Novel A-π-D-A organic dyes for better photovoltaic performance.

In this article, we report two indole-based metal-free organic dyes In-T-2C (3-(5-(3-((2-carboxy-2-cyanovinyl)-1-pentyl-1H-indol-5-yl)thiophen-2-yl)-2-isocyanoacrylic acid) and In-B-C (2-cyano-3-(5-(4-cyanophenyl)-1-pentyl-1H-indol-3-yl)acrylic acid) with A-π-D-A architecture. The molecular structures of metal-free indole-based A-π-D-A organic dyes were elucidated using FT-IR, NMR, HRMS and single-crystal X-ray diffraction techniques. The present investigation examined the features of the synthesized dyes employing photophysical attributes, electrochemical traits and theoretical studies were executed to acquire a detailed comprehension of the geometry, electronic structure and absorption spectra of the synthesized dyes using density functional theory (DFT) and time-dependent density functional theory (TD-DFT). Additionally, dye-sensitized solar cells (DSSCs) were fabricated using newly synthesized dyes and examined their photovoltaic activity. Electrochemical impedance analysis (EIS) was performed to recognize the interfacial charge transfer in the DSSCs. The In-T-2C dye-based DSSC device exhibited an uppermost fill factor (FF) of 0.63, resulting in the uppermost open-circuit voltage (V OC) of 540.2 mV and highest efficiency (η) of 4.12% due to the highest short-circuit current density (J SC) of 12.1 mA cm-2 compared to the In-B-C dye (V OC = 497 mV, J SC = 1.07, FF = 0.70, η = 0.38%).

Improvement of catalytic activity of aluminum complexes for the ring-opening polymerization of ε-caprolactone: aluminum thioamidate and thioureidate systems.

In this study, a series of Al complexes bearing amidates, thioamidates, ureidates, and thioureidates were synthesized and their catalytic activity for ε-caprolactone (CL) polymerization was evaluated. SPr-Al exhibited a higher catalytic activity than OPr-Al (3.2 times as high for CL polymerization; [CL] : [SPr-Al] : [BnOH] = 100 : 0.5 : 2; [SPr-Al] = 10 mM, conv. = 93% after 14 min at 25 °C), and USCl-Al exhibited a higher catalytic activity than UCl-Al (4.6 times as high for CL polymerization; [CL] : [USCl-Al] : [BnOH] = 100 : 0.5 : 2; [USCl-Al] = 10 mM, conv. = 90% after 15 min at 25 °C). Regardless of whether aluminum amidates or ureidates were present, thioligands improved the polymerization rate of aluminum catalysts. Density functional theory calculations revealed that the eight-membered ring [SPr-AlOMe2]2 decomposed into the four-membered ring SPr-AlOMe2. However, [OPr-AlOMe2]2 did not decompose because of its strong bridging Al-O bond. The overall activation energy required for CL polymerization was lower when using [SPr-AlOMe2]2 (18.1 kcal mol-1) as a catalyst than when using [OPr-AlOMe2]2 (23.9 kcal mol-1). This is because the TS2a transition state of SPr-AlOMe2 had a more open coordination geometry with a small N-Al-S angle (72.91°) than did TS3c of [OPr-AlOMe2]2, the crowded highest-energy transition state of [OPr-AlOMe2]2 with a larger N-Al-O angle (99.63°).

Density functional theory studies on graphene/h-boron nitride hybrid nanosheets for supercapacitor electrode applications.

Pristine graphene (C32), hexagonal boron nitride (h-BN), and graphene/h-BN hybrid nanosheets were examined using density functional theory calculations in order to find their suitability as an electrode material for supercapacitor applications. The stability of the structure, charge density, electronic properties, and quantum capacitance of pristine graphene and graphene/h-BN hybrid nanosheets were studied. The structural optimization results reveal that all the nanosheets are stable with zero transverse displacement of atoms along the z-direction. Further, replacing the C-C pair with B-N altered the average bond length and angle, thereby maintaining structural stability. The interaction between graphene and h-BN is higher for C16B8N8 compared to other hybrid nanosheets because of the delocalized distribution of the electron density cloud. The doping of the B-N pair into the graphene nanosheet shifts the Fermi level into either the valence band or the conduction band based on the concentration of the B-N pair. Meanwhile, the effective mass is increased and is relatively high for the hybrid nanosheets with a localized state. The pristine B16N16 nanosheet exhibits a quantum capacitance of 31.539 µF cm-2, while among the hybrid nanosheets, the C4B14N14 nanosheet exhibits a maximum quantum capacitance of 22.518 µF cm-2, and from the outcomes, they are suitable as an electrode for asymmetric supercapacitors.

Modulating the Combinatorial Target Power of MgSnN2 via RF Magnetron Sputtering for Enhanced Optoelectronic Performance: Mechanistic Insights from DFT Studies.

The unique structural features of many ternary nitride materials with strong chemical bonding and band gaps above 2.0 eV are limited and are experimentally unexplored. It is important to identify candidate materials for optoelectronic devices, particularly for light-emitting diodes (LEDs) and absorbers in tandem photovoltaics. Here, we fabricated MgSnN2 thin films, as promising II-IV-N2 semiconductors, on stainless-steel, glass, and silicon substrates via combinatorial radio-frequency magnetron sputtering. The structural defects of the MgSnN2 films were studied as a function of the Sn power density, while the Mg and Sn atomic ratios remained constant. Polycrystalline orthorhombic MgSnN2 was grown on the (120) orientation within a wide optical band gap range of ∼2.20-2.17 eV. The carrier densities of 2.18× 1020 to 1.02 × 1021 cm-3, mobilities between 3.75 and 2.24 cm2/Vs, and a decrease in resistivity from 7.64 to 2.73 × 10-3 Ω cm were confirmed by Hall-effect measurements. These high carrier concentrations suggested that the optical band gap measurements were affected by a Burstein-Moss shift. Furthermore, the electrochemical capacitance properties of the optimal MgSnN2 film exhibited an areal capacitance of 152.5 mF/cm2 at 10 mV/s with high retention stability. The experimental and theoretical results showed that MgSnN2 films were effective semiconductor nitrides toward the progression of solar absorbers and LEDs.

Effect of 1-Substituted 2-(Pyridin-2-yl)-1H-Benzo[d]imidazole Ligand-Coordinated Copper and Cobalt Complex Redox Electrolytes on Performance of Ru(II) Dye-Based Dye-Sensitized Solar Cells.

A comparative study has been attempted on 1-substituted 2-(pyridin-2-yl)-1H-benzo[d]imidazole ligand-coordinated copper and cobalt metal complex electrolytes Cu+/2+[nbpbi]2(PF6-)1/2, Cu+/2+[npbi]2(PF6-)1/2, Co2+/3+[nbpbi]3(PF6-)2/3, and Co2+/3+[npbi]3(PF6-)2/3 in dry acetonitrile coupled with both N3 and N719 dyes in dye-sensitized solar cell (DSSC) devices. Impressively, the copper metal sites coordinated with ligands nbpbi (L1) and npbi (L2) shift the redox potential about 190-200 mV and pave the way to achieve remarkably higher power current efficiency, which is clarified with cyclic voltammetry, electrochemical impedance spectrum, electron lifetime, and quasi Fermi-level experimental results. Overall efficiencies of 4.99, 4.82, 3.26, and 3.19% under 1 sun conditions (100 mW cm-2) were obtained for Cu+/2+[nbpbi]2(PF6-)1/2 and Cu+/2+[npbi]2(PF6-)1/2 electrolytes coupled with the sensitizers (N3 and N719 dyes), which are considerably higher than those acquired for devices containing the cobalt electrolytes. These results signify a record for copper complex-based electrolytes coupled with ruthenium dyes in liquid DSSCs. In particular, bulky acceptor 4-nitro benzyl moiety-substituted 2-(pyridin-2-yl)-benzimidazole (on the N-H position) (ligand L1)-coordinated copper metal complex electrolytes achieved higher efficiency, approaching a suitable redox potential of 0.68 V versus NHE. At the same time, the napthyl moiety-substituted 2-(pyridin-2-yl)-benzimidazole (ligand L2)-coordinated copper metal complex electrolytes showed less redox potential due to its donating nature. It was determined that the Jsc and PCE increment of the devices consisting of Cu+/2+[nbpbi]2(PF6-)1/2 electrolytes was mainly attributed to various factors such as higher chemical capacitance, larger charge, longer electron life time, a downward shift in the quasi Fermi level of TiO2, the slow recombination process, and fast dye regeneration. These results make easily tunable metal complexes bearing a new sort of 1-substituted 2-(pyridin-2-yl)-1H-benzo[d]imidazole ligand-based electrolytes as very promising copper electrolytes for further improvements of extremely efficient liquid DSSCs.

Surfactant-assisted synthesis of copper oxide nanorods for the enhanced photocatalytic degradation of Reactive Black 5 dye in wastewater.

In this study, copper oxide nanorods were synthesized via surfactant-assisted chemical precipitation method and characterized by using X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and UV-Visible spectrometer. XRD result reveals that CuO nanorods were structured in the monoclinic phase. SEM image suggested that synthesized CuO were shaped like nanorod with approximately 20-40 nm width and 500-800 nm length. The observed band gap calculated from UV-Visible absorption studies is 1.45 eV. As-prepared CuO nanorods were applied as a photocatalyst for the degradation of textile dye Reactive Black 5 (RB-5) in aqueous solution under the presence of visible light. The result exhibited that an enhanced degradation of RB-5 was achieved around 98% within 300 min and the experimental values were well matched with the linear fit model (R2 = 0.97) and the observed rate constant found to be 5 × 10-3 min-1. Therefore, as-synthesized CuO nanorods can be applied as a potential photocatalyst material for the degradation of organic pollutants in the wastewater.

Effect of Cross-Linking on the Performances of Starch-Based Biopolymer as Gel Electrolyte for Dye-Sensitized Solar Cell Applications.

Dye-sensitized solar cells (DSSCs) have become a validated and economically credible competitor to the traditional solid-state junction photovoltaic devices. DSSCs based on biopolymer gel electrolyte systems offer the perspective of competitive conversion efficiencies with a very low-cost fabrication. In this paper, a new starch-based biopolymer gel electrolyte system is prepared by mixing lithium iodide and iodine with bare and citric acid cross-linked potato starches with glycerol as the plasticizing agent. The effect of the preparation methods on the starch cross-linking degree as well as the photoconversion efficiency of the resulting DSSC cells is carefully analyzed. Fourier transform spectroscopy, X-ray diffraction, and scanning electron microscopy were used to characterize the morphology and conformational changes of starch in the electrolytes. The conductivity of the biopolymer electrolytes was determined by electrochemical impedance spectroscopy. DSSC based on the starch-gel polymer electrolytes were characterized by photovoltaic measurements and electrochemical impedance spectroscopy. Results clearly show that the cross-linking increases the recombination resistance and open circuit voltage (VOC) of the DSSC, and thereby the photoconversion efficiency of the cell. In particular, electrolytes containing 1.4 g bare and cross-linked starches showed ionic conductivities of σ = 1.61, 0.59, 0.38, and 0.35 S cm-1, and the corresponding DSSCs showed efficiencies of 1.2, 1.4, 0.93, and 1.11%, respectively.

Enhanced photocurrent generation in bacteriorhodopsin based bio-sensitized solar cells using gel electrolyte.

High purity light sensitive photoactive protein Bacteriorhodopsin (BR) was isolated successfully via a simple two phase extraction technique (ATPS) as an alternate method for the tedious sucrose gradient ultracentrifugation procedure (SGU). Bio sensitized solar cells (BSSCs) were fabricated by the integration of BR into TiO2 (photo anode) with acetamide based gel electrolytes and platinum (photo cathode) as a counter electrode. The structural and photoelectrical behaviours of BR and BSSCs were analyzed by Atomic Force Microscopy, Raman spectroscopy, photocurrent and photovoltage (IV) measurement and electrochemical impedance spectroscopy. The short circuit photocurrent (Jsc) and photoelectric conversion efficiency (η) of acetamide based gel electrolyte (AG) (1.08mAcm(-2), 0.49%) are twice higher than that of traditional triiodide based liquid electrolyte (LE) (0.62mAcm(-2), 0.19%). Also, quasi-Fermi level and lifetime of photogenerated electrons in acetamide based gel electrolyte is about four times higher than that observed in traditional triiodide redox electrolyte. A comparison of the observed results with similar BSSCs made of other natural photoactive protein systems shows that BR as sensitizer has better photovoltaic performance. The enhanced photocurrent generation of the BSSC constructed in our study could be due to the interaction of BR with acetamide based modified poly(ethylene)oxide (PEO) gel electrolyte.