Pre-Anodized Graphite Pencil Electrode Coated with a Poly(Thionine) Film for Simultaneous Sensing of 3-Nitrophenol and 4-Nitrophenol in Environmental Water Samples.

A very simple, as well as sensitive and selective, sensing protocol was developed on a pre-anodized graphite pencil electrode surface coated using poly(thionine) (APGE/PTH). The poly(thionine) coated graphite pencil was then used for simultaneous sensing of 3-nitrophenol (3-NP) and 4-nitrophenol (4-NP). The poly(thionine) coated electrode exhibited an enhanced electrocatalytic property towards nitrophenol (3-NP and 4-NP) reduction. Redox peak potential and current of both nitrophenols were found well resolved and their simultaneous analysis was studied. Under optimized experimental conditions, APGE/PTH showed a long linear concentration range from 20 to 230 nM and 15 nM to 280 nM with a calculated limit of detection (LOD) of 4.5 and 4 nM and a sensitivity of 22.45 µA/nM and 27.12 µA/nM for 3-NP and 4-NP, respectively. Real sample analysis using the prepared sensor was tested with different environmental water samples and the sensors exhibited excellent recovery results in the range from 98.16 to 103.43%. Finally, the sensor exposed an promising selectivity, stability, and reproducibility towards sensing of 3-NP and 4-NP.

Superconducting Sr2RuO4 Thin Films without Out-of-Phase Boundaries by Higher-Order Ruddlesden-Popper Intergrowth.

Ruddlesden-Popper (RP) phases (An+1BnO3n+1, n = 1, 2,···) have attracted intensive research with diverse functionalities for device applications. However, the realization of a high-quality RP-phase film is hindered by the formation of out-of-phase boundaries (OPBs) that occur at terrace edges, originating from lattice mismatch in the c-axis direction with the A'B'O3 (n = ∞) substrate. Here, using strontium ruthenate RP-phase Sr2RuO4 (n = 1) as a model system, an experimental approach for suppressing OPBs was developed. By tuning the growth parameters, the Sr3Ru2O7 (n = 2) phase was formed in a controlled manner near the film-substrate interface. This higher-order RP-phase then blocked the subsequent formation of OPBs, resulting in nearly defect-free Sr2RuO4 layer at the upper region of the film. Consequently, the Sr2RuO4 thin films exhibited superconductivity up to 1.15 K, which is the highest among Sr2RuO4 films grown by pulsed laser deposition. This work paves the way for synthesizing pristine RP-phase heterostructures and exploring their unique physical properties.

A Robust Nonprecious CuFe Composite as a Highly Efficient Bifunctional Catalyst for Overall Electrochemical Water Splitting.

To generate hydrogen, which is a clean energy carrier, a combination of electrolysis and renewable energy sources is desirable. In particular, for both the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in electrolysis, it is necessary to develop nonprecious, efficient, and durable catalysts. A robust nonprecious copper-iron (CuFe) bimetallic composite is reported that can be used as a highly efficient bifunctional catalyst for overall water splitting in an alkaline medium. The catalyst exhibits outstanding OER and HER activity, and very low OER and HER overpotentials (218 and 158 mV, respectively) are necessary to attain a current density of 10 mA cm-2 . When used in a two-electrode water electrolyzer system for overall water splitting, it not only achieves high durability (even at a very high current density of 100 mA cm-2 ) but also reduces the potential required to split water into oxygen and hydrogen at 10 mA cm-2 to 1.64 V for 100 h of continuous operation.

Self-Assembled Nanostructured CuCo2 O4 for Electrochemical Energy Storage and the Oxygen Evolution Reaction via Morphology Engineering.

CuCo2 O4 films with different morphologies of either mesoporous nanosheets, cubic, compact-granular, or agglomerated embossing structures are fabricated via a hydrothermal growth technique using various solvents, and their bifunctional activities, electrochemical energy storage and oxygen evolution reaction (OER) for water splitting catalysis in strong alkaline KOH media, are investigated. It is observed that the solvents play an important role in setting the surface morphology and size of the crystallites by controlling nucleation and growth rate. An optimized mesoporous CuCo2 O4 nanosheet electrode shows a high specific capacitance of 1658 F g-1 at 1 A g-1 with excellent restoring capability of ≈99% at 2 A g-1 and superior energy density of 132.64 Wh kg-1 at a power density of 0.72 kW kg-1 . The CuCo2 O4 electrode also exhibits excellent endurance performance with capacity retention of 90% and coulombic efficiency of ≈99% after 5000 charge/discharge cycles. The best OER activity is obtained from the CuCo2 O4 nanosheet sample with the lowest overpotential of ≈290 mV at 20 mA cm-2 and a Tafel slope of 117 mV dec-1 . The superior bifunctional electrochemical activity of the mesoporous CuCo2 O4 nanosheet is a result of electrochemically favorable 2D morphology, which leads to the formation of a very large electrochemically active surface area.

Two-Dimensional Layered Hydroxide Nanoporous Nanohybrids Pillared with Zero-Dimensional Polyoxovanadate Nanoclusters for Enhanced Water Oxidation Catalysis.

The oxygen-evolution reaction (OER) is critical in electrochemical water splitting and requires an efficient, sustainable, and cheap catalyst for successful practical applications. A common development strategy for OER catalysts is to search for facile routes for the synthesis of new catalytic materials with optimized chemical compositions and structures. Here, nickel hydroxide Ni(OH)2 2D nanosheets pillared with 0D polyoxovanadate (POV) nanoclusters as an OER catalyst that can operate in alkaline media are reported. The intercalation of POV nanoclusters into Ni(OH)2 induces the formation of a nanoporous layer-by-layer stacking architecture of 2D Ni(OH)2 nanosheets and 0D POV with a tunable chemical composition. The nanohybrid catalysts remarkably enhance the OER activity of pristine Ni(OH)2 . The present findings demonstrate that the intercalation of 0D POV nanoclusters into Ni(OH)2 is effective for improving water oxidation catalysis and represents a potential method to synthesize novel, porous hydroxide-based nanohybrid materials with superior electrochemical activities.

Strain-Mediated Interlayer Coupling Effects on the Excitonic Behaviors in an Epitaxially Grown MoS2/WS2 van der Waals Heterobilayer.

van der Waals heterostructures composed of two different monolayer crystals have recently attracted attention as a powerful and versatile platform for studying fundamental physics, as well as having great potential in future functional devices because of the diversity in the band alignments and the unique interlayer coupling that occurs at the heterojunction interface. However, despite these attractive features, a fundamental understanding of the underlying physics accounting for the effect of interlayer coupling on the interactions between electrons, photons, and phonons in the stacked heterobilayer is still lacking. Here, we demonstrate a detailed analysis of the strain-dependent excitonic behavior of an epitaxially grown MoS2/WS2 vertical heterostructure under uniaxial tensile and compressive strain that enables the interlayer interactions to be modulated along with the electronic band structure. We find that the strain-modulated interlayer coupling directly affects the characteristic combined vibrational and excitonic properties of each monolayer in the heterobilayer. It is further revealed that the relative photoluminescence intensity ratio of WS2 to MoS2 in our heterobilayer increases monotonically with tensile strain and decreases with compressive strain. We attribute the strain-dependent emission behavior of the heterobilayer to the modulation of the band structure for each monolayer, which is dictated by the alterations in the band gap transitions. These findings present an important pathway toward designing heterostructures and flexible devices.

Formation and magnetic properties of InFeP:Ag nanorods fabricated with noble metal Ag using an ion milling method.

The formation, including the density and height of the InFeP:Ag nanorods doped with noble metal Ag using an ion milling method, was preponderantly determined from transmission electron microscopy and x-ray diffraction analyses. We investigate, in particular, the enhanced ferromagnetism of the well-aligned InFeP:Ag nanorods. Auger electron spectroscopy and x-ray photoelectron spectroscopy measurements were carried out in order to investigate the incorporation of Ag and to verify the local chemical bonding of the InFeP:Ag nanorods. The variation of FWHM for the double-crystal x-ray rocking curve and triple-axis diffraction peaks demonstrates that noble metal Ag is incorporated into the InFeP:Ag nanorods. The noticeable ferromagnetic signature (M-H curve) of the InFeP:Ag nanorods is observed and T c persists up to almost 350 K (3.9 × 10-4 emu g-1), as determined by temperature-dependence magnetization (M-T curve) measurements. This study suggests that the InFeP:Ag nanorods should be a potential candidate for the application of spintronic devices.

Surface-Effect-Induced Optical Bandgap Shrinkage in GaN Nanotubes.

We investigate nontrivial surface effects on the optical properties of self-assembled crystalline GaN nanotubes grown on Si substrates. The excitonic emission is observed to redshift by ∼100 meV with respect to that of bulk GaN. We find that the conduction band edge is mainly dominated by surface atoms, and that a larger number of surface atoms for the tube is likely to increase the bandwidth, thus reducing the optical bandgap. The experimental findings can have important impacts in the understanding of the role of surfaces in nanostructured semiconductors with an enhanced surface/volume ratio.

2D van der Waals Heterostructure with Tellurene Floating-Gate for Wide Range and Multi-Bit Optoelectronic Memory.

Intensive research on optoelectronic memory (OEM) devices based on two-dimensional (2D) van der Waals heterostructures (vdWhs) is being conducted due to their distinctive advantages for electrical-optical writing and multilevel storage. These features make OEM a promising candidate for the logic of reconfigurable operations. However, the realization of nonvolatile OEM with broadband absorption (from visible to infrared) and a high switching ratio remains challenging. Herein, we report a nonvolatile OEM based on a heterostructure consisting of rhenium disulfide (ReS2), hexagonal boron nitride (hBN) and tellurene (2D Te). The 2D Te-based floating-gate (FG) device exhibits excellent performance metrics, including a high switching on/off ratio (∼106), significant endurance (>1000 cycles) and impressive retention (>104 s). In addition, the narrow band gap of 2D Te endows the device with broadband optical programmability from the visible to near-infrared regions at room temperature. Moreover, by applying different gate voltages, light wavelengths, and laser powers, multiple bits can be successfully generated. Additionally, the device is specifically designed to enable reconfigurable inverter logic circuits (including AND and OR gates) through controlled electrical and optical inputs. These significant findings demonstrate that the 2D vdWhs with a 2D Te FG are a valuable approach in the development of high-performance OEM devices.

Accelerating glucose electrolysis on Cu-doped MIL-88B for an energy efficient anodic reaction in water splitting.

This work reports a promising and sustainable method for valorization of abundantly available biomass feedstocks to overcome the thermodynamic high energy barrier of the OER via glucose electrolysis as a proxy anodic reaction, thereby driving the energy-efficient water splitting for green hydrogen generation. For this, a robust and efficient MIL-88B(Fe) based electrocatalyst is engineered via Cu doping. The ultrasonically prepared Cu-doped@ MIL-88B ink when drop-cast on nickel foam (NF) produces thin nano-porous 2D-sheet like films having a thickness of ca. 300 nm and demonstrates an excellent glucose oxidation reaction (GOR) with a lower potential of 1.35 V versus RHE at 10 mA cm-2. In addition, this electrode shows outstanding long-term electrochemical durability for 50 h and exhibits the maximum GOR current load of 350 mA cm-2 at 1.48 V vs. RHE, while the pristine MIL-88B based electrode exhibits a current load of only 180 mA cm-2 at the same potential bias. The remarkably higher current density after doping indicates an accelerated GOR, which is ascribed to the electronic structure modulation of the Fe nodes by Cu, thereby enhancing the active sites and charge transport characteristics of the frameworks. Most importantly, the MOF-based electrodes demonstrate the occurrence of the GOR prior to the OER at a large potential difference, hence assisting the energy-efficient water splitting for green hydrogen production.

Highly durable and sustainable copper-iron-tin-sulphide (Cu2FeSnS4) anode for Li-ion batteries: effect of operating temperatures.

Operating temperatures considerably influence the energy storage mechanism of the anode of Li-ion batteries (LiBs). This effect must be comprehensively studied to facilitate the effective integration of LiBs in practical applications and battery management. In this study, we fabricated a novel anode material, i.e., copper-iron-tin-sulphide (Cu2FeSnS4, CFTS), and investigated the corresponding LiB performance at operating temperatures ranging from 10 °C to 55 °C. The CFTS anode exhibited a discharge capacity of 283.1 mA h g-1 at room temperature (25 °C), which stabilized to 174.0 mA h g-1 in repeated cycles tested at a current density of 0.1 A g-1. The discharge capacity at higher operating temperatures, such as 40 °C and 55 °C, is found to be 209.3 and 230.0 mA h g-1 respectively. In contrast, the discharge capacity decreased to 36.2 mA h g-1 when the temperature decreased to 10 °C. Electrothermal impedance spectroscopy was performed to determine the rate of chemical reactions, mobility of active species, and change in internal resistance at different operating temperatures. In terms of the cycle life, CFTS exhibited outstanding cycling stability for more than 500 charge/discharge cycles, with a 146% capacity retention and more than 80% coulombic efficiency. The electrochemical investigation revealed that the charge storage in the CFTS anode is attributable to capacitive-type and diffusion-controlled mechanisms.

Metal-ion doping in metal-organic-frameworks: modulating the electronic structure and local coordination for enhanced oxygen evolution reaction activity.

The doping of metal-organic frameworks (MOFs) with metal-ions has emerged as a powerful strategy for enhancing their catalytic performance. Doping allows for the tailoring of the electronic structure and local coordination environment of MOFs, thus imparting on them unique properties and enhanced functionalities. This frontier article discusses the impact of metal-ion doping on the electronic structure and local coordination of MOFs, highlighting the effects on their electrocatalytic properties in relation to the oxygen evolution reaction (OER). The fundamental mechanisms underlying these modifications are explored, while recent advances, challenges, and prospects in the field are discussed. In addition, experimental techniques that can be applied to tackle the realization of effective metal-ion doping of MOFs are also noted briefly.

Mechanochemically interlocked cubane copper complex interface for WOLED.

In the rapid development of organic light-emitting diodes (OLEDs), phosphorescent transition metal complexes have played a crucial role as the most promising candidates for next generation display and lighting applications. However, most devices are fabricated using iridium and platinum-based complexes which are expensive and available in very limited quantities, whereas using relatively abundant organometallic complexes for fabrication results mostly in inefficient performance results. To overcome these issues, we have synthesized tetra copper iodide with tetra triphenyl cage like structure (denoted as CIPh) as an emerging class of luminescent material by mechanochemical grinding followed by thermal treatment for application in white OLED. The CIPh complex exhibits considerable quantum yield and a millisecond decay lifetime. Phosphorescent OLEDs were fabricated using CIPh complex as emitter shows a remarkable performance with external quantum efficiency and current efficiency of 5.28 % and 22.76 cd/A, with a high brightness of 4200 cd m-2, respectively. White OLEDs were also fabricated with a fluorescent blue and phosphorescent red emitted with (CIPh) as green emitter and achieved an impressive CRI of 82 with an EQE of over 3 %. This is the first ever attempt at fabricating WOLEDs using organocopper complex.

Precursor silanization assisted synthesis and optical tuning of dual-phase perovskite nanocrystals embedded in silica matrix with high environmental stability.

Ligand-assisted re-precipitation (LARP) is one of the most practicing techniques for synthesizing colloidal nanocrystals (NCs). But due to its fast reaction kinetics, it offers limited synthesis control. In the present study, we report a novel, precursor silanization-based room temperature technique unveiling slow crystallization of Cs4PbBr6/CsPbBr3 dual-phase nanocrystals (DPNCs) protected with a dense silica cloud-like matrix. Unlike conventional LARP, we can observe the tuneable optical bandgap of the DPNCs as a function of reaction time because of the slow reaction kinetics. The as-synthesized DPNCs exhibit a high photoluminescence quantum yield (PLQY) of 76% with ultrahigh stability while retaining âˆ¼ 100% of their initial PLQY in an ambient environment with a relative humidity of 55% for more than 1 year. DPNCs demonstrates ambient photostability of 560 h, and water stability of 25 days. This interesting precursor silanization technique developed here can be extended for the synthesis of other nanomaterials.

Tunning the Zeolitic Imidazole Framework (ZIF8) through the Wet Chemical Route for the Hydrogen Evolution Reaction.

Utilizing zeolitic imidazolate frameworks (ZIFs) poses a significant challenge that demands a facile synthesis method to produce uniform and nanometer-scale materials with high surface areas while achieving high yields. Herein, we demonstrate a facile and cost-effective strategy to systematically produce ZIF8 nanocrystals. Typically, ZIF8 nanocrystal synthesis involves a wet chemical route. As the reaction time decreased (150, 120, and 90 min), the size of the ZIF8 crystals decreased with uniform morphology, and productivity reached as high as 89%. The composition of the product was confirmed through XRD, FE-SEM, TEM, EDS, and Raman spectroscopy. The ZIF8 synthesized with different reaction time was finally employed for catalyzing the electrochemical hydrogen evaluation reaction (HER). The optimized ZIF8-3 obtained at 90 min of reaction time exhibited a superior catalytic action on the HER in alkaline medium, along with a remarkably long-term stability for 24 h compared with the other ZIF8 nanocrystals obtained at different reaction times. Specifically, the optimized ZIF8-3 sample revealed an HER overpotential of 172 mV and a Tafel slope of 104.15 mV·dec-1. This finding, thus, demonstrates ZIF8 as a promising electrocatalyst for the production of high-value-added green and sustainable hydrogen energy.

Nitrogen-Doped CuO@CuS Core-Shell Structure for Highly Efficient Catalytic OER Application.

Water electrolysis is a highly efficient route to produce ideally clean H2 fuel with excellent energy conversion efficiency and high gravimetric energy density, without producing carbon traces, unlike steam methane reforming, and it resolves the issues of environmental contamination via replacing the conventional fossil fuel. Particular importance lies in the advancement of highly effective non-precious catalysts for the oxygen evolution reaction (OER). The electrocatalytic activity of an active catalyst mainly depends on the material conductivity, accessible catalytically active sites, and intrinsic OER reaction kinetics, which can be tuned via introducing N heteroatoms in the catalyst structure. Herein, the efficacious nitrogenation of CuS was accomplished, synthesized using a hydrothermal procedure, and characterized for its electrocatalytic activity towards OER. The nitrogen-doped CuO@CuS (N,CuO@CuS) electrocatalyst exhibited superior OER activity compared to pristine CuS (268 and 602 mV), achieving a low overpotential of 240 and 392 mV at a current density of 10 and 100 mA/cm2, respectively, ascribed to the favorable electronic structural modification triggered by nitrogen incorporation. The N,CuO@CuS also exhibits excellent endurance under varied current rates and a static potential response over 25 h with stability measured at 10 and 100 mA/cm2.

1-D arrays of porous Mn0.21Co2.79O4 nanoneedles with an enhanced electrocatalytic activity toward the oxygen evolution reaction.

Developing effective electrocatalysts for the oxygen evolution reaction (OER) that are highly efficient, abundantly available, inexpensive, and environmentally friendly is critical to improving the overall efficiency of water splitting and the large-scale development of water splitting technologies. We, herein, introduce a facile synthetic strategy for depositing the self-supported arrays of 1D-porous nanoneedles of a manganese cobalt oxide (Mn0.21Co2.79O4: MCO) thin film demonstrating an enhanced electrocatalytic activity for OER in an alkaline electrolyte. For this, an MCO film was synthesized via thermal treatment of a hydroxycarbonate film obtained from a hydrothermal route. The deposited films were characterized through scanning electron microscopy (SEM), X-ray diffractometry (XRD), energy dispersive X-ray analysis (EDX), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). In contrast to a similar 1D-array of a pristine Co3O4 (CO) nanoneedle film, the MCO film exhibits a remarkably enhanced electrocatalytic performance in the OER with an 85 mV lower overpotential for the benchmark current density of 10 mA cm-2. In addition, the MCO film also demonstrates long-term electrochemical stability for the OER in 1.0 M KOH aqueous electrolyte.

Cu@Fe-Redox Capacitive-Based Metal-Organic Framework Film for a High-Performance Supercapacitor Electrode.

A metal-organic framework (MOF) is a highly porous material with abundant redox capacitive sites for intercalation/de-intercalation of charges and, hence, is considered promising for electrode materials in supercapacitors. In addition, dopants can introduce defects and alter the electronic structure of the MOF, which can affect its surface reactivity and electrochemical properties. Herein, we report a copper-doped iron-based MOF (Cu@Fe-MOF/NF) thin film obtained via a simple drop-cast route on a 3D-nickel foam (NF) substrate for the supercapacitor application. The as-deposited Cu@Fe-MOF/NF electrodes exhibit a unique micro-sized bipyramidal structure composited with nanoparticles, revealing a high specific capacitance of 420.54 F g-1 at 3 A g-1 which is twice compared to the nano-cuboidal Fe-MOF/NF (210 F g-1). Furthermore, the asymmetric solid-state (ASSSC) supercapacitor device, derived from the assembly of Cu@Fe-MOF/NFǁrGO/NF electrodes, demonstrates superior performance in terms of energy density (44.20 Wh.kg-1) and electrochemical charge-discharge cycling durability with 88% capacitance retention after 5000 cycles. This work, thus, demonstrates a high potentiality of the Cu@Fe-MOF/NF film electrodes in electrochemical energy-storing devices.

Electrochemical Investigations of Double Perovskite M2NiMnO6 (Where M = Eu, Gd, Tb) for High-Performance Oxygen Evolution Reaction.

Double perovskites are known for their special structures which can be utilized as catalyst electrode materials for electrochemical water splitting to generate carbon-neutral hydrogen energy. In this work, we prepared lanthanide series metal-doped double perovskites at the M site such as M2NiMnO6 (where M = Eu, Gd, Tb) using the solid-state reaction method, and they were investigated for an oxygen evolution reaction (OER) study in an alkaline medium. It is revealed that the catalyst with a configuration of Tb2NiMnO6 has outstanding OER properties such as a low overpotential of 288 mV to achieve a current density of 10 mAcm-2, a lower Tafel slope of 38.76 mVdec-1, and a long cycling stability over 100 h of continuous operation. A-site doping causes an alteration in the oxidation or valence states of the NiMn cations, their porosity, and the oxygen vacancies. This is evidenced in terms of the Mn4+/Mn3+ ratio modifying electronic properties and the surface which facilitates the OER properties of the catalyst. This is discussed using electrochemical impedance spectroscopy (EIS) and electrochemical surface area (ECSA) of the catalysts. The proposed work is promising for the synthesis and utilization of future catalyst electrodes for high-performance electrochemical water splitting.

Nanoflake NiMn Layered Double Hydroxide Coated on Porous Membrane-like Ni-Foam for Sustainable and Efficient Electrocatalytic Oxygen Evolution.

Layered double hydroxides (LDHs) have gained vast importance as an electrocatalyst for water electrolysis to produce carbon-neutral and clean hydrogen energy. In this work, we demonstrated the fabrication of nano-flake-like NiMn LDH thin film electrodes onto porous membrane-like Ni-foam by using a simple and cost-effective electrodeposition method for oxygen evolution reaction (OER). Various Ni1-xMnx LDH (where x = 0.15, 0.25, 0.35, 0.50 and 0.75) thin film electrodes are utilized to achieve the optimal catalyst for an efficient and sustainable OER process. The various composition-dependent surface morphologies and porous-membrane-like structure provided the high electrochemical surface area along with abundant active sites facilitating the OER. The optimized catalyst referred to as Ni0.65Mn0.35 showed excellent OER properties with an ultralow overpotential of 253 mV at a current density of 50 mAcm-2, which outperforms other state-of-the art catalysts reported in the literature. The relatively low Tafel slope of 130 mV dec-1 indicates faster and more favorable reaction kinetics for OER. Moreover, Ni0.65Mn0.35 exhibits excellent durability over continuous operation of 20 h, indicating the great sustainability of the catalyst in an alkaline medium. This study provides knowledge for the fabrication and optimization of the OER catalyst electrode for water electrolysis.