Pd Nanoparticle-Decorated Novel Ternary Bi2O2CO3-Bi2MoO6-CuO Heterojunction for Enhanced Photo-electrocatalytic Ethanol Oxidation.

Recently, photo-electrooxidation of fuel using a noble metal-semiconductor junction has been one of the most promising approaches in fuel cell systems. Herein, we report the development of a Pd-supported Bi2MoO6-Bi2O2CO3-CuO novel ternary heterojunction for ethanol oxidation in alkali in the presence and absence of visible light. Various spectroscopic and microscopic characterization techniques confirm strong coupling between palladium nanoparticles and Bi2MoO6-Bi2O2CO3-CuO ternary heterojunction supports. The photo-electrocatalytic efficacy of the synthesized catalysts was inspected by cyclic voltammetry (CV), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS). The CV study reveals that the forward peak current density (in mA mg-1 of Pd) of the synthesized quaternary heterojunction was about 1482.5, which is 2.4, 4, and 4.6 times higher than that of Pd/CuO (608.3), Pd/Bi2MoO6-Bi2O2CO3 (368.3), and similarly synthesized Pd catalyst (321.5) under visible light radiation. The best heterojunction catalyst shows 2.21-fold higher peak current density in visible light compared to that in dark. CA study reveals that after operation for 6000 s, the current density of the quaternary electrode is 1.5 and 3.4 times greater than that of Pd/CuO and Pd/C catalysts, respectively. The greater photocurrent response, lower photoluminescence (PL) emission intensity, and smaller semicircle arc in the Nyquist plot of the quaternary catalyst demonstrate the efficient segregation and higher charge transfer conductance of photogenerated charges to facilitate the photo-electrooxidation process of ethanol. The stability test shows that the quaternary catalyst loses only 9.8 and 7.7% of its maximum current density after 500 cycles of CV operation in the dark and light, respectively, indicating that light energy is more beneficial in establishing high stability. The dramatic enhancement of the photo-electrocatalytic activity of the quaternary electrode is owing to the lower band gap, high ECSA, enhanced charge separation of photogenerated carriers (e--h+), and all cocatalytic support of Bi2MoO6, Bi2O2CO3, and CuO in Pd/ Bi2MoO6-Bi2O2CO3-CuO under visible light radiation. The morphology and structure of the used quaternary catalyst are tested using FESEM and PXRD. Finally, ex situ FTIR spectroscopy and HPLC techniques help understand the ethanol electrooxidation reaction mechanism.

Unraveling the Charge Transport Mechanism in Mechanochemically Processed Hybrid Perovskite Solar Cell.

The long-term operation of organic-inorganic hybrid perovskite solar cells is hampered by the microscopic strain introduced by the multiple thermal cycles during the synthesis of the material via a solution process route. This setback can be eliminated by a room temperature synthesis scheme. In this work, a mechanochemical synthesis technique at room temperature is employed to process CH3NH3PbI2Br films for fabricating perovskite solar cell devices. The solar cell device has produced a 957 mV Voc, a 16.92 mA/cm2 short circuit current density, and a 10.5% efficiency. These values are higher than the published values on mechanochemically synthesized CH3NH3PbI3. The charge transport properties of the devices are studied using DC conductivity and AC impedance spectroscopy, which show a multichannel transport mechanism having both ionic and electronic contributions. A much smaller defect density in the mechanochemically synthesized hybrid perovskite material is confirmed. A polarization assisted recombination mechanism is observed to have a dominant effect on the overall charge transport mechanism. However, no obvious grain boundary and intralayer lattice defect related responses are found in the perovskite layer. Interfacial charge transport and recombination are found to show major effects on both the temperature dependent and illumination dependent impedance spectra.

Studies on Magnetic and Dielectric Properties of Antiferromagnetically Coupled Dinuclear Cu(II) in a One-Dimensional Cu(II) Coordination Polymer.

A one-dimensional Cu(II) coordination polymer with encapsulated antiferromagnetically coupled binuclear Cu(II) has been synthesized by using 5-nitroisophthalic acid (5-N-IPA) and 4-aminopyridine (4-APY) [Cu2(5-N-IPA)2(4-APY)4] n (1). Electrical properties are examined by complex impedance (Z*), dielectric permittivity (ε*), and ac conductivity studies at different frequencies (10 kHz-5 MHz) and temperatures (253-333 K). The contribution of grain and grain boundary has been explained by a different theoretical model. The variable temperature magnetic susceptibility data for compound 1 were recorded between 300 and 2 K. The shape of the curve (χM T vs T) indicates dominant antiferromagnetic coupling, which results from the interaction between the copper(II) atoms.

Methylammonium Lead Iodide Incorporated Poly(vinylidene fluoride) Nanofibers for Flexible Piezoelectric-Pyroelectric Nanogenerator.

This work introduces a piezoelectric-pyroelectric nanogenerator (P-PNG) based on methylammonium lead iodide (CH3NH3PbI3) incorporated electrospun poly(vinylidene fluoride) (PVDF) nanofibers that are able to harvest mechanical and thermal energies. During the application of a periodic compressive contact force at a frequency of 4 Hz, an output voltage of ∼220 mV is generated. The P-PNG has a piezoelectric coefficient (d33) of ∼19.7 pC/N coupled with a high durability (60 000 cycles) and quick response time (∼1 ms). The maximum generated output power density (∼0.8 mW/m2) is sufficient to charge up a variety of capacitors, with the potential to replace an external power supply to drive portable devices. In addition, upon exposure to cyclic heating and cooling at a temperature of 38 K, a pyroelectric output current of 18.2 pA and a voltage of 41.78 mV were achieved. The fast response time of 1.14 s, reset time of 1.25 s, and pyroelectric coefficient of ∼44 pC/m2 K demonstrate a self-powered temperature sensing capability of the P-PNG. These characteristics make the P-PNG suitable for flexible piezoelectric-pyroelectric energy harvesting for self-powered electronic devices.

Electrochemical Energy Storage Properties of Ni-Mn-Oxide Electrodes for Advance Asymmetric Supercapacitor Application.

In this work, we report a facile one-spot synthesis process and the influence of compositional variation on the electrochemical performance of Ni-Mn-oxides (Ni:Mn = 1:1, 1:2, 1:3, and 1:4) for high-performance advanced energy storage applications. The crystalline structure and the morphology of these synthesized nanocomposites have been demonstrated using X-ray diffraction, field emission scanning electron microscopy, and transmission electron Microscopy. Among these materials, Ni-Mn-oxide with Ni:Mn = 1:3 possesses a large Brunauer?Emmett?Teller specific surface area (127 m2 g?1) with pore size 8.2 nm and exhibits the highest specific capacitance of 1215.5 F g?1 at a scan rate 2 mV s?1 with an excellent long-term cycling stability (?87.2% capacitance retention at 10 A g?1 over 5000 cycles). This work also gives a comparison and explains the influence of different compositional ratios on the electrochemical properties of Ni-Mn-oxides. To demonstrate the possibility of commercial application, an asymmetric supercapacitor device has been constructed by using Ni-Mn-oxide (Ni:Mn = 1:3) as a positive electrode and activated carbon (AC) as a negative electrode. This battery-like device achieves a maximum energy density of 132.3 W h kg?1 at a power density of 1651 W kg?1 and excellent coulombic efficiency of 97% over 3000 cycles at 10 A g?1.

Organo-Lead Halide Perovskite Induced Electroactive ß-Phase in Porous PVDF Films: An Excellent Material for Photoactive Piezoelectric Energy Harvester and Photodetector.

Methylammonium lead iodide (CH3NH3PbI3) (MAPI)-embedded ß-phase comprising porous poly(vinylidene fluoride) (PVDF) composite (MPC) films turns to an excellent material for energy harvester and photodetector (PD). MAPI enables to nucleate up to ∼91% of electroactive phase in PVDF to make it suitable for piezoelectric-based mechanical energy harvesters (PEHs), sensors, and actuators. The piezoelectric energy generation from PEH made with MPC film has been demonstrated under a simple human finger touch motion. In addition, the feasibility of photosensitive properties of MPC films are manifested under the illumination of nonmonochromatic light, which also promises the application as organic photodetectors. Furthermore, fast rising time and instant increase in the current under light illumination have been observed in an MPC-based photodetector (PD), which indicates of its potential utility in efficient photoactive device. Owing to the photoresponsive and electroactive nature of MPC films, a new class of stand-alone self-powered flexible photoactive piezoelectric energy harvester (PPEH) has been fabricated. The simultaneous mechanical energy-harvesting and visible light detection capability of the PPEH is promising in piezo-phototronics technology.