α-Fe2O3/Pt hybrid nanorings and their enhanced photocatalytic activities

In this paper, α-Fe₂O₃ nanorings were synthesized and used as a support to further synthesize hybrid Pt/α-Fe₂O₃ nanorings. Transmission electron microscopy (TEM) analyses clearly suggest that Pt nanoparticles are deposited on the surface of α-Fe₂O₃ nanorings in a well-dispersed state. This metal–semiconductor hybrid system is expected to show high photocatalytic activity towards the degradation of environmental pollutants. Because of the Schottky contact between semiconductor and metal particles, the holes prefer to localize in energetically lower semiconductor, whereas the electrons can move through the heterointerface. This interfacial charge transfer and separation facilitate the redox reactions, results in a high photocatalytic activity. In our case, the as obtained α-Fe₂O₃/Pt hybrids exhibit enhanced photocatalytic performance with a degradation rate of 86.7% for methyl orange, which is much higher than that of pure α-Fe₂O₃ (33.2%).     

Investigation of the Thermal Behavior of Polypyrrole/Carbon Nanotube Composites and Utilization as Capacitive Material or Support for Catalysts

In this study, polypyrrole (PPy)/carbon nanotube (CNT) composites were synthesized by in situ chemical oxidative polymerization of a pyrrole monomer on CNT. Two different types of CNT having different structural properties were used. The composites were characterized using BET surface area analysis, Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and thermogravimetric analysis (TGA) techniques. Thermal decomposition kinetics of PPy/CNT composites was studied by thermal gravimetric analysis techniques (TG/DTG (differential thermal gravimetric)) at different heating rates (2.5, 5, 7.5, and 10?K min^?1). Kinetic parameters of the composites were obtained from the TG and DTG curves using the Kissinger–Akahira–Sunose (KAS) and Flynn–Wall–Ozawa (FWO) models. The electrochemical capacitive properties of the composites were investigated by the cyclic voltammetry (CV) technique. Pt nanoparticles were decorated on the plain CNTs and composite materials via the microwave irradiation method.     

Multi-skeletal PtPdNi nanodendrites as efficient electrocatalyst with high activity and durability towards oxygen reduction reaction

Engineering alloy nanostructures with a combination of highly active noble metals (Pt and Pd) and less electronegative non-noble metal (Ni) is found to be crucial for improving surface reactivity by enriching with active Pt sites. Herein, a multi-skeletal PtPdNi nanodendrites (NDs) was successfully formed by a simple one-pot method with structure directing agent. The modification of Pt electronic structure and their interaction due to compressive strain were explored using benchmark characterization techniques, which showed that the PtPdNi NDs possess Pt-enriched surface, corroborating to more active catalyst sites for oxygen reduction reaction (ORR) in acidic medium. The PtPdNi NDs have a higher electrochemical surface area (63 m² g^?1) and an earlier onset potential (1.01 V) than PtPd NDs, PtNi NDs, and commercial Pt/C catalysts, indicating the outstanding ORR performance. The high mass and specific activities, as well as superior durability after accelerated degradation test (ADT), highlight the remarkable electrocatalytic performance of PtPdNi NDs over others. As a result, enhancing Pt utilization through the formation of PtPdNi NDs could be a reliable strategy to improve ORR electrocatalysis for polymer electrolyte membrane fuel cell (PEMFC) applications.     

Morphological influence of graphitic carbon nanofibers by N–F dual-doping on Pt electrocatalytic activity and stability for oxygen reduction reaction in polymer electrolyte membrane fuel cells

Morphology of carbon nanofibers significantly effects Pt nanoparticles dispersion and specific interaction with the support, which is an important aspect in the fuel cell performance of the electrocatalysts. This study emphasizes, the defects creation and structural evolution comprised due to N–F co-doping on graphitic carbon nanofibers (GNFs) of different morphologies, viz. GNF-linearly aligned platelets (L), antlers (A), herringbone (H), and their specific interaction with Pt nanoparticle in enhancing the oxygen reduction reaction (ORR). GNFs–NF–Pt catalysts exhibit better ORR electrocatalytic activity, superior durability that is solely ascribed to the morphological evolution and the doped N–F heteroatoms, prompting the charge density variations in the resultant carbon fiber matrices. Amongst, H–NF–Pt catalyst performed outstanding ORR activity with exceptional electrochemical stability, which shows only 20 mV loss in the half-wave potential whilst 100 mV loss for Pt/C catalyst on 20,000 potential cycling. The PEMFC comprising H–NF–Pt as cathode catalyst with minimum loading of 0.10 mg cm^?2, delivers power density of 0.942 W cm^?2 at current density of 2.50 A cm^?2 without backpressures in H₂–O₂ feeds. The H–NF–Pt catalyst owing to its hierarchical architectures, performs well in PEMFC at the minimized catalyst loading with outstanding stability that can significantly decrease total price for the fuel cell.     

Comparison of different methods for determination of Pt surface site concentrations for supported Pt electrocatalysts

Platinum surface atom (or site) concentrations for a series of commercially available 10, 20, and 40 wt% Pt/C electrocatalysts have been determined using X-ray diffraction (XRD), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), selective chemisorption, and cyclic voltammetry (CV) methods. Each method of analysis was repeated for a sufficient number of times to determine reproducibility and standard deviation limits. Comparison of the results shows that XRD and STEM methods give Pt surface site concentrations much higher than for chemisorption analysis due to assumptions regarding Pt particle shapes and particle size distributions. The results from CV analysis agree reasonably well with those from chemisorption if the sample amounts and methods of sample deposition preceding CV analysis can be well-controlled and there is no loss of surface exposure by the Nafion over-layer. Because both chemisorption and CV analyses more directly measure actual site concentrations with fewer assumptions, these methods should be considered superior to XRD and STEM analyses. Further, since chemisorption uses substantially larger sample sizes (up to 0.25 g) compared to CV (<0.01 g), reliability of chemisorption data is much more reliable and should be considered as the metric for surface Pt site determination.     

Catalytic activity and selectivity for the ORR of rapidly synthesized M@Pt (M = Pd,Fe3O4, Ru) core–shell nanostructures

We report the performance of M@Pt (M = Pd, Fe₃O₄, Ru) core–shell nanostructures for the ORR in H₂SO₄. The nanomaterials were rapidly synthesized in a total of 120 s applying magnetic (MS), mechanical (UT) and sonochemical (USS) stirring. Pt-alone nanoparticles were also synthesized by UT and served as a reference to evaluate the performance of the core–shell cathodes. Crystalline features were obtained from the Pd and the Fe₃O₄ cores, while Ru cores apparently having quasi-amorphous characteristics or too small particle sizes were formed. Nevertheless, the three core–shell materials showed crystalline Pt features. From Scherrer analysis, it was determined that core–shell nanostructures with particle sizes from 7.3 to 9.2 nm were formed. The electrochemical characterization confirmed that active core–shell cathodes were obtained, with two of the Pd@Pt materials showing catalytic activities as high as that of the Pt-alone nanoparticles, or even higher in terms of mass activity. XPS analysis indicated that mainly Pt(0) species were formed at the cathodes, along with Pt(II) and Pt(IV). It was found that catalysts with high Pt(IV):Pt(II) showed enhanced catalytic activity for the reduction of oxygen. In the presence of ethanol, the evaluated Pd@Pt cathode showed the higher selectivity towards the ORR compared to the other cathodes.     

Synthesis and characterization of carbon-supported Pt–Ru–WOx catalysts by spectroscopic and diffraction methods

Carbon-supported Pt–Ru–WO _x /C catalysts for application in PEMFC anodes were synthesized by a modified Bönnemann method. Their electrocatalytic activity for the oxidation of H₂/CO mixtures and CH₃OH was measured by E/i-curves in PEM single cell arrangements under working conditions. Information about composition, microstructure and nanomorphology was obtained by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), X-ray fluorescence analysis (XFA) and transmission electron microscopy (TEM). X-ray diffraction data at room temperature show only one single Pt f.c.c. phase; no evidence of Ru, W and their oxides, respectively, is found. Hence, the presence of W and Ru as amorphous oxide species seems likely. Surface-sensitive XPS measurements detect Pt⁰, platinum oxide and hydroxide species, metallic Ru, ruthenium oxide, hydrous ruthenium oxide and WO₃. For the crystalline platinum phase particle sizes of less than 2 nm were determined by TEM images and XRD patterns via solving the Scherrer equation. Temperature-dependent XRD measurements were performed to show the influence of ageing on the catalyst structure.     

Design,development and reliability testing of a low power bridge-type micromachined hotplate

In this paper, the development and reliability of a platinum-based microheater with low power consumption are demonstrated. The microheater is fabricated on a thin SiO₂ bridge-type suspended membrane supported by four arms. The structure consists of a 0.6 μm-thick SiO₂ membrane of size 50 μm × 50 μm over which a platinum resistor is laid out. The simulation of the structure was carried out using MEMS-CAD Tool COVENTORWARE. The platinum resistor of 31.0 Ω is fabricated on SiO₂ membrane using lift-off technique. The bulk micromachining technique is used to create the suspended SiO₂ membrane. The temperature coefficient of resistance (TCR) of platinum used for temperature estimation of the hotplate is measured and found to be 2.2 × 10⁻³/°C. The test results indicate that the microhotplate consumes only 11.8 mW when heated up to 400 °C. For reliability testing, the hotplate is continuously operated at higher temperatures. It was found that at 404 °C, 508 °C and 595 °C, the microhotplate continuously operated up to 16.5 h, 4.3 h and 4 min respectively without degrading its performance. It can sustain at least 53 cycles pulse-mode of operation at 540 °C with ultra-low resistance and temperature drifts. The structure has maximum current capability of 19.06 mA and it can also sustain the ultrasonic vibration at least for 30 min without any damage.