Enhanced Heck reaction on flower-like Co(Mg or Ni)Al layered double hydroxide supported ultrafine PdCo alloy nanocluster catalysts: the promotional effect of Co

Abstract

A series of PdCo alloy nanocluster (NC) catalysts x-PdCo_r/Co(Mg or Ni)Al-LDH (x: Pd loading, r: Co/Pd molar ratio) were synthesized by immobilizing ultrafine PdCo_r-PVP NCs on flower-like layered double hydroxide (LDH) supports. The sizes of PdCo alloy NCs of the catalysts can be elaborately tuned in ∼1.6–3.2 nm by both Co/Pd ratios and Pd loadings, and the PdCo NCs are mainly dispersed on the edge sites of LDH nanosheets upon a flower-like morphology. The PdCo bimetallic catalysts 0.81-PdCo_0.10/MgAl-LDH (2.6 ± 0.6 nm), 0.86-PdCo_0.28/MgAl-LDH (2.3 ± 0.7 nm) and 0.79-PdCo_0.54/MgAl-LDH (3.2 ± 0.9 nm) exhibit enhanced activity compared with the monometallic Pd catalyst for Heck coupling of iodobenzene with styrene. Particularly, 0.86-PdCo_0.28/MgAl-LDH shows the highest activity, which can be attributed to its smallest PdCo_0.28 alloy NCs, and the maximum electron density of the Pd⁰ center resulted from the electron transfer from Co and the strongest PdCo_0.28 NCs – LDH synergistic effect. 0.67-PdCo_0.28/CoAl-LDH shows much better activity than those of 0.64-PdCo_0.28/NiAl-LDH and 0.86-PdCo_0.28/MgAl-LDH. The lowest Pd loading sample 0.01-PdCo_0.28/CoAl-LDH (1.6 ± 0.4 nm) shows an ultrahigh turnover frequency of 163 000 h⁻¹ (Pd: 1.9 × 10⁻⁵ mol%), which is the highest value obtained so far. Meanwhile, the catalyst shows excellent adaptability for the substrates and can be reused for 12 runs without significant loss of activity. The present work may provide a new idea for the simple and green synthesis of ultrafine Pd-based non-noble bimetallic catalysts for varied catalytic processes.