Aluminium-doped ZnO (AZO) thin films were deposited by remote plasma sputtering of a ZnO:Al2O3 98:2 wt.% ceramic target in a pulsed DC configuration. The target power was kept constant at 445 W and the RF plasma power was varied between 0.5 and 2.5 kW. The as-deposited AZO thin films exhibited an optimum resistivity of 6.35 x 10-4 .cm and optical transmittance of 92 % at a RF plasma power 1.5 kW. The thin film microstructure, chemical composition, and residual stress were investigated using SEM, RBS, XPS and XRD. Accurate determination of the chemical composition and correct interpretation of GIXRD data for AZO thin films are a particular focus of this work. The AZO layer thickness was 500 - 700 nm and Al content in the range of 2.3 - 3.0 at.%, determined by RBS. The AZO thin films exhibited a strong (002) preferential orientation and grain sizes between 70 and 110 nm. The (103) peak intensity enhancement in GIXRD is proven to be a result of the strong (002) preferential orientation and GIXRD geometrical configuration rather than a change in the crystallite orientation at the surface. XPS depth profiles show preferential sputtering of O and Al using a 500 eV Ar+ beam, which can be reduced, but not eradicated using an 8 keV Ar150+ beam. The preferential sputtering can be successfully modelled using the simulation software TRIDYN. A plasma power of 1.5 kW corresponds to a highly ionised plasma and various microstructural and compositional factors have all contributed to the optimum low resistivity occurring at this plasma power. The grain size exhibits a maximum in the 1.25 - 1.5 kW range and there is improved (002) orientation, minimising grain boundary scattering. The highest carrier concentration and mobility was observed at the plasma power of 1.5 kW which may be associated with the maximum in the aluminium doping concentration (3.0 at.%). The lowest residual stress is also observed at 1.5 kW.
Waterborne coatings emit a low amount of harmful volatile organic compounds (VOCs) into the atmosphere compared to solvent-cast coatings. A typical waterborne formulation for agricultural applications consists of colloidal thermoplastic particles (latex) as the binder, a thickener to raise the viscosity, inorganic filler particles with a water-soluble dispersant, and a colloidal wax to modify surface properties. The formulations typically contain hygroscopic species that are potentially subject to softening by environmental moisture. The hardness, tack adhesion, and coefficient of friction of formulated coatings determines their suitability in applications. However, the relationship of these properties to the components in a coating formulation has not been adequately explored. Furthermore, the relationship between hygroscopic components and properties is an added complication. Here, we have characterized the hardness and tack adhesion of model formulated coatings using a single micro-indentation cycle with a conical indenter under controlled temperatures (above and below the glass transition temperature of a latex binder) and relative humidities. In parallel, we measured the coefficient of kinetic friction, μk, for the same coatings using a bespoke testing rig under controlled environmental conditions. Across a range of temperatures, RH and compositions, we find an inverse correlation between the coating hardness and μk. Any correlation of μk with the roughness of the coatings, which varies with the composition, is less clear. Formulations that contain wax additives have a higher μk at a low RH of 10%, in comparison to formulations without wax. For the wax formulations, μk decreases when the RH is raised, whereas in non-wax formulations, μk increases with increasing RH. Wax-containing coatings are hydrophilic (with a lower water contact angle), however the wax has a lower water permeability. A lubricating layer of water can explain the lower observed μk in these formulations. The addition of wax is also found to planarize the coating surface, which leads to higher tack adhesion in dry coatings in comparison to coatings without wax. Greater adhesive contact in these coatings can explain their higher friction. Our systematic research will aid the design of seed coating formulations to achieve their optimum properties under a wide range of environmental conditions.
In the study presented herein, the catalytic activity and stability of a Ni catalyst supported on Y2O3–ZrO2 was examined for the first time in the glycerol steam reforming reaction and compared with a Ni/ZrO2. The addition of Y2O3 stabilized the ZrO2 tetragonal phase, increased the O2 storage capacity of the support and the medium strength acid sites of the catalyst, and although the Ni/Zr catalyst had a higher concentration of basic sites, the Ni/YZr presented more stable monodentate carbonates. Moreover, the Ni/YZr had substantially higher Ni surface concentration and smaller Ni particles. These properties influence the gaseous products’ distribution by increasing the H2 yield and selectivity and preventing the transformation of CO2 to CO, by inhibiting the reverse water gas shift (RWGS) reaction from taking place. For both catalysts the main liquid products identified were allyl alcohol, acetaldehyde, acetone, acrolein, acetic acid and acetol; these were subsequently quantified. The time-on-stream experiments showed that the Ni/YZr was more stable during reaction and had a higher H2 yield after 20 h (2.17 in comparison to 1.50 mol H2/mol C3H8O3, for the Ni/Zr). Extensive investigation of the carbon deposits showed that although lower amounts of coke were deposited on the Ni/Zr catalyst, these structures were more graphitic in nature and had fewer defects, which means they were harder to oxidize. Moreover, transmission electron microscopy (TEM) analysis showed that sintering of Ni nanoparticles during the reaction was significant for the Ni/Zr catalyst, as the mean particle diameter increased from an initial value of 48.2 to 67.9 nm, while it was almost absent on the Ni/YZr catalyst (the mean particle diameter increased from 42.1 to 47.4 nm).
[Display omitted] •Microwave assisted sol gel method produces selective CO2 methanation Ni catalysts.•The incorporation of Sm3+ and Pr3+ into the CeO2 lattice generates basic positions.•Sm3+ and Pr3+ oxygen vacancies suppress the agglomeration of Ni sites.•Presence of Mg2+ increases basicity and prevents Ni sintering during reaction.•Ni on Pr-Ce highly active, selective and stable for CO2 methanation reaction. The present work reports on the investigation of the catalytic performance for the methanation of CO2 over Ni catalysts based on CeO2, and for the first time, of Ni catalysts supported on binary CeO2-based oxides, namely, Sm2O3-CeO2, Pr2O3-CeO2 and MgO-CeO2. The supports were obtained using the microwave assisted sol-gel method under reflux, while the catalysts were prepared by the wet impregnation method. For the investigation of the morphological, textural, structural and other intrinsic properties of the catalytic materials a variety of characterization techniques were used, i.e., Raman spectroscopy, XRD, N2 physisorption-desorption, CO2-TPD, H2-TPR, H2-TPD, XPS and TEM. Carbon deposition and sintering were investigated using TEM. It was shown that the addition of Sm3+ or Pr3+, incorporated into the lattice of CeO2, generated oxygen vacancies, but the Ni/Pr-Ce catalyst was found to possess more surface oxygen vacancies (e.g. Ce4+-Ov-Pr3+ entities). Moreover, modification of CeO2 using Sm3+ or Pr3+ restricted the agglomeration of nickel active sites and led to the genesis of Lewis basic positions. These characteristics improved the hydrogenation reaction at lower temperature. On the other hand, the addition of Mg2+ resulted at strong metal support interactions reinforcing the resistance of the Ni/Mg-Ce catalyst against sintering. Furthermore, the addition of Sm3+, Pr3+ and Mg2+ cations increased the overall basicity and the moderate adsorption sites and led to the formation of smaller Ni nano particles; these physico-chemical properties enhanced the CO2 methanation reaction. Finally, the activity experiments (WGHSV = 25,000 mL g−1 h−1, H2/CO2 = 4:1, T =350 °C) showed that at lower reaction temperature the Ni/Pr-Ce had the highest catalytic performance in terms of CO2 conversion (54.5%) and CH4 yield (54.5%) and selectivity (100%). The TOF values were found to follow the order Ni/Pr-Ce >> Ni/Mg-Ce > Ni/Sm-Ce > Ni/Ce.
The dry reforming of biogas on a Ni catalyst supported on three commercially available materials (ZrO2, La2O3-ZrO2 and CeO2-ZrO2), has been investigated, paying particular attention to carbon deposition. The DRM efficiency of the catalysts was studied in the temperature range of 500-800oC at three distinct space velocities, and their time-on-stream stability at four temperatures (550, 650, 750 and 800oC) was determined for 10 or 50 h operation. The morphological, textural and other physicochemical characteristics of fresh and spent catalysts together with the amount and type of carbon deposited were examined by a number of techniques including BET-BJH method, CO2 and NH3-TPD, XPS, SEM, TEM, STEM-HAADF, Raman spectroscopy, and TGA/DTG. The impact of the La2O3 and CeO2 modifiers on the DRM performance and time-on-stream stability of the Ni/ZrO2 catalyst was found to be very beneficial: up to 20 and 30% enhancement in CH4 and CO2 conversions respectively, accompanied with a CO-enriched syngas product, while the 50 h time-on-stream catalytic performance deterioration of ~30-35% on Ni/ZrO2 was limited to less than ~15-20% on the La2O3 and CeO2 modified samples. Their influence on the amount and type of carbon formed was substantial: it was revealed that faster oxidation of the deposited carbon at elevated temperatures occurs on the modified catalysts. Correlations between the La2O3 and CeO2-induced modifications on the surface characteristics and physicochemical properties of the catalyst with their concomitant support-mediated effects on the overall DRM performance and carbon deposition were revealed.
Here, we describe the unusual self-assembly of amine-terminated oligoglycine peptides into extended two-dimensional sheets in the presence of silver nanowires. The resulting tectomer sheets are shown to have a strong affinity for the nanowires through a charge-transfer interaction as evidenced by X-ray photoelectron spectroscopy. We show that extended assemblies of metal-peptide hybrids offer additional augmentative functionalities, for instance, the tectomer sheets are hydrophobic in nature and act as a protective layer preventing oxidation and degradation of the nanowires when exposed to atmospheric conditions. Moreover, for silver nanowire percolating networks the presence of the peptide markedly increases the overall electrical conductivity through mechanical squeezing of wire-wire junctions in the network. The peptide-metal interface can be controlled by pH stimulus thus potentially offering new directions where silver nanowire assemblies are used for transparent electrodes ranging from antimicrobial coatings to biosensors.
Interface engineering is an effective means to enhance the performance of thin‐film devices, such as perovskite solar cells (PSCs). Herein, a conjugated polyelectrolyte, poly[(9,9‐bis(3′‐((N,N‐dimethyl)‐N‐ethyl‐ammonium)‐propyl)‐2,7‐fluorene)‐alt‐2,7‐(9,9‐dioctylfluorene)]di‐iodide (PFN‐I), is used at the interfaces between the hole transport layer (HTL)/perovskite and perovskite/electron transport layer simultaneously, to enhance the device power conversion efficiency (PCE) and stability. The fabricated PSCs with an inverted planar heterojunction structure show improved open‐circuit voltage (Voc), short‐circuit current density (Jsc), and fill factor, resulting in PCEs up to 20.56%. The devices maintain over 80% of their initial PCEs after 800 h of exposure to a relative humidity 35–55% at room temperature. All of these improvements are attributed to the functional PFN‐I layers as they provide favorable interface contact and defect reduction.
Triple cation CsFAMA perovskite films fabricated via a one-step method have recently gained attention as an outstanding light-harvesting layer for photovoltaic devices. However, questions remain over the suitability of one-step processes for the production of large-area films, owing to difficulties in controlling the crystallinity, in particular, scaling of the frequently used anti-solvent washing step. This can be mitigated through the use of the two-step method which has recently been used to produce large-area films via techniques such as slot dye coating, spray coating or printing techniques. Nevertheless, the poor solubility of Cs containing salts in IPA solutions has posed a challenge for forming triple cation perovskite films using the two-step method. In this study, we tackle this challenge through fabricating perovskite films on a caesium carbonate (Cs2CO3) precursor layer, enabling Cs incorporation within the film. Synergistically, we find that Cs2CO3 passivates the SnO2 electron transport layer (ETL) through interactions with Sn 3d orbitals, thereby promoting a reduction in trap states. Devices prepared with Cs2CO3 treatment also exhibited an improvement in the power conversion efficiency (PCE) from 19.73% in a control device to 20.96% (AM 1.5G, 100 mW cm−2) in the champion device. The Cs2CO3 treated devices (CsFAMA) showed improved stability, with un-encapsulated devices retaining nearly 80% efficiency after 20 days in ambient air.
A nanoporous and large surface area (∼800 m2/g) graphene-based material was produced by plasma treatment of natural flake graphite and was subsequently surface decorated with platinum (Pt) nano-sized particles via thermal reduction of a Pt precursor (chloroplatinic acid). The carbon-metal nanocomposite showed a ∼2 wt% loading of well-dispersed Pt nanoparticles (
In this study, a critical comparison between two low metal (Ni) loading catalysts is presented, namely Ni/Al2O3 and Ni/AlCeO3 for the glycerol steam reforming (GSR) reaction. The surface and bulk properties of the catalysts were evaluated using a plethora of techniques, such as N2 adsorption/desorption, ICP-AES, XRD, XPS, SEM/EDX, TEM, CO2-TPD, NH3-TPD, H2-TPR. Carbon deposited on the catalysts surfaces was probed using TPO, SEM and TEM. It is demonstrated that Ce-modification of Al2O3 induces an increase of the surface basicity and Ni dispersion. These features lead to a higher conversion of glycerol to gaseous products (60% to 80%), particularly H2 and CO2, enhancement of WGS reaction and a higher resistance to coke deposition. Allyl alcohol was found to be the main liquid product for the Ni/AlCeO3 catalyst, the production of which ceases over 700 oC. It is also highly significant that the Ni/AlCeO3 catalyst demonstrated stable values for H2 yield (2.9-2.3) and selectivity (89-81%), in addition to CO2 (75-67%) and CO (23-29%) selectivity during a (20h) long time-on-stream study. Following the reaction, SEM/EDX and TEM analysis showed heavy coke deposition over the Ni/Al2O3 catalyst, whereas for the Ni/AlCeO3 catalyst TPO studies showed the formation of more defective coke, the latter being more easily oxidized
Highly mesoporous SiO2 encapsulated NixPy crystals, where (x, y) = (5, 4), (2, 1), and (12, 5) were successfully synthesized by adopting thermolytic method using oleylamine (OAm), trioctylphosphine (TOP) and trioctylphosphine oxide (TOPO). The Ni5P4@SiO2 system shows the highest reported activity for the selective hydrogenation of SO2 towards H2S at 320 oC (96 % conversion of SO2 and 99 % selectivity to H2S) which was superior to the activity of the commercial CoMoS@Al2O3 catalyst (64 % conversion of SO2 and 71 % selectivity to H2S at 320 oC). The morphology of the Ni5P4 crystal was finely tuned via adjustment of the synthesis parameters receiving a wide spectrum of morphologies (hollowed, macroporous-network and SiO2 confined ultra-fine clusters). Intrinsic characteristics of the materials were studied using XRD, HRTEM/STEM-HAADF, EDX, BET, H2-TPR, XPS, and experimental and calculated 31P MAS ssNMR towards establishing the structure-performance correlation for the reaction of interest. Characterization of the catalysts after the SO2 hydrogenation reaction proved the preservation of the morphology, crystallinity and Ni/P ratio for all the catalysts.
Highly active nickel phosphide nano clusters (Ni2P) confined in mesoporous SiO2 catalyst were synthesized by a two-step process targeting tight control over the Ni2P size and phase. The Ni precursor was incorporated into the MCM-41 matrix by one-pot synthesis, followed by the phosphorization step which was accomplished in oleylamine with trioctylphosphine at 300 oC so to achieve the phase transformation from Ni to Ni2P. For benchmarking, Ni confined by the mesoporous SiO2 (absence of phosphorization) and 11 nm Ni2P nanoparticles (absence of SiO2), were also prepared. From the microstructural analysis, it was found that the growth of Ni2P nano clusters was restricted by the mesoporous channels, thus forming ultrafine and highly dispersed Ni2P nano clusters (< 2 nm). The above approach led to promising catalytic performance following the order: u-Ni2P@m-SiO2 > n-Ni2P > u-Ni@m-SiO2 > c-Ni2P in the selective hydrogenation of SO2 to S. In particular, u-Ni2P@m-SiO2 exhibited an SO2 conversion of 94 % at 220 oC and ~99 % at 240 oC, which is higher than the 11 nm stand-alone Ni2P particles (43 % at 220 oC and 94 % at 320 oC), highlighting the importance of the role played by SiO2 in stabilizing ultrafine nanoparticles of Ni2P. The reaction activation energy Ea over u-Ni2P@m-SiO2 is ~33 kJ/mol, which is lower than over n-Ni2P (~36 kJ/mol) and c-Ni2P (~66 kJ/mol), suggesting that the reaction becomes energetically favored over the ultrafine Ni2P nano clusters.
Surface-sensitive techniques have been employed to characterise a model polymer substrate surface, poly(ethylene terephthalate) (PET), after a reactive sputter pre-treatment using magnetically enhanced Cu or Ti sputter targets in a mixed Ar-O glow discharge plasma. The plasmas are produced using either medium-frequency pulsed direct current (p-DC) or low-frequency high power impulse (HIPIMS) sources. X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and sessile drop water contact angles were employed to investigate changes in PET surface chemistry and properties following surface modification using different p-DC and HIPIMS process parameters. The XPS results indicate that the chemical composition of plasma-treated PET surfaces (p-DC or HIPIMS) depends strongly on the processing parameters employed such as sputter target material, magnetic array type and power supply technology. XPS results demonstrate that the sputter target material employed is of primary importance as it dictates the quantity of metal deposited/implanted into the PET surface. XPS results show that the use of a Cu target resulted in ∼ 31-35 at.% of Cu incorporated into the PET surface (as CuO), while the use of a Ti target resulted in only 1-4 at. % incorporation (as TiO ). The SIMS spectra and XPS depth profiles of Cu-treated PET indicate that the CuO has formed a discrete film at the surface, offering predominant or total coverage of the underlying PET. However, for Ti-treated PET, both PET and Ti SIMS peaks are observed, and the XPS C1s peak shape is characteristic of PET, indicating that Ti has not formed a discrete film, but instead TiO species have been incorporated, probably as an island-like distribution into the surface of the PET. The formation of CuO and TiO on the PET surface leads to a reduction in the contact angle compared to native PET. Hence, both p-DC and HIPIMS reactive plasma pre-treatments result in a more hydrophilic surface, promoting adhesion and offering a flexible means to introduce a wide range of surface chemistries and properties to polymeric surfaces. Copyright © 2012 John Wiley & Sons, Ltd. Copyright © 2012 John Wiley & Sons, Ltd.
Data produced using both unsized and aminopropyltriethoxysilane (APS) coated fibre will be shown and discussed. By applying a novel method of single fibre thermal conditioning (sf-TC) it was found that retained fibre strength is, in some cases, underestimated and that the temperature range 400-500 °C is the most critical for thermally induced strength loss. This is not related to degradation of the APS surface coating, but rather is likely linked to fundamental changes occurring in the glass network or at the fibre surface. X-ray Photoelectron Spectroscopy (XPS) analysis of treated fibres was performed, but it was not possible to measure any significant changes in surface chemical state. Analysis of water volatilized from unsized fibre was performed using a furnace connected to quadropole mass spectrometer. An asymptotic minimum in volatilized water is reached between 400-500 °C.
We report amorphous GaLaSO-based resistive switching devices, with and without Pb-implantation before deposition of an Al active electrode, which switch due to deposition and dissolution of Al metal filaments. The devices set at 2-3 and 3-4 V with resistance ratios of 6 × 10 and 3 × 10 for the unimplanted and Pb-implanted devices, respectively. The devices reset under positive Al electrode bias, and Al diffused 40 nm further into GaLaSO in the unimplanted device. We attribute the positive reset and higher set bias, compared to devices using Ag or Cu active electrodes, to the greater propensity of Al to oxidise. © 2014 AIP Publishing LLC.
Ni/Al2O3 and Ni/CaO-MgO-Al2O3 catalysts were investigated for the biogas dry reforming reaction using CH4/CO2 mixtures with minimal dilution. Stability tests were conducted between 600 and 800 oC and TGA/DTG, Raman, STEM-HAADF, HR-TEM, XPS techniques were used to characterize the spent samples. Graphitized carbon allotrope structures, carbon nanotubes (CNTs) and amorphous carbon were formed on all samples. Metallic Ni0 was recorded for all (XPS), whereas a strong peak corresponding to Ni2O3/NiAl2O4 was observed for the Ni/Al2O3 sample (650–750°C). Stability tests confirmed that the Ni/CaO-MgO-Al2O3 catalyst deactivates at a more gradual rate and is more active and selective in comparison to the Ni/Al2O3 for all temperatures. The Ni/CaO-MgO-Al2O3 exhibits good durability in terms of conversion and selectivity, whereas the Ni/Al2O3 gradually loses its activity in CH4 and CO2 conversion, with a concomitant decrease of the H2 and CO yield. It can be concluded that doping Al2O3 with CaO-MgO enhances catalytic performance by: (a) maintaining the Ni0 phase during the reaction, due to higher dispersion and stronger active phase-support interactions, (b) leading to a less graphitic and more defective type of deposited carbon, and (c) facilitating the deposited carbon gasification due to the enhanced CO2 adsorption on its increased surface basic sites.
Ni/Al2O3 and Ni/La2O-Al2O3 catalysts were investigated for the biogas reforming reaction using CH4/CO2 mixtures with minimal dilution. Stability tests at various reaction temperatures were conducted and TGA/DTG, Raman, STEM-HAADF, HR-TEM, XPS techniques were used to characterize the spent samples. Graphitized carbon allotrope structures, carbon nanotubes (CNTs) and amorphous carbon were formed on all samples. Metallic Ni0 was recorded for all (XPS), whereas a strong peak corresponding to Ni2O3/NiAl2O4, was observed for the Ni/Al sample (650–750°C). Stability tests confirm that the Ni/LaAl catalyst deactivates at a more gradual rate and is more active and selective in comparison to the Ni/Al for all temperatures. The Ni/LaAl exhibits good durability in terms of conversion and selectivity, whereas the Ni/Al gradually loses its activity in CH4 and CO2 conversion, with a concomitant decrease of the H2 and CO yield. It can be concluded that doping Al2O3 with La2O3 stabilizes the catalyst by (a) maintaining the Ni0 phase during the reaction, due to higher dispersion and stronger active phase-support interactions, (b) leading to a less graphitic and more defective type of deposited carbon and (c) facilitating the deposited carbon gasification due to the enhanced CO2 adsorption on its increased surface basic sites.
Capacitive deionization (CDI) is an emerging desalination technology that still needs further development to enhance its performance for practical implementation. Herein, we present a hybrid CDI approach, which integrates the electrical double-layer (EDL) with the sodium-ion battery concept to improve the separation of sodium and chloride ions from saline water. The hybrid CDI cell is achieved by using hydrothermally-grown and uniformly dispersed prawn-like α-MnO₂/graphene (α-MnO₂/G) nanocomposite as anode material, and graphene at the cathode. In this paper, the effect of MnO₂ morphology on the electrode electrochemical performance and its effect on capacitive deionization performance have been fully investigated. In this configuration, the Na⁺ ions are inserted by the electrochemical reaction at the α-MnO₂/G electrode, whereas Cl⁻ ions are captured by the graphene-based electrode. The morphological dependent electrochemical properties of the obtained nanocomposites were studied deeply through CV and EIS analysis. The established hybrid CID cell provides an electrical capacitance as high as 375 F g⁻¹ at 10 mV s⁻¹, cation-selectivity, good electrical stability and low internal resistance. The hybrid CDI device also shows a stable and reversible salt insertion/de-insertion capacity up to 29.5 mg g⁻¹ at 1.2 V. These results demonstrate the suitability of prawn-like α-MnO₂/G nanocomposite to produce high-performance hybrid CDI cells.
The strength of intercoat adhesion exhibited between a series of polyester/polyurethane (PU) based primer formulations and a standard poly(vinylidene difluoride) (PVdF) based topcoat formulation has been investigated by X-ray photoelectron spectroscopy (XPS). An initial XPS study of changes in surface elemental composition (induced by variation of the peak metal temperature (PMT) achieved during thermal curing), on a subset of the PU primers employed, indicates that beyond a PMT of 232°C changes in PU primer surface composition are negligible. A reference PU primer coating formulation and four variations of this formulation, produced by including, excluding or substituting components/additives in the reference formulation, are characterised by XPS. The PU primer formulation in which a flow agent additive is included exhibits segregation of the flow agent to the primer surface. The PU primer and PVdF topcoat intercoat adhesion failure surfaces resulting from failure at or near the PVdF/PU interface as a result of a peel test are also characterised by XPS. Additionally the PVdF topcoat air-coating surface is characterised by XPS. The interface analyses for the flow agent containing PU primer formulation indicates stripping of the flow agent layer from the PU primer and transfer of the flow agent to the PVdF topcoat interfacial failure surface. Similarly, PU primer formulations in which the concentrations of a crosslinking resin are changed demonstrate that the transfer of carbon and oxygen containing materials from the PU primer to the PVdF topcoat occurs, due to insufficient crosslinking of the polyester component of the PU primer formulation. These results suggest a correlation between the nitrogen concentration at the PU primer surface and the strength of the intercoat adhesion exhibited by the PU primer towards the PVdF topcoat.
γ-Al2O3 is a well known catalyst support. The addition of Ce to γ-Al2O3 is known to beneficially retard the phase transformation of γ-Al2O3 to α-Al2O3 and stabilize the γ-pore structure. In this work, Ce-doped γ-Al2O3 nanowires have been prepared by a novel method employing an anodic aluminium oxide (AAO) template in a 0.01 M cerium nitrate solution, assisted by urea hydrolysis. Calcination at 500 °C for 6 h resulted in the crystallization of the Ce-doped AlOOH gel to form Ce-doped γ-Al2O3 nanowires. Ce3 + ions within the nanowires were present at a concentration of < 1 at.%. On the template surface, a nanocrystalline CeO2 thin film was deposited with a cubic fluorite structure and a crystallite size of 6–7 nm. Characterization of the nanowires and thin films was performed using scanning electron microscopy, transmission electron microscopy, electron energy loss spectroscopy, x-ray photoelectron spectroscopy and x-ray diffraction. The nanowire formation mechanism and urea hydrolysis kinetics are discussed in terms of the pH evolution during the reaction. The Ce-doped γ-Al2O3 nanowires are likely to find useful applications in catalysis and this novel method can be exploited further for doping alumina nanowires with other rare earth elements.
The ultra-low-angle microtomy (ULAM) technique has been developed to impart a cross-sectional, ultra-low-angle taper through polymeric materials such as coatings and paints. ULAM employs a conventional rotary microtome in combination with high-precision, angled sectioning blocks to fabricate the ultra-low-angle tapers. Subsequent investigation of the tapers produced by ULAM may be used in conjunction with X-ray photoelectron spectroscopy (XPS) or time-of-flight secondary ion mass spectrometry (ToF-SIMS), for compositional depth profiling or ‘buried’ interface analysis. Variation in the selection of the ULAM taper angle and/or the analysis interval size employed enables depth resolution at the nanometre or micrometre scales to be achieved. In the work described here scanning electron microscopy (SEM) and atomic force microscopy (AFM) have been employed to investigate the morphology and topography of the surfaces resulting from the ULAM tapering process. It is demonstrated that a correctly mounted polymeric sample, sectioned with a sharp microtome knife, displays little perturbation of the resulting polymeric surface after ULAM processing. Additionally, SEM analysis of the interface region between a poly(vinylidene fluoride) (PVdF) topcoat and polyurethane (PU) primer exposed by ULAM processing reveals that the interface region between the two coatings possesses a well-defined boundary. No evidence of polymeric smearing across the interface is observed. XPS compositional depth profiling across a ‘buried’ PVdF/PU interface, exposed by ULAM processing, is employed to demonstrate the utility of the ULAM technique.
A comparative study of the GSR performance for Ni/CaO-MgO-Al2O3 and Ni/Al2O3 catalysts is reported. Catalysts were synthesized applying the wet impregnation method at a constant metal loading (8 wt %). Synthesized samples were characterized by N2 adsorption/desorption, ICP, BET, XRD, NH3-TPD, CO2-TPD, H2-TPR, XPS, TEM, STEM-HAADF and EDS. The carbon deposited on their surface under reaction conditions was characterized by TPO, Raman and TEM. It was proven that the use of CaO-MgO as alumina modifiers leads to smaller nickel species crystallite size, increased basicity and surface amount of Ni0 phase. Thus, it increases the conversion to gaseous products favoring H2 and CO2 production to the detriment of CO formation, by enhancing the water gas-shift (WGS) reaction. No liquid products were produced by the Ni/modAl catalyst over 550 °C, whereas time on stream results confirmed that deactivation can be prevented, as apart from decreasing the amount of coke deposition the nature of carbon was altered towards less graphitic and more defective structures.
The migration and segregation of a minor silicone containing additive in a multilayer, organic coating system has been investigated by X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The silicone containing additive employed was the most compatible thermally stable, polyester modified poly(dimethyl siloxane) (PDMS) flow agent. A polyester/polyurethane (PU) based primer and a poly(vinylidene difluoride) (PVdF) based topcoat on an aluminium substrate were used as a model, multilayer, organic coating system. XPS and SIMS characterisation of the PU primer formulation (with and without addition of the PDMS based flow agent), confirmed that the PDMS based flow agent segregated to the PU primers air/coating surface. Characterisation of the PVdF topcoats air/coating surface, after application and curing over the PU primers, revealed the presence of the PDMS based flow agent at the PVdF air/coating surface when the topcoat was applied to the PU primer containing the PDMS based flow agent. Ultra-low-angle microtomy (ULAM) was employed to produce an ultra-low-angle taper that passes through the entire thickness of the PVdF topcoat (~20 µm). XPS linescan analysis along the ULAM taper indicated that the PDMS based flow agent had migrated from the PU primer surface into the bulk of the PVdF topcoat. Analysis of the shape of the silicon concentration profile revealed the existence of a silicon concentration gradient and indicated that the PDMS based flow agent was segregating towards the PVdF topcoats air/coating surface. Such migration and segregation phenomena have major implications for formulators in the coatings/paint industries.
A number of analytical techniques were applied to investigate changes to the surface of unsized boron-free E-glass fibres after thermal conditioning at temperatures up to 700 °C. Novel systematic studies were carried out to investigate the fundamental strength loss from thermal conditioning. Surface chemical changes studied using X-ray photoelectron spectroscopy (XPS) showed a consistent increase in the surface concentration of calcium with increasing conditioning temperature, although this did not correlate well with a loss of fibre strength. Scanning electron microscopy fractography confirmed the difficulty of analysing failure-inducing flaws on individual fibre fracture surfaces. Analysis by atomic force microscopy (AFM) did not reveal any likely surface cracks or flaws of significant dimensions to cause failure: the observation of cracks before fibre fracture may not be possible when using this technique. Fibre surface roughness increased over the whole range of the conditioning temperatures investigated. Although surface roughness did not correlate precisely with fibre strength, there was a clear inverse relationship at temperatures exceeding 400 °C. The interpretation of the surface topography that formed between 400–700 °C produced evidence that the initial stage of phase separation by spinodal decomposition may have occurred at the fibre surface.
The aim of the work was to investigate the influence of support on the catalytic performance of Ni catalysts for the glycerol steam reforming reaction. Nickel catalysts (8 wt%) supported on Al2O3, ZrO2, SiO2 were prepared by the wet impregnation technique. The catalysts’ surface and bulk properties, at their calcined, reduced and used forms, were determined by ICP, BET, XRD, NH3-TPD, CO2-TPD, TPR, XPS, TEM, TPO, Raman, SEM techniques. The Ni/Si sample, even if it was less active for T
CO elimination through oxidation over highly active and cost-effective catalysts is a way forward for many processes of industrial and environmental importance. In this study, doped CeO2 with transition metals (TM = Cu, Co, Mn, Fe, Ni, Zr, and Zn) at a level of 20 at. % was tested for CO oxidation. The oxides were prepared using microwave-assisted sol–gel synthesis to improve catalyst’s performance for the reaction of interest. The effect of heteroatoms on the physicochemical properties (structure, morphology, porosity, and reducibility) of the binary oxides M–Ce–O was meticulously investigated and correlated to their CO oxidation activity. It was found that the catalytic activity (per gram basis or TOF, s–1) follows the order Cu–Ce–O > Ce–Co–O > Ni–Ce–O > Mn–Ce–O > Fe–Ce–O > Ce–Zn–O > CeO2. Participation of mobile lattice oxygen species in the CO/O2 reaction does occur, the extent of which is heteroatom-dependent. For that, state-of-the-art transient isotopic 18O-labeled experiments involving 16O/18O exchange followed by step-gas CO/Ar or CO/O2/Ar switches were used to quantify the contribution of lattice oxygen to the reaction. SSITKA-DRIFTS studies probed the formation of carbonates while validating the Mars–van Krevelen (MvK) mechanism. Scanning transmission electron microscopy-high-angle annular dark field imaging coupled with energy-dispersive spectroscopy proved that the elemental composition of dopants in the individual nanoparticle of ceria is less than their composition at a larger scale, allowing the assessment of the doping efficacy. Despite the similar structural features of the catalysts, a clear difference in the Olattice mobility was also found as well as its participation (as expressed with the α descriptor) in the reaction, following the order αCu > αCo> αMn > αZn. Kinetic studies showed that it is rather the pre-exponential (entropic) factor and not the lowering of activation energy that justifies the order of activity of the solids. DFT calculations showed that the adsorption of CO on the Cu-doped CeO2 surface is more favorable (−16.63 eV), followed by Co, Mn, Zn (−14.46, −4.90, and −4.24 eV, respectively), and pure CeO2 (−0.63 eV). Also, copper compensates almost three times more charge (0.37e −) compared to Co and Mn, ca. 0.13e − and 0.10e −, respectively, corroborating for its tendency to be reduced. Surface analysis (X-ray photoelectron spectroscopy), apart from the oxidation state of the elements, revealed a heteroatom–ceria surface interaction (Oa species) of different extents and of different populations of Oa species.
In the study presented herein, nickel catalysts supported on CeO2 and, for the first time in the literature, on La2O3-Sm2O3-CeO2, La2O3-Pr2O3-CeO2 and La2O3-MgO-CeO2 were prepared and evaluated for the reaction of CO2 methanation. The carriers were prepared through a sol-gel microwave assisted method and the catalysts were obtained following wet impregnation. The physicochemical properties of the catalysts prior to reaction were determined through H2-TPR, H2-TPD, Raman spectroscopy, XRD, CO2-TPD, N2 physisorption-desorption, XPS and TEM. The spent catalysts, after the time-on-stream experiments were further characterised using TEM and TGA. It was shown that the simultaneous incorporation of La3+, Pr3+ and La3+, Sm3+ into the crystal structure of cerium oxide created higher population of oxygen vacant sites. Moreover, the co-presence of La3+, Mg2+ and La3+, Pr3+ into the CeO2 increased the plethos of moderate basic sites. These physicochemical properties increased the rate of CO2 methanation reaction at relatively low temperatures. Furthermore, it is argued that the addition of La3+ stabilized the Ni active sites via the probable formation of a new compound (La-O-Ni) on the catalyst surface or synergetic catalytic centers at the interfacial area improving the catalytic properties (activity and stability). Finally, the catalytic performance tests revealed that the addition of La3+ mainly improved the conversion of CO2 and yield of CH4 for the Ni/La-Mg-Ce and Ni/La-Sm-Ce samples. The rCO2 and XCO2 values at 300oC followed the order Ni/La-Sm-Ce >> Ni/La-Mg-Ce > Ni/La-Pr-Ce > Ni/Ce.
Highly visible-light-active S,N-codoped anatase-rutile heterojunctions are reported for the first time. The formation of heterojunctions at a relatively low temperature and visible-light activity are achieved through thiourea modification of the peroxo-titania complex. FT-IR spectroscopic studies indicated the formation of a Ti(4+)-thiourea complex upon reaction between peroxo-titania complex and thiourea. Decomposition of the Ti(4+)-thiourea complex and formation of visible-light-active S,N-codoped TiO(2) heterojunctions are confirmed using X-ray diffraction, Raman spectroscopy, transmission electron microscopy, and UV/vis spectroscopic studies. Existence of sulfur as sulfate ions (S(6+)) and nitrogen as lattice (N-Ti-N) and interstitial (Ti-N-O) species in heterojunctions are identified using X-ray photoelectron spectroscopy (XPS) and FT-IR spectroscopic techniques. UV-vis and valence band XPS studies of these S,N-codoped heterojunctions proved the fact that the formation of isolated S 3p, N 2p, and Π* N-O states between the valence and conduction bands are responsible for the visible-light absorption. Titanium dioxide obtained from the peroxo-titania complex exists as pure anatase up to a calcination temperature as high as 900 °C. Whereas, thiourea-modified samples are converted to S,N-codoped anatase-rutile heterojunctions at a temperature as low as 500 °C. The most active S,N-codoped heterojunction 0.2 TU-TiO(2) calcined at 600 °C exhibits a 2-fold and 8-fold increase in visible-light photocatalytic activities in contrast to the control sample and the commercial photocatalyst Degussa P-25, respectively. It is proposed that the efficient electron-hole separation due to anatase to rutile electron transfer is responsible for the superior visible-light-induced photocatalytic activities of S,N-codoped heterojunctions.
Interface-mediated recombination losses between perovskite and charge transport layers are one of the main reasons that limit the device performance, in particular for the open-circuit voltage (VOC) of perovskite solar cells (PSCs). Here, functional molecular interface engineering (FMIE) is employed to retard the interfacial recombination losses. The FMIE is a facile solution-processed means that introducing functional molecules, the fluorene-based conjugated polyelectrolyte (CPE) and organic halide salt (OHS) on both contacts of the perovskite absorber layer. Through the FMIE, the champion PSCs with an inverted planar heterojunction structure show a remarkable high VOC of 1.18 V whilst maintaining a fill factor (FF) of 0.83, both of which result in improved power conversion efficiencies (PCEs) of 21.33% (with stabilized PCEs of 21.01%). In addition to achieving one of the highest PCEs in the inverted PSCs, the results also highlight the synergistic effect of these two molecules in improving device performance. Therefore, the study provides a straightforward avenue to fabricate highly efficient inverted PSCs.
In the present study, Ni/Ce-Sm-xCu (x = 5, 7, 10 at.%) catalysts were prepared using microwave radiation coupled with sol-gel and followed by wetness impregnation method for the Ni incorporation. Highly dispersed nanocrystallites of CuO and NiO on the Ce-Sm-Cu support were found. Increase of Cu content seems to facilitate the reducibility of the catalyst according to the H₂ temperature-programmed reduction (H₂-TPR). All the catalysts had a variety of weak, medium and strong acid/basic sites that regulate the reaction products. All the catalysts had very high XC3H8O3 for the entire temperature (400–750 °C) range; from ≈84% at 400 °C to ≈94% at 750 °C. Ni/Ce-Sm-10Cu catalyst showed the lowest XC3H8O3-gas implying the Cu content has a detrimental effect on performance, especially between 450–650 °C. In terms of H₂ selectivity (SH2) and H₂ yield (YH2), both appeared to vary in the following order: Ni/Ce-Sm-10Cu ˃ Ni/Ce-Sm-7Cu ˃ Ni/Ce-Sm-5Cu, demonstrating the high impact of Cu content. Following stability tests, all the catalysts accumulated high amounts of carbon, following the order Ni/Ce-Sm-5Cu ˂ Ni/Ce-Sm-7Cu ˂ Ni/Ce-Sm-10Cu (52, 65 and 79 wt.%, respectively) based on the thermogravimetric analysis (TGA) studies. Raman studies showed that the incorporation of Cu in the support matrix controls the extent of carbon graphitization deposited during the reaction at hand.
Significant efforts have been focused on the search of earth-abundant elements to solve growing energy issues and to provide bifunctional behavior for both hydrogen and oxygen evolution reaction. Mixed transition metals could provide promising synergistic electrochemical properties and serve as bi-catalyst for overall water splitting process. In this study, a needle grass array of nanostructured nickel cobalt sulfide (NiCo2S4) was synthesized using a hydrothermal process. The synthesized NiCo2S4 electrodes showed promising electrocatalytic activity with a low overpotential of 148 mV and 293 mV for hydrogen and oxygen evolution reactions, respectively. The electrolyzer cell consisting of two NiCo2S4 electrodes displayed excellent performance with high electrochemical stability and low overall cell potential of 1.61 V to achieve a current density of 10 mA/cm2. Our study suggests that mixed transition metal chalcogenides such as NiCo2S4 could be used as efficient and stable electrocatalyst for overall water splitting process.
Protective coatings have been deposited on electrogalvanized steel by immersion in solutions containing 2-Butyne-1.4-diol propoxylate (CHO), cerium nitrate, sodium nitrate and sodium sulphate for different immersion periods. The surface morphology and chemical composition of the coatings formed on the electrogalvanized steel were studied using field emission gun scanning electron microscopy, X-ray photoelectron spectroscopy and Fourier Transform Infrared Spectroscopy. The corrosion resistance of the electrogalvanized steel prior to and after surface treatment was investigated by electrochemical impedance spectroscopy in 0.1 mol L NaCl solution. The results were compared to the performance of a chromate conversion coating in the same solution. The coatings formed on the electrogalvanized steel surface showed the presence of a mixed organic/inorganic layer containing CeO and CeO which improved the corrosion resistance of the substrate and showed a superior corrosion resistance to that provided by a chromate conversion coating.
The present work investigated the production of Green Diesel through the deoxygenation of palm oil over Ni catalysts supported on γ-Αl2O3, ZrO2 and SiO2 for a continuous flow fixed bed reactor. A comprehensive experimental study was carried out in order to examine the effects of temperature, pressure, LHSV and H2/oil feed ratio on catalytic activity during short (6 h) and long (20 h) time-on-stream experiments. The catalysts were prepared through the wet impregnation method (8 wt.% Ni) and were extensively characterized by N2 adsorption/desorption, XRD, NH3-TPD, CO2-TPD, H2-TPD, H2-TPR, XPS, TEM/HR-TEM and Raman. The characterization of the materials prior to reaction revealed that although relatively small Ni nanoparticles were achieved for all catalysts (4.3 ± 1.6 nm, 6.1 ± 1.8 nm and 6.0 ± 1.8 nm for the Ni/Al2O3, Ni/ZrO2 and Ni/SiO2 catalysts, respectively), NiO was better dispersed on the Ni/ZrO2 catalyst, while the opposite was true for the Ni/SiO2 sample. In the case of Ni/Al2O3, part of Ni could not participate in the reaction due to its entrapment in the NiAl2O4 spinel phase. Regarding performance, although an increase in H2 pressure led to increases in paraffin conversion, the increase of temperature was beneficial only up to a critical value which differed for each catalytic system under consideration (375 oC, 300 oC and 350 oC for the Ni/Al2O3, Ni/ZrO2 and Ni/SiO2 catalysts, respectively). All catalysts favored the deCO2 and deCO deoxygenation paths much more extensively than HDO, irrespective of testing conditions. Time-on-stream experiments showed that all catalysts deactivated after about 6 h, which was attributed to the sintering of the Ni particles and/or their covering by a thin graphitic carbon shell.
A new protocol using time-of-flight secondary ion mass spectrometry (ToF-SIMS) has been developed to identify the deposition order of a fingerprint overlapping an ink line on paper. By taking line scans of fragment ions characteristic of the ink molecules (m/z 358.2 and 372.2) where the fingerprint and ink overlap and by calculating the normalised standard deviation of the intensity variation across the line scan, it is possible to determine whether or not a fingerprint is above ink on a paper substrate. The protocol adopted works for a selection of fingerprints from four donors tested here and for a fingerprint that was aged for six months; for one donor, the very faint fingerprints could not be visualized using either standard procedures (ninhydrin development) or SIMS and therefore the protocol correctly gives an inconclusive result.
Nanoparticles of cerium dioxide (or nanoceria) are of interest because of their oxygen buffering, photocatalytic ability, and high UV absorption. For applications, the nanoceria can be incorporated in a polymer binder, but questions remain about the link between the nanoparticle distribution and the resulting nanocomposite properties. Here, the thermal, mechanical and optical properties of polymer/ceria nanocomposites are correlated with their nanostructures. Specifically, nanocomposites made from waterborne Pickering particles with nanoceria shells are compared to nanocomposites made from blending the equivalent surfactant-free copolymer particles with nanoceria. Two types of nanoceria (protonated or citric acid-coated) are compared in the Pickering particles. A higher surface coverage is obtained with the protonated ceria, which results in a distinct cellular structure with nanoceria walls within the nanocomposite. In the blend of particles, a strong attraction between the protonated nanoceria and the acrylic acid groups of the copolymer likewise leads to a cellular structure. This structure offers transparency in the visible region combined with strong UV absorption, which is desired for UV blocking coating applications. Not having an attraction to the polymer, the citric acid-coated nanoceria forms agglomerates that lead to undesirable light scattering in the nanocomposite and yellowing. This latter type of nanocomposite coating is less effective in protecting substrates from UV damage but provides a better barrier to water. This work shows how the nanoparticle chemical functionalization can be used to manipulate the structure and to tailor the properties of UV-absorbing barrier coatings.
In this letter, we demonstrate a solution-based method for a one-step deposition and surface passivation of the as-grown silicon nanowires (Si NWs). Using N,N-dimethylformamide (DMF) as a mild oxidizing agent, the NWs' surface traps density was reduced by over 2 orders of magnitude from 1×10(13) cm(-2) in pristine NWs to 3.7×10(10) cm(-2) in DMF-treated NWs, leading to a dramatic hysteresis reduction in NW field-effect transistors (FETs) from up to 32 V to a near-zero hysteresis. The change of the polyphenylsilane NW shell stoichiometric composition was confirmed by X-ray photoelectron spectroscopy analysis showing a 35% increase in fully oxidized Si4+ species for DMF-treated NWs compared to dry NW powder. Additionally, a shell oxidation effect induced by DMF resulted is a more stable NW FET performance with steady transistor currents and only 1.5 V hysteresis after 1000 h of air exposure
Ce1-xSmxO2(x=0, 0.2, 0.5 and 0.8) nanofibers (NFs) were synthesized by coupling sol-gel with electrospinning and using poly-vinyl pyrrolidone (PVP) as the polymer medium, in an ethanol/water mixture. Control over the fabrication conditions was achieved through analysis of the most key synthetic factors, which include: (i) the applied field strength; (ii) the solution feed rate and (iii) the PVP content in the electrospinning solution. The optimum microstructural fiber morphology (high quality beeds-free fibers) was achieved using the following electrospinning parameters: an applied voltage of 18.5 kV, a 7 ml/hr of solution feed rate and a 12% (w/w) of PVP composition. Morphological features of the resulting fibers were examined by scanning electron microscopy (SEM). The average fiber diameter was typically found to be in the range of 200-1100 nm and 50-300 nm, before and after calcination at 500 oC, respectively. X-ray diffraction (XRD) results showed that the fluorite cubic structure was preserved for the entire Ce1-xSmxO2 compositional range studied, while elemental analysis using EELS and X-ray photoelectron spectroscopy (XPS) confirmed the purity of the bulk and surface composition of the fibers. Selected area electron diffraction (SAED) and high resolution transmission electron microscopy (HRTEM) proved that the NFs are highly crystalline. The thermal stability of the composite (polymer/inorganic nitrate salts) NFs was further investigated in an inert atmosphere (N2) using thermogravimetric analysis (TGA), which allowed the transformation process of the NFs from composite to oxide to be monitored. The reducibility of the metal oxide NFs (mobility of oxygen species in the fluorite cubic lattice) as well as their thermal stability in successive oxidation-reduction cycles was evaluated using temperature-programmed reduction in a H2 atmosphere (H2-TPR). Acidic-basic features of the NFs and powder surfaces were studied through temperature programmed desorption (TPD) using NH3 and CO2 as probe molecules, where weak, medium and strong acid sites were successfully traced with profound differences depending on the morphology. The NFs’ potential performance towards NH3 oxidation was also evaluated. Two types of basic sites, hydroxyl groups and surface lattice oxygen are present on the NFs, as probed by CO2 adsorption. Pyridine adsorption followed by infrared spectroscopy (Py-FT-IR) studies unveiled the more profound Lewis acid presence in Ce0.5Sm0.5O2 NFs compared to bulk powder Ce0.5Sm0.5O2.
CeO2 and CexSm1-xO2 nanoparticle mixed oxides have been synthesized by microwave assisted sol-gel (MW sol-gel) and conventional sol-gel (C sol-gel) synthesis carried out at 60oC (typical sol-gel) and 100oC (approaching the MW temperature). Different characterization techniques, namely, XRD, BET, Raman, SEM, FTIR, TEM, XPS, H2-TPR, CO2-TPD, and XPS have been employed to understand the process-structure-properties relationship of the catalysts. The CO oxidation performance has been determined both in the absence and in the presence of H2 in the feed gas stream. Microwave heating yields a more thermally stable precursor material, which preserves 75% of its mass up to 600oC, attributable to the different chemical nature of the precursor, compared to the typical sol-gel material with the same composition. Varying the synthesis method has no profound effect on the surface area of the materials, which is in the range 4-35m2/g. Conventional sol-gel synthesis performed at 60 and 100oC yields CeO2 particles with a crystallite size of 29 nm and 24 nm compared to 21-27 nm for MW sol-gel synthesis (at different power values). The MW sol-gel CexSm1-xO2 catalysts exhibit a smaller crystallite size (12-18 nm). The pure ceria nanoparticles were shown to have a stoichiometry of approximately CeO1.95. The presence of Ce3+ and Sm3+ in the mixed oxide particles facilitates the presence of oxygen vacant sites, confirmed by Raman. Oxygen mobile species have been traced using H2-TPR studies and a compressive lattice strain in the 0.45-1.9% range of the cubic CexSm1-xO2 lattice were found to be strongly correlated with the CO oxidation performance in the presence and absence of H2 in the oxidation feed stream. MW sol-gel synthesis led to more active CeO2 and Ce0.5Sm0.5O2 catalysts, demonstrated by T50 (temperature where 50% CO conversion is achieved), being reduced by 131 oC and 47 oC, respectively, compared to typical sol-gel catalysts. Conventional synthesis performed at 100oC leads to a CeO2 catalyst of initially higher activity at a certain temperature window (220-420oC), though with a slower increase of XCO with temperature compared to the MW one. MW sol-gel synthesized Ce0.8Sm0.2O2 exhibited a high performance (~90%) for CO oxidation over a period of more than 20 h in stream. In addition the effect of reaction temperature and contact time (W/F) on the activity of the CeO2-based materials for CO oxidation kinetics were investigated. The activation energy of the reaction was found to be in the 36-43 kJ/mole range depending on the catalyst composition.
The co-doping effect of a rare earth (RE) metal and a transition metal (TM) on ceria oxidation catalysis through the evaluation of samarium-copper co-doped catalysts with Ce-Sm-xCu-O (x: 0–20 at.%, Ce/Sm = 1) nominal compositions, is discussed. The CO oxidation reaction was used as a prototype reaction due to its pivotal role in the fuel cell technology. Ce-Sm-20Cu-O catalyst presented a 64% increase in the CO oxidation activity compared to that of pristine ceria. Diffraction and Raman studies proved that the Cu, Sm co-doping induces many defects related to the dopants (Sm, Cu) and the oxygen vacant sites, while the presence of hybrid CuO/Ce-Sm(Cu)-O fluorite/SmO8 (cubic metastable) phases is the most representative scenario of this oxide microstructure. A size polydispersity of CuO phases was achieved by introducing air cooling during the microwave heating. Cu, Sm atoms were uniformly doped in CeO2 structure according to the HAADF-STEM studies. These results are in agreement with EDS analysis, where Cu, Sm and Ce are located in all the analyzed areas without any preferential distribution. The XPS studies demonstrated the co-presence of Cu2+/Cu1+ and Ce4+/Ce3+ redox couples in agreement with the Bader charge analysis from the ab initio calculations, the latter influencing greatly the oxidation activity of the catalysts. Density functional theory (DFT) calculations shed light on the oxide surface and the underlying mechanism governing the oxidation catalysis taking place. In particular, Cu2+ and Sm3+ dopants were found to be located in the nearest neighbor (NN) sites of oxygen vacancies. Different oxygen vacancies configurations were studied (single vs. double, surface vs. subsurface), where the single vacancies are more stable on the surface, whereas the double vacancies configurations are more stable on the subsurface. Regarding the Ce3+ location, in the presence of single and double oxygen vacancy, the Ce3+ ions prefer to be located in the 1st NN/2nd NN and 2nd NN of the first Ce layer, relative to the oxygen vacancy, respectively. The total Density of States (DOS) analysis of the co-doped systems revealed that the dopants induced new surface states inside the ceria band gap, which can accommodate the unpaired electrons of the vacant oxygen sites. These electronic modifications justify the much lower energy of oxygen vacancy formation (Evf) in both cases, the Sm-doped, and Cu, Sm -doped CeO2 (1 1 1) geometries. Specifically, the Evf lowering upon doping was found to be almost two times larger for the Cu adjacent oxygen vacancies (Cu2+-□) compared to the Sm ones (Sm3+-□), consistent with the CO adsorption trend as the Cu-Sm-CeO2 (1 1 1) system is energetically more favorable than the Sm-CeO2 (1 1 1) and pure CeO2 (1 1 1) surfaces.
The present study provides, for the first time in the literature, a comparative assessment of the catalytic performance of Ni catalysts supported on γ-Al2O3 and γ-Al2O3 modified with La2O3, in a continuous flow trickle bed reactor, for the selective deoxygenation of palm oil. The catalysts were prepared via the wet impregnation method and were characterized, after calcination and/or reduction, by N2 adsorption/desorption, XRD, NH3-TPD, CO2-TPD, H2-TPR, H2-TPD, XPS and TEM, and after the time-on-stream tests, by TGA, TPO, Raman and TEM. Catalytic experiments were performed between 300–400 °C, at a constant pressure (30 bar) and different LHSV (1.2–3.6 h−1). The results show that the incorporation of La2O3 in the Al2O3 support increased the Ni surface atomic concentration (XPS), affected the nature and abundance of surface basicity (CO2-TPD), and despite leading to a drop in surface acidity (NH3-TPD), the Ni/LaAl catalyst presented a larger population of medium-strength acid sites. These characteristics helped promote the SDO process and prevented extended cracking and the formation of coke. Thus, higher triglyceride conversions and n-C15 to n-C18 hydrocarbon yields were achieved with the Ni/LaAl at lower reaction temperatures. Moreover, the Ni/LaAl catalyst was considerably more stable during 20 h of time-on-stream. Examination of the spent catalysts revealed that both carbon deposition and degree of graphitization of the surface coke, as well as, the extent of sintering were lower on the Ni/LaAl catalyst, explaining its excellent performance during time-on-stream.
To contribute to solving global energy problems, a multifunctional CoFe2O4 spinel was synthesized and used as a catalyst for overall water splitting and as an electrode material for supercapacitors. The ultra-fast one-step electrodeposition of CoFe2O4 over conducting substrates provides an economic pathway to high-performance energy devices. Electrodeposited CoFe2O4 on Ni-foam showed a low overpotential of 270 mV and a Tafel slope of 31 mV/dec. The results indicated a higher conductivity for electrodeposited compared with dip-coated CoFe2O4 with enhanced device performance. Moreover, bending and chronoamperometry studies suggest excellent durability of the catalytic electrode for long-term use. The energy storage behavior of CoFe2O4 showed high specific capacitance of 768 F/g at a current density of 0.5 A/g and maintained about 80% retention after 10,000 cycles. These results demonstrate the competitiveness and multifunctional applicability of the CoFe2O4 spinel to be used for energy generation and storage devices.
The interfacial region of a model, multilayer coating system on an aluminium substrate has been investigated by high resolution time-of-flight secondary ion mass spectrometry (ToF-SIMS). Employing ultra-low-angle microtomy (ULAM), the interface between a poly(vinylidene difluoride) (PVdF) based topcoat and a poly(urethane) (PU) based primer ‘buried’ over 20μm below the PVdF topcoat’s air/coating surface was exposed. Imaging ToF-SIMS and subsequent post-processing extraction of mass spectra of the ULAM exposed interface region and the PVdF topcoat and PU primer bulks indicates that the material composition of the polymer-polymer interface region is substantially different to that of the bulk PVdF and PU coatings. Analysis of the negative ion mass spectra obtained from the PVdF/PU interface reveals the presence of a methacrylate based component or additive at the interface region. Reviewing the topcoat and primer coating formulations reveals the PVdF topcoat formulation contains methyl methacrylate (MMA)/ethyl acrylate (EA) acrylic co-polymer components. Negative ion ToF-SIMS analysis of an acrylic co-polymer confirms it is these components that are observed at the PVdF/PU interface. Post-processing extraction of ToF-SIMS images based on the major ions of the MMA/EA co-polymers reveals these components are observed in high concentration at the extremities of the PVdF coating i.e. at the polymer-polymer interface but are also observed to be distributed evenly throughout the bulk of the PVdF topcoat. These findings confirms that a fraction of the MMA/EA acrylic co-polymers in the formulation segregate to the topcoat-primer interface where they enhance the adhesive properties exhibited by the PVdF topcoat towards the underlying PU primer substrate.
Ni3s, Ni3p and Ni2p x-ray photoelectron spectra of mono-and binuclear carboxylate complexes of nickel with various geometry of metal ions environment are obtained. The spectra are calculated in an isolated ion approximation. The dependence of the spectral profiles and the structure of the charge-transfer satellites on the structure of the immediate environment of nickel atoms is established. The data obtained support the results of X-ray diffraction and magnetic studies.
(Ce-La-xCu)O2 catalysts with low (3 at.%) and high (10 at.%) Cu content were prepared by conventional microwave (MW) and enhanced microwave methods where air cooling (AC), while heating, was applied. The catalysts were tested for the CO oxidation reaction in the 25–500 °C range using 4%CO/20%O2/He feed gas. Varying spectroscopic, microscopic and catalytic studies were used to probe the effect of synthesis on the nanostructure and the CO oxidation performance. It was found that the synthesis method adopted impacts on the extent of the Cu doping into the (Ce-La)O2 fluorite lattice, hence leading to one and two phases system in the case of catalyst prepared through enhanced (AC) and conventional (MW) microwave methods, respectively. Furthermore, only Ce4+ species were found on the surface of the (Ce-La-10Cu)O2 catalysts synthesized using MW and AC (XPS studies), whereas oxygen vacant sites which are associated with Ce3+ ions were indicated in the sub-surface/bulk (Raman studies). Ultimately, the catalysts with the low and high Cu loading, prepared under the AC-promoted microwave method, presented a superior performance against CO oxidation, exhibiting an overall improvement of the catalytic activity by 16% and 32%, respectively.
Visible-light-induced antibacterial activity of carbon-doped anatase-brookite titania nano-heterojunction photocatalysts are reported for the first time. These heterostructures were prepared using a novel low temperature (100 °C) non-hydrothermal low power microwave (300 W) assisted method. Formation of interband C 2p states was found to be responsible for the band gap narrowing of the carbon doped heterojunctions. The most active photocatalyst obtained after 60 minutes of microwave irradiation exhibits a 2-fold higher visible-light induced photocatalytic activity in contrast to the standard commercial photocatalyst Evonik-Degussa P-25. Staphylococcus aureus inactivation rate constant for carbon-doped nano-heterojunctions and the standard photocatalyst was 0.0023 and -0.0081 min-1 respectively. It is proposed that the photo-excited electrons (from the C 2p level) are effectively transferred from the conduction band of brookite to that of anatase causing efficient electron-hole separation, which is found to be responsible for the superior visible-light induced photocatalytic and antibacterial activities of carbon-doped anatase-brookite nano-heterojunctions.
Nanograins of Ce-La-xCu-O oxides, of 16 nm2 area size, are tested as materials towards the CO oxidation . Preservation of the cubic lattice structure following La3+ and Cu2+ metal cations doping is confirmed based on the powder X-ray diffraction and Raman studies. From XPS, the presence of mixed Ce3+/Ce4+ and Cu2+/Cu1+ oxidation states was confirmed, which was more profound in the low Cu-content Ce-La-xCu-O catalysts. Cu increases the concentration of oxygen vacant sites in the doped-CeO2 according to the Raman intensity ratio IOv/IF2g of 1.58 and 1.78 with the increase in copper content from 7 to 20 at.% as compared to the lower value of 0.44 for the Ce-La. The mobility of the surface and bulk lattice oxygen is further investigated using 16O/18O isotopic exchange (TIIE), and is found to be Cu at.% dependent. For the case of Ce-La-20Cu, the participation of the lattice oxygen (OL) in the reaction mechanism has been demonstrated using transient experiments. Accordingly, the specific rate (μmol CO m-2s-1) of the CO oxidation reaction is found to be higher for the Ce-La-20Cu and Ce-La-7Cu catalysts, corroborating thus the presence of more mobile/labile oxygen species in those ternary catalysts as opposed to the other lower copper compositions.
The glycerol steam reforming (GSR) reaction for H2 production was studied comparing the performance of Ni supported on ZrO2 and SiO2-ZrO2 catalysts. The surface and bulk properties were determined by ICP, BET, XRD, TPD, TPR, TPO, XPS, SEM and STEM-HAADF. It was suggested that the addition of SiO2 stabilizes the ZrO2 monoclinic structure, restricts the sintering of nickel particles and strengthens the interaction between Ni2+ species and support. It also removes the weak acidic sites and increases the amount of the strong acidic sites, whereas it decreases the amount of the basic sites. Furthermore, it influences the gaseous products’ distribution by increasing H2 yield and not favouring the transformation of CO2 in CO. Thus, a high H2/CO ratio can be achieved accompanying by negligible value for CO/CO2. From the liquid products quantitative analysis, it was suggested that acetone and acetaldehyde were the main products for the Ni/Zr catalyst, for 750oC, whereas for the Ni/SiZr catalyst allyl alcohol was the only liquid product for the same temperature. It was also concluded that the Ni/SiZr sample seems to be more resistant to deactivation however, for both catalysts a substantial amount of carbon exists on the catalytic surface in the shape of carbon nanotubes and amorphous carbon.
PET web samples have been treated by magnetically enhanced glow discharges powered using either medium frequency pulse direct current (p-DC) or low frequency high power pulse (HIPIMS) sources. The plasma pre-treatment processes were carried out in an Ar–O2 atmosphere using either Cu or Ti sputter targets. XPS, AFM and sessile drop water contact angle measurements have been employed to examine changes in surface chemistry and morphology for different pre-treatment process parameters. Deposition of metal oxide onto the PET surface is observed as a result of the sputter magnetron-based glow discharge web treatment. Using the Cu target, both the p-DC and HIPIMS processes result in the formation of a thin CuO layer (with a thickness between 1 and 11 nm) being deposited onto the PET surface. Employing the Ti target, both p-DC and HIPIMS processes give rise to a much lower concentration of Ti (< 5 at.%), in the form of TiO2 on the PET treated surface. The TiO2 is probably distributed as an island-like distribution covering the PET surface. Presence of Cu and Ti oxide constituents on the treated PET is beneficial in aiding the adhesion but alone (i.e. without oxygen plasma activation) is not enough to provide very high levels of hydrophilicity as is clear from sessile drop water contact angle measurements on aged samples. Exposure to the plasma treatments leads to a small amount of roughening of the substrate surface, but the average surface roughness in all cases is below 2.5 nm. The PET structure at the interface with a coating is mostly or wholly preserved. The oxygen plasma treatment, metal oxide deposition and surface roughening resulting from the HIPIMS and p-DC treatments will promote adhesion to any subsequent thin film that is deposited immediately following the plasma treatment.
Nanocrystalline ZnO photocatalysts were prepared by a sol-gel method and modified with fluorine to improve their photocatalytic anti-bacterial activity in visible light. Pathogenic bacteria such as Escherichia coli (Gram-negative) and Staphylococcus aureus (Gram-positive) were employed to evaluate the antimicrobial properties of synthesized materials. The interaction with biological systems was assessed by analysis of the antibacterial properties of bacteria suspended in 2% (w/w) powder solutions. The F-doping was found to be effective against S. aureus (99.99% antibacterial activity) and E. coli (99.87% antibacterial activity) when irradiated with visible light. Production of reactive oxygen species is one of the major factors that negatively impact bacterial growth. In addition, the nanosize of the ZnO particles can also be toxic to microorganisms. The small size and high surface-to-volume ratio of the ZnO nanoparticles are believed to play a role in enhancing antimicrobial activity.