Synergistic Catalysis with MIL-101: Stabilized Highly Active Bimetallic NiPd and CuPd Alloy Nanoparticle Catalysts for C-C Coupling Reactions

Abstract

Highly active bimetallic NiPd/MIL‐101, CuPd/MIL‐101 and CoPd/MIL‐101 alloy nanoparticle catalysts stabilized by MIL‐101 framework, (M/Pd atomic ratio=95:5, M=Ni, Cu and Co) were synthesized, and their catalytic activity for Suzuki reaction at moderate reaction conditions was explored. In contrary to monometallic counterparts, a significant enhancement in catalytic activity, with excellent yields for biaryls (upto 97 %), was observed with these bimetallic NiPd/MIL‐101, CuPd/MIL‐101 and CoPd/MIL‐101 alloy nanoparticle catalysts. Among these catalysts, NiPd/MIL‐101 and CuPd/MIL‐101 displayed highest catalytic activity for the synthesis of biaryls for a wide range of substituted aryl halides and arylboronic acids with electron donating and electron withdrawing substituents, whereas CoPd/MIL‐101 was found to be poorly active. Worthy to mention that, NiPd/MIL‐101 and CuPd/MIL‐101 displayed ca 20 times higher TOF (h−1) than the Pd/MIL‐101 catalyst. The observed high catalytic activity displayed by NiPd/MIL‐101 and CuPd/MIL‐101 was attributed to the synergistic effect due to electronic charge transfer from Ni or Cu to Pd, and high dispersion of NiPd and CuPd nanoparticles on MIL‐101 frameworks.

Catalytically active nanosized Pd9Te4(telluropalladinite) and PdTe (kotulskite) alloys: first precursor-architecture controlled synthesis using palladium complexes of organotellurium compounds as single source precursors

“…In this context, in recent past, nanosized bimetallic alloys have attracted attention of the researchers as they show improved catalytic activity than monometallic catalysts, at nanoscale, due to the electronic and geometrical modifications which arise as a consequence of synergic cooperation between the two metals of alloys. 43–50 In the present study, both Pd 9 Te 4 and PdTe are bimetallic alloys in which active Pd atoms are incorporated in a lattice together with Te. 25,26 Hence, these intermetallic phases are likely to offer the advantage of hosting solid active sites.…”

“…Such alloys include Pd 1 Ni 4 , CuPd, Y 3 Pd 2 , Pd 3 Te 2 and Pd 17 Se 15 . 43,48,52,57,64 The alloy Pd 1 Ni 4 has been graed on carbon nanobers and the resulting system (Pd 1 Ni 4 /CNF) gives only 7% conversion in the reaction of phenylboronic acid and chlorobenzaldehyde aer 5 hours at 80 C using 5 mg of the catalyst (Table 4, entry 1). 52 Its performance is insignicant in comparison to that of palladium telluride alloys in the present study.…”

Ni‐Pd Nanoparticles Embedded in N‐Doped Hierarchical Porous Carbon Derived from Luffa Sponge: Preparation, Characterization and Its Catalytic Activity

“…Oxidative addition of aryl halide to Pd catalyst is the key step in Heck reaction and the rate of this step increase with enhancing the electron density of Pd. In Ni−Pd alloy, the different electronegativity of Ni and Pd lead to electronic charge transfer from Ni to Pd, which causes to increase the electron density of Pd and thus enhance reaction rate . The effect of temperature was explored and the best temperature was chosen 100°C (Table , entry 8, 13, 14).…”

The development of MOFs-based nanomaterials in heterogeneous organocatalysis

“…On the other hand, owing to the character of high porosity, MOFs can be used as hosts to confine the metal nanoparticles in the holes of MOFs (denoted as M@MOFs). Encapsulating the metal nanoparticles in the holes of MOFs can efficiently prevent the metal nanoparticles from leaching and aggregation [18,24,25]. Moreover, it is also in favor of the size-selective catalysis for the different sized substrates [18,26].…”