Unique Multi-Hetero-Interface Engineering of Fe-doped Co-LDH@MoS2-Ni3S2 Nanoflower-Based Electrocatalyst for Overall Water-Splitting: An Experimental and Theoretical Investigation.

Herein, a self-supported, robust, and noble-metal-free 3D hierarchical interface-rich Fe-doped Co-LDH@MoS2-Ni3S2/NF heterostructure electrocatalyst has been prepared through a controllable two-step hydrothermal process. The resultant electrode shows low overpotential of ⁓95 mV for hydrogen evolution reaction (HER), ⁓220 mV for the oxygen evolution reaction (OER) and the two-electrode system requires only a cell voltage of ⁓1.54 V at 10 mA cm-2 current density, respectively. Extensive ab initio calculations were carried out to find out the overpotential for HER, orbital interaction through the determination of electron density of states and quantification of charge transfer by Bader charge analysis. The computed overpotential matched closely with the experimental data. The superior HER performance of the tri-layer is enhanced due to the charge transfer (1.7444e) to Fe-doped Co-LDH from Ni3S2-MoS2 hybrid. This research strategy paves an effective pathway for affordable green H2 production and future efficient non-precious bifunctional electrocatalyst design for overall water electrolysis.

Transition Metal (Cu, Pd, and Ag)-Modified Nb2S2C Monolayer for Highly Efficient Catechol Sensing: A First-Principles Investigation.

Motivated by recent advancements and the escalating application of two-dimensional (2D) gas or molecule sensors, this study explores the potential of the 2D Nb2S2C monolayer for detecting biomolecule catechol (Cc), whose excess concentration is highly dangerous to living beings. We use first-principles density functional theory (DFT) calculations to assess the Cc sensing performance of pure and transition metal (TM = Cu, Pd, Ag)-modified Nb2S2C monolayers. The Nb2S2C monolayer belonging to the new class of synthesized 2D materials, TM carbo-chalcogenides (TMCC), combines distinctive properties from both TM dichalcogenides and TM carbides and exhibits physisorption (-0.66 eV) toward the Cc molecule. Notably, the surface modifications with these TMs significantly enhanced the adsorption energy of Cc. The chemisorption of the Cc molecule on the Pd to Cu-modified monolayer is demonstrated with adsorption energies ranging from -1.09 to -1.3 eV and is due to the robust charge transfer and orbital interactions between the valence orbitals of TMs and Cc. In addition, the modification of the surface by TM leads to an increased work function sensitivity toward the Cc molecule. The study establishes the thermal stability at 300 K and dynamic stability of TM-Nb2S2C through ab initio molecular dynamics (AIMD) simulations and Phonon calculations, respectively. The theoretical estimation of achievable recovery time at 400 and 450 K for Pd and Ag and at 500 K for the Cu-modified Nb2S2C monolayer, respectively, confirms the potential practical application of the sensor for Cc detection. These compelling characteristics position the Nb2S2C monolayer as a promising nanomaterial for detecting Cc molecules in the environment.

Hydrogen spillover inspired bifunctional Platinum/Rhodium Oxide-Nitrogen-Doped carbon composite for enhanced hydrogen evolution and oxidation reactions in base.

The poor activity of Pt-based-catalysts for alkaline hydrogen oxidation/evolution reaction (HOR/HER) encourages scientific society to design an effective electrocatalyst to develop alkaline fuel cells/electrolyzers. Herein, platinum/rhodium oxide-nitrogen-doped carbon (Pt/Rh2O3-CNx) composite is prepared for alkaline HER and HOR inspired by hydrogen spillover. The HER performance of Pt/Rh2O3-CNx is âˆ¼ 6 times higher than Pt/C. In HOR, Pt/Rh2O3-CNx possesses an exchange current density of 657.60 mA/mgmetal, which is âˆ¼ 3.4 times higher than Pt/C. Hydrogen and hydroxyl binding energy (HBE and OHBE) contribute equally to alkaline HOR/HER. The experimental and theoretical evidence suggests that the enhanced HER and HOR activity of Pt/Rh2O3-CNx may be due to hydrogen spillover from Pt to Rh2O3. Small work function difference [0.08 eV] of the system suggested hydrogen-spillover is feasible, which has been justified by reaction-free energy calculations. We proposed that the dissociation of hydrogen (H2) and water (H2O) occurs at Pt to form Pt-adsorbed hydrogen species (Pt-Had). Then, some Had moves to Rh2O3 through hydrogen spillover and reacts with neighboring Had or adsorbed hydroxyl species (OHad) to form H2 or H2O, which enhances the HER and HOR activity, respectively. The role of water-metal-hydroxyl species in the electrical double layer was also demonstrated on alkaline HOR/HER. This work may help to design the hydrogen-spillover-based catalysts for several renewable energy technologies.

Electrochemical reconstruction of a 1D Cu(PyDC)(H2O) MOF into in situ formed Cu-Cu2O heterostructures on carbon cloth as an efficient electrocatalyst for CO2 conversion.

Electrochemical carbon dioxide (CO2) conversion has enormous potential for reducing high atmospheric CO2 levels and producing valuable products simultaneously; however the development of inexpensive catalysts remains a great challenge. In this work, we successfully synthesised a 1D Cu-based metal-organic framework [Cu(PyDC)(H2O)], which crystallizes in an orthorhombic system with the Pccn space group, by the hydrothermal method. Among the different catalysts utilized, the heterostructures of cathodized Cu-Cu2O@CC demonstrate increased efficiency in producing CH3OH and C2H4, achieving maximum FE values of 37.4% and 40.53%, respectively. Also, the product formation rates of CH3OH and C2H4 reach up to 667 and 1921 µmol h-1 cm-2. On the other side, Cu-Cu2O/NC-700 carbon composites simultaneously produced C1-C3 products with a total FE of 23.27%. Furthermore, a comprehensive study involving detailed DFT simulations is used to calculate the energetic stability and catalytic activity towards the CO2 reduction of Cu(111), Cu2O(111), and Cu@Cu2O(111) surfaces. During the early phase of electrochemical treatment, Cu(II) carboxylate nodes (Cu-O) in the Cu(PyDC)(H2O) MOF were reduced to Cu and Cu2O, with a possible synergistic enhancement from the PyDC ligands. Thus, the improved activity and product enhancement are closely associated with the cathodized reconstruction of Cu-Cu2O@CC heterostructures on carbon cloth. Hence, this study provides efficient derivatives of Cu-based MOFs for notable electrocatalytic activity in CO2 reduction and gives valuable insights towards the advancement of practical CO2 conversion technology.

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.

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 NiMo3S4/BP (black phosphorous) hybrid with a 3D hierarchical structure. After optimization, the NiMo3S4/BP hybrid displays a high specific capacitance of 830 F/g at 1 A/g compared to the pristine NiMo3S4 electrode. The fabricated NiMo3S4/BP//NiCo2S4/Ti3C2Tx 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 NiMo3S4/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 NiMo3S4/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.

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.

Defect engineered N-S codoped TiO2 nanoparticles for photocatalytic and optical limiting applications: Experimental and DFT insights.

N-S codoped TiO2 nanoparticles (NPs) were synthesized using a sol-gel cum hydrothermal approach, with ammonium sulfate as the nitrogen and sulfur source compound. The calcination temperature was varied from 500 to 700 °C. The pristine samples exhibited a mixed phase of anatase and brookite, while the doped samples exhibited only the anatase phase, as confirmed by X-ray diffraction (XRD) analysis. Fourier-transform infrared spectroscopy (FTIR) confirmed the presence of N-H vibrations and S-O bidentate complexation with Ti4+ ions. Electron paramagnetic resonance (EPR) revealed the presence of Ti3+ signals, confirming the creation of oxygen defects in the doped samples. The absorption and emission properties of the samples were investigated using ultraviolet-visible (UV-Vis) and photoluminescence (PL) spectroscopy. Vibrating sample magnetometry (VSM) analysis confirms the room-temperature ferromagnetic behavior of the N-S doped TiO2, which was attributed to the presence of oxygen vacancies, as evidenced by the EPR and PL results. The N-S doped TiO2 samples demonstrated superior photocatalytic degradation of Rhodamine B (RhB), Methylene Blue (MB), and Congo Red (CR) dyes under visible light illumination compared to the pristine TiO2. This enhanced performance was attributed to the presence of N and S dopants in TiO2, which create new energy levels within the band structure of TiO2, allowing for efficient absorption of visible light and subsequent generation of reactive species for dye degradation. N-S doping modifies the electronic structure of TiO2, enhancing two-photon absorption (TPA). This increased TPA efficiency suggests promising applications in optical devices, such as laser protection systems and optical limiters. Density Functional Theory (DFT) investigation also confirms that the presence of oxygen vacancies generates energy states below the conduction band. This, in turn, benefits the absorption of more visible light during photocatalytic activities and leads to a notable nonlinear absorption in optical limiting. Overall, the N-S doping strategy significantly improves the photocatalytic and optical limiting performance of TiO2 NPs, making them promising candidates for a wide range of applications.

ß-Bi2O3-Bi2WO6 Nanocomposite Ornated with meso-Tetraphenylporphyrin: Interfacial Electrochemistry and Photoresponsive Detection of Nanomolar Hexavalent Cr.

Hexavalent chromium exposure via inhalation, ingestion, or both has been proven to adversely affect internal organs, induce toxic effects, cause allergies, and contribute to the development of cancer. It requires a substantial and challenging effort to detect several heavy metal ions conveniently, sensitively, and reliably by using materials that are easy to synthesize and have a high yield. The impact of light on the electrocatalytic oxidation/reduction process proves an environmentally friendly methodology with numerous applications in pollution control. The extensive use of photoactive materials in photoelectrochemical (PEC) sensors necessitates the development of stable and highly effective photoactive materials. Hence, the solvothermal synthesis of the organic-inorganic hybrid nanocomposite ß-Bi2O3-Bi2WO6/H2TPP with varying weight percentages of meso-tetraphenylporphyrin (H2TPP) resulted in a selective electrode for electrocatalytic and photoelectrocatalytic reduction of Cr6+ on fluorine-doped tin oxide (FTO) by an adsorption-reduction mechanism. H2TPP increases the active site density and provides an effective surface area for efficient adsorption by providing both pyridinic- and pyrrolic-N atoms to ß-Bi2O3-Bi2WO6/H2TPP. H2TPP could effectively adsorb Cr6+ in the ß-Bi2O3-Bi2WO6/H2TPP composite system through electrostatic interaction, and the adsorbed Cr6+ ions were reduced to trivalent chromium Cr3+, resulting in promising Cr6+ sensing. The projected density of states and Bader charge calculations result in the electrostatic attraction among the N-2p orbital of H2TPP and the 3d and 4s orbitals of the Cr atom, resulting in the adsorption of the hexavalent Cr atom onto the active center of H2TPP. Moreover, the addition of H2TPP results in the development of a mesoporous surface that offers strong electrical conductivity, a substantial surface area, improved charge-mass transport, intimate contact between the electrolyte and catalyst, an extended fluorescence lifetime, and increased stability. The role of pH values was thoroughly investigated. All electrochemical and photoelectrochemical studies were carried out on 5 wt % H2TPP-ornated ß-Bi2O3-Bi2WO6. Nanocomposite ß-Bi2O3-Bi2WO6/5 wt % H2TPP demonstrated reliable cyclic stability, reproducibility, good sensitivity (8.005 µA mM cm-2), and a low limit of detection (LOD) (8.0 nM) toward photoelectrocatalytic reduction of Cr6+. The interference study in the presence of a few inorganic entities exhibited excellent selectivity. This tale amplification approach for developing a ß-Bi2O3-Bi2WO6/5 wt % H2TPP nanocomposite system suggests a deeper understanding of the application of photoelectrocatalytic reduction of Cr6+ in environmental remediation with real samples under light irradiation.

Hydrogen spillover enhances alkaline hydrogen electrocatalysis on interface-rich metallic Pt-supported MoO3.

Efficient and cost-effective electrocatalysts for the hydrogen oxidation/evolution reaction (HOR/HER) are essential for commercializing alkaline fuel cells and electrolyzers. The sluggish HER/HOR reaction kinetics in base is the key issue that requires resolution so that commercialization may proceed. It is also quite challenging to decrease the noble metal loading without sacrificing performance. Herein, we report improved HER/HOR activity as a result of hydrogen spillover on platinum-supported MoO3 (Pt/MoO3-CNx-400) with a Pt loading of 20%. The catalyst exhibited a decreased over-potential of 66.8 mV to reach 10 mA cm-2 current density with a Tafel slope of 41.2 mV dec-1 for the HER in base. The Pt/MoO3-CNx-400 also exhibited satisfactory HOR activity in base. The mass-specific exchange current density of Pt/MoO3-CNx-400 and commercial Pt/C are 505.7 and 245 mA mgPt-1, respectively. The experimental results suggest that the hydrogen binding energy (HBE) is the key descriptor for the HER/HOR. We also demonstrated that the enhanced HER/HOR performance was due to the hydrogen spillover from Pt to MoO3 sites that enhanced the Volmer/Heyrovsky process, which led to high HER/HOR activity and was supported by the experimental and theoretical investigations. The work function value of Pt [Φ = 5.39 eV) is less than that of ß-MoO3 (011) [Φ = 7.09 eV], which revealed the charge transfer from Pt to the ß-MoO3 (011) surface. This suggested the feasibility of hydrogen spillover, and was further confirmed by the relative hydrogen adsorption energy [ΔGH] at different sites. Based on these findings, we propose that the H2O or H2 dissociation takes place on Pt and interfaces to form Pt-Had or (Pt/MoO3)-Had, and some of the Had shifted to MoO3 sites through hydrogen spillover. Then, Had at the Pt and interface, and MoO3 sites reacted with H2O and HO- to form H2 or H2O molecules, thereby boosting the HER/HOR activity. This work may provide valuable information for the development of hydrogen-spillover-based electrocatalysts for use in various renewable energy devices.

Influence of vacancy defects on 2D BeN4monolayer for NH3adsorption: a density functional theory investigation.

Two-dimensional materials have attracted a great deal of interest in developing nanodevices for gas-sensing applications over the years. The 2D BeN4monolayer, a recently synthesized single-layered Dirac semimetal, has the potential to function as a gas sensor. This study analyzes the NH3sensing capacity of the pristine and vacancy-induced BeN4monolayers using first-principles density functional theory (DFT) calculations. As per the results, the NH3molecule is physisorbed on the pristine BeN4via weak Van der Waals interaction with a poor adsorption energy of -0.41 eV and negligible charge transfer. Introducing Be vacancy in BeN4increased the NH3adsorption energy to -0.83 eV due to the improved charge transfer (0.044 e) from the defective monolayer to the NH3molecule. The structural stability, sufficient recovery time (74 s) at room temperature, and superior work function sensitivity promise the potential application of defective BeN4as an NH3sensor. This research will be a theoretical groundwork for creating innovative BeN4-based NH3gas sensors.

2D BN-biphenylene: structure stability and properties tenability from a DFT perspective.

With state-of-the-art density functional theory and ab initio molecular dynamics, we explored the BN-analog of a recently synthesized 2D biphenylene sheet. Its dynamical, thermal, and mechanical stability has been confirmed with phonon spectrum calculations, ab initio molecular dynamics (AIMD), and Born criteria, and its synthesis feasibility has been ascertained in terms of cohesive energy. The phonon spectrum and AIMD results show all positive frequencies and negligible variations in structure (bond length), kinetic and total energy for 5 ps, respectively. Having found this stable BN-BPh, we have analyzed its electronic, mechanical, optical, and vibration properties. Electronic property results (density of states and band structure) show that the BN-equivalent of metallic BPh has a large band gap of 3.12 eV and 4.48 eV with the PBE and HSE06 DFT functionals, respectively, similar to the graphene BN-equivalent (hBN) with a band gap of 6.1 eV. The mechanical strength of BN-BPh is close to that of BPh with a difference of ∼15 N m-1 and ∼10 N m-1 along the x- and y-directions, and its Young's modulus indicates that BN-BPh is stiffer than BN-graphyne. The optical absorption coefficient of BN-BPh shows a first peak at 4.48 eV (3.12 eV) with the HSE06 (PBE) functional. Infrared and Raman spectrum intensity and irreducible representation are computed, and the first IR (Raman) peak is found at 1300 cm-1 (1000 cm-1) for BN-BPh. Finally, substitutions of external atoms such as P, Al, As, C, Li, Mg, S, and Si for B and N atoms in BN-BPh tune its electronic properties to semiconducting, semi-metallic, and even metallic. Considering its mechanical, optical, and band gap tunability, BN-BPh might be useful in electronic, optical, and spintronics devices, even in high-pressure environments.

Metal-decorated γ-graphyne as a drug transporting agent for the mercaptopurine chemotherapy drug: a DFT study.

In recent years, carbon-based two-dimensional (2D) materials have gained popularity as the carriers of various anticancer therapy drugs, which could reduce the crucial side effects by directly applying the drugs to the intended tumor cells. In this study, through first-principles density functional theory simulations, we have investigated the adsorption properties of a famous cancer chemotherapy drug called mercaptopurine (MC) on a 2D γ-graphyne (GYN) monolayer. Analyzing the geometric and electronic properties, we can summarize that the MC interaction with the pristine GYN is weak, with a small adsorption energy of -0.15 eV, which is too low for potential applications. Therefore, we have decorated the GYN monolayer with biocompatible metals such as Al, Ag, and Cu to trigger the adsorption capacity. The Al- and Cu-decorated GYN offered improved adsorption towards MC compared to the pristine case. The drug release from these metal-decorated systems was examined by creating an acidic environment. In addition, the desorption temperature of the drug from the system was also evaluated using ab initio molecular dynamics simulations. The calculations demonstrated that the Al-decorated GYN is a potential vehicle for MC drug delivery because of the favourable adsorption energy of -0.63 eV, charge transfer of 0.17e and desorption temperature above 270 K. The current research will stimulate the investigation of other low-dimensional carbon materials for drug-delivery applications.

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.

Electric-Field Emission Mechanism in Q-Carbon Field Emitters.

In this paper, we report the excellent field emission properties of Q-carbon and analyze its field emission characteristics through structural, morphological, and electronic property correlations, supported by density functional theory (DFT) simulation studies. The Q-carbon field emitters show impressive and stable field emission properties, such as a low turn-on electric field of ∼2.38 V/µm, a high emission current density of ∼33 µA/cm2, and a critical field of ∼2.44 V/µm for the transition from a linear region to the saturation region in the F-N plot. The outstanding field emission properties of Q-carbon are attributed to (i) a unique sp2/sp3 mixture in Q-carbon, (ii) sp2-bonded highly conductive amorphous carbon-rich channels inside the Q-carbon cluster, (iii) a large local field enhancement due to the local geometry and microstructure of Q-carbon, and (iv) the presence of sp2-bonded amorphous carbon regions in the composite film. The temperature-dependent field emission properties, such as extreme sensitivity and an enhancement in the emission current density with temperature, can be explained by the local density of states near the Fermi level and the excellent thermal stability of the Q-carbon field emitters. From DFT simulation studies, the computed work function and the field-enhancement factor were determined to be 3.62 eV and ∼2300, respectively, which explains the excellent field emission characteristics of Q-carbon. The obtained field emission properties, in most cases, were superior to those from other carbon/diamond-based field emitters, which will open new frontiers in field emission-based electronic applications.

Defect-Engineering of 2D Dichalcogenide VSe2 to Enhance Ammonia Sensing: Acumens from DFT Calculations.

Opportune sensing of ammonia (NH3) gas is industrially important for avoiding hazards. With the advent of nanostructured 2D materials, it is felt vital to miniaturize the detector architecture so as to attain more and more efficacy with simultaneous cost reduction. Adaptation of layered transition metal dichalcogenide as the host may be a potential answer to such challenges. The current study presents a theoretical in-depth analysis regarding improvement in efficient detection of NH3 using layered vanadium di-selenide (VSe2) with the introduction of point defects. The poor affinity between VSe2 and NH3 forbids the use of the former in the nano-sensing device's fabrications. The adsorption and electronic properties of VSe2 nanomaterials can be tuned with defect induction, which would modulate the sensing properties. The introduction of Se vacancy to pristine VSe2 was found to cause about an eight-fold increase (from -012 eV to -0.97 eV) in adsorption energy. A charge transfer from the N 2p orbital of NH3 to the V 3d orbital of VSe2 has been observed to cause appreciable NH3 detection by VSe2. In addition to that, the stability of the best-defected system has been confirmed through molecular dynamics simulation, and the possibility of repeated usability has been analyzed for calculating recovery time. Our theoretical results clearly indicate that Se-vacant layered VSe2 can be an efficient NH3 sensor if practically produced in the future. The presented results will thus potentially be useful for experimentalists in designing and developing VSe2-based NH3 sensors.

Highly Stable Electrochemical Supercapacitor Performance of Self-Assembled Ferromagnetic Q-Carbon.

Novel phase Q-carbon thin films exhibit some intriguing features and have been explored for various potential applications. Herein, we report the growth of different Q-carbon structures (i.e., filaments, clusters, and microdots) by varying the laser energy density from 0.5 to 1.0 J/cm2 during pulsed laser annealing of amorphous diamond-like carbon films with different sp3-sp2 carbon compositions. These unique nano- and microstructures of Q-carbon demonstrate exceptionally stable electrochemical performance by cyclic voltammetry, galvanostatic charging-discharging, and electrochemical impedance spectroscopy for energy applications. The temperature-dependent magnetic studies (magnetization vs magnetic field and temperature) reveal the ferromagnetic nature of the Q-carbon microdots. The saturation magnetization and coercive field values decrease from 132 to 14 emu/cc and 155 to 92 Oe by increasing the temperature from 2 to 300 K, respectively. The electrochemical performances of Q-carbon filament, cluster, and microdot thin-film supercapacitors were investigated by two-electrode configurations, and the highest areal specific capacitance of ∼156 mF/cm2 was observed at a current density of 0.15 mA/cm2 in the Q-carbon microdot thin film. The Q-carbon microdot electrodes demonstrate an exceptional capacitance retention performance of ∼97.2% and Coulombic efficiency of ∼96.5% after 3000 cycles due to their expectational reversibility in the charging-discharging process. The kinetic feature of the ion diffusion associated with the charge storage property is also investigated, and small changes in equivalent series resistance of ∼9.5% and contact resistance of ∼9.1% confirm outstanding stability with active charge kinetics during the stability test. A high areal power density of ∼5.84 W/cm2 was obtained at an areal energy density of ∼0.058 W h/cm2 for the Q-carbon microdot structure. The theoretical quantum capacitance was obtained at ∼400 mF/cm2 by density functional theory calculation, which gives an idea about the overall capacitance value. The obtained areal specific capacitance, power density, and impressive long-term cyclic stability of Q-carbon thin-film microdot electrodes endorse substantial promise in high-performance supercapacitor applications.

Anab initiostudy of catechol sensing in pristine and transition metal decoratedγ-graphyne.

Catechol is a toxic biomolecule due to its low degradability to the ecosystem and unpredictable impact on human health. In this work, we have investigated the catechol sensing properties of pristine and transition metal (Ag, Au, Pd, and Ti) decoratedγ-graphyne (GY) systems by employing the density functional theory and first-principles molecular dynamics approach. Simulation results revealed that Pd and Ti atom is more suitable than Ag and Au atom for the decoration of the GY structure with a large charge transfer of 0.29e and 1.54e from valence d-orbitals of the Pd/Ti atom to the carbon-2p orbitals of GY. The GY + Ti system offers excellent electrochemical sensing towards catechol with charge donation of 0.14e from catechol O-p orbitals to Ti-d orbitals, while the catechol molecule is physisorbed to pristine GY with only 0.04e of charge transfer. There exists an energy barrier of 5.19 eV for the diffusion of the Ti atom, which prevents the system from metal-metal clustering. To verify the thermal stability of the sensing material, we have conducted the molecular dynamics simulations at 300 K. We have reported feasible recovery times of 2.05 × 10-5s and 4.7 × 102s for sensing substrate GY + Pd and GY + Ti, respectively, at 500 K of UV light.