Development of Magnetizable, Nickel-Ferrite-Decorated Carbon Nanocomposites as Hydrogenation Catalyst for Aniline Synthesis.

Catalysts with magnetic properties can be easily recovered from the reaction medium without loss by using a magnetic field, which highly improves their applicability. To design such systems, we have successfully combined the magnetic properties of nickel ferrite nanoparticles with the positive properties of carbon-based catalyst supports. Amine-functionalized NiFe2O4 nanoparticles were deposited on the surfaces of nitrogen-doped bamboo-like carbon nanotubes (N-BCNT) and carbon nanolayers (CNL) by using a coprecipitation process. The magnetizable catalyst supports were decorated by Pd nanoparticles, and their catalytic activity was tested through the hydrogenation of nitrobenzene (NB). By using the prepared catalysts, high nitrobenzene conversion (100% for 120 min at 333 K) and a high aniline yield (99%) were achieved. The Pd/NiFe2O4-CNL catalyst was remarkable in terms of stability during the reuse tests due to the strong interaction formed between the catalytically active metal and its support (the activity was retained during four cycles of 120 min at 333 K). Furthermore, despite the long-lasting mechanical stress, no significant palladium loss (only 0.08 wt%) was detected.

Amine Functionalization Leads to Enhanced Performance for Nickel- and Cobalt-Ferrite-Supported Palladium Catalysts in Nitrobenzene Hydrogenation.

Easy preparation, good yield and easy recovery are the key challenges in the development of industrial catalysts. To meet all these three criteria, we have prepared intelligent, magnetizable NiFe2O4- and CoFe2O4-supported palladium catalysts that can be easily and completely recovered from the reaction medium by magnetic separation. The fast and facile preparation was achieved by a solvothermal method followed by sonochemical-assisted decomposition of the palladium nanoparticles onto the surface of the magnetic nanoparticles. The metal-support interaction was enhanced by amine functionalization of the supports using monoethanolamine. The performance and stability of the non-functionalized and amine-functionalized NiFe2O4- and CoFe2O4-supported palladium catalysts were compared in the industrially important nitrobenzene hydrogenation reaction. All catalysts showed high catalytic activity during aniline synthesis; complete nitrobenzene conversion and high aniline yield (above 97 n/n%) and selectivity (above 98 n/n%) were achieved. However, during reuse tests, the activity of the non-functionalized catalysts decreased, as the palladium was leached from the surface of the support. On the other hand, in the case of their amine-functionalized counterparts, there was no decrease in activity, and a non-significant decrease in palladium content could be measured. Based on these results, it can be concluded that amine functionalization of transition metal ferrites may result in more effective catalysts due to the enhanced metal-carrier interaction between the support and the precious metal.

Preparation and Testing of a Palladium-Decorated Nitrogen-Doped Carbon Foam Catalyst for the Hydrogenation of Benzophenone.

Catalytic activity of a palladium catalyst with a porous carbon support was prepared and tested for benzophenone hydrogenation. The selectivity and yields toward the two possible reaction products (benzhydrol and diphenylmethane) can be directed by the applied solvent. It was found that in isopropanol, the prepared support was selective towards diphenylmethane with high conversion (99% selectivity and 99% benzophenone conversion on 323 K after 240 min). This selectivity might be explained by the presence of the incorporated structural nitrogens in the support.

Palladium Decorated N-Doped Carbon Foam as a Highly Active and Selective Catalyst for Nitrobenzene Hydrogenation.

Carbon foam was synthesized by the carbonization of 4-nitroaniline. The reaction is an alternative of the well-known "carbon snake" (or sugar snake) demonstration experiment, which leads to the formation of nitrogen-doped carbon foils due to its nitrogen content. The synthesized carbon foils were grinded to achieve an efficient catalyst support. Palladium nanoparticles were deposited onto the surface of the support, which showed continuous distribution. The prepared Pd nanoparticle decorated carbon foils showed high catalytic activity in nitrobenzene hydrogenation. By applying the designed catalyst, total nitrobenzene conversion, a 99.1 n/n% aniline yield, and an exceptionally high selectivity (99.8 n/n%) were reached. Furthermore, the catalyst remained active during the reuse tests (four cycles) even without regeneration.

Preparation of highly effective carbon black supported Pd-Pt bimetallic catalysts for nitrobenzene hydrogenation.

Carbon black (CB) supported palladium-platinum catalysts were prepared with and without nickel(II) oxide or iron(III) oxide promoter materials. By applying ultrasonic cavitation highly efficient CB supported catalysts were created. The designed catalyst preparation is a one-step procedure, as post-treatments (e.g. calcination, hydrogen activation) are not necessary. The activation of the catalysts occurs during their preparation due to the ultrasonic cavitation. Thus, a fast and simple catalyst preparation procedure have been developed. The activity of the catalysts was compared in nitrobenzene hydrogenation at different temperatures in the range of 283-323 K at 20 bar hydrogen pressure. In terms of selectivity and aniline yield, no significant differences were detected even when promoters were present. By using the NiO promoter, the activation energy was extremely low (7.6 ± 0.7 kJ mol-1). The selectivity was over 99% in every case, and 99.6% aniline yield was achieved without any promoters (99.7% with NiO), while less than 1.0% by-products were formed. The reaction rate was high with every catalyst, and no significant differences were detected. All in all, the prepared catalysts show excellent catalytic activity in the hydrogenation of nitrobenzene.

Development of Highly Efficient, Glassy Carbon Foam Supported, Palladium Catalysts for Hydrogenation of Nitrobenzene.

Glassy carbon foam (GCF) catalyst supports were synthesized from waste polyurethane elastomers by impregnating them in sucrose solution followed by pyrolysis and activation (AC) using N2 and CO2 gas. The palladium nanoparticles were formed from Pd(NO3)2. The formed palladium nanoparticles are highly dispersive because the mean diameters are 8.0 ± 4.3 (Pd/GCF), 7.6 ± 4.2 (Pd/GCF-AC1) and 4.4 ± 1.6 nm (Pd/GCF-AC2). Oxidative post-treatment by CO2 of the supports resulted in the formation of hydroxyl groups on the GCF surfaces, leading to a decrease in zeta potential. The decreased zeta potential increased the wettability of the GCF supports. This, and the interactions between -OH groups and Pd ions, decreased the particle size of palladium. The catalysts were tested in the hydrogenation of nitrobenzene. The non-treated, glassy-carbon-supported catalyst (Pd/GCF) resulted in a 99.2% aniline yield at 293 K and 50 bar hydrogen pressure, but the reaction was slightly slower than other catalysts. The catalysts on the post-treated (activated) supports showed higher catalytic activity and the rate of hydrogenation was higher. The maximum attained aniline selectivities were 99.0% (Pd/GCF-AC1) at 293 K and 98.0% (Pd/GCF-AC2) at 323 K.

Synthesis Optimization and Characterization of Nitrogen-Doped Bamboo-Shaped Carbon Nanotubes.

Nitrogen-doped bamboo-shaped carbon nanotubes (N-BCNT) were synthesized from butylamine using the catalytic chemical vapor deposition (CCVD) process. The carbon source was nitrogen content organic molecules, namely butylamine. Reaction conditions such as temperature, amount of carbon source and catalyst were optimized to produce high quality N-BCNT samples. The nitrogen content was measured by CHNS element analysis, while the butylamine conversion was calculated based on the weight of deposited carbon materials. The bamboo structure of the nanotubes was examined by high resolution transmission electron microscopy (HRTEM). Two different types of nitrogen incorporation forms, the pyridinic and the graphitic, were identified in the samples by X-ray photoelectron spectroscopy (XPS). The lattice defects were measured by Raman spectroscopy. The proportion of defect sites influenced by the nitrogen content which can be controlled by the synthesis temperature. The optimal conditions were identified for the economical synthesis of N-BCNTs with high nitrogen content for various applications.

Development and Application of Carbon-Layer-Stabilized, Nitrogen-Doped, Bamboo-Like Carbon Nanotube Catalysts in CO2 Hydrogenation.

Nitrogen-doped, bamboo-like carbon nanotubes (BCNTs) were synthesized from butylamine by catalytic chemical vapor deposition (CCVD method). The nanotubes were oxidized by H2SO4/HNO3 treatment and used to prepare calcium alginate gelled BCNT spheres. These beads were first carbonized and then Pd, Rh and Ni nanoparticles were anchored on the surface of the spheres. These systems were then applied as catalysts in CO2 hydrogenation. The BCNT support was examined by Raman spectroscopy, dynamic light scattering (DLS) and X-ray photoelectron spectroscopy (XPS). The prepared catalysts were characterized by HRTEM and SEM. The oxidation pretreatment of BCNTs was successful, with the electrokinetic potential of the water-based dispersion of BCNTs measuring -59.9 mV, meaning the nanotube dispersion is stable. Pyridinic and graphitic types of incorporated nitrogen centers were identified in the structure of the nanotubes, according to the XPS measurements. The Pd-containing BCNT sphere catalyst was the most efficient in the catalytic studies. The highest conversion was reached on the Pd catalyst at 723 K, as well as at 873 K. The difference in the formation rate of CO was much less at 873 K between the Pd and Rh compared to the 723 K values. Accordingly, the application of Pd-containing BCNT/carbon-supported catalyst favored the generation of CO. However, the Ni-BCNT/carbon catalyst leads to the formation of CH4 as the major product.