• Energy Research

Two new bi-anchoring organic sensitizers of type D-(π-A)2 comprising the identical π-spacer (thiophene-2-acetonitrile) and electron acceptor (malonic acid) but different aryl amine as electron donors (diphenylamine and carbazole) were synthesized, characterized and fabricated metal free dye-sensitized solar cell devices. The intra molecular charge transfer property and electrochemical property of these dyes were investigated by molecular absorption, emission, cyclic voltammetric experiments and in addition, quantum chemical calculation studies were performed to provide sufficient driving force for the electron injection into the conduction band of TiO2 which leads to efficient charge collection. Among the fabricated devices, carbazole based device exhibits high current conversion efficiency (η=4.7%) with a short circuit current density (JSC) 15.3 mA/cm(2), an open circuit photo voltage (VOC) of 0.59 V and a fill factor of 0.44 under AM 1.5 illumination (85 mW/cm(2)) compared to diphenylamine based device.

Lignocellulosic biomass waste is a cheap, eco-friendly, and sustainable raw material for a wide array of applications. In the present study, an easy, fast, and economically feasible route has been proposed for the preparation of different zero-valent metal nanoparticles (ZV-MNPs) based on Cu, Co, Ag, and Ni NPs using empty fruit bunch (EFB) biomass residue as support material. The catalytic efficiency of ZV-MNPs/EFB catalyst was investigated against five model pollutants, such as methyl orange (MO), congo red (CR), methylene blue (MB), acridine orange (AO), and 4-nitrophenol (4-NP) using NaBH4 as a source of hydrogen and electron. Comparative study revealed that among as-prepared ZV-MNPs/EFB catalysts, Cu-NPs immobilized onto EFB (Cu/EFB) exhibited maximum catalytic efficiency towards pollutant abasement. Degradation reactions were highly efficient, and were completed within a short time (4 min) in case of MO, CR, and MB, whilst AO and 4-NP were reduced in less than 15 min. Kinetic investigation revealed that the degradation rate of model pollutants accorded with pseudo-first order model. Furthermore, supported catalysts were easily recovered after the completion of experiment by simply pulling the catalyst from reaction system. Recyclability tests performed on Cu/EFB revealed that more than 97% of the reduction was achieved in case of MO dye for four successive cycles of reuse. The as-prepared heterostructure showed multifunctional properties, such as enhanced uptake of contaminants, high catalytic efficiency, and easy recovery, hence, offers great prospects in wastewater purification.

AbstractStabilization of zero-valent CuNi nanoparticles (NPs) supported on Cicer arietenum (CP) is reported here for the reduction and removal of persistent organic pollutants. The functional groups and interactions of NPs with the CP were determined by ATR-FTIR. The crystallinity, morphology, and the elemental composition of the samples were determined through powder XRD, FESEM, and EDS techniques, respectively. The XRD spectrum displayed a sharp crystalline peak at 43.9 for CuNi. The Cu and Ni zero-valent NPs displayed a peak at almost the same region, and thus, both the peaks are merged and appeared as a single peak. The chemical reduction/degradation of eight model pollutants, viz., 2-nitrophenol (ONP), 3-nitrophenol (MNP), 4-nitrophenol (PNP), 2,4-dinitrophenol (DNP), methyl orange (MO), congo red (CR), methylene blue (MB), and rhodamine B (RB) were carried out in the presence of NaBH4. The kapp value of 0.1 mM 4NP was highest which was 1.8 × 10−1 min−1 while the slowest rate was observed for CR and RB with kapp 5.5 × 10−3 and 5.4 × 10−3 min−1 respectively. This article helps in the removal of toxic organic pollutants through green supported NPs.

AbstractThe formation of hydrocarbon pool (HCP) species during methanol‐to‐olefin (MTO) and ethanol‐to‐olefin (ETO) processes have been studied on individual micron‐sized SAPO‐34 crystals with a combination of in situ UV/Vis, confocal fluorescence, and synchrotron‐based IR microspectroscopic techniques. With in situ UV/Vis microspectroscopy, the intensity changes of the λ=400 nm absorption band, ascribed to polyalkylated benzene (PAB) carbocations, have been monitored and fitted with a first‐order kinetics at low reaction temperatures. The calculated activation energy (Ea) for MTO, approximately 98 kJ mol−1, shows a strong correlation with the theoretical values for the methylation of aromatics. This provides evidence that methylation reactions are the rate‐determining steps for the formation of PAB. In contrast for ETO, the Ea value is approximately 60 kJ mol−1, which is comparable to the Ea values for the condensation of light olefins into aromatics. Confocal fluorescence microscopy demonstrates that during MTO the formation of the initial HCP species are concentrated in the outer rim of the SAPO‐34 crystal when the reaction temperature is at 600 K or lower, whereas larger HCP species are gradually formed inwards the crystal at higher temperatures. In the case of ETO, the observed egg‐white distribution of HCP at 509 K suggests that the ETO process is kinetically controlled, whereas the square‐shaped HCP distribution at 650 K is indicative of a diffusion‐controlled process. Finally, synchrotron‐based IR microspectroscopy revealed a higher degree of alkylation for aromatics for MTO as compared to ETO, whereas high reaction temperatures favor dealkylation processes for both the MTO and ETO processes.

AbstractHydrogen is considered as the “holy grail” for the energy community. One of the most promising strategies to produce hydrogen is to split water using renewable energy such as solar radiation. The abundance of water and solar energy enables the potential of scaling‐up of this new technology, if suitable electrocatalysts and solar cells are developed. In this work, a series of materials made of earth‐abundant elements was investigated for hydrogen evolution or oxygen evolution reaction. Among the developed catalysts, MoS2 and NiFe showed the best activities for proton reduction and water oxidation, respectively. These catalysts were further integrated into an alkaline electrolyzer, which delivered a current density of 10 mA cm−2 at a cell voltage of 1.9 V for water splitting. Using two in‐series‐connected perovskite solar cells (PSCs) as a power source, a remarkable solar‐to‐hydrogen conversion efficiency of 12.67 % was achieved in an alkaline electrolyzer with a partial current density of 10.3 mA cm−2 for hydrogen production. The usage of earth‐abundant catalysts in this study, together with the employment of low‐cost perovskite light absorber, shows the potential of scaling up this type of photovoltaic electrolyzer for sustainable hydrogen production.

This study is based on the construction of an enzymatic bioanode adopting the exclusively reported layer-by-layer (LBL) assembly of Ppy-Ag-GO/ferritin (Frt)/glucose oxidase (GOx). The glassy carbon (GC) electrode was immobilised with the conducting polypyrrole (Ppy)-silver nanoparticles (Ag)-graphene oxide (GO) based biocomposite as electron transfer elevator, horse spleen ferritin (Frt) protein as electron transfer mediator and glucose oxidase (GOx) enzyme in layer by layer configuration. The fabricated bioanode exhibited good electrochemical performance with a maximum current response of 5.7mAcm-2 accompanied with biocompatibility and environmental stability because of the synergistic effect between outstanding properties of PPy, silver and GO, thereby, showing superior catalytic efficiency for the oxidation of glucose.

The effect of solvents on the absorption and emission spectra of 1,4-bis(5-phenyl-2-oxazolyl)benzene (POPOP) laser dye has been studied in various solvents at 298 K. A bathochromic shift was observed in absorption and fluorescence spectra upon increase of solvent polarity, which indicates that this transition is π-𝜋∗. The ground and excited state dipole moments were calculated as 2.23 and 6.34 Debye, respectively. The dye solution in MeOH, n-heptane, and methyl isobutyl ketone gives laser emission in the blue region upon excitation by a 337.1 nm nitrogen pulse; the gain coefficient and emission cross section as well as normalized photostability have been determined. Excitation energy transfer from POPOP to rhodamine B and fluorescine was studied to improve the laser emission from these dyes. Such an energy transfer dye laser system (ETDL) obeys a long range columbic energy transfer mechanism with a critical transfer distance, R0, of 25 and 33 Å and kq equal to 10.4×1012 and 26.2×1012M−1s−1 for the POPOP/RB and POPOP/fluorescine pair, respectively. The POPOP dye is highly photostable in polar protic and polar aprotic solvents, while it displays photodecomposition in chloromethane solvent via formation of a contact ion pair. The photochemical quantum yield and rate of photodecomposition depend on the electron affinity of solvent.