Counteranion effects on the catalytic activity of copper salts immobilized on the 2,2′-bipyridine-functionalized metal–organic framework MOF-253

Abstract

The charge-neutral, aluminium-based metal-organic framework containing accessible 2,2-bipyridine (bpy) sites, MOF-253, is a suitable host material for the immobilization of various copper catalysts. The catalytic performance of CuCl 2 , Cu(NO 3) 2 , Cu(BF 4) 2 and Cu(CF 3 SO 3) 2 before and after coordination to the bpy ligands in MOF-253 was studied in the Meinwald rearrangement of ␣-pinene oxide to campholenic aldehyde (CA). The coordination environment of Cu 2+ in MOF-253 was further studied via EPR spectroscopy. Although the catalytic activity of the copper salts decreased upon heterogenization through coordination with the bpy linker, the selectivity to campholenic aldehyde markedly increased. Furthermore, the catalytic performance of the MOF loaded with copper salts was shown to vary greatly with the choice of charge compensating anion, allowing for improvement of the heterogeneous catalyst.

The duality of UiO-67-Pt MOFs: connecting treatment conditions and encapsulated Pt species byoperandoXAS

“…65 In this respect, there are multiple choices of relatively easy ways to functionalize the linker of UiO-67 with metal sites by substituting a fraction of the standard bpdc linkers with a bipyridine-dicarboxylate (bpydc) linker, as described in the Experimental section. In such a way, Fe(II), 86 Ni(II), 87 Cu(II), [88][89][90][91][92] Ru(II), 93 Rh(III), 94,95 Pd(II), 96 Re(I), 93 Ir(III) 93,95 Pt(II), 92,[97][98][99][100] and Pt(IV) 92,98,99 have already been successfully grafted to the two N atoms of the functionalized bpydc linker of different MOFs. In this paper, we present a study done on UiO-67 functionalized with Pt, a metal chosen for its extensive and interesting chemistry in catalysis.…”

Immobilization of Cu Complex into Zr-Based MOF with Bipyridine Units for Heterogeneous Selective Oxidation

“…The controllable nanospace in the framework of MOFs is a suitable candidate for a host of catalytically active species and will provide an accurately controlled reaction field. [30][31][32][33] In this context, it is anticipated that immobilization of Cu homogeneous complexes into MOF structures will enable the development of efficient and recyclable heterogeneous catalysts. We herein report the immobilization of CuBr2 within Zr-based MOF with an organic linker of 2,2'-bipyridine-5,5'-dicarboxylic acid (Zr-MOF-bpy-CuBr2) and its application for selective oxidation of cyclooctene to cyclooctene oxide, as shown in Fig.…”

MOF-enabled confinement and related effects for chemical catalyst presentation and utilization

“…Bipyridine ligands have been incorporated extensively in numerous MOFs, both as linkers and as tethered nonstructural ligands, and then used to heterogenize numerous kinds of catalysts. [144][145][146][147][148][149][150][164][165][166] Fig. 17 shows one example.…”