Quaternary phosphonium polymer-supported dual-ionically bound [Rh(CO)I3]2- catalyst for heterogeneous ethanol carbonylation

被引：10

作者：

Ren, Zhou ^{[1
]}

Liu, Yang ^{[2
,4
]}

Lyu, Yuan ^{[1
]}

Song, Xiangen ^{[1
]}

Zheng, Changyong ^{[1
,4
]}

Jiang, Zheng ^{[2
]}

Ding, Yunjie ^{[1
,3
]}

机构：

[1] Chinese Acad Sci, Dalian Inst Chem Phys, Dalian Natl Lab Clean Energy, Dalian 116023, Liaoning, Peoples R China

[2] Chinese Acad Sci, Shanghai Inst Appl Phys, Shanghai Synchrotron Radiat Facil, Shanghai 201204, Peoples R China

[3] Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Catalysis, Dalian 116023, Liaoning, Peoples R China

[4] Univ Chinese Acad Sci, Beijing 100049, Peoples R China

来源：

CHINESE JOURNAL OF CATALYSIS | 2021年 / 42卷 / 04期

基金：

国家重点研发计划; 中国国家自然科学基金;

关键词：

Heterogeneous ethanol carbonylation; Single-site catalyst; Carbonylation active center; Rh(CO)I-3](2-); Ultrastable dual-ionically bound; immobilization; Porous ionic polymer; VAPOR-PHASE CARBONYLATION; ACETIC-ACID SYNTHESIS; OXIDATIVE ADDITION; COMPLEX CATALYST; METHANOL; RH; HYDROFORMYLATION; FRAMEWORK; SITE; PERFORMANCE;

D O I：

10.1016/S1872-2067(20)63676-2

中图分类号：

O69 [应用化学];

学科分类号：

081704 ;

摘要：

A single-Rh-site catalyst (Rh-TPISP) that was ionically-embedded on a P(V) quaternary phosphonium porous polymer was evaluated for heterogeneous ethanol carbonylation. The [Rh(CO)I-3](2-) unit was proposed to be the active center of Rh-TPISP for the carbonylation reaction based on detailed Rh L3-edge X-ray absorption near edge structure (XANES), X-ray photoelectron spectroscopy (XPS), and Rh extended X-ray absorption fine structure (EXAFS) analyses. As the highlight of this study, Rh-TPISP displayed distinctly higher activity for heterogeneous ethanol carbonylation than the reported catalytic systems in which [Rh(CO)(2)I-2]- is the traditional active center. A TOF of 350 h(-1) was obtained for the reaction over [Rh(CO)I-3](2-), with >95% propionyl selectivity at 3.5 MPa and 468 K. No deactivation was detected during a near 1000 h running test. The more electron-rich Rh center was thought to be crucial for explaining the superior activity and selectivity of Rh-TPISP, and the formation of two ionic bonds between [Rh(CO)I-3](2-) and the cationic P(V) framework ([P](+)) of the polymer was suggested to play a key role in firmly immobilizing the active species to prevent Rh leaching. (C) 2021, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

引用

页码：606 / 617

页数：12