Copper supported on phenanthroline‐functionalized porous polymer as an active catalyst for the oxidative carbonylation of methanol

Abstract

Porous organic polymer has recently attracted tremendous interest because of its potential to combine the best features of homogeneous and heterogeneous catalysts. In this study, copper supported on phenanthroline‐functionalized porous polymer (Cu@PCP‐Phen) was prepared by a co‐polymerization method and used as a heterogeneous catalyst for dimethyl carbonate synthesis via the oxidative carbonylation of methanol. The catalyst was characterized by N2 adsorption, scanning electron microscopy, transmission electron microscopy, 13C solid‐state nuclear magnetic resonance, and X‐ray photoelectron spectroscopy, which suggested that it possessed a big surface area, hierarchical porous structure, and strong electron‐donating effect toward copper species. The Cu@PCP‐Phen catalyst showed high catalytic activity, which was significantly higher than those achieved with Cu‐based catalysts under similar reaction conditions. In addition, the catalyst can be easily separated and reused at least six times with only a slight decrease in activity. The salient features of this protocol are the simplicity in handling of the catalyst, high catalytic activity, excellent selectivity, low copper leaching, and good catalyst recyclability.

Mechanistic Investigation of Oxidative Methanol Carbonylation with Mixed Cu(I)/Cu(II)–N-Methylimidazole Catalysts

“…11,12 Thus, many researchers had tried to add, e.g., amines and pyridines as promoters or immobilized copper salts on supports in order to avoid these problems. 13 Nitrogen-containing ligands such as N-methylimidazole (NMI) can coordinate with copper ions to form copper−organic complex catalysts, promoting the dissolution and increasing the catalytic activity of cuprous chloride, which significantly reduces the corrosion of equipment. 14 Although CuCl 2 has better solubility in methanol than CuCl, it is known that its catalytic activity and selectivity are much inferior to those of the above-mentioned slurry CuCl catalyst.…”

“…CuCl and CuCl 2 are known as effective catalysts for oxidative carbonylation of methanol. , However, the poor solubility of CuCl in methanol made the industrial reaction system a slurry liquid and chloride loss led to equipment corrosion and catalyst deactivation. , Thus, many researchers had tried to add, e.g., amines and pyridines as promoters or immobilized copper salts on supports in order to avoid these problems . Nitrogen-containing ligands such as N -methylimidazole (NMI) can coordinate with copper ions to form copper–organic complex catalysts, promoting the dissolution and increasing the catalytic activity of cuprous chloride, which significantly reduces the corrosion of equipment .…”

Role of metal co‐cations in improving CuY zeolite performance for DMC synthesis: A theoretical study

“…[1][2][3][4][5] Recently, development of effective catalysts to produce DMC through oxidative carbonylation of methanol, which is thermodynamically favorable has received greater attention. [6][7][8][9][10][11][12][13][14][15][16][17][18] Being, chloride-free, CuY zeolite has shown greate potential to obtain high activity and excellent selectivity for oxidative carbonylation reaction. [16][17][18][19][20][21][22][23] Generally, Cu exchanged zeolite Y, CuY was prepared by ion-exchange of NaY zeolite with the ammonia solution of copper nitrate, followed by calcination at high temperatures in an inert atmosphere.…”