas Conversion.

Despite wide studies demonstrating the versatility of the metal oxide-zeolite (OXZEO) catalyst concept to tackle the selectivity challenge in syngas chemistry, the active sites of metal oxides and the mechanism of CO/H2 activation remain to be elucidated. Herein, we demonstrate experimentally the role of Cr in zinc-chromium oxides and unveil visually, for the first time, the active sites for CO activation employing scanning transmission electron microscopy-electron energy loss spectroscopy using the volumetric density of surface carbon species as a descriptor. The ZnCr2O4 spinel surface with atomic ZnOx overlayer is the most active site for C-O bond dissociation, particularly at the narrow ZnCr2O4(110) facets constrained between the (311) and (111) facets, followed by the Cr-doped wurtzite ZnO surface. In comparison, the surfaces of ZnCr2O4 with aggregated ZnOx overlayers, pure ZnO, and the stoichiometric ZnCr2O4 exhibit a significantly lower activity. In situ synchrotron-based vacuum ultraviolet photoionization mass spectrometric study on different temperature programmed surface reactions with isotopes of C18O, 13CO, and D2 validates direct CO dissociation over ZnCrn oxides in CO, forming CH2 and further to hydrocarbons if H2 is present and CH2CO intermediates in syngas. The activity of CO dissociation and hydrogenation over ZnCrn oxides correlates well with the syngas-to-light-olefins activity of ZnCrn-SAPO-18 composite catalysts as a function of the Cr/Zn ratio.

Controlled evolution of surface microstructure and phase boundary of ZnO nanoparticles for the multiple sensitization effects on triethylamine detection.

In ZnO gas sensors, donor defects (such as zinc interstitials and oxygen vacancies) are considered active sites for the chemical adsorption and ionization of oxygen on the surface of ZnO, which can significantly enhance the sensor's response. However, the influence of the surface microstructure and phase boundaries of ZnO nanoparticles on the chemical adsorption and ionization of surface oxygen has rarely been explored. In this study, we developed a mixed-phase ZnO nanoparticle gas sensor with a rich phase boundary showing 198-50 ppm improvement in response to triethylamine at 340 °C. This is attributed to the generation of defects originating from lattice mismatch at the ZnO - zincite phase boundaries, which providing more active sites for adsorption of oxygen and triethylamine molecules. This work demonstrates a feasible method of combining surface microstructure regulation with pyrolysis strategies to develop ZnO sensors with significantly enhanced gas response performance.

Bimetallic Co-Mn catalysts for synergistic enhancement of VOC gas-sensing performance of ZnO hierarchical nanostructures.

The synergistic effect between bonding dissimilar metals is a very effective way to improve the performance of metal catalysts. In this work, we prepared a series of bimetallic co-doped ZnO hierarchical nanostructures by controlling Mn and Co contents. The gas-sensing properties of the sensors based on the bimetallic co-doped ZnO hierarchical nanostructures were studied systematically through different volatile organic compound (VOC) vapors for the temperature range from 160 to 400 °C. In the testing of normal butanol gas by the bimetallic co-doped ZnO sensor, its performance was tens of times higher than that of pure zinc oxide, and the response values to other VOCs tested were very low, which also indicates that the sensor has good selectivity. The promoted performance is attributed to the increase of adsorbed oxygen content on the surface of the sensor material due to the bimetallic synergistic enhancement effect. XPS spectra of O 1s region of the sensor show that the adsorbed oxygen content is 22.4%, which is higher than that of the pure ZnO (8.5%). The synergistic effect between bimetallic Mn and Co leads to electron enrichment on the surface of ZnO. Electron enrichment can not only promote the activation of ZnO, but also can help to improve the gas-sensing performance.

A ZnO&GeSe composite electron transport layer for organic solar cells

The deposition of 2D GeSe on the surface of ZnO improves the surface stability of ZnO and reduces the probability of forming defect vacancies on the surface of ZnO, thereby achieving high photoelectric conversion efficiency.

Cutting-edge developments in zinc oxide nanoparticles: synthesis and applications for enhanced antimicrobial and UV protection in healthcare solutions.

This paper presents a comprehensive review of recent advancements in utilizing zinc oxide nanoparticles (ZnO NPs) to enhance antimicrobial and UV protective properties in healthcare solutions. It delves into the synthesis techniques of ZnO NPs and elucidates their antimicrobial efficacy, exploring the underlying mechanisms governing their action against a spectrum of pathogens. Factors impacting the antimicrobial performance of ZnO NPs, including size, surface characteristics, and environmental variables, are extensively analyzed. Moreover, recent studies showcasing the effectiveness of ZnO NPs against diverse pathogens are critically examined, underscoring their potential utility in combatting microbial infections. The study further investigates the UV protective capabilities of ZnO NPs, elucidating the mechanisms by which they offer UV protection and reviewing recent innovations in leveraging them for UV-blocking applications in healthcare. It also dissects the factors influencing the UV shielding performance of ZnO NPs, such as particle size, dispersion quality, and surface coatings. Additionally, the paper addresses challenges associated with integrating ZnO NPs into healthcare products and presents future perspectives for overcoming these hurdles. It emphasizes the imperative for continued research efforts and collaborative initiatives to fully harness the potential of ZnO NPs in developing advanced healthcare solutions with augmented antimicrobial and UV protective attributes. By advancing our understanding and leveraging innovative approaches, ZnO NPs hold promise for addressing pressing healthcare needs and enhancing patient care outcomes.

Theoretical insights into the generation and reactivity of hydride on the ZnO(101̄0) surface.

ZnO is an important catalytic material for CO/CO2 hydrogenation. In this work, the pristine ZnO(101̄0) and the surfaces with Zn-O dimer vacancies (ZnO(101̄0)-(Zn-O)DiV) and oxygen vacancies are calculated. We find that the hydride (H-) species can be generated via heterolytic H2 dissociation on these surfaces, and that ZnO(101̄0)-(Zn-O)DiV only needs to overcome the energy barrier of ∼0.10 eV. This is because the ZnO system has flexible orbitals for electron storage and release and the low-coordinated Zn3c atoms at the defect sites can form stable Zn-H- covalent bonds with high symmetry. Flexible Zn orbitals also impart the unique feature of activating multiple electrophilic adsorbates simultaneously as excess electrons exist. Moreover, we show that the covalent Zn-H- species can regulate the catalytic activity and selectivity for CO2 hydrogenation by preferentially producing *HCOO intermediates at Zn-O dimer vacancies. These results may help in the design of efficient Zn-based hydrogenation catalysts.

Interfacial properties of a ZnO/PTFE composite from density functional tight-binding simulations.

Metal-oxide-reinforced plastic nanocomposites are widely used in high-tech industries, but the reinforcement mechanism of the metal oxide is not fully understood. Here we investigate the interfacial properties of a zinc-oxide-reinforced amorphous polytetrafluoroethylene (a-PTFE) composite as a prototype for such composites using superlattice modeling and density functional tight-binding molecular dynamics simulations. To study the ZnO/a-PTFE composites, the superlattice supercells are built using a ZnO (112̄0) surface supercell and a-PTFE layer with an experimental density of 1.8 g cm-3 and various thicknesses. Our calculations demonstrate that the binding energy between ZnO and a-PTFE is negative, indicating their attractive binding, and electron accumulation occurs in the middle space between ZnO and a-PTFE, as well as around ZnO, evidencing that the newly formed interfacial chemical bonds are partially covalent. We further reveal that the tensile stress and elastic moduli of the ZnO/a-PTFE superlattice increases with increasing ZnO fraction, with values placed between those of ZnO and a-PTFE, which confirms the enhancement of the mechanical strength of the composites by incorporating ZnO into the a-PTFE matrix. This work provides a design guideline for developing high-performance metal-oxide-reinforced plastic composites.

Defects Healing of the ZnO Surface by Filling with Au Atom Catalysts for Efficient Photocatalytic H2 Production (Small 4/2024)

Defects Healing of the ZnO Surface by Filling with Au Atom Catalysts for Efficient Photocatalytic H₂ Production (Small 4/2024)

Effective surface passivation of GaAs nanowire photodetectors by a thin ZnO capping.

The III-V nanowire (NW) structure is a good candidate for developing photodetectors. However, high-density surface states caused by the large surface-to-volume ratio severely limit their performance, which is difficult to solve in conventional ways. Here, a robust surface passivation method, using a thin layer of ZnO capping, is developed for promoting NW photodetector performance. 11 cycles of ZnO, grown on pure zinc blende high-quality GaAs NWs by atomic layer deposition, significantly alleviates the undesirable effect of the surface states, without noticeable degradation in NW morphology. An average 20-fold increase in micro-photoluminescence intensity is observed for passivated NWs, which leads to the development of detectors with high responsivity, specific detectivity, and optical gain of 9.46 × 105 A W-1, 3.93 × 1014 Jones, and 2.2 × 108 %, respectively, under low-intensity 532 nm illumination. Passivated NW detectors outperform their counterparts treated by conventional methods, so far as we know, which shows the potential and effectiveness of thin ZnO surface passivation on NW devices.

Nanostructured antimicrobial ZnO surfaces coated with an imidazolium-based ionic liquid

The global COVID-19 pandemic and concerns about antimicrobial resistance have intensified research towards the development of innovative methods and technologies to suppress the spread of infectious pathogens facilitated by high touch surfaces.