Bridging TiO2 nanoparticles using graphene for use in dye‐sensitized solar cells

The use of graphene to bridge TiO₂ particles in the photoanode of dye‐sensitized solar cell for reduced electrical resistance has been investigated. The difficulty in dispersing graphene in TiO₂ paste was overcome by first dispersing graphene oxide (GO) into the TiO₂ paste. The GO was then reduced to graphene after the sintering of TiO₂. This is shown through transmission electron microscopy and X‐ray photoelectron spectroscopy analysis. Cell performance was evaluated using a solar simulator, incident photon to electron conversion efficiency, intensity modulated photocurrent/photovoltage spectroscopy under blue light, and electrochemical impedance spectroscopy. Depending on the amount of graphene in the photoanode, the cell performance was enhanced to different degrees. A maximum increase of 11.4% in the cell efficiency has been obtained. In particular, the inclusion of graphene has reduced the electron diffusion time by as much as 23.4%, i.e. from 4.74 to 3.63 ms and increased the electron lifetime by as much as 42.3%, i.e. from 19.58 to 27.85 ms. Copyright © 2014 John Wiley & Sons, Ltd.     

Review: Enhancement of composite anode materials for low-temperature solid oxide fuels

Solid oxide fuel cell (SOFC) technology is attractive for its high-energy efficiency and expanded fuel flexibility. It is also more environmentally benign than conventional power generation systems. Recently, increasing attention has been paid to intermediate-to-low-temperature solid oxide fuel cells, which operating at 400–800 °C. Reducing its operating temperature can render SOFC more competitive with other types of fuel cells and portable energy storage system (EES) over a range of applications (eg: transportation, portable, stationary) and more conducive for commercialization. The high-performance composite anode requirements for low operating temperature (400–600 °C) demand microstructural and chemical stability, high electronic conductivity, and good electrochemical performance. The current high-temperature anode, Ni-YSZ (nickel-yttria stabilized zirconia) is generally reported with high interfacial resistance at reduced temperatures. This review highlights several potential composite anode materials (Ni-based and Ni-free) that have been developed for low-temperature SOFCs within the past 10 years. This literature survey shows that most of these anodes still exhibit relatively high polarization resistance. Focus is also given on reducing polarization resistance to maintain the cell power density. In literature, common approaches that have been adopted to enhance the performance of anodes are (i) selecting high-performance electrolyte, (ii) exploiting nanopowder properties, and (iii) adding noble metals as electrocatalysts.     

Reacting flow coupling with thermal impacts in a single solid oxide fuel cell

Thermal impacts are the major concern for the designs of electrolyte of Solid Oxide fuel cells (SOFCs) due to the high temperature operating conditions. In this study, the coupling dynamics of electrochemical reacting flows with heat transfer and generations of thermal strains and stresses (thermal impact) of solid electrolyte and porous electrodes are investigated in a single SOFC by numerical simulations. Modeling results from a test case show that the coupling is necessary as the electrochemical and thermal properties of the cell strongly depends on temperature, meanwhile, the thermal strains and stresses on temperature gradients. The differences in current density and thermal strain gradients predicted by coupling and decoupling simulations are as larger as 20% because of the strong dependents of ionic conductivity of the electrolyte material on temperature, the maximum thermal strain, thermal stresses, and temperature are all about 5%. It is identified that the high operation voltage benefits to the thermal strain, which decreases 20% when the cell operating from 0.5 V–0.7 V.     

Monodisperse rutheniumcopper alloy nanoparticles decorated on reduced graphene oxide for dehydrogenation of DMAB

In this study, we report a superior dehydrogenation catalyst for dimethylamine borane, which exhibited one of the best catalytic activities. The newly formed catalyst system contains well dispersed ruthenium-copper nanomaterials on reduced graphene oxide (3.86 ± 0.47 nm), which was prepared by using the ultrasonic double reduction technique. The characterization of monodisperse ruthenium-copper alloy nanoparticles was performed using some advanced analytical methods such as TEM, HRTEM, XPS, Raman spectroscopic analysis. The experiments results revealed that the monodisperse ruthenium-copper alloy catalyst (RuCu@rGO) has one of the highest catalytic activity compared to previous studies, having a high turnover frequency value (256.70 h⁻¹). The detailed kinetic parameters such as activation energy, enthalpy, and entropy values were also calculated for the dehydrogenation of dimethylamine borane at room temperature. Also, the results showed that the monodisperse RuCu@rGO catalyst has high durability and reusability as retained its 81% initial catalytic activity even after 4th runs for the dehydrogenation of dimethylamine borane.     

Nano-to-macroporous TiO2 (anatase) by cold sintering process

Cold Sintering Process (CSP) was applied on commercial nanopowders to produce nanostructured TiO₂ anatase with nano-to-macro porosity. Nanoporous TiO₂ based materials were obtained by applying CSP at 150 °C and pressures up to 500 MPa on three TiO₂ nanopowders with different specific surface area (s.s.a. = 50, 90 and 370 m²/g), using water as transient aqueous environment. Although TiO₂ is insoluble in water, a density of 68% and s.s.a. = 117 m²/g were achieved from the powder with the highest specific surface area. A post annealing process at 500 °C increased the density up to 73% with a s.s.a. = 59 m²/g, and the crystallites dimensions passed from 110 Å in the powder to 130 Å in CSP material and 172 Å after post annealing. Finally, macroporosity was produced by using thermoplastic polymer beads as sacrificial templates within TiO₂ nanopowder during CSP, followed by a debonding at 500 °C.     

A remarkable three-component RuO2-MnCo2O4/rGO nanocatalyst towards methanol electrooxidation

A three-part nano-catalyst including ruthenium oxide, manganese cobalt oxide, and reduced graphene oxide nanosheet in form of RuO₂-MnCo₂O₄/rGO is synthesized by one-step hydrothermal synthesis. The material is placed on a glassy carbon electrode (GCE) for electrochemical studies. The ability of these nano-catalysts in the oxidation process of methanol in an alkaline medium for usage in direct methanol fuel cells (DMFC) was examined with electrochemical tests of cyclic voltammetry (CV), linear sweep voltammetry (LSV), and electrochemical impedance spectroscopy (EIS). The effect of the addition of rGO to the nanocatalyst structure in the methanol oxidation reaction (MOR) process was investigated. We introduced the RuO₂-MnCo₂O₄/rGO as a nanocatalyst with excellent cyclic stability of 97% after 5000 cycles in the MOR process. Besides, the study of the Tafel plots and the effect of temperature and scan rate in the MOR process showed that RuO₂-MnCo₂O₄/rGO nanocatalyst has better electrochemical properties than MnCo₂O₄ and RuO₂-MnCo₂O₄. This high electrocatalytic activity could be related to the synergistic effect of placement of metal oxides of ruthenium, manganese, and cobalt near each other and putting them on rGO, which enhances conductivity and surface area and improve electron transfer. The decrease in the resistance against charge transfer and the increment in the anodic current density illustrated that the reaction rate is enhanced at higher temperature. Thus RuO₂-MnCo₂O₄/rGO shows robust stability and superior performance for MOR.     

Copper substituted nickel ferrite nanoparticles anchored onto the graphene sheets as electrode materials for supercapacitors fabrication

Nickel ferrites with high theoretical capacitance value as compared to the other metal oxides have been applied as electrode material for energy storage devices i.e. batteries and supercapacitors. High tendency towards aggregation and less specific surface area make the metal oxides poor candidate for electrochemical applications. Therefore, the improvements in the electrochemical properties of nickel ferrites (NiFe₂O₄) are required. Here, we report the synthesis of graphene nano-sheets decorated with spherical copper substituted nickel ferrite nanoparticles for supercapacitors electrode fabrication. The copper substituted and unsubstituted NiFe₂O₄ nanoparticles were prepared via wet chemical co-precipitation route. Reduced graphene oxide (rGO) was prepared via well-known Hummer's method. After structural characterization of both ferrite (Ni_1-xCu_xFe₂O₄) nanoparticles and rGO, the ferrite particles were decorated onto the graphene sheets to obtain Ni_1-xCu_xFe₂O₄@rGO nanocomposites. The confirmation of preparation of these nanocomposites was confirmed by scanning electron microscopy (SEM). The electrochemical measurements of nanoparticles and their nanocomposites (Ni_0.9Cu_0.1Fe₂O₄@rGO) confirmed that the nanocomposites due to highly conductive nature and relatively high surface area showed better capacitive behavior as compared to bare nanoparticles. This enhanced electrochemical energy storage properties of nanocomposites were attributed to the graphene and also supported by electrical (I-V) measurements. The cyclic stability experiments results showed ~65% capacitance retention after 1000 cycles. However this retention was enhanced from 65% to 75% for the copper substituted nanoparticles (Ni_0.9Cu_0.1Fe₂O₄) and 65–85% for graphene based composites. All this data suggest that these nanoparticles and their composites can be utilized for supercapacitors electrodes fabrication.     

Perovskite ceramic oxide as an efficient electrocatalyst for nitrogen fixation

The electrochemical conversion of N₂ to NH₃ is an interesting research topic as it provided an alternative and energy-saving method compared with the traditional way of NH₃ production. Although different materials have been proposed for N₂ reduction, the use of defects in oxides was only reported recently and the relevant working mechanism was not fully revealed. In this study, Sr was used as the dopant for LaFeO₃ to create oxygen vacancies, forming the Sr-doped LFO (La_0.5Sr_0.5FeO_3-δ) perovskite oxide. The La_0.5Sr_0.5FeO_3-δ ceramic oxide used as a catalyst achieves an NH₃ yield of 11.51 μgh^?1 mg^?1 and the desirable faradic efficiency (F.E.) of 0.54% at ?0.6 V vs reversible hydrogen electrode (RHE), which surpassed that of LaFeO₃ nanoparticles. The ¹⁵N isotope labeling method was employed to prove the La_0.5Sr_0.5FeO_3-δ catalyst had the function of converting N₂ into NH₃ under the electrolysis condition. The first principle calculations were used to investigate the mechanism at the atomistic level, revealing that the free energy barriers changed significantly with the introduction of oxygen vacancies that accelerated the overall nitrogen reduction reaction (NRR) procedure.     

The influence of nitrogen doping on reduced graphene oxide as highly cyclable Li-ion battery anode with enhanced performance

A straightforward, one-step route has been established to fabricate reduced- (rGO) and nitrogen-doped reduced graphene oxide (NrGO) with remarkable lithium-ion storage properties. The graphene oxide (GO) was synthesized as starting material by improved Hummers’ method. Thereafter, thermally annealing GO with NH₃ at elevated temperature to synthesize NrGO was yielded a more open structure with nitrogen sites suitable for enhanced Li intercalation. NrGO exhibited a reversible capacity of 240 mAhg^?1 at 10 Ag^-1 after 500 cycles with 90% capacity retention, which is the best result achieved among graphene oxide-based anodes at this current density. In contrast to rGO, NrGO cells exhibited a gradually increasing capacity profile, reaching up to 114% of the initial capacity at 0.1, 2, and 10 Ag^-1 current densities. Results showed that high occupancy of pyridinic N within NrGO enhanced battery performance and cell kinetics upon cycling which offers long-time operability at high current density.     

Preparation of polyacrylonitrile/graphene oxide by in situ polymerization

Highly oriented molecular structure is essential for high‐performance carbon fibers. The addition of a small amount of graphene sheets may enhance the degree of molecular orientation of precursor fibers during spinning and stabilization by limiting the disorientation of the chain segments. Graphene sheets merge into the carbon fiber structure during carbonization. The structure and properties of polyacrylonitrile containing graphene oxide (GO) prepared by in situ polymerization were investigated. With increasing GO loading, the molecular weight of the polymer decreased gradually from 69 000 g mol^?1 for the sample without GO to 60 600 g mol^?1 for the sample with 2.5 wt% loading of GO. Scanning electron microscopy and X‐ray diffraction results indicated that GO was dispersed in single layers in the polymer matrix. The degree of crystallization of the polymer with 0.5 wt% GO was increased by 8%. Moreover, differential scanning calorimetry and thermogravimetric analysis showed that an appropriate amount of GO, e.g. 0.5 wt%, made the carbon yield of the polymer increase by 5.0 wt%, because the GO in the composite improved the intermolecular crosslinking reaction. Copyright © 2012 Society of Chemical Industry