Aqueous Titania Interfaces.

Water-metal oxide interfaces are central to many phenomena and applications, ranging from material corrosion and dissolution to photoelectrochemistry and bioengineering. In particular, the discovery of photocatalytic water splitting on TiO2 has motivated intensive studies of water-TiO2 interfaces for decades. So far, a broad understanding of the interaction of water vapor with several TiO2 surfaces has been obtained. However, much less is known about liquid water-TiO2 interfaces, which are more relevant to many practical applications. Probing these complex systems at the molecular level is experimentally challenging and is sometimes possible only through computational studies. This review summarizes recent advances in the atomistic understanding, mostly through computational simulations, of the structure and dynamics of interfacial water on TiO2 surfaces. The main focus is on the nature, molecular or dissociated, of water in direct contact with low-index defect-free crystalline surfaces. The hydroxyls resulting from water dissociation are essential in the photooxidation of water and critically affect the surface chemistry of TiO2.

Liquid-Metal-Based Spin-Coating Exfoliation for Atomically Thin Metal Oxide Synthesis.

Two-dimensional (2D) semiconductors possess exceptional electronic, optical, and magnetic properties, making them highly desirable for widespread applications. However, conventional mechanical exfoliation and epitaxial growth methods are insufficient in meeting the demand for atomically thin films covering large areas while maintaining high quality. Herein, leveraging liquid metal oxidation reaction, we propose a motorized spin-coating exfoliation strategy to efficiently produce large-area 2D metal oxide (2DMO) semiconductors with high crystallinity, atomically thin thickness, and flat surfaces on diverse substrates. Moreover, we realized a 2D gallium oxide-based deep ultraviolet solar-blind photodetector featuring a metal-semiconductor-metal structure, showcasing high responsivity (8.24 A W-1) at 254 nm and excellent sensitivity (4.3 × 1012 cm Hz1/2 W-1). This novel liquid-metal-based spin-coating exfoliation strategy offers great potential for synthesizing atomically thin 2D semiconductors, opening new avenues for future functional electronic and optical applications.

Probing the Interaction between Individual Metal Nanocrystals and Two-Dimensional Metal Oxides via Electron Energy Loss Spectroscopy.

Metal nanoparticles can photosensitize two-dimensional metal oxides, facilitating their electrical connection to devices and enhancing their abilities in catalysis and sensing. In this study, we investigated how individual silver nanoparticles interact with two-dimensional tin oxide and antimony-doped indium oxide using electron energy loss spectroscopy (EELS). The measurement of the spectral line width of the longitudinal plasmon resonance of the nanoparticles in absence and presence of 2D materials allowed us to quantify the contribution of chemical interface damping to the line width. Our analysis reveals that a stronger interaction (damping) occurs with 2D antimony-doped indium oxide due to its highly homogeneous surface. The results of this study offer new insight into the interaction between metal nanoparticles and 2D materials.

Chemical Bath Deposited Antimony Oxide Thin Films for Efficient Perovskite Solar Cells.

The metal oxide electron transport layers (ETLs) of n-i-p perovskite solar cells (PSCs) are dominated by TiO2 and SnO2, while the efficacy of the other metal oxide ETLs still lags far behind. Herein, an emerging, economical, and environmentally friendly metal oxide, antimony oxide (Sb2Ox, x = 2.17), prepared by chemical bath deposition is reported as an alternative ETL for PSCs. The deposited Sb2Ox film is amorphous and very thin (∼10 nm) but conformal on rough fluorine-doped tin oxide substrates, showing matched energy levels, efficient electron extraction, and then reduced nonradiative recombination in PSCs. The champion PSC based on the Sb2Ox ETL delivers an impressive power conversion efficiency of 24.7% under one sun illumination, which represents the state-of-the-art performance of all metal oxide ETL-based PSCs. Additionally, the Sb2Ox-based devices show improved operational and thermal stability compared to their SnO2-based counterparts. Armed with these findings, we believe this work offers an optional ETL for perovskites-based optoelectronic devices.

Protein Aggregation on Metal Oxides Governs Catalytic Activity and Cellular Uptake.

Engineering of catalytically active inorganic nanomaterials holds promising prospects for biomedicine. Catalytically active metal oxides show applications in enhancing wound healing but have also been employed to induce cell death in photodynamic or radiation therapy. Upon introduction into a biological system, nanomaterials are exposed to complex fluids, causing interaction and adsorption of ions and proteins. While protein corona formation on nanomaterials is acknowledged, its modulation of nanomaterial catalytic efficacy is less understood. In this study, proteomic analyses and nano-analytic methodologies quantify and characterize adsorbed proteins, correlating this protein layer with metal oxide catalytic activity in vitro and in vivo. The protein corona comprises up to 280 different proteins, constituting up to 38% by weight. Enhanced complement factors and other opsonins on nanocatalyst surfaces lead to their uptake into macrophages when applied topically, localizing >99% of the nanomaterials in tissue-resident macrophages. Initially, the formation of the protein corona significantly reduces the nanocatalysts' activity, but this activity can be partially recovered in endosomal conditions due to the proteolytic degradation of the corona. Overall, the research reveals the complex relationship between physisorbed proteins and the catalytic characteristics of specific metal oxide nanoparticles, providing design parameters for optimizing nanocatalysts in complex biological environments.

Advances in Defect Engineering of Metal Oxides for Photocatalytic CO2 Reduction.

Photocatalytic CO2 reduction technology, capable of converting low-density solar energy into high-density chemical energy, stands as a promising approach to alleviate the energy crisis and achieve carbon neutrality. Semiconductor metal oxides, characterized by their abundant reserves, good stability, and easily tunable structures, have found extensive applications in the field of photocatalysis. However, the wide bandgap inherent in metal oxides contributes to their poor efficiency in photocatalytic CO2 reduction. Defect engineering presents an effective strategy to address these challenges. This paper reviews the research progress in defect engineering to enhance the photocatalytic CO2 reduction performance of metal oxides, summarizing defect classifications, preparation methods, and characterization techniques. The focus is on defect engineering, represented by vacancies and doping, for improving the performance of metal oxide photocatalysts. This includes advancements in expanding the photoresponse range, enhancing photogenerated charge separation, and promoting CO2 molecule activation. Finally, the paper provides a summary of the current issues and challenges faced by defect engineering, along with a prospective outlook on the future development of photocatalytic CO2 reduction technology.

Layer-By-Layer Assembly of Atomically Precise Alloy Nanoclusters Photosystems for Solar Water Oxidation.

Atomically precise metal nanoclusters (NCs) have garnered tremendous attention as light-harvesting antennas in heterogeneous photocatalysis due to unique atomic stacking mode, quantum confinement effect, and enriched active sites. However, metal NCs as photosensitizers suffer from extremely short carrier lifetime, poor photostability, and difficulty in carrier migration, which hinder the wide-spread utilization of metal NCs in solar energy conversion. To solve these problems, herein, Ag-doped glutathione (GSH)-capped gold NCs, i.e., alloy Au1- x Agx @GSH NCs and non-conjugated insulating polymer of poly(diallyl-dimethylammonium chloride) (PDDA) are utilized as the building blocks for layer-by-layer assembly of spatially multilayered alloy NCs/metal oxide (MO) photosystems. The alternately deposited ultrathin PDDA layer in-between Au1- x Agx @GSH NCs on the MO substrate functions as an efficient charge flow mediator to relay the directional photoelectron transfer over Au1- x Agx @GSH NCs, giving rise to the cascade charge transfer chain. This peculiar carrier migration mode endowed by exquisite interface configuration design significantly boosts the unidirectional electron migration from the Au1- x Agx @GSH NCs to the MO substrate, substantially improving the visible-light-driven photoelectrochemical water oxidation performances of MO/(PDDA-Au1- x Agx )n multilayer heterostructured photoanodes. The work will inspire the rational construction of alloy metal NCs-based photosystems for modulating spatially controllable charge transfer pathway for solar energy conversion.

Defective Tungsten Oxides with Stacking Faults for Proton Exchange Membrane Green-Hydrogen Generation.

Defects can introduce atomic structural modulation and tailor performance of materials. Herein, it demonstrates that semiconductor WO3 with inert electrocatalytic behavior can be activated through defect-induced tensile strains. Structural characterizations reveal that when simply treated in Ar/H2 atmosphere, oxygen vacancies will generate in WO3 and cause defective structures. Stacking faults are found in defects, thus modulating electronic structure and transforming electrocatalytic-inert WO3 into highly active electrocatalysts. Density functional theory (DFT) calculations are performed to calculate *H adsorption energies on various WOx surfaces, revealing the oxygen vacancy composition and strain predicted to optimize the catalytic activity of hydrogen evolution reaction (HER). Such defective tungsten oxides can be integrated into commercial proton exchange membrane (PEM) electrolyser with comparable performance toward Pt-based PEM. This work demonstrates defective metal oxides as promising non-noble metal catalysts for commercial PEM green-hydrogen generation.

Recent Development on Transition Metal Oxides-Based Core-Shell Structures for Boosted Energy Density Supercapacitors.

In recent years, nanomaterials exploration and synthesis have played a crucial role in advancing energy storage research, particularly in supercapacitor development. Researchers have diversified materials, including metal oxides, chalcogenides, and composites, as well as carbon materials, to enhance energy and power density. Balancing energy density with electrochemical stability remains challenging, driving intensified efforts in advancing electrode materials. This review focuses on recent progress in designing and synthesizing core-shell materials tailored for supercapacitors. The core-shell architecture offers advantages such as increased surface area, redox active sites, electrical conductivity, ion diffusion kinetics, specific capacitance, and cyclability. The review explores the impact of core and shell materials, specifically transition metal oxides (TMOs), on supercapacitor electrochemical behavior. Metal oxide choices, such as cobalt oxide as a preferred core and manganese oxide as a shell, are discussed. The review also highlights characterization techniques for assessing structural, morphological, and electrochemical properties of core-shell materials. Overall, it provides a comprehensive overview of ongoing TMOs-based core-shell material research for supercapacitors, showcasing their potential to enhance energy storage for applications ranging from gadgets to electric vehicles. The review outlines existing challenges and future opportunities in evolving TMOs-based core-shell materials for supercapacitor advancements, holding promise for high-efficiency energy storage devices.

Electrochemical Deposition for Cultivating Nano- and Microstructured Electroactive Materials for Supercapacitors: Recent Developments and Future Perspectives.

The globe is currently dealing with serious issues related to the world economy and population expansion, which has led to a significant increase in the need for energy. One of the most promising energy devices for the next generation of energy technology is the supercapacitor (SC). Among the numerous nanostructured materials examined for SC electrodes, inorganic nanosheets are considered to be the most favorable electrode materials because of their excellent electrochemical performance due to their large surface area, very low layer thickness, and tunable diverse composition. Various inorganic nanosheets (NS) such as metal oxides, metal chalcogenides, metal hydroxides, and MXenes show substantial electrochemical activity. Herein, a comprehensive survey of inorganic NS arrays synthesized through the electrodeposition method is reported with the discussion on detailed growth mechanism and their application in the fabrication of SC electrodes/devices for powering flexible and wearable electronics appliances. To begin with, the first section will feature the various types of electrodeposition working mechanism, SC types and their working mechanisms, importance of nanosheet structure for SCs. This review gives a profound interpretation of supercapacitor electrode materials and their performances in different domains. Finally, a perspective on NS array through electrodeposition method applications in diverse fields is extensively examined.

Complex Metal Oxides as Emerging Inorganic Hole-Transporting Materials for Perovskite Solar Cells.

Perovskite solar cells (PSCs) have achieved revolutionary progress during the past decades with a rapidly boosting rate in power conversion efficiencies from 3.8% to 26.1%. However, high-efficiency PSCs with organic hole-transporting materials (HTMs) suffer from inferior long-term stability and high costs. The replacement of organic HTMs with inorganic counterparts such as metal oxides can solve the above-mentioned problems to realize highly robust and cost-effective PSCs. Nevertheless, the widely used simple metal oxide-based HTMs are limited by the low conductivity and poor light transmittance due to the fixed atomic environment. As an emerging family of inorganic HTMs, complex metal oxides with superior structural/compositional flexibility have attracted rapidly increasing interest recently, showing superior carrier conductivity/mobility and superb light transmittance. Herein, the recent advancements in the design and development of complex metal oxide-based HTMs for high-performance PSCs are summarized by emphasizing the superiority of complex metal oxides as HTMs over simple metal oxide-based counterparts. Consequently, several distinct strategies for the design of complex metal oxide-based HTMs are proposed. Last, the future directions and remaining challenges of inorganic complex metal oxide-based HTMs for PSCs are also presented. This review aims to provide valuable guidelines for the further advancements of robust, high-efficiency, and low-cost PSCs.

An Active Strategy to Reduce Residual Alkali for High-Performance Layered Oxide Cathode Materials of Sodium-Ion Batteries.

Residual alkali is one of the biggest challenges for the commercialization of sodium-based layered transition metal oxide cathode materials since it can even inevitably appear during the production process. Herein, taking O3-type Na0.9Ni0.25Mn0.4Fe0.2Mg0.1Ti0.05O2 as an example, an active strategy is proposed to reduce residual alkali by slowing the cooling rate, which can be achieved in one-step preparation method. It is suggested that slow cooling can significantly enhance the internal uniformity of the material, facilitating the reintegration of Na+ into the bulk material during the calcination cooling phase, therefore substantially reducing residual alkali. The strategy can remarkably suppress the slurry gelation and gas evolution and enhance the structural stability. Compared to naturally cooled cathode materials, the capacity retention of the slowly cooled electrode material increases from 76.2% to 85.7% after 300 cycles at 1 C. This work offers a versatile approach to the development of advanced cathode materials toward practical applications.

Controlled Fabrication of Metallic MoO2 Nanosheets towards High-Performance p-Type 2D Transistors.

Two-dimensional (2D) semiconducting transition metal dichalcogenides (TMDCs) are extensively employed as channel materials in advanced electronic devices. The electrical contacts between electrodes and 2D semiconductors play a crucial role in the development of high-performance transistors. While numerous strategies for electrode interface engineering have been proposed to enhance the performance of n-type 2D transistors, upgrading p-type ones in a similar manner remains a challenge. In this work, significant improvements in a p-type WSe2 transistor are demonstrated by utilizing metallic MoO2 nanosheets as the electrode contact, which are controllably fabricated through physical vapor deposition and subsequent annealing. The MoO2 nanosheets exhibit an exceptional electrical conductivity of 8.4 × 104 S m‒1 and a breakdown current density of 3.3 × 106 A cm‒2. The work function of MoO2 nanosheets is determined to be ≈5.1 eV, making them suitable for contacting p-type 2D semiconductors. Employing MoO2 nanosheets as the electrode contact in WSe2 transistors results in a notable increase in the field-effect mobility to 92.0 cm2 V‒1 s‒1, which is one order of magnitude higher than the counterpart devices with conventional electrodes. This study not only introduces an intriguing 2D metal oxide to improve the electrical contact in p-type 2D transistors, but also offers an effective approach to fabricating all-2D devices.

The role of ion dissolution in metal and metal oxide surface inactivation of SARS-CoV-2.

Anti-viral surface coatings are under development to prevent viral fomite transmission from high-traffic touch surfaces in public spaces. Copper's anti-viral properties have been widely documented, but the anti-viral mechanism of copper surfaces is not fully understood. We screened a series of metal and metal oxide surfaces for anti-viral activity against severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2), the causative agent of coronavirus disease (COVID-19). Copper and copper oxide surfaces exhibited superior anti-SARS-CoV-2 activity; however, the level of anti-viral activity was dependent on the composition of the carrier solution used to deliver virus inoculum. We demonstrate that copper ions released into solution from test surfaces can mediate virus inactivation, indicating a copper ion dissolution-dependent anti-viral mechanism. The level of anti-viral activity is, however, not dependent on the amount of copper ions released into solution per se. Instead, our findings suggest that degree of virus inactivation is dependent on copper ion complexation with other biomolecules (e.g., proteins/metabolites) in the virus carrier solution that compete with viral components. Although using tissue culture-derived virus inoculum is experimentally convenient to evaluate the anti-viral activity of copper-derived test surfaces, we propose that the high organic content of tissue culture medium reduces the availability of "uncomplexed" copper ions to interact with the virus, negatively affecting virus inactivation and hence surface anti-viral performance. We propose that laboratory anti-viral surface testing should include virus delivered in a physiologically relevant carrier solution (saliva or nasal secretions when testing respiratory viruses) to accurately predict real-life surface anti-viral performance when deployed in public spaces.IMPORTANCEThe purpose of evaluating the anti-viral activity of test surfaces in the laboratory is to identify surfaces that will perform efficiently in preventing fomite transmission when deployed on high-traffic touch surfaces in public spaces. The conventional method in laboratory testing is to use tissue culture-derived virus inoculum; however, this study demonstrates that anti-viral performance of test copper-containing surfaces is dependent on the composition of the carrier solution in which the virus inoculum is delivered to test surfaces. Therefore, we recommend that laboratory surface testing should include virus delivered in a physiologically relevant carrier solution to accurately predict real-life test surface performance in public spaces. Understanding the mechanism of virus inactivation is key to future rational design of improved anti-viral surfaces. Here, we demonstrate that release of copper ions from copper surfaces into small liquid droplets containing SARS-CoV-2 is a mechanism by which the virus that causes COVID-19 can be inactivated.

Autocombustion Route Derived Zinc Ferrite Nanoparticles as Chemiresistive Sensor for Detection of Alcohol Vapors.

Prolonged exposure to alcohol vapors can have detrimental effects on human health, potentially leading to eye irritation, dizziness, and in some cases, damage to the nervous system. The present article aims to provide a comprehensive understanding on the synthesis and characterization of zinc ferrite (ZnFe2O4) nanoparticles, as well as their interactions with a range of alcohol vapors, including methanol, ethanol, n-propanol, and isopropanol. These alcohols differ in their molecular weight, boiling points, diffusivity, and other properties. The study reveals the semiconducting ZnFe2O4 nanoparticulate sensor's capability for reversible, repeatable, and sensitive detection of alcohol vapors. The sensor exhibits the highest response to ethanol within operating temperature range (225-300 °C). An attempt is made to establish a correlation between the properties of the target analytes and the observed sensing signals. Additionally, the response conductance transients of ZnFe2O4 under the exposure to the studied alcohol vapors are modeled based on the Langmuir-Hinshelwood adsorption mechanism. The characteristic time constants obtained from this modeling are justified with respect to the properties of the analytes.

Carbon Nanosheets-Based Supercapacitor Materials: Recent Advances and Prospects.

The need for inexpensive and ecologically sustainable energy storage technologies is rising rapidly along with the severity of the world's environmental challenges as well as with the rising demand for portable electronics and hybrid vehicles. Supercapacitors have drawn a lot of attentions lately in this regard because of their ultrahigh power density, outstanding electrochemical stability, and environmental friendliness. Due to various advantages, carbon materials are the choice of designer for developing commercial electrodes for various applications including devising supercapacitors. Two-dimensional (2D) carbon nanosheets (CNSs) with a large surface area and excellent electronic transport properties have fired up the interest of researchers due to their unique properties and potential applications in energy storage. Such engineered 2D porous CNS may significantly improve the energy storage performance of supercapacitor by enabling fast ion transport and charge transfer kinetics. This article summarizes the most recent and significant advances in the area of activated, porous, graphene-based various CNSs and their composites with a special focus on their use as supercapacitor electrodes. A succinct overview about their syntheses and key characterizations regarding their different structural aspects have been discussed. The present challenges and prospects in using CNS in supercapacitor applications are highlighted.

Resent Development of Binder-Free Electrodes of Transition Metal Oxides and Nanohybrids for High Performance Supercapacitors - A Review.

The entire world is aware of the serious issue of global warming and therefore utilizing renewable energy sources is the most encouraging steps toward solving energy crises, and as a result, energy storage solutions are necessary. The supercapacitors (SCs) have a high-power density and a long cycle life, they are promising as an electrochemical conversion and storage device. In order to achieve high electrochemical performance, electrode fabrication must be implemented properly. Electrochemically inactive and insulating binders are utilized in the conventional slurry coating method of making electrodes to provide adhesion between the electrode material and the substrate. This results in an undesirable "dead mass," which lowers the overall device performance. In this review, we focused on binder-free SCs electrodes based on transition metal oxides and composites. With the best examples providing the critical aspects, the benefits of binder-free electrodes over slurry-coated electrodes are addressed. Additionally, different metal-oxides used in the fabrication of binder-free electrodes are assessed, taking into account the various synthesis methods, giving an overall picture of the work done for binder-free electrodes. The future outlook is provided along with the benefits and drawbacks of binder-free electrodes based on transition metal oxides.

Haze factor of silver nanowires in variable refractive index environment: experimental and simulation approaches.

While silver nanowires (Ag NWs) have been demonstrated as a highly efficient transparent conducting material, they suffer from strong light scattering, which is quantified by a large haze factor (HF) in the optical spectrum. Here we investigate the influence of the dielectric environment on the light scattering of Ag NWs by comparing experimental measurements and simulations. In air, two peaks on the HF spectra are observed experimentally at the wavelength ofλI= 350 nm andλII= 380 nm and are attributed by simulations to the influence of the Ag NWs pentagonal shape on the localized surface plasmon resonance. The relative intensity between the two peaks is found to be dependent on whether the Ag NWs are in contact with the glass substrate or not. The HF behaviour in the near IR region seems to be dominated by Rayleigh scattering following simulations results. Dielectric environments of Ag NWs with various refractive indexes were obtained experimentally by the conformal deposition of different metal oxide coatings using atomic layer deposition, including Al-doped zinc oxide, Al2O3and SiO2coatings. The HF is found to be correlated with the refractive index environment in terms of HF peaks position, intensity and broadening. This trend of HF peaks is supported by a theoretical model to understand the optical mechanism behind this phenomenon.

Neuromorphic learning with Mott insulator NiO.

Habituation and sensitization (nonassociative learning) are among the most fundamental forms of learning and memory behavior present in organisms that enable adaptation and learning in dynamic environments. Emulating such features of intelligence found in nature in the solid state can serve as inspiration for algorithmic simulations in artificial neural networks and potential use in neuromorphic computing. Here, we demonstrate nonassociative learning with a prototypical Mott insulator, nickel oxide (NiO), under a variety of external stimuli at and above room temperature. Similar to biological species such as Aplysia, habituation and sensitization of NiO possess time-dependent plasticity relying on both strength and time interval between stimuli. A combination of experimental approaches and first-principles calculations reveals that such learning behavior of NiO results from dynamic modulation of its defect and electronic structure. An artificial neural network model inspired by such nonassociative learning is simulated to show advantages for an unsupervised clustering task in accuracy and reducing catastrophic interference, which could help mitigate the stability-plasticity dilemma. Mott insulators can therefore serve as building blocks to examine learning behavior noted in biology and inspire new learning algorithms for artificial intelligence.

Genuine divalent magnesium-ion storage and fast diffusion kinetics in metal oxides at room temperature.

Rechargeable magnesium batteries represent a viable alternative to lithium-ion technology that can potentially overcome its safety, cost, and energy density limitations. Nevertheless, the development of a competitive room temperature magnesium battery has been hindered by the sluggish dissociation of electrolyte complexes and the low mobility of Mg2+ ions in solids, especially in metal oxides that are generally used in lithium-ion batteries. Herein, we introduce a generic proton-assisted method for the dissociation of the strong Mg-Cl bond to enable genuine Mg2+ intercalation into an oxide host lattice; meanwhile, the anisotropic Smoluchowski effect produced by titanium oxide lattices results in unusually fast Mg2+ diffusion kinetics along the atomic trough direction with a record high ion conductivity of 1.8 × 10-4 S ⋅ cm-1 on the same order as polymer electrolyte. The realization of genuine Mg2+ storage and fast diffusion kinetics enabled a rare high-power Mg-intercalation battery with inorganic oxides. The success of this work provides important information on engineering surface and interlayer chemistries of layered materials to tackle the sluggish intercalation kinetics of multivalent ions.