Lewis acidic Fe3+-driven catalytic active Ni3+ formation in Fe-free metal-organic framework for enhanced electrochemical glucose sensing.

Manipulating metal valence states and porosity in the metal-organic framework (MOF) by alloying has been a unique tool for creating high-valent metal sites and pore environments in a structure that are inaccessible by other methods, favorable for accelerating the catalytic activity towards sensing applications. Herein, we report Fe3+-driven formation of catalytic active Ni3+ species in the amine-crafted benzene-dicarboxylate (BDC-NH2)-based MOF as a high-performance electrocatalyst for glucose sensing. This work took the benefit of different bonding stability between BDC-NH2 ligand, and Fe3+ and Ni2+ metal precursor ions in the heterometallic NixFe(1-x)-BDC-NH2 MOF. The FeCl3 that interacts weakly with ligand, oxidizes the Ni2+ precursor to Ni3+-based MOF owing to its Lewis acidic behavior and was subsequently removed from the structure supported by Ni atoms, during solvothermal synthesis. This enables to create mesopores within a highly stable Ni-MOF structure with optimal feed composition of Ni0.7Fe0.3-BDC-NH2. The Ni3+-based Ni0.7Fe0.3-BDC-NH2 demonstrates superior catalytic properties towards glucose sensing with a high sensitivity of 13,435 µA mM-1 cm-2 compared to the parent Ni2+-based Ni-BDC-NH2 (10897 µA mM-1cm-2), along with low detection limit (0.9 µM), short response time (≤5 s), excellent selectivity, and higher stability. This presented approach for fabricating high-valent nickel species, with a controlled quantity of Fe3+ integrated into the structure allowing pore engineering of MOFs, opens new avenues for designing high-performing MOF catalysts with porous framework for sensing applications.

Larvicidal and anti-termite activities of microbial biosurfactant produced by Enterobacter cloacae SJ2 isolated from marine sponge Clathria sp.

The widespread use of synthetic pesticides has resulted in a number of issues, including a rise in insecticide-resistant organisms, environmental degradation, and a hazard to human health. As a result, new microbial derived insecticides that are safe for human health and the environment are urgently needed. In this study, rhamnolipid biosurfactants produced from Enterobacter cloacae SJ2 was used to evaluate the toxicity towards mosquito larvae (Culex quinquefasciatus) and termites (Odontotermes obesus). Results showed dose dependent mortality rate was observed between the treatments. The 48 h LC50 (median lethal concentration) values of the biosurfactant were determined for termite and mosquito larvae following the non-linear regression curve fit method. Results showed larvicidal activity and anti-termite activity of biosurfactants with 48 h LC50 value (95% confidence interval) of 26.49 mg/L (25.40 to 27.57) and 33.43 mg/L (31.09 to 35.68), respectively. According to a histopathological investigation, the biosurfactant treatment caused substantial tissue damage in cellular organelles of larvae and termites. The findings of this study suggest that the microbial biosurfactant produced by E. cloacae SJ2 is an excellent and potentially effective agent for controlling Cx. quinquefasciatus and O. obesus.

Atypical performance of CoO-accelerated interface tweaking in hierarchical cobalt phosphide/oxide@P-doped rGO heterostructures for hybrid supercapacitors.

Designing two-dimensional (2D) heterostructures based on suitable energy materials is a promising strategy to achieve high-performance supercapacitors with hybridized transition metal and carbonaceous-based electrodes. The influence of each component and its content on the capacitor performance necessitates deeper insights. In this study, a 2D/2D heterostructure made of hierarchical pseudocapacitive cobalt phosphide/oxide and P-doped reduced graphene oxide (PrGO) nanosheets (CoP/CoO@PrGO) was fabricated using porous zeolitic-imidazolate framework precursor. The decoration of 2D leaf-like CoP/CoO hybrid onto PrGO could create a unique interface with a large number of active sites, CoO-driven creation of pseudocapacitive surface POx species, and high P content (∼3 at.%) in PrGO, thus promoting the Faradaic reaction, electrical conductivity, and overall charge storage. This framework yields a high specific capacitance of 405 F g-1 at 5 A g-1 and excellent cycling stability (over 100 % after 10,000 cycles), superior to those of pristine CoP@PrGO (300 F g-1 at 5 A g-1). Furthermore, the fabricated asymmetric supercapacitor delivers reasonable energy density of 4.2 Wh kg-1 at a power density of 785 W kg-1 and cycling stability of âˆ¼100 % after 10,000 cycles. Therefore, CoP/CoO@PrGO with its unique interfacial properties can promote the development of heterostructure electrode for high-performance supercapacitors.

Influence of bioaugmentation in crude oil contaminated soil by Pseudomonas species on the removal of total petroleum hydrocarbon.

This study aimed to carry out the bioaugmentation of crude oil/motor oil contaminated soil. The mixture of novel strains Pseudomonas aeruginosa PP3 and Pseudomonas aeruginosa PP4 were used in this bioaugmentation studies. The four different bioaugmentation systems (BS 1-4) were carried out in this experiment labelled as BS 1 (Crude oil contaminated soil), BS 2 (BS 1 + bacterial consortia), BS 3 (Motor oil sludge contaminated soil), and BS 4 (BS 3 + bacterial consortia). The total petroleum hydrocarbon (TPH) was investigated for monitor the effectiveness of bioaugmentation process. The highest TPH removal rate was recorded on BS 4 (9091 mg Kg -1) was about 67% followed by 52% on BS 2 (8584 mg Kg -1) respectively. The percentage of biodegradation efficiency (BE) of residual crude and motor oil contaminated soil were evaluated by GCMS analysis and the results showed that 65% (BS 2) and 83% (BS 4) respectively. Further the bioaugmented soil was subjected to the plant cultivation (Lablab purpureus) and the results revealed that the L. purpureus was rapidly grown in the systems BS 4 and BS 2 than the system BS 1 and BS 2 which was due to the lesser biodegradation of the crude oil contents. In resultant, it can be concluded that the soil was suitable for the cultivation of plant. Overall, this study revealed that the selected bacterial consortia were effectively degraded the hydrocarbon and act as a potential bioremediator in the hydrocarbon polluted soil in a short period.

A Complementary Co-Ni Phosphide/Bimetallic Alloy-Interspersed N-Doped Graphene Electrocatalyst for Overall Alkaline Water Splitting.

Echinops-like bimetallic CoNiP-CoNi alloy is synthesized from a metal-organic framework (MOF) and serves as an efficient catalyst for the oxygen evolution reaction (OER), with a low overpotential of 300 mV in 1 M KOH at 10 mA cm-2 (η10 ). The cooperative effect of Ni and Co metal, as well as the interfacial properties of the integrated semiconducting phosphide/metallic alloy and electronic conductivity of the MOF-derived carbon regulate the performance of the catalyst. Moreover, the bimetallic CoNiP/CoNi alloy catalyst is interspersed with N-doped graphene, forming a triad catalyst that demonstrates superior activity towards the hydrogen evolution reaction (η10 =150 mV) and excellent durability, owing to interfacial effects of the triad catalyst, large electrochemical active surface area, and enhanced conductivity from N-doped graphene. The stability of the carbon-containing catalyst during OER (oxidation) is altered by the high reactivity of heteroatom dopant. The assembled CoNiP/CoNi/N-RGO||CoNiP/CoNi water electrolyzer delivers a reasonable cell potential of 1.76 V at 10 mA cm-2 . The synthesized bimetallic CoNiP/CoNi alloy-based triad catalyst thus demonstrates excellent electrocatalytic activity and high durability suitable for efficient alkaline water splitting.

Composition engineering of ZIF-derived cobalt phosphide/cobalt monoxide heterostructures for high-performance asymmetric supercapacitors.

The fabrication of interpenetrated heterostructures from desirable energy materials for the development of efficient supercapacitors is promising yet challenging. Herein, a leaf-shaped cobalt phosphide/cobalt oxide heterostructure, (CoPx)1-y/CoOy (0.44 > y > 0.06), was synthesized from 2D-zeolitic-imidazolate-framework (ZIF-Co-L) molecular precursor via phosphidation of the Co3O4 intermediate. The efficient construction of heterostructure through the variation of surface/bulk composition significantly alters the interfacial properties and electronic structure, yielding enhanced supercapacitor performance. Further, gas-phase phosphidation entails a core-shell formation mechanism via gas diffusion, regulated by the Kirkendall effect. The optimized heterostructure (y = 0.10) exhibits remarkable interfacial properties derived from the CoO/Co0/CoP interface, thus facilitating a high specific capacitance (467 F g-1 at 5 A g-1) and excellent cycling stability (~91% after 10000 cycles) at 30 A g-1. A further increase in the cyclability (~107%) was achieved by employing a graphene hybrid. Further, an asymmetric supercapacitor device was fabricated, that delivers reasonably high energy density of 12.7 Wh kg-1 at a power density of 370 W kg-1 and cycling stability of ~93% after 10000 cycles. This study reports on the modulation of interfacial properties of CoPx/CoO heterostructure to enhance energy storage performance via bulk/surface compositional variation, thereby providing a strategy to develop heterostructure electrodes for high-performance supercapacitor.

Scanty graphene-driven phase control and heteroatom functionalization of ZIF-67-derived CoP-draped N-doped carbon/graphene as a hybrid electrode for high-performance asymmetric supercapacitor.

Zeolitic imidazolate framework (ZIF)-derived materials have been explored as promising electrode for energy storage, owing to their tunable composition, high porous structure, and heteroatom-based active sites. Herein, we report cobalt phosphide-draped N-doped carbon/graphene hybrid (CoP-NPC/GS) synthesized from ZIF-67 precursor via a single-step in-situ carbonization and phosphidation. The CoP-NPC/GS hybrid performed as a promising positive electrode with superior electrochemical performance - high capacitance (165 F g-1 at 7 A g-1 compared to 97 F g-1 for CoP-NPC), enhanced rate capability, and promoted cycling stability (~88% after 10,000 cycles). Excellent performance of the CoP-NPC/GS was derived from scanty graphene (2 wt%)-driven compositional variation, which promotes the redox-active CoP phase and higher nitrogen content offering enhanced electronic conductivity. Besides, CoP-NPC/GS performed well as a negative electrode, derived from double-layer capacitance of porous carbon, realizing a capacitance of ~71 F g-1 at 1 A g-1 but inferior to CoP-NPC, which was regulated by pyridinic nitrogen-induced pseudocapacitance. A fabricated CoP-NPC/GS||CoP-NPC asymmetric device displayed an energy density of 10 Wh Kg-1 at 700 W kg-1, with excellent cyclability (~100%) till 11,000 cycles. This study clarifies the role of scanty graphene on the phase control and heteroatom functionalization of phosphide-based electrode, beneficial for enhanced supercapacitive performance.

Publisher Correction: Probing molecule-like isolated octahedra via phase stabilization of zero-dimensional cesium lead halide nanocrystals.

The original version of this Article contained an error in the title, which incorrectly read 'Probing molecule-like isolated octahedra via-phase stabilization of zero-dimensional cesium lead halide nanocrystals.' The correct version states 'via phase stabilization' in place of 'via-phase stabilization'. This has been corrected in both the PDF and HTML versions of the Article.

Probing molecule-like isolated octahedra via-phase stabilization of zero-dimensional cesium lead halide nanocrystals.

Zero-dimensional (0D) inorganic perovskites have recently emerged as an interesting class of material owing to their intrinsic Pb2+ emission, polaron formation, and large exciton binding energy. They have a unique quantum-confined structure, originating from the complete isolation of octahedra exhibiting single-molecule behavior. Herein, we probe the optical behavior of single-molecule-like isolated octahedra in 0D Cesium lead halide (Cs4PbX6, X = Cl, Br/Cl, Br) nanocrystals through isovalent manganese doping at lead sites. The incorporation of manganese induced phase stabilization of 0D Cs4PbX6 over CsPbX3 by lowering the symmetry of PbX6 via enhanced octahedral distortion. This approach enables the synthesis of CsPbX3 free Cs4PbX6 nanocrystals. A high photoluminescence quantum yield for manganese emission was obtained in colloidal (29%) and solid (21%, powder) forms. These performances can be attributed to structure-induced confinement effects, which enhance the energy transfer from localized host exciton states to Mn2+ dopant within the isolated octahedra.

A Phosphosilicate Compound, NaCa3PSiO8: Structure Solution and Luminescence Properties.

NaCa3PSiO8 was synthesized in a microwave-assisted solid-state reaction. The crystal structure of the synthesized compound was solved using a least-squares method, followed by simulated annealing. The compound was crystallized in the orthorhombic space group Pna21, belonging to Laue class mmm. The structure consisted of two layers of cation planes, each of which contained three cation channels. The cation channels in each of the layers ran antiparallel to that of the adjacent layer. All the major cations together constituted four distinct crystallographic sites. The Rietveld refinement of the powder X-ray diffraction data, followed by the maximum-entropy method analysis, confirmed the obtained structure solutions. The electronic band structure of the compound was analyzed through density function theory calculations. Luminescence properties of the compound, upon activating with Eu2+ ions, were analyzed through photoluminescence measurements and decay profile analysis. The compound was found to exhibit green luminescence centered at ∼502 nm, with a typical broadband emission due to the transition from the crystal-field split 4f65d to 4f7 levels.

Colloidal Organolead Halide Perovskite with a High Mn Solubility Limit: A Step Toward Pb-Free Luminescent Quantum Dots.

Organolead halide perovskites have emerged as a promising optoelectronic material for lighting due to its high quantum yield, color-tunable, and narrow emission. Despite their unique properties, toxicity has intensified the search for ecofriendly alternatives through partial or complete replacement of lead. Herein, we report a room-temperature synthesized Mn2+-substituted 3D-organolead perovskite displacing ∼90% of lead, simultaneously retaining its unique excitonic emission, with an additional orange emission of Mn2+ via energy transfer. A high Mn solubility limit of 90% was attained for the first time in lead halide perovskites, facilitated by the flexible organic cation (CH3NH3)+ network, preserving the perovskite structure. The emission intensities of the exciton and Mn were influenced by the halide identity that regulates the energy transfer to Mn. Homogeneous emission and electron spin resonance characteristics of Mn2+ indicate a uniform distribution of Mn. These results suggest that low-toxicity 3D-CH3NH3Pb1-xMnxBr3-(2x+1)Cl2x+1 nanocrystals may be exploited as magnetically doped quantum dots with unique optoelectronic properties.

Engineering the Lattice Site Occupancy of Apatite-Structure Phosphors for Effective Broad-Band Emission through Cation Pairing.

A series of britholite compounds were synthesized by simultaneous introduction of trivalent La3+ and Si4+ ions into an apatite structure. The variations in the average structure, electronic band structure, and microstructural properties resulting from the introduction of cation pairs were analyzed as a function of their concentration. The effects of the structural variance and microstructural properties on the broad-band-emitting activator ions were studied by introducing Eu2+ ions as activators. For the resulting compound, which had dual emission bands in the blue and yellow regions of the spectrum, the emission peak position and strength were dependent upon the concentration of La3+-Si4+ pairs. By engineering the relative sizes of the two possible activator sites in the structure, 4f and 6h, through the introduction of a combination of trivalent La3+ and a polyanion, the preferential site occupancy of the activator ions was favorably altered. Additionally, the activator ions responsible for the lower-Stokes-shifted blue component of the emission functioned as a sensitizer of the larger-Stokes-shifted yellow-emitting activators, and predominantly yellow-emitting phosphors were achieved. The feasibility of developing a white light-emitting solid-state device using the developed phosphor was also demonstrated.

High-performance spinel-rich Li1.5MnTiO4+δ ultralong nanofibers as cathode materials for Li-ion batteries.

Recently, composite materials based on Li-Mn-Ti-O system were developed to target low cost and environmentally benign cathodes for Li-ion batteries. The spinel-layered Li1.5MnTiO4+δ bulk particles showed excellent cycle stability but poor rate performance. To address this drawback, ultralong nanofibers of a Li1.5MnTiO4+δ spinel-layered heterostructure were synthesized by electrospinning. Uniform nanofibers with diameters of about 80 nm were formed of tiny octahedral particles wrapped together into 30 µm long fibers. The Li1.5MnTiO4+δ nanofibers exhibited an improved rate capability compared to both Li1.5MnTiO4+δ nanoparticles and bulk particles. The uniform one-dimensional nanostructure of the composite cathode exhibited enhanced capacities of 235 and 170 mAh g-1 at C/5 and 1 C rates, respectively. Its unique structure provided a large effective contact area for Li+ diffusion, and low charge transfer resistance. Moreover, the layered phase contributed to its capacity in over 3 V region, which increased specific energy (726 Wh kg-1) compared to the bulk particles (534 Wh kg-1).

A zero-thermal-quenching phosphor.

Phosphor-converted white light-emitting diodes (pc-WLEDs) are efficient light sources used in lighting, high-tech displays, and electronic devices. One of the most significant challenges of pc-WLEDs is the thermal quenching, in which the phosphor suffers from emission loss with increasing temperature during high-power LED operation. Here, we report a blue-emitting Na3-2xSc2(PO4)3:xEu2+ phosphor (λem = 453 nm) that does not exhibit thermal quenching even up to 200 °C. This phenomenon of zero thermal quenching originates from the ability of the phosphor to compensate the emission losses and therefore sustain the luminescence with increasing temperature. The findings are explained by polymorphic modification and possible energy transfer from electron-hole pairs at the thermally activated defect levels to the Eu2+ 5d-band with increasing temperature. Our results could initiate the exploration of phosphors with zero thermal quenching for high-power LED applications.

Hydrophobic Organic Skin as a Protective Shield for Moisture-Sensitive Phosphor-Based Optoelectronic Devices.

A moisture-stable, red-emitting fluoride phosphor with an organic hydrophobic skin is reported. A simple strategy was employed to form a metal-free, organic, passivating skin using oleic acid (OA) as a hydrophobic encapsulant via solvothermal treatment. Unlike other phosphor coatings that suffer from initial efficiency loss, the OA-passivated K2SiF6:Mn4+ (KSF-OA) phosphor exhibited the unique property of stable emission efficiency. Control of thickness and a highly transparent passivating layer helped to retain the emission efficiency of the material after encapsulation. A moisture-stable KSF-OA phosphor could be synthesized because of the exceptionally hydrophobic nature of OA and the formation of hydrogen bonds (F···H) resulting from the strong interactions between the fluorine in KSF and hydrogen in OA. The KSF-OA phosphor exhibited excellent moisture stability and maintained 85% of its emission intensity even after 450 h at high temperature (85 °C) and humidity (85%). As a proof-of-concept, this strategy was used for another moisture-sensitive SrSi2O2N2:Eu2+ phosphor which showed enhanced moisture stability, retaining 85% of emission intensity after 500 h under the same conditions. White light-emitting devices were fabricated using surface-passivated KSF and Y3Al5O12:Ce3+ which exhibited excellent color rendering index of 86, under blue LED excitation.

Influence of Ti(4+) on the electrochemical performance of Li-rich layered oxides - high power and long cycle life of Li2Ru1-xTixO3 cathodes.

Li-rich layered oxides are the most attractive cathodes for lithium-ion batteries due to their high capacity (>250 mAh g(-1)). However, their application in electric vehicles is hampered by low power density and poor cycle life. To address these, layered Li2Ru0.75Ti0.25O3 (LRTO) was synthesized and the influence of electroinactive Ti(4+) on the electrochemical performance of Li2RuO3 was investigated. LRTO exhibited a reversible capacity of 240 mAh g(-1) under 14.3 mA g(-1) with 0.11 mol of Li loss after 100 cycles compared to 0.22 mol of Li for Li2Ru0.75Sn0.25O3. More Li(+) can be extracted from LRTO (0.96 mol of Li) even after 250 cycles at 143 mA g(-1) than Li2RuO3 (0.79 mol of Li). High reversible Li extraction and long cycle life were attributed to structural stability of the LiM2 layer in the presence of Ti(4+), facilitating the lithium diffusion kinetics. The versatility of the Li2MO3 structure may initiate exploration of Ti-based Li-rich layered oxides for vehicular applications.