Balázs Endrődi

Enhanced Photoelectrochemical Performance of Cuprous Oxide/Graphene Nanohybrids

Combination of an oxide semiconductor with a highly conductive nanocarbon framework (such as graphene or carbon nanotubes) is an attractive avenue to assemble efficient photoelectrodes for solar fuel generation. To fully exploit the possible synergies of the hybrid formation, however, precise knowledge of these systems is required to allow rational design and morphological engineering. In this paper, we present the controlled electrochemical deposition of nanocrystalline p-Cu2O on the surface of different graphene substrates. The developed synthetic protocol allowed tuning of the morphological features of the hybrids as deduced from electron microscopy. (Photo)electrochemical measurements (including photovoltammetry, electrochemical impedance spectroscopy, photocurrent transient analysis) demonstrated better performance for the 2D graphene containing photoelectrodes, compared to the bare Cu2O films, the enhanced performance being rooted in suppressed charge carrier recombination. To elucidate the precise role of graphene, comparative studies were performed with carbon nanotube (CNT) films and 3D graphene foams. These studies revealed, after allowing for the effect of increased surface area, that the 3D graphene substrate outperformed the other two nanocarbons. Its interconnected structure facilitated effective charge separation and transport, leading to better harvesting of the generated photoelectrons. These hybrid assemblies are shown to be potentially attractive candidates in photoelectrochemical energy conversion schemes, namely CO2 reduction.

Reasons behind the improved thermoelectric properties of poly(3-hexylthiophene) nanofiber networks

Enhanced thermoelectric properties of poly(3-hexylthiophene) nanofiber networks, doped in their reaction with silver cations, are presented. The role of charge carrier concentration and mobility (influenced by the supramolecular structure and nanoscale morphology) is discussed. The nanonet structure leads to a six fold increase in the ZT value compared to the bulk polymer counterpart.

Controlled Photocatalytic Synthesis of Core–Shell SiC/Polyaniline Hybrid Nanostructures

Hybrid materials of electrically conducting polymers and inorganic semiconductors form an exciting class of functional materials. To fully exploit the potential synergies of the hybrid formation, however, sophisticated synthetic methods are required that allow for the fine-tuning of the nanoscale structure of the organic/inorganic interface. Here we present the photocatalytic deposition of a conducting polymer (polyaniline) on the surface of silicon carbide (SiC) nanoparticles. The polymerization is facilitated on the SiC surface, via the oxidation of the monomer molecules by ultraviolet-visible (UV-vis) light irradiation through the photogenerated holes. The synthesized core–shell nanostructures were characterized by UV-vis, Raman, and Fourier Transformed Infrared (FT-IR) Spectroscopy, thermogravimetric analysis, transmission and scanning electron microscopy, and electrochemical methods. It was found that the composition of the hybrids can be varied by simply changing the irradiation time. In addition, we proved the crucial importance of the irradiation wavelength in forming conductive polyaniline, instead of its overoxidized, insulating counterpart. Overall, we conclude that photocatalytic deposition is a promising and versatile approach for the synthesis of conducting polymers with controlled properties on semiconductor surfaces. The presented findings may trigger further studies using photocatalysis as a synthetic strategy to obtain nanoscale hybrid architectures of different semiconductors.

Flow-driven pattern formation in the calcium-oxalate system.

The precipitation reaction of calcium oxalate is studied experimentally in the presence of spatial gradients by controlled flow of calcium into oxalate solution. The density difference between the reactants leads to strong convection in the form of a gravity current that drives the spatiotemporal pattern formation. The phase diagram of the system is constructed, the evolving precipitate patterns are analyzed and quantitatively characterized by their diameters and the average height of the gravity flow. The compact structures of calcium oxalate monohydrate produced at low flow rates are replaced by the thermodynamically unstable calcium oxalate dihydrate favored in the presence of a strong gravity current.

Electrochemical synthesis and characterization of poly(3-hexylthiophene)/single-walled carbon nanotube array hybrid materials

AbstractIn this study, we demonstrate that by directly employing single-walled carbon nanotube arrays (SWCNT-arrays)—grown on conductive substrates—as working electrodes, selective and uniform electrodeposition of a conducting polymer, namely poly(3-hexylthiophene), can be achieved on the surface of the nanotubes. The overall kinetic pattern of the electrodeposition was studied by separating the deposition charge from the one related to the redox transformation of the polymer film deposited during the precedent cycles. Both the structure and the electrochemical properties of the hybrid materials were studied as a function of the electrodeposition cycles, thus the amount of the formed polymer. The hybrids were characterized by electron microscopic (SEM, TEM) and vibrational spectroscopic (Raman spectroscopy) means. The obtained results were compared and contrasted with those gathered on macroscopic-sized multi-walled carbon nanotube array-based composites in our group recently. Overall, we conclude that electrochemical polymerization is an attractive tool to synthesize conducting polymer/SWCNT hybrid materials with controlled composition and morphology. Graphical abstractHighy organized nanostructures of conduction polymer/SWCNT array hybrids were obtained via electrodeposition

Development of polymer–dopant interactions during electropolymerization, a key factor in determining the redox behaviour of conducting polymers

Investigation of ionic motion in connection with the redox transformation of conjugated polymers (CP) has always been at the leading edge of research. Motivated by recent proofs for the chemical bond formation between chloride ion and α-positioned carbon in poly (3,4–ethylenedioxythiophene) (PEDOT), comprehensive studies have been extended to another strongly electronegative halide (F−) and to another CP, polypyrrole (PPy). As the electrochemical quartz crystal nanobalance (EQCN) results proved, the movement of the bulky Bu4N+ cations has been exclusively experienced during the redox processes of both systems. Moreover, the decisive role of the anions being present in the polymerization solution in determining the redox capacity and, consequently, the maximum doping level of the films was evidenced. On the grounds of the systematic experiments, the strong and permanent chemical interaction of highly electronegative anions and the polymer has been demonstrated as a general phenomenon. Importantly, this observation requires the necessary reconsideration of specific polymer–dopant interactions and calls attention to the necessity of careful design of the polymerization procedure.