Oxide Research Articles

Observation of the Transition from Triple Bonds to Single Bonds between Ru-Ge Bonding in RuGeO(CO)n- (n = 3-5).

This work reports the observation and characterization of heterobinuclear transition-metal main-group metal oxide carbonyl complex anions, RuGeO(CO)n- (n = 3-5), by combining mass-selected photoelectron velocity map imaging spectroscopy and quantum chemistry calculations. The experimentally determined vertical electron detachment energy of RuGeO(CO)3- surpasses those of RuGeO(CO)4- and RuGeO(CO)5-, which is attributed to distinctive bonding features. RuGeO(CO)3- manifests one covalent σ and two Ru-to-Ge dative π bonds, contrasting with the sole covalent σ bond present in RuGeO(CO)4- and RuGeO(CO)5-. Unpaired spin density distribution analysis reveals a 17-electron configuration at the Ru center in RuGeO(CO)3- and an 18-electron configuration in RuGeO(CO)4- and RuGeO(CO)5-. This work closes a gap in the quantitative physicochemical characterization of heteronuclear oxide carbonyl complexes, enhancing our insights into catalytic processes of CO/GeO on the metal surface at the molecular level.

Experimental Reactivity of (MoO3)NO- (N = 1-21) Cluster Anions with C1-C4 Alkanes: A Simple Model to Predict the Reactivity with Methane.

Metal oxide clusters with atomic oxygen radical anions are important model systems to study the mechanisms of activating and transforming very stable alkane molecules under ambient conditions. It is extremely challenging to characterize the activation and conversion of methane, the most stable alkane molecule, by metal oxide cluster anions due to the low reactivity of the anionic species. In this study, using a ship-lock type reactor that could be run at relatively high pressure conditions to provide a high number of collisions in ion-molecule reactions, the rate constants of the reactions between (MoO3)NO- (N = 1-21) cluster anions and the light alkanes (C1-C4) were measured under thermal collision conditions. The relationships among the reaction rates of different alkanes were obtained to establish a model to predict the low rate constants with methane from the high rate constants with C2-C4 alkanes. The model was tested by using available experimental results in literature. This study provides a new method to estimate the relatively low reactivity of atomic oxygen radical anions with methane on metal oxide clusters.

Low-Temperature Decomposition and Oxidation of the Nerve Agent Simulant on Mesoporous Nickel Oxide and Cu-Doped Nickel Oxide.

In an effort to develop the next frontier filtration material for chemical warfare agent (CWA) decomposition, we synthesized mesoporous NiO and CuxNi1-xO (x = 0.10 and 0.20) and studied the decomposition of CWA simulant diisopropyl fluorophosphate (DIFP) on their surfaces. Mesoporous NiO and CuxNi1-xO were fully characterized and found to be a solid solution with no phase separation up to 20% copper dopant. The synthesized materials were successfully templated producing ordered mesoporous metal oxides with high surface areas (67.89- 94.38 m2/g). Through Raman spectroscopy, we showed that pure NiO contained a high concentration of Ni2+ vacancies, while Cu2+ reduced these defects. Through in situ infrared spectroscopy, we determined the surface species formed, potential pathways, and driving factors for decomposition. Upon exposure of DIFP, all materials produced similar decomposition products CO, CO2, carbonyls, and carbonates. However, decomposition reactions were sustained longer on mesoporous NiO, facilitated by the higher Ni2+ vacancy concentration. NiO was further studied with DIFP, first at low dosing temperatures (-50 °C), which still resulted in the production of CO and carbonates, and then, second, with a higher pretreatment temperature, which showed the importance of terminal hydroxyls/water to fully oxidize decomposition products to CO2. Mesoporous NiO demonstrated high decomposition and oxidation capabilities at temperatures below room temperature, all without any external excitation or noble metals, making it a promising frontier filtration material for CWA decomposition.

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.

Boosting Photocatalytic Hydrogen Production by MOF-derived Metal Oxide Heterojunctions witha 10.0% Apparent Quantum Yield.

Photocatalytic hydrogen production offers an alternative pathway to establish a sustainable energy economy. While numerous photoactive materials exhibit potential for generating hydrogen from water, the synergy achieved by combining two different materials with complementary properties in the form of heterojunctions can significantly their photocatalytic activity. Our study describes the design and generation of the metal-organic framework-derived (MOF) metal oxide heterojunction composed of RuO2/N,S-TiO2. The RuO2/N,S-TiO2 is generated through the pyrolysis of MOFs, Ru- HKUST-1, and the amino-functionalized MIL-125-NH2. Among the various RuO2/N,S- TiO2 materials tested, the material characterized by the lowest RuO2 content, exhibited the highest hydrogen evolution rate, producing 10,761 μmol·hr-1·g-1 of hydrogen with an apparent quantum-yield of 10.0% in pure water. In addition to RuO2/N,S-TiO2, we generated two other MOF-derived metal-oxide heterojunctions, ZnO/N,S-TiO2 and In2O3/N,S-TiO2, leading to apparent quantum yields of 0.7% and 0.3%, respectively. The remarkable photocatalytic activity observed in RuO2/N,S-TiO2 is thought to be attributed to the synergistic effects arising from the combination of metallic properties inherent in the metal oxides, their band alignment, porosity, and surface properties inherited from the parent MOFs. The photocatalytic efficiency of RuO2/N,S-TiO2 was further demonstrated in actual water samples, producing hydrogen with a rate of 8,190 μmol·hr-1·g-1 in tap water.

Insights into the Electrochemical CO2RR Performance and Binding of Small Molecules on Quaternary Thiospinels Ag2FeSn3S8 and Cu2FeSn3S8.

Using a mechanical synthesis method in the form of ball milling and an additional annealing step, a novel and accelerated route for the synthesis of the thiospinels toyohaite (Ag2FeSn3S8) and rhodostannite (Cu2FeSn3S8) was discovered. Both thiospinels display faradaic efficiencies of up to 73% for CO2 reduction to CO using an organic electrolyte in an H-type cell. The materials were furthermore implemented in a zero-gap electrolyzer, with toyohaite producing 22% CO and 52% H2 at 100 mA cm-2 and rhodostannite 28% CO and 37% H2. The catalytically active sites are studied using density functional theory, revealing strong CO binding interactions on both Ag and Cu, whereas Sn is found to contribute to the decomposition of Ag2FeSn3S8 and Cu2FeSn3S8 by coordination with oxygen. Postmortem analysis of the thiospinel-based electrodes by means of SEM-EDX, XRD, XPS, and Mössbauer spectroscopy showed sulfur leaching from the catalysts after applying 100 mA cm-2. These spectroscopic results-in conjunction with DFT calculations of the oxidized surfaces-suggest that the catalytically active species consists of metal oxides. As a conversion of the metal sulfides into the corresponding metallic species was observed via XRD, the decomposition pathways of both catalysts were also computed using DFT; thus, elucidating the energetically most favorable decomposition products and expanding the possible composition of the catalysts postelectrolysis.

Boosting Photocatalytic Hydrogen Production by MOF‐derived Metal Oxide Heterojunctions with a 10.0% Apparent Quantum Yield

Boosting Photocatalytic Hydrogen Production by MOF‐derived Metal Oxide Heterojunctions with a 10.0% Apparent Quantum Yield

Graphitic Carbon Nitride Structures on Carbon Cloth Containing Ultra- and Nano-Dispersed NiO for Photoactivated Oxygen Evolution.

The development of low-cost and high-efficiency oxygen evolution reaction (OER) photoelectrocatalysts is a key requirement for H2 generation via solar-assisted water splitting. In this study, we report on an amenable fabrication route to carbon cloth-supported graphitic carbon nitride (gCN) nanoarchitectures, featuring a modular dispersion of NiO as co-catalyst. The synergistic interaction between gCN and NiO, along with the tailoring of their size and spatial distribution, yield very attractive OER performances and durability in freshwater splitting, of great significance for practical end-uses. The potential of gCN electrocatalysts containing ultra-dispersed, i. e. "quasi-atomic" NiO, exhibiting a higher activity than the ones containing nickel oxide nanoaggregates, is further highlighted by their activity even in real seawater. This work suggests that efficient OER catalysts can be designed through the construction of optimized interfaces between transition metal oxides and carbon nitride, yielding inexpensive and promising noble metal-free systems for real-world applications.

A novel MTCMOS based 8T2M NVSRAM design for low power applications with high temperature endurance

Abstract This research investigates, for the first time, a novel eight-transistor-two-memristor (8T2M) nonvolatile 
static random access memory (NVSRAM) with 7-nm technology. The key innovation in this design lies 
in the incorporation of multiple-threshold complementary metal oxide semiconductor (MTCMOS) 
technology with power gating technique, which enables efficient power management and enhanced 
performance with low leakage current. The implementation of multiple threshold voltage levels allows 
for dynamic control of transistor behavior, optimizing power consumption and read/write speeds. As 
compared to a traditional six-transistor (6T) static random access memory (SRAM) cell, it has been 
ascertained that there is a 33% enhancement in the read margin and an 18% improvement in the write 
margin. Moreover, the delay for read, write ‘0’ and write ‘1’ is also minimized by 63.89%, 37.99% and 
42.77%. Furthermore, the power attenuation is also reduced for read and write by 63.02% and 81.6%, 
respectively with respect to a conventional SRAM.

High Performance Flexible Supercapacitor Based on Single Precursor Derived NiFe2O4 Spinel with Tailored Cationic Distribution and Oxygen Vacancies in Acidic Medium

AbstractSpinel metal oxides are extensively studied for supercapacitors (SCs) in alkaline electrolytes, where charge storage capacity is limited by surface site availability due to surface reconstruction forming metal hydroxides/oxyhydroxides. The use of an acidic medium, which can boost the charge storage capacity of spinel oxides offering an additional channel of intercalation‐deintercalation of protons, is underexplored. Moreover, the impact of chemical compositions and the cationic distributions is crucial on the electrocatalysis performance of spinel oxides, however, such a correlation is first time reported for charge storage properties of spinel ferrite NiFe2O4 nanoparticles (NFO NPs). Besides, a low‐cost and scalable synthesis of NFO NPs involving the thermal decomposition of Ni‐Fe glycolate, followed by controlled air‐calcination is reported. Thus crafted NFO NPs‐based device shows impressive specific capacitance (2112 F g−1 at 10 A g−1) in half‐cell configuration. A flexible all‐solid‐state asymmetric device (full‐cell) configuration depicts impressive energy density (20.7 Wh kg−1), power density (4000 W kg−1), gravimetric capacitance (140 F g−1 at 2 A g−1), and retention of its performance (≈75% after 10,000 charging/discharging cycles). The results depict a new insight toward the tuning of electronic and charge storage properties in NFO, which otherwise are predominately attributed to only the crystallite size and morphological effects.

Junctionless Structure Indium-Tin Oxide Thin-Film Transistors Enabling Enhanced Mechanical and Contact Stability.

In recent years, considerable attention has focused on high-performance and flexible crystalline metal oxide thin-film transistors (TFTs). However, achieving both high performance and flexibility in semiconductor devices is challenging due to the inherently conductive and brittle nature of crystalline metal oxide. In this study, we propose a facile way to overcome this limitation by employing a junctionless (JL) TFT structure via oxygen plasma treatment of the crystalline indium-tin oxide (ITO) films. The oxygen plasma treatment significantly reduced oxygen vacancies in the ITO films, contributing to the significant reduction in the carrier concentration from 4.67 × 1020 to 1.39 × 1016. Importantly, this reduction was achieved without inducing any noticeable structural changes in the ITO, enabling the successful realization of ITO JL TFTs with an adjustable threshold voltage. Furthermore, the ITO JL TFTs demonstrate good stability and reliability under various bias stress conditions, aging in the air atmosphere, and high-temperature processes. In addition, the ITO JL TFTs exhibit low light sensitivity due to the wide bandgap of ITO and further suppression of Vo defects, making them suitable for applications requiring stable performance under light exposure. To compare and analyze the flexibility of the JL structure and conventional structure with additional source/drain (S/D) junction in ITO TFTs with nonencapsulation, we utilized mechanical simulations and transmission line method (TLM). By employing the JL structure in ITO TFT through carefully optimized oxygen plasma treatment, we successfully mitigated stress concentration at the S/D-channel interface. This resulted in a JL ITO TFT that exhibited a change in contact resistance of less than 20% even after 20,000 bending cycles. Consequently, a stable and flexible ITO TFT with field-effect mobility (μFE) of 12.74 cm2/(V s) was realized, outperforming conventionally structured ITO TFTs with additional S/D junction, where the contact resistance nearly tripled.

Efficient hydrogen production via hydrolysis of NaBH4 by the Co/Co3O4–Cu2O–ZnO catalyst prepared using mixed metal oxides as support material

Efficient hydrogen production via hydrolysis of NaBH4 by the Co/Co3O4–Cu2O–ZnO catalyst prepared using mixed metal oxides as support material

Transport Properties in GaN Metal–Oxide–Semiconductor Field‐Effect Transistor Almost Free of Interface Traps with AlSiO/AlN/p‐Type GaN Gate Stack

The factors limiting channel mobility in AlSiO/p‐type GaN metal–oxide–semiconductor (MOS) field‐effect transistors are examined by performing Hall‐effect measurements in conjunction with a gate bias, with and without a thin AlN interlayer. In the absence of this interlayer, the free carrier concentration associated with the Hall effect is significantly reduced compared with the net gate charge density estimated from capacitance–voltage data, indicating that electrons are trapped to a significant extent at the MOS interface. These interface traps are found to have an energy ≈20 meV above the Fermi level in strong inversion based on temperature‐dependent Hall effect data. The insertion of a 0.8 nm‐thick AlN interlayer eliminates charge trapping such that almost all gate charges are mobile. The mobility components could be divided into types based on their effect on the effective electric field perpendicular to the channel. Coulomb scattering centers resulting from interface states are evidently reduced by inserting the AlN interlayer, which also enhances the channel mobility to over 150 cm2 V−1s−1.

Durability of metal oxide nanostructures synthesized by hot water treatment

AbstractMetal oxide nanostructures (MONSTRs) have become popular in various fields. This study investigates the durability of MONSTRs synthesized through hot water treatment (HWT) using copper, aluminum, and zinc as the source metals of choice. The physical durability tests include pressure, scratch, and scotch tape adhesion tests, and chemical durability tests such as corrosion resistance tests, heat resistance, and solar exposure tests. Results showed that MONSTRs synthesized from HWT are highly durable under the tested conditions except for NaOH and HCl immersion tests for copper oxide and zinc oxide. The study concluded that HWT is a sustainable synthesis method for MONSTRs. Graphical Abstract

Catalytic properties of trivalent rare-earth oxides with intrinsic surface oxygen vacancy

Oxygen vacancy (Ov) is an anionic defect widely existed in metal oxide lattice, as exemplified by CeO2, TiO2, and ZnO. As Ov can modify the band structure of solid, it improves the physicochemical properties such as the semiconducting performance and catalytic behaviours. We report here a new type of Ov as an intrinsic part of a perfect crystalline surface. Such non-defect Ov stems from the irregular hexagonal sawtooth-shaped structure in the (111) plane of trivalent rare earth oxides (RE2O3). The materials with such intrinsic Ov structure exhibit excellent performance in ammonia decomposition reaction with surface Ru active sites. Extremely high H2 formation rate has been achieved at ~1 wt% of Ru loading over Sm2O3, Y2O3 and Gd2O3 surface, which is 1.5–20 times higher than reported values in the literature. The discovery of intrinsic Ov suggests great potentials of applying RE oxides in heterogeneous catalysis and surface chemistry.

Reverse Hydrogen Spillover on Metal Oxides for Water-Promoted Catalytic Oxidation Reactions.

Understanding the water-involved mechanism on metal oxide surface and the dynamic interaction of water with active sites is crucial in solving water poisoning in catalytic reactions. Herein, this work solves this problem by designing the water-promoted function of metal oxides in the ethanol oxidation reaction. In situ multimodal spectroscopies unveil that the competitive adsorption of water-dissociated *OH species with O2 at Sn active sites results in water poisoning and the sluggish proton transfer in CoO-SnO2 imparts water-resistant effect. Carbon material as electron donor and proton transport channel optimizes the Co active sites and expedites the reverse hydrogen spillover from CoO to SnO2. The water-promoted function arises from spillover protons facilitating O2 activation on the SnO2 surface, leading to crucial *OOH intermediate formation for catalyzing C-H and C-C cleavage. Consequently, the tailored CoO-C-SnO2 showcases a remarkable 60-fold enhancement in ethanol oxidation reaction compared to bare SnO2 under high-humidity conditions.

Carbon Dioxide Capture by Niobium Polyoxometalate Fragmentation.

High oxidation state metal cations in the form of oxides, oxoanions, or oxoperoxoanions have diverse roles in carbon dioxide removal (direct air capture and point source). Features include providing basic oxygens for chemisorption reactions, direct binding of carbonate, and catalyzing low-temperature CO2 release to regenerate capture media. Moreover, metal oxides and aqueous metal-oxo species are stable in harsh, point-source conditions. Here, we demonstrate aqueous niobium polyoxometalate (POM) carbon capture ability, specifically [Nb6O19]8-, Nb6. Upon exposure of aqueous Nb6 to CO2, Nb6 fragments and binds chemisorbed carbonate, evidenced by crystallization of Nb-carbonate POMs including [Nb22O53(CO3)16]28-and [Nb10O25(CO3)6]12-. While Rb/Cs+ counter cations yield crystal structures to understand the chemisorption processes, K+ counter cations enable higher capture efficiency (based on CO3/Nb ratio), determined by CHN analysis and thermogravimetry-mass spectrometry of the isolated solids. Sum frequency generation spectroscopy also showed higher carbon capture efficiency of the K-Nb6 solutions at the air-water interface, while small-angle X-ray scattering (SAXS) provided insights into the role of the alkalis in influencing these processes. Tetramethylammonium counter cations, like K+, demonstrate high efficiency of carbonate chemisorption at the interface, but SAXS and Raman of the bulk showed a predominance of a Nb24-POM (HxNb24O72, x ∼ 9) that does not bind carbonate. Control experiments show that carbonate detected at the interface is Nb-bound, and the Nb-carbonate species are stabilized by alkalis, demonstrating their supporting role in aqueous Nb-POM CO2 chemisorption. Of fundamental importance, this study presents rare examples of directing POM speciation with a gas, instead of liquid phase acid or base.

Three-dimensional integrated metal-oxide transistors

AbstractThe monolithic three-dimensional vertical integration of thin-film transistor (TFT) technologies could be used to create high-density, energy-efficient and low-cost integrated circuits. However, the development of scalable processes for integrating three-dimensional TFT devices is challenging. Here, we report the monolithic three-dimensional integration of indium oxide (In2O3) TFTs on a silicon/silicon dioxide (Si/SiO2) substrate at room temperature. We use an approach that is compatible with complementary metal–oxide–semiconductor (CMOS) processes to stack ten n-channel In2O3 TFTs. Different architectures—including bottom-, top- and dual-gate TFTs—can be fabricated at different layers in the stack. Our dual-gate devices exhibit enhanced electrical performance with a maximum field-effect mobility of 15 cm2 V−1 s−1, a subthreshold swing of 0.4 V dec−1 and a current on/off ratio of 108. By monolithically integrating dual-gate In2O3 TFTs at different locations in the stack, we created unipolar invertor circuits with a signal gain of around 50 and wide noise margins. The dual-gate devices also allow fine-tuning of the invertors to achieve symmetric voltage-transfer characteristics and optimal noise margins.

Recovery of valuable metal elements from spent lithium-ion battery via a low temperature ammonium persulfate roasting approach

A low-cost and eco-friendly recycling method is crucial for recovering valuable elements from end-of-life lithium-ion batteries (LIBs), which plays a vital role in addressing resource scarcity and reducing the environmental impact. This study aims to develop a low-temperature pyro-metallurgical combined process to recycle spent LiNi0.5Co0.2Mn0.3O2 (NCM523). Unlike traditional pyrometallurgy methods that generate liquid alloys and slags at temperatures exceeding 1000 °C, the (NH4)2S2O8 roasting approach operates at 350 °C and converts NCM523 to water-soluble sulfates, exhibiting remarkable leaching efficiencies of Li, Ni, Co, and Mn, with values of 99.43 %, 99.87 %, 98.88 %, and 99.19 %, respectively. Systematic studies were conducted to investigate the influence of roasting temperature, (NH4)2S2O8-to-NCM mass ratio, and roasting time on the sulfation process. Furthermore, the mechanism of sulfation reaction was identified by combining experiments with thermodynamic calculation. At temperatures above 160 °C, (NH4)2S2O8 decomposes into (NH4)2S2O7, which reacts with NCM. Lithium in a layered structure forms Li2SO4, while transition elements form MnSO4, Li2Co (SO4)2, and NiSO4. At around 350 °C, (NH4)2S2O8 further decomposes into NH4HSO4, releasing SO2 and NH3. SO2 reacts with remaining NCM or unsulfated transition metal oxides, converting them into MnSO4, Li2Co (SO4)2, and NiSO4. Above 800 °C, the metal sulfates decompose into stable oxides. This study presents a low-temperature sulfation method that effectively disintegrates the crystal structure of lithium metal oxides without the need for acids or reducing agents.

Fabrication of NiO-CuO/RGO Composite for Lithium Storage Property

The lithium storage performance of binary transition metal oxide/graphene composites as anode materials has been attracting more interest from researchers, based on the fact that binary transition metal oxides and graphene are expected to create a synergistic effect and exhibit improved lithium storage characteristics. In this work, a NiO-CuO/reduced graphene oxide composite (NiO-CuO/RGO) was prepared by an ultrasonic agitation process. When the NiO-CuO/RGO is applied to the anode material for lithium-ion batteries (LIBs), the batteries display high discharge capacities (at 730 mA h/g after 100 cycles at 100 mA/g), high-rate performance (311 mA h/g with 5000 mA/g), and excellent stable cyclability (375 mA h/g within 2000 mA/g after 400 cycles). Such results indicate that the combination of NiO-CuO and RGO leads to enhanced lithium storage performance, for the RGO sheets inhibit the large volume change of binary NiO-CuO and enhance the fast transport of both lithium ions and electrons during the repeated lithium cycling processes.