Mechanism of Oxygen Reduction Reaction in Alkaline Medium on Nitrogen-Doped Graphyne and Graphdiyne Families: A First Principles Study.

Using extensive first principles protocols, a systematic investigation is performed to probe the oxygen reduction reaction (ORR) mechanism on nitrogen (N) doped graphynes (Gys, e. g. αGy, ßGy, γGy and 6,6,12Gy) and graphdiyne (Gdy) in alkaline medium. We considered both associative and dissociative pathways, as well as two distinct intermediate forks for each of them depending on the first protonation site(s). Following the dissociative approach, the activation energy to form an O2 dissociated configuration is found as a function of the distances migrated by the O atoms over the catalyst surface and the amount of charge transferred from the C atoms linked to N. N doped αGy and 6,6,12Gy emerged as the best electrocatalyst comparing both pathways having lowest overpotentials of 0.88 and 0.82 V, respectively. The rate-limiting steps for the two different intermediate routes are observed to be dependent on the first protonation site(s) and related to the desorption of the OH radical from the sp hybridized C atom site(s) linked to N. Hence, the OH adsorption energy is identified as a descriptor for the efficiency of the ORR for the considered systems. The stabilities of the ORR intermediates are further elaborated in terms of pH and electrode potential.

Thermally induced intra-molecular transformation and metalation of free-base porphyrin on Au(111) surface steered by surface confinement and ad-atoms.

We investigated chemical transformations of a fluorinated free-base porphyrin, 5,10,15,20-tetrakis(4-fluorophenyl)-21,23H-porphyrin (2H-4FTPP) under a Au(111) surface confinement and including gold adatoms by using an experiment and density functional theory based first-principles calculations. Annealing of 2H-4FTPP led to cyclodehydrogenation of the molecule to a π-extended fused aromatic planar compound, 2H-4FPP, and metallation of the porphyrin ring by Au atoms to Au-4FPP complex. Noticeable lowering of bond-dissociation energies of the pyrrole's C-H bonds of the Au(111) supported molecule with respect to their values in the gas phase explained the observed on-surface planarization. Our findings also indicate that Au adatoms may catalyze cleavage of C-H/F bonds in temperature-initiated processes on Au surfaces. BDEs and explicit inclusion of Au adatoms helps to rationalize thermally induced chemical reactions on the respective surface.

Resonant energy transfer in a van der Waals stacked MoS2 - functionalized graphene quantum dot composite with ab initio validation.

Graphene-based van der Waals (vdW) heterostructures can facilitate exciting charge transfer dynamics in between structural layers with the emission of excitonic quasi-particles. However, the chemical formation of such heterostructures has been elusive thus far. In this work, a simple chemical approach is described to form such van der Waals (vdW) heterostructures using few layer MoS2 sheet embedded quantum dots (QDs) and amine-functionalized graphene quantum dots (GQDs) to probe the energy transfer mechanism for tunable photoluminescence (PL). Our findings reveal an interesting non-radiative Förster-type energy transfer with the quenching of functional GQD PL intensity after GQD/MoS2 composite formation, which validates the existing charge transfer dynamics analogous to 0D and 2D systems. The non-radiative type of energy transfer characteristic from GQD into the MoS2 layer through vdW interactions has been confirmed by photoluminescence, time decay analyses and ab initio calculations with the shifting of the Fermi level in the density of states towards the conduction band in the stacked configuration. These results are encouraging for the fundamental exploration of optical properties in other chemically prepared QD/2D based heterostructures to understand the charge transfer mechanism and fingerprint luminescence quenching for future optoelectronic device and optical sensing applications.

Neutralizing the Charge Imbalance Problem in Eu3+-Activated BaAl2O4 Nanophosphors: Theoretical Insights and Experimental Validation Considering K+ Codoping.

In recent years, rare-earth-doped nanophosphors have attracted great attention in the field of luminescent materials for advanced solid-state lighting and high-resolution display applications. However, the low efficiency of concurrent red phosphors creates a major bottleneck for easy commercialization of these devices. In this work, intense red-light-emitting K+-codoped BaAl2O4:Eu3+ nanophosphors having an average crystallite size of 54 nm were synthesized via a modified sol-gel method. The derived nanophosphors exhibit strong red emission produced by the 5D0 → 7F J (J = 0, 1, 2, 3, 4) transitions of Eu3+ upon UV and low-voltage electron beam excitation. Comparative photoluminescence (PL) analysis is executed for Eu3+-activated and K+-coactivated BaAl2O4:Eu3+ nanophosphors, demonstrating remarkable enhancement in PL intensity as well as thermal stability due to K+ codoping. The origin of this PL enhancement is also analyzed from first-principles calculations using density functional theory. Achievement of charge compensation with the addition of a K+ coactivator plays an important role in increasing the radiative lifetime and color purity of the codoped nanophosphors. Obtained results substantially approve the promising prospects of this nanophosphor in the promptly growing field of solid-state lighting and field emission display devices.

Band edge tuned ZnxCd1-xS solid solution nanopowders for efficient solar photocatalysis.

This work highlights the synthesis of zinc blende ZnxCd1-xS ternary solid solutions with a tunable bandgap. Composition dependent band gaps are realized due to the effective band edge tuning of the solid solutions which in turn show decent photocatalytic behaviour. The bandgap of ZnxCd1-xS increases as Zn composition increases. It is interesting to note that the highest catalytic activity is observed for Zn0.8Cd0.2S (Eg = 2.83 eV) in the visible spectra due to the presence of defect states in the bandgap around 2.35 eV which has been explicated according to the results of photoluminescence spectra. Density of states (DOS) analysis provides further theoretical insight into the more negative conduction band edge for x = 0.8 than other samples. It also determines generation of intermediate states due to sulfur vacancy which is responsible for more electron-hole generation and the highest rate of Methyl Orange (MO) degradation under natural sunlight irradiation.

Negative-charge-functionalized carbon nanodot: a low-cost smart cold emitter.

Cold emission properties of carbon nanodots (CNDs) evaluated using ANSYS Maxwell software are predicted to be size-dependent and then verified experimentally. In order to correlate the electron emission properties with the size of CNDs, the work function values were determined using ultraviolet photoelectron spectroscopy. This is the first report on theoretical calculations based on density functional theory and experimental results that confirm the work function dependency on the charge state of the functional group attached on the particle surface. The smallest CND (2.5 nm) has the highest percentage of negatively charged groups as well as the lowest work function (5.18 eV). The smallest dimension with the lowest work function assures that this sample is the best suited for field emission. It shows excellent field emission properties with a high current density of ∼1.45 mA cm-2 at 2 V µm-1 electric field, turn-on field as low as 0.04 V µm-1, very high field enhancement factor of 2.7 × 105 and high stability. Overall, the zero-dimensional CNDs showed superior field emission activity as compared to the higher dimensional carbon nanomaterials.

Cu2O/g-C3N4 nanocomposites: an insight into the band structure tuning and catalytic efficiencies.

We demonstrate an easy and scalable room-temperature synthesis of Cu2O nanoparticle incorporated graphitic carbon nitride composites without the aid of any inert atmosphere. First principles calculations based upon density functional theory, in addition to the experimental validations, have been employed to investigate the electronic and optical properties of the nanocomposites. An insight into the band structure tunability, phase stabilisation and the dependancy of the catalytic properties of the nanocomposites upon the amount of Cu loading, in the form of Cu oxides, have been provided in this work.

Local Field Enhancement-Induced Enriched Cathodoluminescence Behavior from CuI-RGO Nanophosphor Composite for Field-Emission Display Applications.

Field-emission displays (FEDs) constitute one of the major foci of the cutting edge materials research because of the increasingly escalating demand for high-resolution display panels. However, poor efficiencies of the concurrent low voltage cathodoluminescence (CL) phosphors have created a serious bottleneck in the commercialization of such devices. Herein we report a novel CuI-RGO composite nanophosphor that exhibits bright red emission under low voltage electron beam excitation. Quantitative assessment of CL spectra reveals that CuI-RGO nanocomposite phosphor leads to the 4-fold enhancement in the CL intensity as compared to the pristine CuI counterpart. Addition of RGO in the CuI matrix facilitates efficient triggering of luminescence centers that are activated by local electric field enhancement at the CuI-RGO contact points. In addition, conducting RGO also reduces the negative loading problem on the surface of the nanophosphor composite. The concept presented here opens up a novel generic route for enhancing CL intensity of the existing (nano)phosphors as well as validates the bright prospects of the CuI-RGO composite nanophosphor in this rapidly growing field.

Colossal magnetoresistance in amino-functionalized graphene quantum dots at room temperature: manifestation of weak anti-localization and doorway to spintronics.

In this work, we have demonstrated the signatures of localized surface distortions and disorders in functionalized graphene quantum dots (fGQD) and consequences in magneto-transport under weak field regime (∼1 Tesla) at room temperature. Observed positive colossal magnetoresistance (MR) and its suppression is primarily explained by weak anti-localization phenomenon where competitive valley (inter and intra) dependent scattering takes place at room temperature under low magnetic field; analogous to low mobility disordered graphene samples. Furthermore, using ab-initio analysis we show that sub-lattice sensitive spin-polarized ground state exists in the GQD as a result of pz orbital asymmetry in GQD carbon atoms with amino functional groups. This spin polarized ground state is believed to help the weak anti-localization dependent magneto transport by generating more disorder and strain in a GQD lattice under applied magnetic field and lays the premise for future graphene quantum dot based spintronic applications.

Implications of boron doping on electrocatalytic activities of graphyne and graphdiyne families: a first principles study.

Dispersive force corrected density functional theory is used to map the oxygen reduction reaction (ORR) kinetics of six kinds of graphyne (Gy) and graphdiyne (Gdy) systems (namely αGy, ßGy, γGy, δGy, 6,6,12Gy, RGy and Gdy) with substitutional boron (B) atom doping. To this end, the most favorable sites for B doping of each structures are determined by comparing their formation energies and then the best configuration for di-oxygen (O2) adsorption is computed by analyzing the corresponding adsorption energies. Even though oxygen adsorption is found to be energetically favorable on all of these and all Gys and Gdy are found to distinctly favor the four electron pathways for ORR, a reaction scheme with monotonically exothermic ΔG is observed only for B doped RGy. Further computations performed by varying electrode potential indicated this monotonically exothermic nature of the ΔG of B doped RGy to persist in the range 0-0.22 V and also indicated the first (H(+) + e) transfer step to be the rate limiting step.

Hierarchical cupric oxide nanostructures on copper substrate for cold cathode emission: an experimental venture with theoretical correlation.

In this paper we report a facile route for the synthesis of controlled CuO nanoarchitectures directly grown on a copper substrate by a one-step simple chemical route with varying concentration of non-ionic surfactant PEG-6K. The phase purity and degree of crystallinity of the as-developed nanostructures were systemically investigated by X-ray diffraction, X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy (HRTEM). A detailed analysis by field emission scanning electron microscopy confirmed the uniformity of the prepared nanostructures on the substrates. These architectures displayed substantial improvement of field emission properties with respect to other structures of CuO reported so far. A particular nanostructure (needle) among them showed a down shift of the turn-on field to 2.2 V µm(-1) coupled with a good enhancement factor (ß) ∼516, which are deemed as sufficient for electron emission based applications such as field emission displays and vacuum nanoelectronic devices. The origin of this efficient field emission from CuO nanoarchitectures, were probed computationally by investigating the local electric field distribution through finite element based simulation method using the ANSYS Maxwell simulation package.

A carbon fiber-ZnS nanocomposite for dual application as an efficient cold cathode as well as a luminescent anode for display technology.

In the current work we present a simple technique to develop a carbon nanofiber (CNF)/zinc sulfide (ZnS) composite material for excellent FED application. CNFs and ZnS microspheres were synthesized by following a simple thermal chemical vapor deposition and hydrothermal procedure, respectively. A rigorous chemical mixture of CNF and ZnS was prepared to produce the CNF-ZnS composite material. The cathodo-luminescence intensity of the composite improved immensely compared to pure ZnS, also the composite material showed better field emission than pure CNFs. For pure CNF the turn-on field was found to be 2.1 V µm(-1) whereas for the CNF-ZnS composite it reduced to a value of 1.72 V µm(-1). Altogether the composite happened to be an ideal element for both the anode and cathode of a FED system. Furthermore, simulation of our CNF-ZnS composite system using the finite element modeling method also ensured the betterment of field emission from CNF after surface attachment of ZnS nanoclusters.

Correlation of C-reactive protein and body mass index with diabetic retinopathy in Indian population.

BACKGROUND: Association of C-reactive protein (CRP) and body mass index (BMI) with diabetic retinopathy (DR) has conflicting reports. METHOD: Sixty diabetes patients each with DR (Group A), no DR (Group B) and 60 healthy volunteers (control, group C) were studied. CRP was measured. BMI was calculated. RESULT: Significant difference in CRP was observed between groups A & B (p=0.000) and A & C (p=0.007). No significant difference in BMI was observed. Central macular thickness correlated positively with CRP and negatively with BMI. CONCLUSION: We observed strong association of CRP with DR and no significant relationship between DR and BMI.

A first-principles investigation of oxygen reduction reaction catalysis capabilities of As decorated defect graphene.

Single and multiple As adatom adsorptions on double vacancy (DV) defect graphene sheets are extensively analyzed using dispersive force corrected density functional theory (DFT). Defect pentagonal and heptagonal bridge sites and the immediate neighborhood of the defect center are found to be most favorable for this purpose. Quantitative analysis of electronic structures revealed the As-C bonding to be mostly ionic in nature with some covalency arising from the overlap of As p states and C p states. For multiple As adatoms adsorption in close vicinity, ionicity of the As-C bonds are found to decrease to support As-As cohesion; the net result of which is manifested as better binding of dioxygen molecule with them and additional weakening of the O-O bond in the adsorbed state. Free energy profile of oxygen reduction reaction (ORR) cycle using multiple As atom adsorbed DV graphene as electrocatalyst predicts high affinity towards four electron process and forbids the formation of H2O2via two electron process. Other traits, such as no intermediate O-O-H formation and high stability of the catalytic system throughout the reaction process indicate As adatoms adsorbed on DV graphene system to be efficient and highly stable as an alternate Pt free ORR electrocatalyst.

Rules of boron-nitrogen doping in defect graphene sheets: a first-principles investigation of band-gap tuning and oxygen reduction reaction catalysis capabilities.

Introduction of defects and nitrogen doping are two of the most pursued methods to tailor the properties of graphene for better suitability to applications such as catalysis and energy conversion. Doping nitrogen atoms at defect sites of graphene and codoping them along with boron atoms can further increase the efficiency of such systems due to better stability of nitrogen at defect sites and stabilization provided by B-N bonding. Systematic exploration of the possible doping/codoping configurations reflecting defect regions of graphene presents a prevalent doping site for nitrogen-rich BN clusters and they are also highly suitable for modulating (0.2-0.9 eV) the band gap of defect graphene. Such codoped systems perform significantly better than the platinum surface, undoped defect graphene, and the single nitrogen or boron atom doped defect graphene system for dioxygen adsorption. Significant stretching of the O-O bond indicates a lowering of the bond breakage barrier, which is advantageous for applications in the oxygen reduction reaction.

Efficient and persistent cold cathode emission from CuPc nanotubes: a joint experimental and simulation investigation.

In the current report, chemically synthesized copper phthalocyanine (CuPc) nanotubes are shown to exhibit unprecedentedly well cold cathode emission characteristics with turn-on field (3.2 V µ m(-1)) and stable emission during long intervals (200 min). Simulation of electric field distribution via finite element method around an isolated nanotube emitter in a manner parallel to the experimental setup (inter-electrode distance = 180 µm) exhibits good corroboration of theoretical premises with experimental findings. Obtained results strongly indicate CuPc nanotubes to be potential candidate as cold cathode emitter for electron emission based applications such as field emission displays and vacuum nano-electronic devices.

Amino-functionalized graphene quantum dots: origin of tunable heterogeneous photoluminescence.

Graphene quantum dots are known to exhibit tunable photoluminescence (PL) through manipulation of edge functionality under various synthesis conditions. Here, we report observation of excitation dependent anomalous m-n type fingerprint PL transition in synthesized amino functionalized graphene quantum dots (5-7 nm). The effect of band-to-band π*-π and interstate to band n-π induced transitions led to effective multicolor emission under changeable excitation wavelength in the functionalized system. A reasonable assertion that equi-coupling of π*-π and n-π transitions activated the heterogeneous dual mode cyan emission was made upon observation of the PL spectra. Furthermore, investigation of incremented dimensional scaling through facile synthesis of amino functionalized quantum graphene flakes (20-30 nm) revealed it had negligible effect on the modulated PL pattern. Moreover, an effort was made to trace the origin of excitation dependent tunable heterogeneous photoluminescence through the framework of energy band diagram hypothesis and first principles analysis. Ab initio results suggested formation of an interband state as a manifestation of p orbital hybridization between C-N atoms at the edge sites. Therefore comprehensive theoretical and experimental analysis revealed that newly created energy levels can exist as an interband within the energy gap in functionalized graphene quantum structures yielding excitation dependent tunable PL for optoelectronic applications.