Koppány L. Juhász

Heck coupling reactions catalysed by Pd particles generated in silica in the presence of an ionic liquid

Silica-supported Pd catalysts were synthesized in the presence of the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate. Two samples with extremely low Pd loadings, 0.35Pd and 0.08Pd, with Pd contents 0.35 and 0.08%, respectively, were subjected to further investigations. Structural characterization was performed by ICP-AES and Raman measurements. Raman spectra indicated the presence of the ionic liquid in the Pd-silica samples. The samples were tested as catalysts in the Heck coupling reactions of methyl acrylate and styrene, with substituted bromoarenes and chloroarenes. Both samples proved to be highly efficient catalysts and displayed excellent activities and selectivities for the reactions of activated haloarenes including chloroarenes, which could be efficiently transformed without applying harsh reaction conditions. As expected, the presence of an electron withdrawing group (EWG) on the aromatic ring of the haloarene was found to increase both the conversion and the selectivity to an appreciable extent. For the transformations of bromoarenes, the sample with the lowest Pd loading proved to be a more efficient catalyst. Upon recycling of the catalysts, a considerable activity loss was detected, which was attributed to an extensive leaching of Pd into the solution, as confirmed by hot filtration measurements.

On-chip integrated vertically aligned carbon nanotube based super- and pseudocapacitors

On-chip energy storage and management will have transformative impacts in developing advanced electronic platforms with built-in energy needs for operation of integrated circuits driving a microprocessor. Though success in growing stand-alone energy storage elements such as electrochemical capacitors (super and pseusocapacitors) on a variety of substrates is a promising step towards this direction. In this work, on-chip energy storage is demonstrated using architectures of highly aligned vertical carbon nanotubes (CNTs) acting as supercapacitors, capable of providing large device capacitances. The efficiency of these structures is further increased by incorporating electrochemically active nanoparticles such as MnOx to form pseudocapacitive architectures thus enhancing device capacitance areal specific capacitance of 37 mF/cm2. The demonstrated on-chip integration is up and down-scalable, compatible with standard CMOS processes, and offers lightweight energy storage what is vital for portable and autonomous device operation with numerous advantages as compared to electronics built from discrete components.

Photoelectrochemistry by Design: Tailoring the Nanoscale Structure of Pt/NiO Composites Leads to Enhanced Photoelectrochemical Hydrogen Evolution Performance

Photoelectrochemical hydrogen evolution is a promising avenue to store the energy of sunlight in the form of chemical bonds. The recent rapid development of new synthetic approaches enables the nanoscale engineering of semiconductor photoelectrodes, thus tailoring their physicochemical properties toward efficient H2 formation. In this work, we carried out the parallel optimization of the morphological features of the semiconductor light absorber (NiO) and the cocatalyst (Pt). While nanoporous NiO films were obtained by electrochemical anodization, the monodisperse Pt nanoparticles were synthesized using wet chemical methods. The Pt/NiO nanocomposites were characterized by XRD, XPS, SEM, ED, TEM, cyclic voltammetry, photovoltammetry, EIS, etc. The relative enhancement of the photocurrent was demonstrated as a function of the nanoparticle size and loading. For mass-specific surface activity the smallest nanoparticles (2.0 and 4.8 nm) showed the best performance. After deconvoluting the trivial geometrical effects (stemming from the variation of Pt particle size and thus the electroactive surface area), however, the intermediate particle sizes (4.8 and 7.2 nm) were found to be optimal. Under optimized conditions, a 20-fold increase in the photocurrent (and thus the H2 evolution rates) was observed for the nanostructured Pt/NiO composite, compared to the benchmark nanoparticulate NiO film.

Determination of the Platinum Concentration of a Pt/Silica Nanocomposite Decorated with Ultra Small Pt Nanoparticles Using Single Particle Inductively Coupled Plasma Mass Spectrometry

In this study, the performance of five analytical techniques applicable to the determination of the load concentration of ultra small nanoparticles in a Pt/SiO2 nanocomposite was critically evaluated. Four of the techniques (SEM-EDS, TEM imaging, XPS and solution-mode ICP-MS) are often used for the characterization of nanoparticles, whereas single particle ICP-MS (spICP-MS) is an upcoming, novel methodology. After experimentally testing and discussing the pros and cons of each analytical technique, it was found that spICP-MS is one of the most accurate, precise and practical techniques for the analysis of nanocomposites. This technique works directly with dispersions, the measurement only takes a few minutes, it gives highly reliable results, largely free from interference from precursor residues and can also provide additional information about the particles. Although the individual measurement of ultra small nanoparticles is not yet possible by spICP-MS, the cumulative signal from such load particles in a nanocomposite allows the accurate determination of the load concentration. The spICP-MS result was concordant with the result obtained by TEM imaging, whereas SEM-EDS, XPS and solution-mode ICP-MS strongly overestimated the concentration.

Effect of Particle Restructuring During Reduction Processes Over Polydopamine-Supported Pd Nanoparticles

The effect of catalyst restructuring on the polydopamine-supported Pd catalyzed transfer hydrogenation of ethyl 4-nitrobenzoate and the catalytic hydrogenation of (E)-2-methyl-2-butenoic acid is reported. Transmission electron microscopy investigation of different catalyst pre-treatment and reaction conditions revealed high catalytic activity in both reactions unless drastic aggregation of the active metal occurred. In the transfer hydrogenation reaction aggregation was primarily dependent on the H-source used, while in the catalytic hydrogenation additives in combination with the reductive environment led to extensive Pd aggregation and thus decreased catalytic activity. The enantioselective hydrogenation of (E)-2-methyl-2-butenoic acid showed increased enantioselectivity and decreased conversion with increased particle size.

Outstanding Activity and Selectivity of Controlled Size Pt Nanoparticles Over WO3 Nanowires in Ethanol Decomposition Reaction

Pt nanoparticles with controlled size of 1.5 and 6.5 nm were anchored onto the surface of WO₃ nanowires (WO₃NW) as well as on MCF-17 silica. In the case of WO₃NW and MCF-17 supported nanoparticles, 1.5 nm Pt nanoparticles were more active in ethanol decomposition reaction at 533 K. 6.5 nm Pt/WO₃NW catalyst showed ~6 times higher activity compared to MCF-17 supported 6.5 nm Pt nanoparticles. While MCF-17 supported catalysts produced hydrogen, methane, carbon-monoxide and acetaldehyde, the tungsten-oxide supported Pt nanoparticles produced a huge amount of acetone as well as ethene with a high acetaldehyde selectivity besides H₂, CH₄ and CO. The hydrogen formation was significantly higher when the Pt size was 1.5 nm. The metallic nanoparticles, the acid sites and the oxidized centers of support play important role in the formation of decomposition products of ethanol.

Size-Dependent H2 Sensing Over Supported Pt Nanoparticles

Catalyst size affects the overall kinetics and mechanism of almost all heterogeneous chemical reactions. Since the functional sensing materials in resistive chemical sensors are practically the very same nanomaterials as the catalysts in heterogeneous chemistry, a plausible question arises: Is there any effect of the catalyst size on the sensor properties? Our study attempts to give an insight into the problem by analyzing the response and sensitivity of resistive H₂ sensors based on WO₃ nanowire supported Pt nanoparticles having size of 1.5±0.4 nm, 6.2±0.8 nm, 3.7±0.5 nm and 8.3±1.3 nm. The results show that Pt nanoparticles of larger size are more active in H₂ sensing than their smaller counterparts and indicate that the detection mechanism is more complex than just considering the number of surface atoms of the catalyst.

Random networks of core-shell-like Cu-Cu 2 O/CuO nanowires as surface plasmon resonance-enhanced sensors

The rapid oxide formation on pristine unprotected copper surfaces limits the direct application of Cu nanomaterials in electronics and sensor assemblies with physical contacts. However, it is not clear whether the growing cuprous (Cu2O) and cupric oxides (CuO) and the formation of core-shell-like Cu-Cu2O/CuO nanowires would cause any compromise for non-contact optical measurements, where light absorption and subsequent charge oscillation and separation take place such as those in surface plasmon-assisted and photocatalytic processes, respectively. Therefore, we analyze how the surface potential of hydrothermally synthetized copper nanowires changes as a function of time in ambient conditions using Kelvin probe force microscopy in dark and under light illumination to reveal charge accumulation on the nanowires and on the supporting gold substrate. Further, we perform finite element modeling of the optical absorption to predict plasmonic behavior of the nanostructures. The results suggest that the core-shell-like Cu-Cu2O/CuO nanowires may be useful both in photocatalytic and in surface plasmon-enhanced processes. Here, by exploiting the latter, we show that regardless of the native surface oxide formation, random networks of the nanowires on gold substrates work as excellent amplification media for surface-enhanced Raman spectroscopy as demonstrated in sensing of Rhodamine 6G dye molecules.