Utilization of waste tyres pyrolysis oil vapour in the synthesis of Zeolite Templated Carbons (ZTCs) for hydrogen storage application.

In this study, we investigated the potential for use of waste tyre pyrolysis oil vapour as a carbon precursor in the synthesis of zeolite templated carbons (ZTC). With Zeolite 13X as the template, the ZTCs were synthesised using two methods namely: 1-step process which involved the carbonization of gaseous carbon precursor in the zeolite template (in this case, ethylene and pyrolysis oil vapour) and the 2-step synthesis method involved the impregnation of zeolite pores with furfural alcohol prior to carbonization of the gaseous carbon precursor. The replication of the zeolite 13X structural ordering was successful using both methods. The 2-step synthesized ZTCs were found to possess the highest specific surface area (3341 m2 g-1) and also had the highest H2 storage capacity (2.5 wt.%). The study therefore confirmed an additional novel strategy for value-addition of waste tyre pyrolysis by-products.

Preparation of carbon nanofibers/tubes using waste tyres pyrolysis oil and coal fly ash derived catalyst.

In this study, two waste materials namely; coal fly ash (CFA) and waste tyres pyrolysis oil, were successfuly utilized in the synthesis of carbon nanofibers/tubes (CNF/Ts). In addition, Fe-rich CFA magnetic fraction (Mag-CFA) and ethylene gas were also used for comparison purposes. The carbons obtained from CFA were found to be anchored on the surface of the cenosphere and consisted of both CNTs and CNFs, whereas those obtained from Mag-CFA consisted of only multi-walled carbon nanotubes (MWCNTs). The study further showed that the type of carbon precursor and support material played an important role in determining the nanocarbon growth mechanism. The findings from this research have demonstrated that it is possible to utilize waste tyres pyrolysis oil vapor as a substitute for some expensive commercial carbonaceous gases.

Microwave-enhanced electrochemical cycling performance of the LiNi0.2Mn1.8O4 spinel cathode material at elevated temperature.

The well-established poor electrochemical cycling performance of the LiMn2O4 (LMO) spinel cathode material for lithium-ion batteries at elevated temperature stems from the instability of the Mn(3+) concentration. In this work, a microwave-assisted solid-state reaction has been used to dope LMO with a very low amount of nickel (i.e., LiNi0.2Mn1.8O4, herein abbreviated as LMNO) for lithium-ion batteries from Mn3O4 which is prepared from electrolytic manganese oxide (EMD, γ-MnO2). To establish the impact of microwave irradiation on the electrochemical cycling performance at an elevated temperature (60 °C), the Mn(3+) concentration in the pristine and microwave-treated LMNO samples was independently confirmed by XRD, XPS, (6)LiMAS-NMR and electrochemical studies including electrochemical impedance spectroscopy (EIS). The microwave-treated sample (LMNOmic) allowed for the clear exposure of the {111} facets of the spinel, optimized the Mn(3+) content, promoting structural and cycle stability at elevated temperature. At room temperature, both the pristine (LMNO) and microwave-treated (LMNOmic) samples gave comparable cycling performance (>96% capacity retention and ca. 100% coulombic efficiency after 100 consecutive cycling). However, at an elevated temperature (60 °C), the LMNOmic gave an improved cycling stability (>80% capacity retention and ca. 90% coulombic efficiency after 100 consecutive cycling) compared to the LMNO. For the first time, the impact of microwave irradiation on tuning the average manganese redox state of the spinel material to enhance the cycling performance of the LiNi0.2Mn1.8O4 at elevated temperature and lithium-ion diffusion kinetics has been clearly demonstrated.

Nanostructured Carbon Fibres (NCF): Fabrication and Application in Supercapacitor Electrode.

A facile interconnected nanofibre electrode material derived from polybenzimidazol (PBI) was fabricated for a supercapacitor using a centrifugal spinning technique. The PBI solution in a mixture of dimethyl acetamide (DMA) and N, N-dimethylformamide (DMF) was electrospun to an interconnection of fine nanofibres. The as-prepared material was characterised by using various techniques, which include scanning electron microscopy (SEM), X-ray diffractometry (XRD), Raman, X-ray photoelectron spectroscopy (XPS), and Brunauer-Emmett-Teller (BET) among others. The specific surface area of the interconnected NCF material was noticed to be around 49 m2 g-1. Electrochemical properties of the material prepared as a single-electrode are methodically studied by adopting cyclic voltammetry, electrochemical impedance spectroscopy, and constant-current charge-discharge techniques. A maximum specific capacitance of 78.4 F g-1 was observed for the electrode at a specific current of 0.5 A g-1 in a 2.5 M KNO3 solution. The electrode could also retain 96.7% of its initial capacitance after a 5000 charge-discharge cycles at 5 A g-1. The observed capacitance and good cycling stability of the electrode are supported by its specific surface area, pore volume, and conductivity. The results obtained for this material indicate its potential as suitable candidate electrode for supercapacitor application.

Mesoporous Mn-substituted MnxZn1-xCo2O4 ternary spinel microspheres with enhanced electrochemical performance for supercapacitor applications.

Extensive investigations have been carried out on spinel mixed transition metal oxide-based materials for high-performance electrochemical energy storage applications. In this study, mesoporous Mn-substituted MnxZn1-xCo2O4 (ZMC) ternary oxide microspheres (x = 0, 0.3, 0.5, 0.7, and 1) were fabricated as electrode materials for supercapacitors through a facile coprecipitation method. Electron microscopy analysis revealed the formation of microspheres comprising interconnected aggregates of nanoparticles. Furthermore, the substitution of Mn into ZnCo2O4 significantly improved the surface area of the synthesized samples. The electrochemical test results demonstrate that the ZMC3 oxide microspheres with an optimal Mn substitution exhibited enhanced performance, displaying the largest specific capacitance of 589.9 F g-1 at 1 A g-1. Additionally, the ZMC3 electrode maintained a capacitance retention of 92.1% after 1000 cycles and exhibited a significant rate capability at a current density of 10 A g-1. This improved performance can be ascribed to the synergistic effects of multiple metals resulting from Mn substitution, along with an increase in the surface area, which tailors the redox behavior of ZnCo2O4 (ZC) and facilitates charge transfer. These findings indicate that the incorporation of Mn into mixed transition metal oxides holds promise as an effective strategy for designing high-performance electrodes for energy storage applications.

Electro-Design of Bimetallic PdTe Electrocatalyst for Ethanol Oxidation: Combined Experimental Approach and Ab Initio Density Functional Theory (DFT)-Based Study.

An alternative electrosynthesis of PdTe, using the electrochemical atomic layer deposition (E-ALD) method, is reported. The cyclic voltammetry technique was used to analyze Au substrate in copper (Cu2+), and a tellurous (Te4+) solution was used to identify UPDs and set the E-ALD cycle program. Results obtained using atomic force microscopy (AFM) and scanning electron microscopy (SEM) techniques reveal the nanometer-sized flat morphology of the systems, indicating the epitaxial characteristics of Pd and PdTe nanofilms. The effect of the Pd:Te ratio on the crystalline structure, electronic properties, and magnetic properties was investigated using a combination of density functional theory (DFT) and X-ray diffraction techniques. Te-containing electrocatalysts showed improved peak current response and negative onset potential toward ethanol oxidation (5 mA; -0.49 V) than Pd (2.0 mA; -0.3 V). Moreover, DFT ab initio calculation results obtained when the effect of Te content on oxygen adsorption was studied revealed that the d-band center shifted relative to the Fermi level: -1.83 eV, -1.98 eV, and -2.14 eV for Pd, Pd3Te, and Pd3Te2, respectively. The results signify the weakening of the CO-like species and the improvement in the PdTe catalytic activity. Thus, the electronic and geometric effects are the descriptors of Pd3Te2 activity. The results suggest that Pd2Te2 is a potential candidate electrocatalyst that can be used for the fabrication of ethanol fuel cells.

Electrodeposition of multilayered bimetallic nanoclusters of ruthenium and platinum via surface-limited redox-replacement reactions for electrocatalytic applications.

An electrochemical synthesis of multilayered bimetallic Ru|Pt nanoclusters, supported on glassy carbon, is reported for the first time. The novel nanoclusters were synthesized via surface-limited redox-replacement reactions involving sacrificial Cu, deposited prior to the formation of each individual noble metal layer, in a sequential fashion. It has been shown that the Cu adlayers control the morphology and electrochemical properties of the resultant nanostructures. Sequentially deposited Ru|Pt nanoclusters exhibited superior electrocatalytic activity (when compared to equivalent monometallic Pt and an alloy-type codeposited Pt-Ru nanostructures) with respect to methanol electrooxidation in an acidic medium. Moreover, it has been established that the electrochemical process taking place at the Ru|Pt nanoclusters followed the bifunctional mechanism. Electrokinetic studies of the oxygen reduction reaction (ORR) were also performed. Analysis of hydrodynamic linear sweep voltammetric experiments, performed at various flow rates on oxygen-saturated acidic medium, revealed that the Pt and Ru|Pt nanoclusters exhibited direct four- and two-electron ORR pathways, respectively. A specially designed electrochemical flow-cell was used for automated sequential electrodeposition of the multilayered nanoclusters of predefined composition and electrochemical and electrocatalytic investigations.

Single step synthesis of bio-inspired NiO/C as Pd support catalyst for dual application: Alkaline direct ethanol fuel cell and CO2 electro-reduction.

Carbon dioxide (CO2) is considered a useful greenhouse gas that can be captured and be used in the electro-syntheses of useful chemicals or fuels. On the other hand, there's also a tremendous interest on ethanol beneficiation as it is largely produced from crops, and it is regarded as a potential candidate for low temperature fuel cell applications. Although ethanol possesses good advantages, its resistant to oxidation poses a threat. The main objective of the study is to synthesis bio-inspired metal oxide-support catalyst which will help enhance the activity, efficiency and selectivity of Pd catalyst in CO2 reduction, Fuel cell performance and ethanol oxidation. Here, Pd nanoparticles were supported on NiO/C through a green facile one-step process using pomegranate peel extracts as reducing agent. A series of characterizations were carried out to provide proof for and to quantify the presence of Pd, Ni, O and C in the prepared sample. Microscopic methods confirmed the successful preparation of pure NiO/C and (%5 Pd) Pd-NiO/C, evident by the key elemental components, mixed nanostructures and co-existence of Pd and NiO/C. The resultant Pd-NiO/C nanocatalyst revealed higher activity towards the oxidation of ethanol and that the nanocatalyst is more tolerant to poising by intermediate oxidation species. Enhanced cell performance with current and power densities of 66 mA cm-2 and 26 mW cm-2 relative to the commercial Pd/C were obtained under passive conditions at 1 M ethanol in 1MKOH. In addition, the nanocatalyst showed good selectivity to HCOOH with enhanced current efficiencies of 45%.

Polymer-Based Shaping Strategy for Zeolite Templated Carbons (ZTC) and Their Metal Organic Framework (MOF) Composites for Improved Hydrogen Storage Properties.

Porous materials such as metal organic frameworks (MOFs), zeolite templated carbons (ZTC), and some porous polymers have endeared the research community for their attractiveness for hydrogen (H2) storage applications. This is due to their remarkable properties, which among others include high surface areas, high porosity, tunability, high thermal, and chemical stability. However, despite their extraordinary properties, their lack of processability due to their inherent powdery nature presents a constraining factor for their full potential for applications in hydrogen storage systems. Additionally, the poor thermal conductivity in some of these materials also contributes to the limitations for their use in this type of application. Therefore, there is a need to develop strategies for producing functional porous composites that are easy-to-handle and with enhanced heat transfer properties while still retaining their high hydrogen adsorption capacities. Herein, we present a simple shaping approach for ZTCs and their MOFs composite using a polymer of intrinsic microporosity (PIM-1). The intrinsic characteristics of the individual porous materials are transferred to the resulting composites leading to improved processability without adversely altering their porous nature. The surface area and hydrogen uptake capacity for the obtained shaped composites were found to be within the range of 1,054-2,433 m2g-1 and 1.22-1.87 H2 wt. %, respectively at 1 bar and 77 K. In summary, the synergistic performance of the obtained materials is comparative to their powder counterparts with additional complementing properties.

The effect of polyaniline on TiO2 nanoparticles as anode materials for lithium ion batteries.

Polyaniline (PANI) additives have been shown to have a significant effect on titanium dioxide (TiO2) nanoparticles as lithium ion battery anode materials. TiO2/PANI composites were prepared using a solid coating method with different ratios of PANI and then characterized using XRD and SEM. These composites have shown increased reversible capacity compared with pure TiO2. At the current rate of 20 and 200 mAg(-1), maximum capacities were also found on 15 % PANI incorporated TiO2 composite with 281 mAh g(-1) and 168.2 mAh g(-1), respectively, and 230 and 99.6 mAh g(-1) were obtained in the case of pure TiO2. Among all the composite materials, 10 % PANI incorporated TiO2 composite exhibited the highest reversible capacity with cycle stability after 100 cycles at the current rate of 200 mAg(-1), suggestive that the optimal ratio is 10 % PANI of TiO2/polyaniline. The cycle stability showed swift fade when the ratio of PANI in the composites exceeded 10 % though the highest initial capacity was achieved on 15 % PANI in the composites. These results suggest that PANI has effectively enhanced the reversible capacity of commercial TiO2, and may be a promising polymer matrix materials for lithium ion batteries.

Microwave-assisted synthesis of high-voltage nanostructured LiMn1.5Ni0.5O4 spinel: tuning the Mn3+ content and electrochemical performance.

The LiMn1.5Ni0.5O4 spinel is an important lithium ion battery cathode material that has continued to receive major research attention because of its high operating voltage (∼4.8 V). This study interrogates the impact of microwave irradiation on the Mn(3+) concentration and electrochemistry of the LiMn1.5Ni0.5O4 spinel. It is shown that microwave is capable of tuning the Mn(3+) content of the spinel for enhanced electrochemical performance (high capacity, high capacity retention, excellent rate capability, and fast Li(+) insertion/extraction kinetics). This finding promises to revolutionize the application of microwave irradiation for improved performance of the LiMn1.5Ni0.5O4 spinel, especially in high rate applications.

Preliminary studies in the electrodeposition of PbSe/PbTe superlattice thin films via electrochemical atomic layer deposition (ALD).

This paper concerns the electrochemical growth of compound semiconductor thin film superlattice structures using electrochemical atomic layer deposition (ALD). Electrochemical ALD is the electrochemical analogue of atomic layer epitaxy (ALE) and ALD, methods based on nanofilm formation an atomic layer at a time, using surface-limited reactions. Underpotential deposition (UPD) is a type of electrochemical surfaced-limited reaction used in the present studies for the formation of PbSe/PbTe superlattices via electrochemical ALD. PbSe/PbTe thin-film superlattices with modulation wavelengths (periods) of 4.2 and 7.0 nm are reported here. These films were characterized using electron probe microanalysis, X- ray diffraction, atomic force microscopy (AFM), and infrared reflection absorption measurements. The 4.2 nm period superlattice was grown after deposition of 10 PbSe cycles, as a prelayer, resulting in an overall composition of PbSe0.52Te0.48. The 7.0 nm period superlattice was grown after deposition of 100 PbTe cycle prelayer, resulting for an overall composition of PbSe0.44Te0.56. The primary Bragg diffraction peak position, 2theta, for the 4.2 superlattice was consistent with the average (111) angles for PbSe and PbTe. First-order satellite peaks, as well as a second, were observed, indicating a high-quality superlattice film. For the 7.0 nm superlattice, Bragg peaks for both the (200) and (111) planes of the PbSe/PbTe superlattice were observed, with satellite peaks shifted 1 degrees closer to the (111), consistent with the larger period of the superlattice. AFM suggested conformal superlattice growth on the Au on glass substrate. Band gaps for the 4.2 and 7.0 nm period superlattices were measured as 0.48 and 0.38 eV, respectively.