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

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

Abstract

Abstract:

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.

Key words: Heterogeneous ethanol carbonylation, Single-site catalyst, Carbonylation active center [Rh(CO)I₃]^2-, Ultrastable dual-ionically bound immobilization, Porous ionic polymer

Zhou Ren, Yang Liu, Yuan Lyu, Xiangen Song, Changyong Zheng, Zheng Jiang, Yunjie Ding. Quaternary phosphonium polymer-supported dual-ionically bound [Rh(CO)I₃]^2- catalyst for heterogeneous ethanol carbonylation[J]. Chinese Journal of Catalysis, 2021, 42(4): 606-617.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63676-2

https://www.cjcatal.com/EN/Y2021/V42/I4/606

Figures/Tables 16

Table 1 The comparison of three methods for the propanoic acid production.

Method	Catalyst	Property	T/K	P/MPa	Conversion/ %	Selectivity/ %
Oxidation of propionaldehyde (from hydroformylation of ethylene) [34]	Co/Mn	Two-step; Complicated separation; Autoclave	353-373	0.6-2.0	97	95
Reppe carbonylation [37]	Ni (and Ru)	One-step; High pressure; Low propionate selectivity; Autoclave	473	10	80	70
Homogeneous/Heterogeneous ethanol carbonylation [38,50,51]	Rh	One-Step; Autoclave/Fixed-bed	443-473	0.1-4.5	5-100	5-96.6

Scheme 1. Model of the process to prepare Rh-TPISP as catalyst for heterogeneous ethanol carbonylation.

Fig. 1. P K-edge XANES of standard [PPh3Et]+I- sample for P(V) species (A), TPISP (B), fresh Rh-TPISP (C), spent Rh-TPISP (D) and standard PPh3 sample for P(III) species (E).

Fig. 2. N2 sorption isotherms (A) and pore size distributions (B) of TPISP and Rh-TPISP analyzed by DFT method.

Fig. 3. HAADF-STEM images of fresh Rh-TPISP (A) and spent Rh-TPISP (B).

Fig. 4. Rh 3d XPS spectra of fresh Rh-TPISP (A) and spent Rh-TPISP (B).

Fig. 5. Rh L3-edge normalized XANES of fresh Rh-TPISP (A), spent Rh-TPISP (B) catalyst, Rh2(CO)4Cl2 (C), and Rh powder (D).

Fig. 6. Raw spectra and fitting analysis of Rh K-edge k2-weighted Fourier transform spectra from EXAFS of fresh Rh-TPISP (A,B), spent Rh-TPISP (C,D) and [PPh3Et]+[Rh(CO)2I2]- (E,F), and the deduced molecular structures of (A), (C) and (E).

Fig. 7. Wavelet Transform of Rh foil (A), fresh Rh-TPSIP (B) and spent Rh-TPISP (C).

Table 2 Fitting results of Rh K-edge EXAFS traces of fresh Rh-TPISP, spent Rh-TPISP and [PPh3Et]+[Rh(CO)2I2]- from Fig. 6.

Samples	Shell	N	R (Å)	σ (10^-3 Å²)	R factor
Rh foil	Rh-Rh	12.0	2.68	—	—
Fresh Rh-TPISP	Rh-C	0.9 ± 0.4	2.04 ± 0.04	3.2 ± 0.0	0.014
Fresh Rh-TPISP	Rh-I	3.1 ± 0.4	2.69 ± 0.01	2.9 ± 1.0	0.014
Spent Rh-TPISP	Rh-C	1.0 ± 0.0	2.04 ± 0.06	3.0 ± 0.0	0.015
Spent Rh-TPISP	Rh-I	3.1 ± 0.5	2.69 ± 0.01	2.4 ± 1.1	0.015
standard sample of [PPh₃Et]⁺[Rh(CO)₂I₂]^-	Rh-C	2.3 ± 0.4	1.84 ± 0.01	2.5 ± 1.0	0.019
standard sample of [PPh₃Et]⁺[Rh(CO)₂I₂]^-	Rh-I	2.0 ± 0.1	2.70 ± 0.01	2.8 ± 0.1	0.019

Fig. 8. IR spectra of TPISP (A), fresh Rh-TPISP (B), spent Rh-TPISP (C), and [PPh3Et]+[Rh(CO)2I2]- (D).

Table 3 The influence of reaction temperature on heterogeneous ethanol carbonylation over Rh-TPISP catalyst.

Temperature (K)	Selectivity (%)			Conversion (%)	TOF (h^-1)
Temperature (K)	Ethylene	Propionic acid	Ethyl propionate	Conversion (%)	TOF (h^-1)
433	0	17.1	82.9	1.1	77
453	11.2	10.2	78.6	2.5	178
468	14.7	7.2	78.1	5.1	348
483	26.6	2.9	70.5	9.3	602

Table 4 The influence of pressure on heterogeneous ethanol carbonylation over Rh-TPISP catalyst.

Pressure (MPa)	Selectivity (%)			Conversion (%)	TOF (h^-1)
Pressure (MPa)	Ethylene	Propanoic acid	Ethyl propionate	Conversion (%)	TOF (h^-1)
0.5	25.5	3.7	70.8	3.5	208
1	18.9	3.7	77.4	4.8	314
2.5	14.7	7.2	78.1	5.1	348
3.5	4.4	9.3	86.3	6.9	436

Table 5 The comparison of the heterogeneous Rh-TPISP system with the homogeneous system for ethanol carbonylation.

Catalysts	Process	Active center	T/K	P/MPa MPa	T^b/h	Conversion^c/%	S^d/% (EP:PA:C₂H₄)	TOF_propionyl^e/h^-1
Rh-TPISP^a	Heterogeneous	[Rh(CO)I₃]^2-	468	3.5	17	7.6	88.8:0.7:0.5	491
Rhaq ^a ([PPh₃Et]⁺[Rh(CO)₂I₂]^-)	Homogeneous	[Rh(CO)₂I₂]^-	468	3.8	3	1	81.0:19.0:0	281

Fig. 9. Stability test of Rh-TPISP for heterogeneous ethanol carbonylation.

Scheme 2. Proposed mechanism for heterogeneous ethanol carbonylation on Rh-TPISP according to typical homogeneous ethanol carbonylation [50] and heterogeneous ethanol carbonylation [65].

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

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