Three-Dimensional Ni-MOF as a High-Performance Supercapacitor Anode Material; Experimental and Theoretical Insight.

A three-dimensional (3D) Ni-MOF of the formula [Ni(C4H4N2)(CHO2)2]n, has been reported, which shows a capacitance of 2150 F/g at a current density of 1A/g in a three-electrode setup (5.0 M KOH). Post-mortem analysis of the sample after three-electrode measurements revealed the bias-induced transformation of Ni-MOF to Ni(OH)2, which has organic constituents intercalated within the sample exhibiting better storage performance than bulk Ni(OH)2. Afterward, the synthesized MOF and reduced graphene (rGO) were used as the anode and cathode electrode material, respectively, and a two-electrode asymmetric supercapacitor device (ASC) setup was designed that exhibited a capacitance of 125 F/g (at 0.2 A/g) with a high energy density of 50.17 Wh/kg at a power density of 335.1 W/kg. The ASC further has a very high reversibility (97.9% Coulombic efficiency) and cyclic stability (94%) after 5000 constant charge-discharge cycles. Its applicability was also demonstrated by running a digital watch. Using sophisticated density functional theory simulations, the electronic properties, diffusion energy barrier for the electrolytic ions (K+), and quantum capacitance for the Ni(OH)2 electrode have been reported. The lower diffusion energy barrier (0.275 eV) and higher quantum capacitance (1150 µF/cm2) are attributed to the higher charge storage performance of the Ni-MOF-transformed Ni(OH)2 electrode as observed in the experiment.

Computational Design for Enhanced Hydrogen Storage on the Newly Synthesized 2D Polyaramid via Titanium and Zirconium Decoration.

2D polyaramid (2DPA) is a porous and polymeric material that has been synthesized recently. Titanium and zirconium decoration over 2DPA increases their affinity for hydrogen substantially, making them suitable for onboard and reversible hydrogen storage, particularly in light-duty vehicles. By decorating a single unit cell of 2DPA with two transition metal (TM) atoms, hydrogen storage of up to 6.422 and 6.792 wt % of H2 with average binding energies of -0.399 and -0.480 eV is predicted for 2DPA + Ti and 2DPA + Zr, respectively. The binding of Ti and Zr with 2DPA is accompanied by a flow of charge (-1.474e for Ti and -1.696e for Zr) from the TM toward the 2DPA sheet. Further, the interaction between H2 and the TM may proceed via Kubas interaction between the d orbital of the TM in 2DPA + TM and H 1s orbitals of H2, with a net flow of charge from the TM toward H2 (-0.218e for Ti and -0.391e for Zr). The desorption of H2 bound to 2DPA + Zr is endothermic (∼0.57 eV) and close in magnitude to the binding energy of the first H2 (∼-0.544 eV). The 2DPA + TM systems show structural and dynamic stability at high temperatures, as evident from ab initio molecular dynamics simulations and phonon spectra. The movement of TM atoms across the 2DPA sheet to form clusters may be hindered by the considerable barrier energy (∼4.9 eV for Ti). Through these systematic density functional theory simulations, we predict that Ti- and Zr-decorated 2DPA are high-performance hydrogen storage materials and can be explored by experimentalists.

Catechol Sensing Performance of Pd-Functionalized Two-Dimensional Polyaramid: A DFT Investigation.

Catechol (Cc) molecule adsorption on a pristine and transition metal (TMs = Sc, Pd, and Cu)-functionalized two-dimensional polyaramid (2DPA) monolayer is systematically studied by the first-principles density functional theory method. The weak physisorption (-0.29 eV) and charge transfer of the Cc molecule with p-2DPA result in a very quick recovery time (150 µs), hindering the Cc sensing capability of p-2DPA. Although TM functionalization greatly improved the adsorption ability, the Pd-functionalized 2DPA was shown to be the best choice for Cc adsorption due to the reasonable adsorption energy of -1.39 eV and expedited charge transfer between the Cc and Pd atom. The change of band gap and, hence, the conductivity of the Pd-2DPA system in response to the adsorption of the Cc molecule demonstrate its higher sensitivity than that of p-2DPA. The work function sensitivity of Pd-2DPA upon the Cc adsorption is also investigated. In addition to the change in the electronic properties, the change in the optical properties of Pd-2DPA after Cc adsorption is also analyzed. The structural stability of Pd-2DPA is validated by performing ab initio molecular dynamics simulations at 300 K. The complete desorption of the Cc molecule from Pd-2DPA is attained by annealing the material at 550 K under visible light (τ = 5.4 s) and at 450 K under UV light (τ = 3.7 s). Moreover, the higher diffusion energy barrier of +1.35 eV confirmed that the functionalized Pd atoms did not diffuse through the crystal to form clusters. This study could lay a theoretical foundation for developing possibly new-generation sensors for detecting Cc molecules.

Construction of Nickel Molybdenum Sulfide/Black Phosphorous 3D Hierarchical Structure Toward High Performance Supercapacitor Electrodes.

Supercapacitors (SCs) with outstanding versatility have a lot of potential applications in next-generation electronics. However, their practical uses are limited by their short working potential window and ultralow-specific capacity. Herein, the facile one-step in-situ hydrothermal synthesis is employed for the construction of a NiMo3 S4 /BP (black phosphorous) hybrid with a 3D hierarchical structure. After optimization, the NiMo3 S4 /BP hybrid displays a high specific capacitance of 830 F/g at 1 A/g compared to the pristine NiMo3 S4 electrode. The fabricated NiMo3 S4 /BP//NiCo2 S4 /Ti3 C2 Tx asymmetric supercapacitor exhibits a better specific capacitance of 120 F/g at 0.5 A/g, which also demonstrates a high energy density of 54 Wh/kg at 1148.53 W/kg and good cycle stability with capacity retention of 86% and 97% of Coulombic efficiency after 6000 cycles. Further from the DFT simulations, the hybrid NiMo3 S4 /BP structure shows higher conductivity and quantum capacitance, which demonstrate greater charge storage capability, due to enhanced electronic states near the Fermi level. The lower diffusion energy barrier for the electrolyte K+ ions in the hybrid structure is facilitated by improved charge transfer performance for the hybrid NiMo3 S4 /BP. This work highlights the potential significance of hybrid nanoarchitectonics and compositional tunability as an emerging method for improving the charge storage capabilities of active electrodes.

Experimental and computational investigation on the charge storage performance of a novel Al2O3-reduced graphene oxide hybrid electrode.

The advancements in electrochemical capacitors have noticed a remarkable enhancement in the performance for smart electronic device applications, which has led to the invention of novel and low-cost electroactive materials. Herein, we synthesized nanostructured Al2O3 and Al2O3-reduced graphene oxide (Al2O3-rGO) hybrid through hydrothermal and post-hydrothermal calcination processes. The synthesized materials were subject to standard characterisation processes to verify their morphological and structural details. The electrochemical performances of nanostructured Al2O3 and Al2O3- rGO hybrid were evaluated through computational and experimental analyses. Due to the superior electrical conductivity of reduced graphene oxide and the synergistic effect of both EDLC and pseudocapacitive behaviour, the Al2O3- rGO hybrid shows much improved electrochemical performance (~ 15-fold) as compared to bare Al2O3. Further, a symmetric supercapacitor device (SSD) was designed using the Al2O3- rGO hybrid electrodes, and detailed electrochemical performance was evaluated. The fabricated Al2O3- rGO hybrid-based SSD showed 98.56% capacity retention when subjected to ~ 10,000 charge-discharge cycles. Both the systems (Al2O3 and its rGO hybrid) have been analysed extensively with the help of Density Functional Theory simulation technique to provide detailed structural and electronic properties. With the introduction of reduced graphene oxide, the available electronic states near the Fermi level are greatly enhanced, imparting a significant increment in the conductivity of the hybrid system. The lower diffusion energy barrier for electrolyte ions and higher quantum capacitance for the hybrid structure compared to pristine Al2O3 justify improvement in charge storage performance for the hybrid structure, supporting our experimental findings.

Laterally Grown Strain-Engineered Semitransparent Perovskite Solar Cells with 16.01% Efficiency.

Hybrid organometallic halide perovskite-based semitransparent solar cell research has garnered significant attention recently due to their promising applications for smart windows, tandem devices, wearable electronics, displays, and sustainable internet-of-things. Though considerable progress has been made, stability, controlling the crystalline qualities, and growth orientation in perovskite thin films play crucial roles in improving the photovoltaic (PV) performance. Recently, strain modulation within the perovskite gathers an immense interest that is achieved by the ex situ process. However, little work is reported on in situ strain modulation, which is presented here. Apart from the challenges in the fabrication of high-efficiency perovskite solar cell (PSC) devices under ambient conditions, the stability of organic hole-transporting materials needs urgent attention. Herein, a single-step deposition of formamidiniumchloride (FACl)-mediated CH3NH3PbI3 (MAPbI3) thin films without an inert atmosphere and CuI as the inorganic hole-transporting material is demonstrated for their potential application toward semitransparent PSCs. The FACl amount in MAPbI3 (mg/mL) plays a critical role in controlling the crystallinity, growth orientations, and in situ strains, which modulate the charge carrier transport dynamics, thereby improving the efficiency of the PSC device. A photoconversion efficiency of 16.01% has been achieved from MAPbI3 with 20 mg/mL of FACl additive incorporation. The modification of the structural, electronic, and optical properties and the origin of strain in the as-synthesized MAPbI3 domains due to the addition of FACl are further validated with experimental findings in detail using density functional theory simulations.

Theoretical model study of adsorbed antimalarial-graphene dimers: doping effects, photophysical parameters, intermolecular interactions, edge adsorption, and SERS.

Future diagnostics and therapy applications are in part riding on the discovery and implementation of new optical techniques and strategies (which often derive from dyads) for example, prediction of features in surface-enhanced Raman spectroscopy requires the study of chromophore-chromophore interactions involve intermolecular forces, drug delivery, and photo mechanisms which are of great interest. New matches between chromophore systems (i.e. FRET), and π-delocalized surfaces are important to study. We explore low-molecular weight drug molecules and their interaction with the reporter material/surface of graphene. Bonding, charge transfer and orbital interactions for 2-amino-5-(1-methyl-5-nitro-2-imidazolyl)-1,3,4-thiadiazole (megazol or AMIT) on graphene were carried out. The graphene model substrate was monotonically/monatomically substituted (doped) with one neutral heteroatom (N/O/S/B) in place of one carbon center; chemical adsorption of AMIT is due to charge transfer from doped graphene to AMIT (DFT). Our AMIT-nanocluster studies show that the nanoclusters will act as a sensor component for the detection of drugs due to SERS. Our findings identified that the greater the energy of the charge transfer, the stronger the calculated chemical adsorption. Additionally, charge transfer is highest for the N-doped systems and least for pristine graphene, resulting in a stronger adsorption energy for N-doped graphene. Mulliken charge analysis of structures confirms enhancement found in QD-AMIT systems.Communicated by Ramaswamy H. Sarma.

Spinel NiFe2O4 nanoparticles decorated 2D Ti3C2 MXene sheets for efficient water splitting: Experiments and theories.

Design and demonstration of cost-effective, robust, and earth-abundant electrocatalysts for efficient water splitting have attracted a great deal of interest. Herein, we have decorated NiFe2O4 nanoparticles on the emerging novel two-dimensional (2D) Ti3C2 (MXene) sheets in order to achieve better electrocatalytic performance for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). The synthesized NiFe2O4/Ti3C2 composite showed extraordinary kinetic metrics for electrocatalytic OER, revealing a low overpotential of 266 mV at a current density of 10 mA/cm2, and a small Tafel slope of 73.6 mV/dec. For HER, the composite exhibited an overpotential of 173 mV at 10 mA/cm2 with a small Tafel slope of 112.2 mV/dec. The high electrocatalytic performance of NiFe2O4/Ti3C2 composite is believed to be originated from a well-constructed nanoparticle-sheet interface, synergistic effect, and the high metallic conductivity of Ti3C2 MXene sheets. These experimental results are further supported by the state-of-the-art density functional theory (DFT) simulations. The study providing information about the structure, electronic properties, bonding, and interaction mechanism between Ti3C2 (MXene) and NiFe2O4. Moreover, offering the values of the theoretical overpotential of Ti3C2 (MXene), NiFe2O4, and the NiFe2O4/Ti3C2 composite for both OER and HER activities. Interestingly, the theoretical overpotential follows the qualitative trend of NiFe2O4/Ti3C2 < NiFe2O4 < Ti3C2 MXene for OER and NiFe2O4/Ti3C2 < Ti3C2 MXene < NiFe2O4 for HER, agreeing with the experimental observations. There is charge transfer from NiFe2O4 to MXene leading to enhancement in electronic states near Fermi level which may be due to interactions between C 2p orbital of Ti3C2 MXene and 3d orbital of Ni and Fe. Therefore, this work provides new insights for designing new efficient non-noble metal-based electrocatalysts in the future.

Effect of fluoride on mechanical properties of NiTi and CuNiTi orthodontic archwires: an in vitro study.

INTRODUCTION: After debonding, white spot may appear on the area below the bracket, which is the early clinical sign of carious lesion. There is increased caries risk underneath and adjacent to orthodontic bands and brackets, which call for maximum use of caries preventive procedures using various fluoride application methods. OBJECTIVE: The aim of the study was to evaluate alterations in the mechanical properties (modulus of elasticity and yield strength) in loading and unloading phases for different orthodontic archwires (nickel-titanium [NiTi] and copper-nickel-titanium [CuNiTi]) when exposed routinely to fluoride prophylactic agents for a predetermined period of time. METHODS: Preformed rectangular NiTi and CuNiTi wires were immersed in fluoride solution and artificial saliva (control) for 90 minutes at 37ºC. After immersion, specimens were tested using a 3-point bend test on a universal testing machine. RESULTS: There is a significant reduction in the unloading yield strength when the NiTi and CuNiTi wires were exposed to APF gel. CONCLUSION: The result suggests that use of topical fluoride agents affect the mechanical properties of the wires, leading to increase in treatment duration. Fluoride prophylactic agents must be used with caution in patients undergoing orthodontic treatment. Injudicious use of these agents may cause corrosive effects on the orthodontic wire surfaces, with alteration in their mechanical properties.

Effect of fluoride on mechanical properties of NiTi and CuNiTi orthodontic archwires: an in vitro study

ABSTRACT Introduction: After debonding, white spot may appear on the area below the bracket, which is the early clinical sign of carious lesion. There is increased caries risk underneath and adjacent to orthodontic bands and brackets, which call for maximum use of caries preventive procedures using various fluoride application methods. Objective: The aim of the study was to evaluate alterations in the mechanical properties (modulus of elasticity and yield strength) in loading and unloading phases for different orthodontic archwires (nickel-titanium [NiTi] and copper-nickel-titanium [CuNiTi]) when exposed routinely to fluoride prophylactic agents for a predetermined period of time. Methods: Preformed rectangular NiTi and CuNiTi wires were immersed in fluoride solution and artificial saliva (control) for 90 minutes at 37ºC. After immersion, specimens were tested using a 3-point bend test on a universal testing machine. Results: There is a significant reduction in the unloading yield strength when the NiTi and CuNiTi wires were exposed to APF gel. Conclusion: The result suggests that use of topical fluoride agents affect the mechanical properties of the wires, leading to increase in treatment duration. Fluoride prophylactic agents must be used with caution in patients undergoing orthodontic treatment. Injudicious use of these agents may cause corrosive effects on the orthodontic wire surfaces, with alteration in their mechanical properties.

RESUMO Introdução: Após a remoção dos braquetes, manchas brancas podem aparecer na área embaixo deles, as quais são o sinal clínico inicial da lesão cariosa. Existe um maior risco de cáries embaixo e ao redor das bandas e braquetes ortodônticos, o que exige a máxima utilização de procedimentos preventivos de cárie, usando diferentes métodos com aplicação de flúor. Objetivo: O objetivo do presente estudo foi avaliar alterações nas propriedades mecânicas (módulo de elasticidade e resistência ao escoamento), nas fases de carregamento e descarregamento de diferentes fios ortodônticos (níquel-titânio [NiTi] e níquel-titânio com adição de cobre [CuNiTi]), quando expostos rotineiramente a agentes profiláticos fluoretados, utilizados durante um período de tempo predeterminado. Métodos: Os fios pré-contornados retangulares de NiTi e CuNiTi foram imersos em solução fluoretada e saliva artificial (controle) durante 90 minutos a 37°C. Após a imersão, as amostras foram testadas utilizando-se um teste de flexão em três pontos, em uma máquina universal de testes. Resultados: Houve uma redução significativa na resistência ao escoamento na fase de descarregamento quando os fios de NiTi e CuNiTi foram expostos ao gel fluoretado. Conclusão: O resultado sugere que o uso tópico de agentes fluoretados afeta as propriedades mecânicas dos fios, levando a um aumento na duração do tratamento. Os agentes profiláticos fluoretados devem ser utilizados com cautela em pacientes submetidos a tratamento ortodôntico. O uso indiscriminado desses agentes pode causar efeitos corrosivos na superfície dos fios ortodônticos e consequente alteração das suas propriedades mecânicas.

Awareness of orthodontic treatment among school teachers in Karad Taluka.

INTRODUCTION: Health is defined as a state of complete physical, mental, and social well-being. Awareness of orthodontic treatment varies in different regions. Undergoing orthodontic treatment to correct malocclusion would be very beneficial to children as it could help eliminate bullying by peers regarding facial appearance. This kind of bullying by peers could affect the child psychologically. MATERIALS AND METHODS: A questionnaire survey was conducted in Karad Taluka in Maharashtra. A total of 378 subjects were selected. The schools were randomly selected. A questionnaire including general information, knowledge, and awareness of orthodontic treatment was prepared, and the teachers were given 15 min to fill it. Since it was a short period of time to gather information from other sources, the participants answered the questionnaire using their own knowledge. The purpose of this questionnaire, which consisted of 12 questions in both English and Marathi was to evaluate the level of knowledge the teachers had about orthodontic treatment. The purpose of the study and questionnaire forms were explained by the examiner. The responses of the teachers to the questions were recorded on a 2-point Likert scale {YES or NO}. RESULTS: Simple descriptive statistics was applied to describe the study variables. A Chi-square test of independence was performed to check independence between answers and gender for each question. CONCLUSION: Within limits of this study, it may be concluded that knowledge of available treatments was more in males compared to females in rural areas.

Invitro Study of the Effect of Different Samples of Water Used for Washing the Etchant on Bracket Bond Strength.

BACKGROUND: Bonding is a very important step in the orthodontic treatment planning. Effective bonding enhances the treatment by reducing the bond failure and thereby reducing the treatment duration and also increases efficiency in orthodontic mechanics. The success of the bonded brackets is negatively affected by contamination with oral fluids such as blood and saliva. AIM: The aim of the present study was to evaluate the effect of hardness of water used in removing the etchant on the bracket bond strength. MATERIALS AND METHODS: Seventy five extracted premolars were divided in three groups of 25 each. The teeth in all the three groups were etched with 35% phosphoric acid. The etchant in each of the group I, II and III was removed using distilled water (soft), corporation water (moderately hard) and hard water respectively. Stainless steel brackets were attached using light cure bonding agent (transbond XT, 3M UNITEK) and cured for 10sec with a light cure unit. The shear bond strength was evaluated by mechanical testing machine. Statistically significant differences were defined for p < 0.05. RESULT: The results showed significant increase in bond strength in samples where in soft water was used for cleaning the etchant on the bonding surface. CONCLUSION: Hardness of water used for washing the etchant affects the bracket bond strength. Shear bond strength of soft water is significantly increased compared to moderately hard and very hard water.

Effect of fluoride prophylactic agents on the surface topography of NiTi and CuNiTi wires.

AIM: The aim of this study was to see the effect of topical fluoride on surface texture on nickel-titanium and copper-nickel-titanium orthodontic archwires. MATERIALS AND METHODS: Preformed rectangular NiTi and CuNiTi wires were immersed in in fluoride solution and artificial saliva (control) for 90 minutes at 37°C. after immersion optical microscope was used to see the fluoride effect on the wire topography. RESULTS: The acidulated fluoride agents appeared to cause greater corrosive effects as compared to the neutral fluoride agents. CONCLUSION: The result suggest that using topical fluoride agents leads to corrosion of surface topography indirectly affecting the mechanical properties of the wire that will lead to prolonged orthodontic treatment. CLINICAL SIGNIFICANCE: The use of topical fluoride agents has to be limited in patients with prolonged orthodontic treatment as it causes the corrosion of the NiTi and CuNiTi wires.