Artificial Synapse Based on a δ-FAPbI3/Atomic-Layer-Deposited SnO2 Bilayer Memristor.

Halide perovskite-based resistive switching memory (memristor) has potential in an artificial synapse. However, an abrupt switch behavior observed for a formamidinium lead triiodide (FAPbI3)-based memristor is undesirable for an artificial synapse. Here, we report on the δ-FAPbI3/atomic-layer-deposited (ALD)-SnO2 bilayer memristor for gradual analogue resistive switching. In comparison to a single-layer δ-FAPbI3 memristor, the heterojunction δ-FAPbI3/ALD-SnO2 bilayer effectively reduces the current level in the high-resistance state. The analog resistive switching characteristics of δ-FAPbI3/ALD-SnO2 demonstrate exceptional linearity and potentiation/depression performance, resembling an artificial synapse for neuromorphic computing. The nonlinearity of long-term potentiation and long-term depression is notably decreased from 12.26 to 0.60 and from -8.79 to -3.47, respectively. Moreover, the δ-FAPbI3/ALD-SnO2 bilayer achieves a recognition rate of ≤94.04% based on the modified National Institute of Standards and Technology database (MNIST), establishing its potential in an efficient artificial synapse.

Substantially Accelerated Response and Recovery in Pd-Decorated WO3 Nanorods Gasochromic Hydrogen Sensor.

The development of hydrogen (H2) gas sensors is essential for the safe and efficient adoption of H2 gas as a clean, renewable energy source in the challenges against climate change, given its flammability and associated safety risks. Among various H2 sensors, gasochromic sensors have attracted great interest due to their highly intuitive and low power operation, but slow kinetics, especially slow recovery rate limited its further practical application. This study introduces Pd-decorated amorphous WO3 nanorods (Pd-WO3 NRs) as an innovative gasochromic H2 sensor, demonstrating rapid and highly reversible color changes for H2 detection. In specific, the amorphous nanostructure exhibits notable porosity, enabling rapid detection and recovery by facilitating effective H2 gas interaction and efficient diffusion of hydrogen ions (H+) dissociated from the Pd nanoparticles (Pd NPs). The optimized Pd-WO3 NRs sensor achieves an impressive response time of 14 s and a recovery time of 1 s to 5% H2. The impressively fast recovery time of 1 s is observed under a wide range of H2 concentrations (0.2-5%), making this study a fundamental solution to the challenged slow recovery of gasochromic H2 sensors.

Recent Advances in Electrochemical, Photochemical, and Photoelectrochemical Reduction of CO2 to C2+ Products.

Environmental problems such as global warming are one of the most prominent global challenges. Researchers are investigating various methods for decreasing CO2 emissions. The CO2 reduction reaction via electrochemical, photochemical, and photoelectrochemical processes has been a popular research topic because the energy it requires can be sourced from renewable sources. The CO2 reduction reaction converts stable CO2 molecules into useful products such as CO, CH4 , C2 H4 , and C2 H5 OH. To obtain economic benefits from these products, it is important to convert them into hydrocarbons above C2 . Numerous investigations have demonstrated the uniqueness of the CC coupling reaction of Cu-based catalysts for the conversion of CO2 into useful hydrocarbons above C2 for electrocatalysis. Herein, the principle of semiconductors for photocatalysis is briefly introduced, followed by a description of the obstacles for C2+ production. This review presents an overview of the mechanism of hydrocarbon formation above C2 , along with advances in the improvement, direction, and comprehension of the CO2 reduction reaction via electrochemical, photochemical, and photoelectrochemical processes.

Ambient Stable All Inorganic CsCu2I3 Artificial Synapses for Neurocomputing.

In resistive switching memories or artificial synaptic devices, halide perovskites have attracted attention for their unusual features such as rapid ion migration, adjustable composition, and facile synthesis. Herein, the environmentally friendly and highly air stable CsCu2I3 perovskite films are used as the active layer in the Au/CsCu2I3/ITO/glass artificial synapses. The device shows variable synaptic plasticities such as long-term and short-term synaptic plasticity, paired-pulse facilitation, and spike-timing-dependent plasticity by combining potentiation and depression along the formation of conductive filaments. The performances of the devices are maintained for 160 days under ambient conditions. Additionally, the accuracy evaluation of the CsCu2I3-based artificial synapses performs exceptionally well with the MNIST and Fashion MNIST data sets, demonstrating high learning accuracy in deep neural networks. Using the novel B-site engineered halide perovskite material with extreme air stability, this study paves the way for artificial synaptic devices for next-generation in-memory hardware.

Visible Light Driven Ultrasensitive and Selective NO2 Detection in Tin Oxide Nanoparticles with Sulfur Doping Assisted by l-Cysteine.

In the pandemic era, the development of high-performance indoor air quality monitoring sensors has become more critical than ever. NO2 is one of the most toxic gases in daily life, which induces severe respiratory diseases. Thus, the real-time monitoring of low concentrations of NO2 is highly required. Herein, a visible light-driven ultrasensitive and selective chemoresistive NO2 sensor is presented based on sulfur-doped SnO2 nanoparticles. Sulfur-doped SnO2 nanoparticles are synthesized by incorporating l-cysteine as a sulfur doping agent, which also increases the surface area. The cationic and anionic doping of sulfur induces the formation of intermediate states in the band gap, highly contributing to the substantial enhancement of gas sensing performance under visible light illumination. Extraordinary gas sensing performances such as the gas response of 418 to 5 ppm of NO2 and a detection limit of 0.9 ppt are achieved under blue light illumination. Even under red light illumination, sulfur-doped SnO2 nanoparticles exhibit stable gas sensing. The endurance to humidity and long-term stability of the sensor are outstanding, which amplify the capability as an indoor air quality monitoring sensor. Overall, this study suggests an innovative strategy for developing the next generation of electronic noses.

Surface-Tailored Medium Entropy Alloys as Radically Low Overpotential Oxygen Evolution Electrocatalysts.

Numerous studies have explored new materials for electrocatalysts, but it is difficult to discover materials that surpass the catalytic activity of current commercially available noble metal electrocatalysts. In contrast to conventional transition metal alloys, high-entropy alloys (HEAs) have immense potential to maximize their catalytic properties because of their high stability and compositional diversity as oxygen evolution reactions (OERs). This work presents medium-entropy alloys (MEAs) as OER electrocatalysts to simultaneously satisfy the requirement of high catalytic activity and long-term stability. The surface of MEA electrocatalyst is tailored to suit the OER via anodizing and cyclic voltammetry activation methods. Optimized electrical properties and hydrophilicity of the surface enable an extremely low overpotential of 187 mV for achieving the current density of 10 mA cm-2 alkaline media. Furthermore, a combined photovoltaic-electrochemical system with MEA electrocatalyst and a perovskite/Si tandem solar cell exhibits a solar-to-hydrogen conversion efficiency of 20.6% for an unassisted hydrogen generation system. These results present a new pathway for designing sustainable high efficiency water splitting cells.

Emerging Two-Dimensional-Based Nanostructured Catalysts: Applications in Sustainable Organic Transformations.

The extension of green and sustainable materials in the preparation of heterogeneous catalysts for organic transformations has increased over the past few decades. Because of their unique and intriguing physical and chemical properties, two-dimensional (2D) nanostructured materials have attracted widespread attention and have been used in a variety of applications, such as catalysis, electronics, and energy storage. A promising pathway to enhance the performance of 2D nanomaterials is their coupling with other functional materials to form heterogeneous or hybrid structures. Herein, we discuss the use of 2D-based nanostructured catalysts for enhancing organic transformations and highlight selected examples to demonstrate the synthesis, advantages, challenges, efficiency, and reusability of the introduced heterogeneous catalysts for cross-coupling and reduction reactions.

Development of Organic/Inorganic Hybrid Materials for Fully Degradable Reactive Oxygen Species-Releasing Stents for Antirestenosis.

Despite innovative advances in stent technology, restenosis remains a crucial issue for the clinical implantation of stents. Reactive oxygen species (ROS) are known to potentially accelerate re-endothelialization and lower the risk of restenosis by selectively controlling endothelial cells and smooth muscle cells. Recently, several studies have been conducted to develop biodegradable polymeric stents. As biodegradable polymers are not electrically conductive, double metallic layers are required to constitute a galvanic couple for ROS generation. Here, we report a new biodegradable hybrid material composed of a biodegradable polymer substrate and double anodic/cathodic metallic layers for enhancing re-endothelialization and suppressing restenosis. Pure Zn and Mg films (3 µm thick) were deposited onto poly-l-lactic acid (PLLA) substrates by DC magnetron sputtering, and a long-term immersion test using biodegradable hybrid materials was performed in phosphate-buffered solution (PBS) for 2 weeks. The concentrations of superoxide anions and hydrogen peroxide generated by the corrosion of biodegradable metallic films were monitored every 1 or 2 days. Both superoxide anions and hydrogen peroxide were seamlessly generated even after the complete consumption of the anodic Mg layer. It was confirmed that the superoxide anions and hydrogen peroxide were formed not only by the galvanic corrosion between the anode and cathode layers but also by the corrosion of a single Mg or Zn layer. The corrosion products of the Mg and Zn films in PBS were phosphate, oxide, or chloride of the biodegradable metals. Thus, it is concluded that ROS generation by the corrosion of PLLA-based hybrid materials can be sustained until the exhaustion of the cathode metal layer.

Magnetite Metal-Organic Frameworks: Applications in Environmental Remediation of Heavy Metals, Organic Contaminants, and Other Pollutants.

Due to the increasing environmental pollution caused by human activities, environmental remediation has become an important subject for humans and environmental safety. The quest for beneficial pathways to remove organic and inorganic contaminants has been the theme of considerable investigations in the past decade. The easy and quick separation made magnetic solid-phase extraction (MSPE) a popular method for the removal of different pollutants from the environment. Metal-organic frameworks (MOFs) are a class of porous materials best known for their ultrahigh porosity. Moreover, these materials can be easily modified with useful ligands and form various composites with varying characteristics, thus rendering them an ideal candidate as adsorbing agents for MSPE. Herein, research on MSPE, encompassing MOFs as sorbents and Fe3O4 as a magnetic component, is surveyed for environmental applications. Initially, assorted pollutants and their threats to human and environmental safety are introduced with a brief introduction to MOFs and MSPE. Subsequently, the deployment of magnetic MOFs (MMOFs) as sorbents for the removal of various organic and inorganic pollutants from the environment is deliberated, encompassing the outlooks and perspectives of this field.

Enhanced Spin Seebeck Thermopower in Pt/Holey MoS2/Y3Fe5O12 Hybrid Structure.

We first observed the spin-to-charge conversion due to both the inverse Rashba-Edelstein effect (IREE) and inverse spin-Hall effect in a holey multilayer molybdenum disulfide (MoS2) intermediate layer in a Pt/YIG structure via LSSE measurements under nonequilibrium magnetization. We found an enhancement of approximately 238%, 307%, and 290% in the longitudinal spin Seebeck effect (LSSE) voltage, spin-to-charge current, and thermoelectric (TE) power factor, respectively, compared with the monolayer MoS2 interlayer in a Pt/YIG structure. Such an enhancement in the LSSE performance of Pt/holey MoS2/YIG can be explained by the improvement of spin accumulation in the Pt layer by induced spin fluctuation as well as increased additional spin-to-charge conversion due to in-plane IREE. Our findings represent a significant achievement in the understanding of spin transport in atomically thin MoS2 interlayers and pave the way toward large-area TE energy-harvesting devices in two-dimensional transition metal dichalcogenide materials.

Boosting Unassisted Alkaline Solar Water Splitting Using Silicon Photocathode with TiO2 Nanorods Decorated by Edge-Rich MoS2 Nanoplates.

To construct a highly efficient photoelectrochemical tandem device with silicon photocathode operating in alkaline conditions, it is desirable to develop stable and active catalysts which enable the photocathode to reliably perform under an alkaline environment. With nanostructured passivation layer and edge-exposed transition metal disulfides, silicon photocathode provides new opportunities for achieving unbiased alkaline solar water splitting. Here, the TiO2 nanorod arrays decorated by edge-rich MoS2 nanoplates are elaborately synthesized and deposited on p-Si. The vertically aligned TiO2 nanorods fully stabilize the Si surface and improve anti-reflectance. Moreover, MoS2 nanoplates with exposed edge sites provide catalytically active regions resulting in the kinetically favored hydrogen evolution under an alkaline environment. Interfacial energy band bending between p-Si and catalyst layers facilitates the transport of photogenerated electrons under steady-state illumination. Consequently, the MoS2 nanoplates/TiO2 nanorods/p-Si photocathode exhibits significantly improved photoelectrochemical-hydrogen evolution reaction (PEC-HER) performance in alkaline media with a high photocurrent density of 10 mA cm-2 at 0 V versus RHE and high stability. By integrating rationally designed photocathode with earth-abundant Fe60 (NiCo)30 Cr10 anode and perovskite/Si tandem photovoltaic cell, an unassisted alkaline solar water splitting is accomplished with a current density of 5.4 mA cm-2 corresponding to 6.6% solar-to-hydrogen efficiency, which is the highest among p-Si photocathodes.

Enhanced Oxygen Evolution Electrocatalysis in Strained A-Site Cation Deficient LaNiO3 Perovskite Thin Films.

As the BO6 octahedral structure in perovskite oxide is strongly linked with electronic behavior, it is actively studied for various fields such as metal-insulator transition, superconductivity, and so on. However, the research about the relationship between water-splitting activity and BO6 structure is largely lacking. Here, we report the oxygen evolution reaction (OER) of LaNiO3 (LNO) by changing the NiO6 structure using compositional change and strain. The 5 atom % La deficiency in LNO resulted in an increase of the Ni-O-Ni bond angle and an expansion of bandwidth, enhancing the charge transfer ability. In-plane compressive strain derives the higher dz2 orbital occupancy, leading to suitable metal-oxygen bond strength for OER. Because of the synergistic effect of A-site deficiency and compressive strain, the overpotential (η) of compressively strained L0.95NO film is reduced to 130 mV at j = 30 µA/cm2 compared with nonstrained LNO (η = 280 mV), indicating a significant enhancement in OER.

Lead-Free Dual-Phase Halide Perovskites for Preconditioned Conducting-Bridge Memory.

Organometallic and all-inorganic halide perovskites (HPs) have recently emerged as promising candidate materials for resistive switching (RS) nonvolatile memory due to their current-voltage hysteresis caused by fast ion migration. Lead-free and all-inorganic HPs have been researched for non-toxic and environmentally friendly RS memory devices. However, only HP-based devices with electrochemically active top electrode (TE) exhibit ultra-low operating voltages and high on/off ratio RS properties. The active TE easily reacts to halide ions in HP films, and the devices have a low device durability. Herein, RS memory devices based on an air-stable lead-free all-inorganic dual-phase HP (AgBi2 I7 -Cs3 Bi2 I9 ) are successfully fabricated with inert metal electrodes. The devices with Au TE show filamentary RS behavior by conducting-bridge involving Ag cations in HPs with ultra-low operating voltages (<0.15 V), high on/off ratio (>107 ), multilevel data storage, and long retention times (>5 × 104 s). The use of a closed-loop pulse switching method improves reversible RS properties up to 103 cycles with high on/off ratio above 106 . With an extremely small bending radius of 1 mm, the devices are operable with reasonable RS characteristics. This work provides a promising material strategy for lead-free all-inorganic HP-based nonvolatile memory devices for practical applications.

Recent Advances in the Aptamer-Based Electrochemical Biosensors for Detecting Aflatoxin B1 and Its Pertinent Metabolite Aflatoxin M1.

The notable toxicological impacts of aflatoxin B1 (AFB1) and its main metabolite, aflatoxin M1 (AFM1), on human being health make the evaluation of food quality highly significant. Due to the toxicity of those metabolites-even very low content in foodstuffs-it is crucial to design a sensitive and reliable procedure for their detection. Electrochemical aptamer-based biosensors are considered the most encouraging option, based on multi-placed analysis, rapid response, high sensitivity and specificity. The present review specifically emphasizes the potential utilization of the electrochemical aptasensors for determining the AFM1 and AFB1 with different electrodes.

Recent Advances in Electrochemical Sensors and Biosensors for Detecting Bisphenol A.

In recent years, several studies have focused on environmental pollutants. Bisphenol A (BPA) is one prominent industrial raw material, and its extensive utilization and release into the environment constitute an environmental hazard. BPA is considered as to be an endocrine disruptor which mimics hormones, and has a direct relationship to the development and growth of animal and human reproductive systems. Moreover, intensive exposure to the compound is related to prostate and breast cancer, infertility, obesity, and diabetes. Hence, accurate and reliable determination techniques are crucial for preventing human exposure to BPA. Experts in the field have published general electrochemical procedures for detecting BPA. The present timely review critically evaluates diverse chemically modified electrodes using various substances that have been reported in numerous studies in the recent decade for use in electrochemical sensors and biosensors to detect BPA. Additionally, the essential contributions of these substances for the design of electrochemical sensors are presented. It has been predicted that chemically modified electrode-based sensing systems will be possible options for the monitoring of detrimental pollutants.

Tailoring of Interfacial Band Offsets by an Atomically Thin Polar Insulating Layer To Enhance the Water-Splitting Performance of Oxide Heterojunction Photoanodes.

An important factor in the performance of photoelectrochemical water splitting is the band edge alignment of the photoelectrodes for efficient transport and transfer of photogenerated carriers. Many studies for improving charge transfer ability between the electrode and the electrolyte have been reported, while research to improve charge transfer at the interface of the photoactive semiconductor and the conducting substrate is largely lacking. Here, we demonstrate that the water-splitting performance of an oxide heterostructured photoelectrode can be increased 6-fold by inserting an atomically thin polar LaAlO3 interlayer compared with that of an oxide heterostructure without an insertion to modify interfacial band offsets. The electrically lowered Schottky barrier is driven by the atomically thin layer, and the charge transfer resistance between the oxides is reduced by up to 2 orders of magnitude upon insertion of LaAlO3, a wide-gap (5.6 eV) insulator. We show that the critical thickness of the polar layer for enhancing the charge transfer is 3 unit cells. The dipole moment from the polar sheets of LaAlO3 introduces an internal electric field, which modifies the effective band offsets in the device. This work serves as a proof of concept that photoelectrochemical performance can be improved by manipulating the band offsets of the heterostructure interface, suggesting a new design strategy for heterostructured water-splitting photoelectrodes.

Ionic-Activated Chemiresistive Gas Sensors for Room-Temperature Operation.

The development of high performance gas sensors that operate at room temperature has attracted considerable attention. Unfortunately, the conventional mechanism of chemiresistive sensors is restricted at room temperature by insufficient reaction energy with target molecules. Herein, novel strategy for room temperature gas sensors is reported using an ionic-activated sensing mechanism. The investigation reveals that a hydroxide layer is developed by the applied voltages on the SnO2 surface in the presence of humidity, leading to increased electrical conductivity. Surprisingly, the experimental results indicate ideal sensing behavior at room temperature for NO2 detection with sub-parts-per-trillion (132.3 ppt) detection and fast recovery (25.7 s) to 5 ppm NO2 under humid conditions. The ionic-activated sensing mechanism is proposed as a cascade process involving the formation of ionic conduction, reaction with a target gas, and demonstrates the novelty of the approach. It is believed that the results presented will open new pathways as a promising method for room temperature gas sensors.

Identification of an Actual Strain-Induced Effect on Fast Ion Conduction in a Thin-Film Electrolyte.

Strain-induced fast ion conduction has been a research area of interest for nanoscale energy conversion and storage systems. However, because of significant discrepancies in the interpretation of strain effects, there remains a lack of understanding of how fast ionic transport can be achieved by strain effects and how strain can be controlled in a nanoscale system. In this study, we investigated strain effects on the ionic conductivity of Gd0.2Ce0.8O1.9-δ (100) thin films under well controlled experimental conditions, in which errors due to the external environment could not intervene during the conductivity measurement. In order to avoid any interference from perpendicular-to-surface defects, such as grain boundaries, the ionic conductivity was measured in the out-of-plane direction by electrochemical impedance spectroscopy analysis. With varying film thickness, we found that a thicker film has a lower activation energy of ionic conduction. In addition, careful strain analysis using both reciprocal space mapping and strain mapping in transmission electron microscopy shows that a thicker film has a higher tensile strain than a thinner film. Furthermore, the tensile strain of thicker film was mostly developed near a grain boundary, which indicates that intrinsic strain is dominant rather than epitaxial or thermal strain during thin-film deposition and growth via the Volmer-Weber (island) growth mode.

Facile synthesis of CsPbBr3/PbSe composite clusters.

In this work, CsPbBr3 and PbSe nanocomposites were synthesized to protect perovskite material from self-enlargement during reaction. UV absorption and photoluminescence (PL) spectra indicate that the addition of Se into CsPbBr3 quantum dots modified the electronic structure of CsPbBr3, increasing the band gap from 2.38 to 2.48 eV as the Cs:Se ratio increased to 1:3. Thus, the emission color of CsPbBr3 perovskite quantum dots was modified from green to blue by increasing the Se ratio in composites. According to X-ray diffraction patterns, the structure of CsPbBr3 quantum dots changed from cubic to orthorhombic due to the introduction of PbSe at the surface. Transmission electron microscopy and X-ray photoemission spectroscopy confirmed that the atomic distribution in CsPbBr3/PbSe composite clusters is uniform and the composite materials were well formed. The PL intensity of a CsPbBr3/PbSe sample with a 1:1 Cs:Se ratio maintained 50% of its initial intensity after keeping the sample for 81 h in air, while the PL intensity of CsPbBr3 reduced to 20% of its initial intensity. Therefore, it is considered that low amounts of Se could improve the stability of CsPbBr3 quantum dots.

Dominance of Plasmonic Resonant Energy Transfer over Direct Electron Transfer in Substantially Enhanced Water Oxidation Activity of BiVO4 by Shape-Controlled Au Nanoparticles.

The performance of plasmonic Au nanostructure/metal oxide heterointerface shows great promise in enhancing photoactivity, due to its ability to confine light to the small volume inside the semiconductor and modify the interfacial electronic band structure. While the shape control of Au nanoparticles (NPs) is crucial for moderate bandgap semiconductors, because plasmonic resonance by interband excitations overlaps above the absorption edge of semiconductors, its critical role in water splitting is still not fully understood. Here, first, the plasmonic effects of shape-controlled Au NPs on bismuth vanadate (BiVO4 ) are studied, and a largely enhanced photoactivity of BiVO4 is reported by introducing the octahedral Au NPs. The octahedral Au NP/BiVO4 achieves 2.4 mA cm-2 at the 1.23 V versus reversible hydrogen electrode, which is the threefold enhancement compared to BiVO4 . It is the highest value among the previously reported plasmonic Au NPs/BiVO4 . Improved photoactivity is attributed to the localized surface plasmon resonance; direct electron transfer (DET), plasmonic resonant energy transfer (PRET). The PRET can be stressed over DET when considering the moderate bandgap semiconductor. Enhanced water oxidation induced by the shape-controlled Au NPs is applicable to moderate semiconductors, and shows a systematic study to explore new efficient plasmonic solar water splitting cells.