Bimetallic nanoparticles supported on Ce-BTC for highly efficient and stable reduction of nitroarenes: Towards environmental sustainability.

The development of a catalyst with a consistent and clearly defined crystal structure is crucial for establishing an efficient catalytic performance system. This study focuses on catalyzing the reduction of nitroarenes to amino-derivatives in an aquatic environment at ambient temperature, employing metallic (Au) and bimetallic (Au-Pd or Au-Ag) nanoparticles loaded on a Ce-BTC metal-organic framework using a facile sol-immobilization approach. Diverse analytical instruments, comprising SEM, TEM, XRD, FT-IR, XPS, TGA, and N2 isotherm, have been utilized to characterize the synthesized catalysts. Among the catalysts that were fabricated, Au-Pd@Ce-BTC displayed the maximum catalytic efficacy, offering a rate constant (kapp) of 0.5841 min-1, conversion percentages reaching 99.7%, and a KAF of 116.8 min-1g-1. Moreover, it exhibited remarkable recyclability over five consecutive cycles. This catalyst offers the advantages of operating under ambient reaction conditions and exhibiting tolerance to a broad range of substrates containing various functional moieties. The mechanistic understanding of nitroarene reduction and the factors contributing to the superior activity of Au-Pd/Ce-BTC are explored through spectroscopic and porosity analyses. Spectroscopic measurements indicate that the elevated Auo and Pdo/Pd2+ ratio, increased surface area, and the synergistic collaboration of the bimetallic NPs are key factors contributing to the heightened activity of Au-Pd/Ce-BTC. These findings hold significant appeal from both an industrial and academic standpoint.

Efficient Dual-Function Catalyst: Palladium-Copper Nanoparticles Immobilized on Co-Cr LDH for Seamless Aerobic Oxidation of Benzyl Alcohol and Nitrobenzene Reduction.

Layered double hydroxides (LDHs) present exciting possibilities across various industries, ranging from catalytic applications to water remediation. By immobilizing nanoparticles, LDHs' characteristics and functionality can be enhanced, allowing for synergetic interactions that further expand their potential uses. A simple chemical method was developed to produce well-dispersed Pd-Cu NPs on a Co-Cr LDH support using a combination of in situ coprecipitation/hydrothermal and sol-immobilization techniques. The Pd-Cu@Co-Cr LDH catalysts was obtained, showing its catalytic activity in promoting the aerobic oxidation of alcohols and enabling the reduction of nitro-compounds through NaBH4 mediation. The physicochemical properties of the prepared catalyst were comprehensively investigated utilizing a range of analytical techniques, comprising FTIR, XRD, XPS, TGA, nitrogen adsorption isotherm, FESEM, and HRTEM-EDX. The findings showed the significance of immobilizing the bimetallic Pd-Cu nanoparticles on the Co-Cr LDH via an exceptional performance in the aerobic oxidation of benzyl alcohol (16% conversion, 99.9% selectivity to benzaldehyde) and the reduction of nitrobenzene (98.2% conversion, rate constant of 0.0921 min-1). The improved catalytic efficacy in benzyl alcohol oxidation and nitrobenzene reduction on the Pd-Cu@Co-Cr LDH catalyst is attributed to the uniform distribution and small size of the Pd-Cu NPs as active sites on the Co-Cr LDH surface. The prepared catalyst demonstrated exceptional stability during repeated runs. This study paves the way for multiple opportunities in tailoring, producing, and precisely controlling catalysts for various organic transformation reactions.

A Facile Approach of Fabricating Bifunctional Catalysts for Redox Applications by Uniformly Immobilized Metallic Nanoparticles on NiCr LDH.

This study discloses the development of NiCr LDH, Ag@NiCr LDH, and Pd@NiCr LDH bifunction catalysts using a hydrothermal coprecipitation method followed by sol immobilization of metallic nanoparticles. The structures and morphologies of the synthesized nanocomposites were analyzed using FTIR, XRD, XPS, BET, FESEM-EDX, and HRTEM. The catalytic effectiveness of the samples was evaluated by tracking the progression of NaBH4-mediated nitrobenzene (NB) reduction to aniline and CO oxidation using UV-visible spectrophotometry and an infrared gas analyzer, respectively. Pd@NiCr LDH displayed much higher performance for both reactions than the bare NiCr LDH. The catalyst Pd@NiCr LDH showed robust catalytic activity in both the oxidation of carbon monoxide (T50% (136.1 °C) and T100% (200.2 °C)) and NaBH4-mediated nitrobenzene reduction (98.7% conversion and 0.365 min-1 rate constant). The results disclose that the Ni2+@ Cr3+/Cr6+ @Pd° ion pairs inside the LDH act as a charge transfer center and hence significantly enhance the catalytic performance. As a result, this research offers the novel NiCr LDH catalyst as a bifunctional catalyst for air depollution control and the organic transformation process.

Effect of Carbon Support, Capping Agent Amount, and Pd NPs Size for Bio-Adipic Acid Production from Muconic Acid and Sodium Muconate.

The effect of support, stabilizing agent, and Pd nanoparticles (NPs) size was studied for sodium muconate and t,t-muconic acid hydrogenation to bio-adipic acid. Three different activated carbons (AC) were used (Norit, KB, and G60) and carbon morphology did not affect the substrate conversion, but it greatly influenced the adipic acid yield. 1% Pd/KB Darco catalyst, which has the highest surface area and Pd surface exposure, and the smallest NPs size displayed the highest activity. Furthermore, the effect of the amount of the protective agent was studied varying metal/protective agent weight ratios in the range of 1/0.00-1/1.20, using KB as the chosen support. For sodium muconate reduction 1% Pd/KB_1.2 catalyst gave the best results in terms of activity (0.73 s-1), conversion, and adipic acid yield (94.8%), while for t,t-muconic acid hydrogenation the best activity result (0.85 s-1) was obtained with 1% Pd/KB_0.0 catalyst. Correlating the results obtained from XPS and TEM analyses with catalytic results, we found that the amount of PVA (polyvinyl alcohol) influences mean Pd NPs size, Pd(0)/Pd(II) ratio, and Pd surface exposure. Pd(0)/Pd(II) ratio and Pd NPs size affected adipic acid yield and activity during sodium muconate hydrogenation, respectively, while adipic acid yield was related by exposed Pd amount during t,t-muconic acid hydrogenation. The synthesized catalysts showed higher activity than commercial 5% Pd/AC.