Aqueous Phase Reforming over Platinum Catalysts on Doped Carbon Supports: Exploring Platinum-Heteroatom Interactions.

A series of platinum catalysts supported on carbon nanofibers with various heteroatom dopings were synthesized to investigate the effect of the local platinum environment on the catalytic activity and selectivity in aqueous phase reforming (APR) of ethylene glycol (EG). Typical carbon dopants such as oxygen, nitrogen, sulfur, phosphorus, and boron were chosen based on their ability to bring acidic or basic functional groups to the carbon surface. In situ X-ray absorption spectroscopy (XAS) was used to identify the platinum oxidation state and platinum species formed during APR of EG through multivariate curve resolution alternating least-squares analysis, observing differences in activity, selectivity, and platinum local environment among the catalysts. The platinum-based catalyst on the nitrogen-doped carbon support demonstrated the most favorable properties for H2 production due to high Pt dispersion and basicity (H2 site time yield 22.7 h-1). Direct Pt-N-O coordination was identified by XAS in this catalyst. The sulfur-doped catalyst presented Pt-S contributions with the lowest EG conversion rate and minimal production of the gas phase components. Boron and phosphorus-doped catalysts showed moderate activity, which was affected by low platinum dispersion on the carbon support. The phosphorus-doped catalyst showed preferential selectivity to alcohols in the liquid phase, associated with the presence of acid sites and Pt-P contributions observed under APR conditions.

Excess-Methane CO2 Reforming over Reduced KIT-6-Ni-Y Mesoporous Silicas Monitored by In Situ XAS-XRD.

Making Europe less dependent on imported fuels requires a long-term strategy. Low-quality natural gas and biogas could be used to mitigate the energy crisis, and excess-methane dry reforming has the potential to upgrade a mixture of CH4 and CO2. Herein, nickel-based KIT-6-supported catalysts (KIT-6-Ni) were modified with 3, 6, and 8 wt % of yttrium (Y/Ni molar ratio of 0.5, 1.07, and 1.5) to investigate the influence of this element on catalytic performance. Yttrium was well dispersed, preserving the mesopore structure of KIT-6. The yttrium addition increased the total basicity, contributing to a lower deactivation factor and remarkably stable syngas production compared to the catalyst containing only Ni. In situ XAS-XRD showed that Y allowed for the reduction of Ni2+ to Ni0 at significantly lower temperatures. A significant difference in the rate of reduction was observed for the studied samples. The analysis showed that the data of linear combination fitting of XANES can demonstrate linear fits with the reduction rate of NiO. The reduction rate of bulk and weakly interacting NiO increased for Y-promoted samples, while a decrease in the rate was registered for species strongly interacting with the support. The latter decreased more with increasing yttrium content. EXAFS analysis showed that Ni is completely reduced in the samples. Under excess-methane dry reforming conditions, the studied catalysts remained fully reduced and showed resistance to sintering of Ni particles. HRTEM results of KIT-6-Ni5-Y8 indicated that metallic Ni particles were decorated by Y2O3 and/or NiYO3. The dominant deactivation mechanism was the carbon encapsulation of Ni particles and the growth of filaments.

Optimizing the shape anisotropy of gold nanoparticles for enhanced light harvesting and photocatalytic applications.

Hybrid nanoparticles (NP) of bismutite nanodisks (BSC ND) with gold nanoparticles (Au NP) of different aspect ratios (AR), such as spheres, rods and etched rods were synthesized via a facile sonochemical method. To better control the shapes of Au NP deposited on the substrate, these were pre-synthesized prior to the deposition using a modified seed mediated growth method by altering the pH and supersaturation of the growth solution. The shift in the peak position and shape of the localized surface plasmon resonance (LSPR) absorption band associated with fine-tuning of the shape of Au NP, led to enhanced light harvesting capabilities of the hybrid. Introducing shape anisotropy in the NP brought about narrowing of bandgap and lowering of PL intensity in the hybrids, suggesting better electronic contact of the NP with BSC, and effective suppression of recombination effects. Hybrids of BSC with Au nanorods showed 14% improved degradation of methylene blue (MB) dye compared to the hybrids with nanospheres. With this study, we provide a novel promising strategy to maximize the light harvesting capacity of semiconductors by tailoring the AR of Au NP, for improved solar to chemical energy conversion.

Co-Precipitated Ni-Mg-Al Hydrotalcite-Derived Catalyst Promoted with Vanadium for CO2 Methanation.

Co-precipitated Ni-Mg-Al hydrotalcite-derived catalyst promoted with vanadium were synthesized with different V loadings (0-4 wt%) and studied in CO2 methanation. The promotion with V significantly changes textural properties (specific surface area and mesoporosity) and improves the dispersion of nickel. Moreover, the vanadium promotion strongly influences the surface basicity by increasing the total number of basic sites. An optimal loading of 2 wt% leads to the highest activity in CO2 methanation, which is directly correlated with specific surface area, as well as the basic properties of the studied catalysts.

Improved lifetime and stability of copper species in hierarchical, copper-incorporated CuSAPO-34 verified by catalytic model reactions.

The first successful synthesis of hierarchical CuSAPO-34 (3.9 wt% Cu) is reported using the polymer Pluronic F127 as a mesoporous structure directing agent (SDA). X-Ray absorption spectroscopy (XAS) revealed single site Cu2+ with 4 nearest oxygen neighbours at 1.96 Å. A catalytic model reaction, the selective reduction of NO with different sized hydrocarbons as reductants, explained that Cu2+ is accessible and reactive in both micro- and mesopores of the hierarchical CuSAPO-34. The presence of mesopores resulted in superior lifetime of the hierarchical CuSAPO-34 in the catalytic model reaction, selective oxidation of propene.

Evaluation of Reoxidation Thresholds for γ-Al2O3-Supported Cobalt Catalysts under Fischer-Tropsch Synthesis Conditions.

Size-dependent phenomena at the nanoscale influence many applications, notably in the science of heterogeneous catalysis. In cobalt-based Fischer-Tropsch synthesis (FTS), the size of Co nanoparticles (NPs) dictates to a high degree catalyst's performance in terms of activity, selectivity, and stability. Here, a highly dispersed Re/Co/γ-Al2O3 catalyst with high Co surface area per gram of catalyst was exposed to industrially relevant FTS conditions and monitored in situ by synchrotron X-ray radiation. X-ray absorption near-edge structure spectra were obtained on the cobalt K edge and Re L3 edge of the working catalyst. The experimental results demonstrate development of tetrahedrally coordinated Co2+ forming at the expense of metallic Co(0). The structure of the oxide resembles CoAl2O4 and appears at the onset (first 5-10 h) of the reaction. Reoxidation of Co(0) is more pronounced close to the outlet of the reactor, where higher pH2O is anticipated. The state of the Re promoter does not change during the FT process. We propose that reoxidation of small Co NPs is followed by spreading of Co oxide that leads to the formation of CoxAlyOz phases. Hence, in order to avoid an irreversible loss of the active phase during process start-up, catalyst design should be restricted to Co NPs larger than 5.3 nm.

Multivariate curve resolution applied to in situ X-ray absorption spectroscopy data: an efficient tool for data processing and analysis.

Large datasets containing many spectra commonly associated with in situ or operando experiments call for new data treatment strategies as conventional scan by scan data analysis methods have become a time-consuming bottleneck. Several convenient automated data processing procedures like least square fitting of reference spectra exist but are based on assumptions. Here we present the application of multivariate curve resolution (MCR) as a blind-source separation method to efficiently process a large data set of an in situ X-ray absorption spectroscopy experiment where the sample undergoes a periodic concentration perturbation. MCR was applied to data from a reversible reduction-oxidation reaction of a rhenium promoted cobalt Fischer-Tropsch synthesis catalyst. The MCR algorithm was capable of extracting in a highly automated manner the component spectra with a different kinetic evolution together with their respective concentration profiles without the use of reference spectra. The modulative nature of our experiments allows for averaging of a number of identical periods and hence an increase in the signal to noise ratio (S/N) which is efficiently exploited by MCR. The practical and added value of the approach in extracting information from large and complex datasets, typical for in situ and operando studies, is highlighted.

Coaxial carbon/metal oxide/aligned carbon nanotube arrays as high-performance anodes for lithium ion batteries.

Coaxial carbon/metal oxide/aligned carbon nanotube (ACNT) arrays over stainless-steel foil are reported as high-performance binder-free anodes for lithium ion batteries. The coaxial arrays were prepared by growth of ACNTs over stainless-steel foil followed by coating with metal oxide and carbon. The carbon/manganese oxide/ACNT arrays can deliver an initial capacity of 738 mAh g(-1) with 99.9 % capacity retention up to 100 cycles and a capacity of 374 mAh g(-1) at a high current density of 6000 mA g(-1). The external carbon layer was recognized as a key component for high performance, and the mechanism of performance enhancement was investigated by electrochemical impedance spectroscopy, electron microscopy, and X-ray diffraction analysis. The layer increases rate capability by enhancing electrical conductivity and maintaining a low mass-transfer resistance and also improves cyclic stability by avoiding aggregation of metal-oxide particles and stabilizing the solid electrolyte interface. The resultant principle of rational electrode design was applied to an iron oxide-based system, and similar improvements were found. These coaxial nanotube arrays present a promising strategy for the rational design of high-performance binder-free anodes for lithium ion batteries.

Towards a highly-efficient fuel-cell catalyst: optimization of Pt particle size, supports and surface-oxygen group concentration.

In the present work, methanol oxidation reaction was investigated on Pt particles of various diameters on carbon-nanofibers and carbon-black supports with different surface-oxygen concentrations, aiming for a better understanding of the relationship between the catalyst properties and the electrochemical performance. The pre-synthesized Pt nanoparticles in ethylene glycol, prepared by the polyol method without using any capping agents, were deposited on different carbon supports. Removal of oxygen-groups from the carbon supports had profound positive effects on not only the Pt dispersion but also the specific activity. The edge structures on the stacked graphene sheets in the platelet carbon-nanofibers provided a strong interaction with the Pt particles, significantly reconstructing them in the process. Such reconstruction resulted in the formation of more plated Pt particles on the CNF than on the carbon-black and exposure of more Pt atoms with relatively high co-ordination numbers, and thereby higher specific activity. Owing to the combined advantages of optimum Pt particle diameter, an oxygen-free surface and the unique properties of CNFs, Pt supported on heat-treated CNFs exhibited a higher mass activity twice of that of its commercial counterpart.

Molecular dynamics simulations of the interactions between platinum clusters and carbon platelets.

Molecular dynamics simulations have been performed with two reactive force fields to investigate the structure of a Pt100 cluster adsorbed on the three distinct sides of a carbon platelet. A revised Reax force field for the carbon-platinum system is presented. In the simulations, carbon platelet edges both with and without hydrogen termination have been studied. It is found that the initial mismatch between the atomic structure of the platelet egde and the adsorbed face of the Pt100 cluster leads to a desorption of a few platinum atoms from the cluster and the subsequent restructuring of the cluster. Consequently, the average Pt-Pt bond length is enlarged in agreement with experimental results. This change in the bond length is supposed to play an important role in the enhancement of the catalytic activity, which is demonstrated by studying the changes in the bond order of the platinum atoms. We found an overall shift to lower values as well as a loss of the well-defined peak structure in the bond-order distribution.

Spectroscopic characterization of cobalt-containing mesoporous materials.

Cobalt-containing mesoporous materials that have been prepared using different procedures have been comparatively characterized by transmission electron microscopy/energy-dispersive X-ray spectroscopy (TEM/EDS), extended X-ray absorption fine structure spectroscopy (EXAFS), X-ray absorption near edge spectroscopy (XANES), and ultraviolet-visible (UV-vis), near-infrared (NIR), and mid-infrared (mid-IR) spectroscopies, and the results provide new insights into the local environment and properties of cobalt in this type of material. TEM/EDS analyses have shown that tetraethyl orthosilicate (TEOS) may be less appropriate as a silicon source during the syntheses of cobalt-containing mesoporous materials, because the distribution of cobalt throughout the framework may become uneven. EXAFS has been determined to be the most suitable method for direct verification of framework incorporation, by identifying silicon as the backscatterer in the second shell. Such a direct verification may not be obtained using UV-vis spectroscopy. From EXAFS analyses, it is also possible to distinguish between surface-bound and framework-incorporated cobalt. There is a good agreement between the results obtained from XANES and UV-vis regarding the coordination symmetry of cobalt in the samples. The presence of cobalt in the silica framework has been determined to create Lewis acid sites, and these acid sites are suggested to be located at tetrahedral cobalt sites at the surface.