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

DOI: 10.1016/S1872-2067(20)63676-2

Source and publish data:

Cuihua Xuebao/Chinese Journal of Catalysis p. 606 - 617 (2021)

Update date:2022-08-10

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Authors:

Ding, Yunjie

Jiang, Zheng

Liu, Yang

Lyu, Yuan

Ren, Zhou

Song, Xiangen

Zheng, Changyong

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Article abstract of DOI:10.1016/S1872-2067(20)63676-2

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)I₃]^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)₂I₂]^? is the traditional active center. A TOF of 350 h^?1 was obtained for the reaction over [Rh(CO)I₃]^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)I₃]^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.

Full text of DOI:10.1016/S1872-2067(20)63676-2

Chinese Journal of Catalysis 42 (2021) 606–617

a v a i l a b l e a t w w w . s c i e n c e d i r e c t . c o m

j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / c h n j c

Article

Quaternary phosphonium polymer‐supported dual‐ionically bound

[Rh(CO)I₃]^2–catalyst for heterogeneous ethanol carbonylation

Zhou Ren ^a,†, Yang Liu ^b,d,†, Yuan Lyu ^a,*, Xiangen Song^a, Changyong Zheng^a,d, Zheng Jiang ^b,#

Yunjie Ding ^a,c,$

^aDalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China

^bShanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201204, China

^cState Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China

^dUniversity of Chinese Academy of Sciences, Beijing 100049, China

A R T I C L E I N F O

A B S T R A C T

Article history:

Received 11 June 2020

Accepted 8 July 2020

A single‐Rh‐site catalyst (Rh‐TPISP) that was ionically‐embedded on a P(V) quaternary phospho‐

nium porous polymer was evaluated for heterogeneous ethanol carbonylation. The [Rh(CO)I₃]^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)₂I₂]^–is the traditional active center. A TOF of 350 h^–1

was obtained for the reaction over [Rh(CO)I₃]^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 cen‐

ter 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)I₃]^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.

Available online 5 September 2020

Keywords:

Heterogeneous ethanol carbonylation

Single‐site catalyst

Carbonylation active center

[Rh(CO)I₃]^2–

Ultrastable dual‐ionically bound

immobilization

Porous ionic polymer

1. Introduction

neous processes while retaining satisfactory activity, selectivi‐

ty, and stability, to easily recover the noble metal catalysts, has

Noble metal species (especially Rh or Ir complexes) dis‐

solved in liquid reaction media are widely used as catalysts for

homogeneous carbonylation [1]/hydroformylation [2] and are

generally active and selective, but are difficult to separate from

the reaction mixture. Heterogenizing the traditional homoge‐

remained a remarkable challenge for decades [3].

Supported heterogeneous catalysts prepared by traditional

methods such as precipitation or impregnation are usually less

efficient and non‐selective because the supported metal is gen‐

erally loaded on the support as nanoparticles or clusters [4–8]

* Corresponding author. E‐mail: luyuan@dicp.ac.cn

^#Corresponding author. E‐mail: jiangzheng@sinap.ac.cn

^$Corresponding author. Tel/Fax: +86‐411‐84379143; E‐mail: dyj@dicp.ac.cn

^†Contributed to this work equally.

This work was supported by the National Key R&D Program of China (2017YFB0602203), the Strategic Priority Research Program of the Chinese

Academy of Sciences (XDA21020300) and the National Natural Science Foundation of China (XDB17020400).

DOI: 10.1016/S1872‐2067(20)63676‐2 | http://www.sciencedirect.com/science/journal/18722067 | Chin. J. Catal., Vol. 42, No. 4, April 2021

Chinese Journal of Catalysis, 42 (2021) 606-617. doi:10.1016/S1872-2067(20)63676-2

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