PdO/CuO Nanoparticles on Zeolite-Y for Nitroarene Reduction and Methanol Oxidation

Abstract

Selective reduction of various nitroarenes to amines was achieved up to 93% under autoclave condition in isopropanol using catalytic amount of palladium oxide/copper oxide (PdO/CuO) nanoparticles (NPs) supported on mesoporous zeolite-Y, PdO/CuO-Y. The catalyst was also found to be highly effective for one-pot cascade synthesis of the 3,3′-diaminobiphenyl from 3-nitrophenylboronic acid (NPBA). The hybridization of PdO/CuO-Y with multiwalled carbon nanotubes (MWCNTs) resulted in a highly effective and durable electrocatalyst for the methanol oxidation reaction (MOR). The mass activity of the electrocatalyst was found to be 690 A/g and was stable for 4000 s. The catalytic activity of the PdO/CuO-Y catalyst was found to be superior in terms of productivity and recyclability in comparison to that of the bared PdO/CuO NPs separated by the ultracentrifugation (UC) method. On the other hand, the one modified with the carbon matrix retained the same activity and reduced the reaction time in nitroarene reduction reaction (NAR) under identical conditions. Electrochemical studies and density functional theory (DFT) calculations were performed to understand the mechanism of the NAR process. Both the experimental and theoretical evidence explicitly demonstrated the individual role of both palladium (Pd) and copper (Cu). Pd was found to be the active site for nitroarene interaction, while CuO NPs played an important role in isopropanol oxidation.

Incorporation of copper nanoparticles into the nitrogen‐doped carbon derived from nitrile functionalized ionic liquid as the non‐precious heterogeneous catalytic system toward nitro compounds reduction reaction, a first principle calculation

“…Nitro reduction reaction is one of the most substantial chemical reactions employed in the industry because of the aromatic amines that are used as intermediates in the synthesis of important and diverse materials, such as dyes, pharmaceuticals, antioxidants, polymers, pesticides, and many of the precursors needed in agriculture 31‐33 . Different types of transition metals, such as Palladium (Pd), Cobalt (Co), Nickel (Ni), Silver (Ag), Iron (Fe), and Copper (Cu), have exhibited an excellent efficiency and selectivity towards nitroarenes reduction reaction 34‐36 . Among them, copper nanoparticles have attracted the most attention from researchers due to their low toxicity, better economical aspect compared to other metals (such as Pd), and their availability.…”

“…[31][32][33] Different types of transition metals, such as Palladium (Pd), Cobalt (Co), Nickel (Ni), Silver (Ag), Iron (Fe), and Copper (Cu), have exhibited an excellent efficiency and selectivity towards nitroarenes reduction reaction. [34][35][36] Among them, copper nanoparticles have attracted the most attention from researchers due to their low toxicity, better economical aspect compared to other metals (such as Pd), and their availability. As most of the catalytic process occurs on the surface of the metals, the high ratio of their surface area to their size affects the efficiency and reactivity of NPs.…”

“…Accordingly, to select the ideal host, many factors should be considered, including thermal and chemical stability, tunable pore size, surface area, etc. To date, various types of solid host have been introduced by researchers, such as graphene, metal oxide, polymers, zeolite, and carbon-based materials that supply an excellent performance toward immobilization of metal nanoparticles; 36,[39][40][41] therefore, to develop a new support, researchers should design and introduce a new class of precursor.…”

Density Functional Theory plus U Study of Methanol Adsorption and Decomposition on CuO Surfaces with Oxygen Vacancy

“…Among MO catalysts, copper oxide (CuO) has been widely studied and used, as it is a kind of reducible oxide and demonstrates excellent catalytic activity as well as high selectivity for CH3OH decomposition. Even in PM/CuO co-catalysts, CuO nanoparticles play an important role in CH3OH oxidation (Sharma et al, 2019). Cu-based composite oxides show outstanding performance on CH3OH oxidation because of facilitated electron transfer that lowers the reaction activation barrier (Norsic et al, 2016).…”

Biosynthesis of Cu nanoparticles supported on carbon nanotubes and its catalytic performance under different test conditions

“…9 The reductive transformation of nitroaromatics on the surface of non-noble metal catalysts such as copper (Cu) nanoparticles attracted considerable attention owing to the excellent catalytic efficiency and lower cost of preparation of such catalysts. [10][11][12][13][14][15][16] Copper nanoparticles with a high surface-to-volume ratio can dramatically enhance the number of active sites per unit area in the catalysts. 17 However, owing to their high surface energy, they have a strong tendency to agglomerate, and this reduces their catalytic ability considerably.…”