Palladium-based pseudohomogeneous catalyst for highly selective aerobic oxidation of benzylic alcohols to aldehydes.

This study presents a novel class of pseudohomogeneous catalysts (PHC) based on carbon quantum dots functionalized with terpyridine ligands (CQDs-Tpy) to immobilize and stabilize palladium nanoparticles (Pd NPs). Extensive characterization techniques clearly confirmed the successful stabilization of Pd NPs on CQDs-Tpy. The effectiveness of the catalyst was demonstrated in the selective aerobic oxidation of primary and secondary of benzylic alcohols to aldehydes in the absence of additives and phase transfer catalyst (PTC). Remarkably, the reactions predominantly yielded aldehydes without further oxidation to carboxylic acids. By employing low catalyst loadings (0.13 mol%), high conversions (up to 89%) and excellent selectivity (> 99%) of the aldehyde derivatives were achieved. Moreover, the CQDs-Tpy/Pd NPs catalyst displayed suitable catalytic activity and recyclability, offering potential economic advantages. This promising approach opens up new opportunities in the field of catalysis for designing subnanometric metal-based PHCs.

Photocatalytic removal of imidacloprid pesticide from wastewater using CdS QDs passivated by CQDs containing thiol groups.

Over the past decade, CdS QDs have become versatile semiconductors. Surface modification of CdS QDs has become an interesting case study, as it can eliminate surface defects and improve their photochemical properties. In this study, we report a new strategy of using carbon quantum dots containing a large number of thiol groups (CQDs-SH) as a passivating agent for the stabilization of CdS quantum dots (QDs). Various characterization techniques have clearly revealed that the CdS QDs have been successfully passivated by CQDs-SH. The photocatalytic performance of CQDs-SH/CdS QDs was investigated for the degradation of the insecticide imidacloprid from an aqueous solution. Parameters affecting the photodegradation process, including the light source, photocatalyst amount, initial concentration of the pollutant, radiation time, pH, oxidizing agent, and temperature, were investigated. Furthermore, the HPLC technique was applied to quantitatively analyze imidacloprid and its degradation products. The results of the HPLC analysis revealed that under simulated visible light at pH 9, imidacloprid scarcely existed after 90 min of irradiation (90.13% degradation). The LC-MS method was also used to detect the degradation products and investigate the mechanism of photodegradation of the pesticide. The results showed that the CQDs-SH/CdS QDs composite was a promising photocatalyst for the degradation of imidacloprid in wastewater.

Design and introduction of quaternary ammonium hydroxide-functionalized graphene oxide quantum dots as a pseudo-homogeneous catalyst for epoxidation of α,ß-unsaturated ketones.

In present work, design and synthesis of a novel pseudo-homogeneous catalyst is described. For this purpose, amine-functionalized graphene oxide quantum dots (N-GOQDs) were prepared from graphene oxide (GO) by a facile one-step oxidative fragmentation approach. The prepared N-GOQDs were then modified with quaternary ammonium hydroxide groups. Various characterization techniques clearly revealed that the quaternary ammonium hydroxide-functionalized GOQDs (N-GOQDs/OH-) have been successfully synthesized. TEM image revealed that the GOQDs particles are almost regularly spherical in shape and mono-dispersed with particle sizes < 10 nm. The efficiency of the synthesized N-GOQDs/OH- as a pseudo-homogeneous catalyst in epoxidation of α,ß-unsaturated ketones in the presence of aqueous H2O2 as an oxidant at room temperature was investigated. The corresponding epoxide products were obtained in good to high yields. This procedure has the advantages of a green oxidant, high yields, involvement of non-toxic reagents and reusability of the catalyst without discernible loss in activity.

Pseudohomogeneous metallic catalyst based on tungstate-decorated amphiphilic carbon quantum dots for selective oxidative scission of alkenes to aldehyde.

Herein, we present an interesting role of tungstate-decorated amphiphilic carbon quantum dots (A-CQDs/W) in the selective oxidative cleavage of alkenes to aldehydes. In this work, for the first time, we disclose an unprecedented tungstate-based oxidative system incorporating A-CQDs as a bridge to the homogeneous catalyst for selective and efficient cleavage of a wide substrate scope of alkenes into aldehydes. The A-CQDs/W were synthesized via a one-step hydrothermal synthesis approach using 1-aminopropyl-3-methyl-imidazolium chloride and stearic acid for the surface modification, following by anion-exchange to immobilize WO4-2 to A-CQDs. The A-CQDs/W act as a pseudohomogeneous metallic catalyst (PMC) for selective oxidative scission of alkenes under phase transfer catalysts (PTC) free condition without over oxidation to acids, using water and H2O2 as a green oxidant. Thanks to the sub-nanometric size and novel engineered chemical structure, this PMC and reactants are in the same phase, besides they can be easily isolated from each other by extraction processes. The synthesized PMC exhibited excellent solubility and stability in various solvents. Interestingly, the system's high conversion efficiency was preserved even after eight catalytic cycles indicating the recyclability of the synthesized PMC. We believe that this study provides a significant and conceptually novel advance in oxidative cleavage chemistry.