Copper‐doped sulfonic acid‐functionalized MIL‐101(Cr) metal–organic framework for efficient aerobic oxidation reactions

Abstract

A series of Cr‐based metal–organic framework MIL‐101‐SO3H bearing sulfonic acid functional groups were utilized for the immobilization of catalytically active copper species via a post‐synthetic metalation method. The novel materials were fully characterized by scanning electron microscopy, X‐ray diffraction, energy dispersive X‐ray spectroscopy (EDX), X‐ray photoelectron spectroscopy (XPS), the Brunauer–Emmett–Teller method, and thermogravimetric analysis. XPS and the EDX element map both suggested that Cu2+ is coordinately bonded to the MIL‐101‐SO3H, which forms the MIL‐101‐SO3@Cu structure. The obtained copper‐doped MIL‐101‐SO3@Cu‐1, MIL‐101‐SO3@Cu‐2, and MIL‐101‐SO3@Cu‐3 catalysts were utilized in the selective oxidation of alcohols and epoxidation of olefins using molecular oxygen as an oxidant. Catalytic aerobic oxidation optimization showed that MIL‐101‐SO3@Cu‐1 is the optimal catalyst and it can be reused ten times without compromising the yield and selectivity.

Amphiphilic Polyampholytes for Fouling-Resistant and Easily Tunable Membranes

“…Staining is further supported by the formation of sulfonate−copper complexes. 46 Figure 3 shows brightfield TEM images of P−, P0, and P+ copolymers. All images show a disordered bicontinuous morphology with a network of percolated ionic nanochannels (dark regions) surrounded by the hydrophobic phase (light regions).…”

Complete and Versatile Post‐Synthetic Modification on Iron‐Triazole Spin Crossover Complexes: A Relevant Material Elaboration Method

“…Therefore the synthesis of a wide variety of molecules is facilitated and this is of particular interest in the fields of catalysis (where the catalytic activity is highly dependent on the structure of the catalyst) and sensors (where the selectivity towards guest molecules could be modulated by the electronic and steric hindrance of the functionalized group on the MOF). [2,17,19,[28][29][30][31][32][33] This strategy allows to have better control in the final material; two important examples of this are: 1) in the biological area; once the protein is biosynthesized, it can be covalently modified on the amino acid side chain or in the backbone of the protein, the phosphorylation being the most common post-translational modification (PTM). [34] 2) in coordination chemistry, to generate co-catalysts associating MOF with multimetal sites to avoid competition between the metal sites, [22,29,35] for example, Neppolian et al [35] synthesized Ti-MOF complexes and then associated them by the coordination of the amino functional group on the Ti-MOF to transition metals such as Ni or Cu.…”

“…[2,17,19,[28][29][30][31][32][33] This strategy allows to have better control in the final material; two important examples of this are: 1) in the biological area; once the protein is biosynthesized, it can be covalently modified on the amino acid side chain or in the backbone of the protein, the phosphorylation being the most common post-translational modification (PTM). [34] 2) in coordination chemistry, to generate co-catalysts associating MOF with multimetal sites to avoid competition between the metal sites, [22,29,35] for example, Neppolian et al [35] synthesized Ti-MOF complexes and then associated them by the coordination of the amino functional group on the Ti-MOF to transition metals such as Ni or Cu. In addition to the advantages on chemical transformations, PSM reactions can provide a template for the solid state structure, in other words, main features of solid-state structures present in the "parent" materials can be preserved in the functionalized material in contrast with direct methods.…”

“…An advantage of biphasic reaction is that the material can be simply isolated and recovered since it is not in the same phase than other reagents. Therefore the synthesis of a wide variety of molecules is facilitated and this is of particular interest in the fields of catalysis (where the catalytic activity is highly dependent on the structure of the catalyst) and sensors (where the selectivity towards guest molecules could be modulated by the electronic and steric hindrance of the functionalized group on the MOF) [2,17,19,28–33] . This strategy allows to have better control in the final material; two important examples of this are: 1) in the biological area; once the protein is biosynthesized, it can be covalently modified on the amino acid side chain or in the backbone of the protein, the phosphorylation being the most common post‐translational modification (PTM) [34] .…”

“…This strategy allows to have better control in the final material; two important examples of this are: 1) in the biological area; once the protein is biosynthesized, it can be covalently modified on the amino acid side chain or in the backbone of the protein, the phosphorylation being the most common post‐translational modification (PTM) [34] . 2) in coordination chemistry, to generate co‐catalysts associating MOF with multimetal sites to avoid competition between the metal sites, [22,29,35] for example, Neppolian et al [35] . synthesized Ti‐MOF complexes and then associated them by the coordination of the amino functional group on the Ti‐MOF to transition metals such as Ni or Cu.…”