Confinement of atomically dispersed Rh catalysts within porous monophosphine polymers for regioselective hydroformylation of alkenes

被引：62

作者：

Zhao, Kang ^{[1
,2
]}

Wang, Hongli ^{[1
,3
]}

Wang, Xinzhi ^{[1
,2
]}

Li, Teng ^{[1
]}

Dai, Xingchao ^{[1
]}

Zhang, Liping ^{[1
,2
]}

Cui, Xinjiang ^{[1
]}

Shi, Feng ^{[1
]}

机构：

[1] Chinese Acad Sci, State Key Lab Oxo Synth & Select Oxidat, Lanzhou Inst Chem Phys, 18 Tianshui Middle Rd, Lanzhou 730000, Peoples R China

[2] Univ Chinese Acad Sci, 19A Yuquanlu, Beijing 100049, Peoples R China

[3] Dalian Natl Lab Clean Energy, Dalian 116023, Peoples R China

来源：

JOURNAL OF CATALYSIS | 2021年 / 401卷

关键词：

Regioselective hydroformylation; Confinement effect; Porous monophosphine polymers; Single-atom Rh catalysts; In-situ encapsulation; HIGHLY SELECTIVE HYDROFORMYLATION; ORGANIC POLYMERS; HETEROGENEOUS HYDROFORMYLATION; RHODIUM CATALYSTS; SUPPORTED RHODIUM; LINEAR ALDEHYDES; INTERNAL OLEFINS; COMPLEXES; XANTPHOS; PROGRESS;

D O I：

10.1016/j.jcat.2021.08.004

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Precisely controlling the regioselectivity with monophosphine ligand is a long-standing challenge in hydroformylation. Herein, we describe the one-pot encapsulation of single-atom Rh catalysts within por-ous monophosphine polymers for regioselective heterogeneous hydroformylation of alkenes. The opti-mized catalyst (Rh@POP-PTBA-HA-50) shows remarkable enhancement of regioselectivity compared with the combination of Rh(CO)(2)(acac) and monophosphine ligand (PTBA), and the linear aldehyde selec-tivity increases from 62% to 92%. In addition, this catalyst shows excellent catalytic activity (one run TON at least 60,000) and good stability. Detailed studies reveal that the encapsulation of atomically dispersed Rh catalysts within porous monophosphine polymers may endow the catalysts with high regioselectivity, while the encirclement of metal active species by abundant but dispersive phosphine ligand would strengthen the stability of the catalysts through multiple-sites-coordination. The present study provides meaningful insights for designing heterogeneous catalysts with good regioselectivity, and merging the advantages of homogeneous and heterogeneous catalysis. (C) 2021 Elsevier Inc. All rights reserved.

引用

页码：321 / 330

页数：10

共 65 条

[1] Metal supported on dendronized magnetic nanoparticles: Highly selective hydroformylation catalysts [J].