通过“双离子键”固载于季鏻盐聚合物的[Rh(CO)I3]2-物种在多相乙醇羰基化中的应用

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

催化学报 ›› 2021, Vol. 42 ›› Issue (4): 606-617.DOI: 10.1016/S1872-2067(20)63676-2

通过“双离子键”固载于季鏻盐聚合物的[Rh(CO)I₃]^2-物种在多相乙醇羰基化中的应用

任周^a,†, 刘洋^b,d,†, 吕元^a^,^*(), 宋宪根^a, 郑长勇^a^,^d, 姜政^b^,^#(), 丁云杰^a^,^c^,^$()

^a中国科学院大连化学物理研究所, 洁净能源国家实验室(筹), 辽宁大连116023
^b中国科学院上海应用物理研究所, 上海同步辐射中心, 上海201204
^c中国科学院大连化学物理研究所, 催化基础国家重点实验室, 辽宁大连116023
^d中国科学院大学, 北京100049

收稿日期:2020-06-11 接受日期:2020-07-08 出版日期:2021-04-18 发布日期:2021-01-22
通讯作者: 吕元,姜政,丁云杰
作者简介:^†共同第一作者.
基金资助:
国家重点研发计划(2017YFB0602203);中国科学院战略性先导科技专项(XDA21020300);国家自然科学基金(XDB17020400)

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

Received:2020-06-11 Accepted:2020-07-08 Online:2021-04-18 Published:2021-01-22
Contact: Yuan Lyu,Zheng Jiang,Yunjie Ding
About author:^$Tel/Fax: +86-411-84379143; E-mail: dyj@dicp.ac.cn
^#E-mail: jiangzheng@sinap.ac.cn;
^*E-mail: luyuan@dicp.ac.cn;
First author contact:^†Contributed to this work equally.
Supported by:
National Key R&D Program of China(2017YFB0602203);Strategic Priority Research Program of the Chinese Academy of Sciences(XDA21020300);National Natural Science Foundation of China(XDB17020400)

摘要/Abstract

摘要：

贵金属物种(Rh或Ir络合物)在均相羰基化和氢甲酰化催化过程得到了广泛的应用, 但始终存在分离繁琐等问题, 其均相多相化可很大程度上简化分离操作, 故一直广受重视. 单位点催化剂因其具有可与均相相比拟的较高金属利用率和选择性而成为均相多相化的重要研究方向之一. 研究发现, 在碘物种存在的情况下用于固载金属物种的配位键容易断裂, 进而导致金属物种的流失, 而通过离子键固载的[Rh(CO)₂I₂]^-物种更加稳定, 比如著名的甲醇羰基化“Acetica^TM”工艺中, [Rh(CO)₂I₂]^-负一价阴离子物种是以离子键的方式固定在带有阳离子骨架的甲基化聚乙烯吡啶树脂上. 与甲醇羰基化过程类似的乙醇羰基化过程是生产重要化工中间体丙酸的主要途径之一, 但该过程的均相多相化始终存在着稳定性差这一关键问题. 为了解决这一问题, 基于之前将固载于季鏻盐聚合物的[Rh(CO)I₃]^2-应用于甲醇羰基化的工作, 我们将类似的季鏻盐聚合物固载Rh基催化剂Rh-TPISP用于多相乙醇羰基化过程, 通过多种表征进一步证明了Rh物种和P物种结构, 并提出了“双离子键”模型.
P的K边XANES证明了聚合物TPISP的季鏻化阳离子骨架特征. HAADF-STEM测试表明Rh-TPISP中的Rh呈现单位点分散的状态. Rh的XPS和XANES结果证明了Rh-TPISP中Rh物种的价态介于0~+1. 通过EXAFS的拟合解析给出了[Rh(CO)I₃]^2-活性中心结构. 由于[Rh(CO)₂I₂]^-为经典的羰基化活性中心, 为了进一步证明该结构的正确性, 我们将Rh-TPISP的EXAFS和IR谱图与标样[PPh₃Et]⁺[Rh(CO)₂I₂]^-对比发现: 在EXAFS谱图中, Rh-TPISP中的Rh-C峰高低于[PPh₃Et]⁺[Rh(CO)₂I₂]^-的Rh-C峰高, 而Rh-TPISP中的Rh-I峰高高于[PPh₃Et]⁺[Rh(CO)₂I₂]^-的Rh-I峰高, 这就说明Rh-TPISP中Rh物种的Rh-C配位数小于2, 而Rh-I配位数大于2; 在IR谱图中, 标样[PPh₃Et]⁺[Rh(CO)₂I₂]^-中有两个羰基振动峰, 与该物种的两个Rh-C配位键相符, 而Rh-TPISP中的只有一个羰基振动峰, 说明Rh-C配位数为1. 因此, Rh-TPISP催化剂的季鏻盐骨架中的每个P物种带有一个正电荷, 每个带有两个负电荷的[Rh(CO)I₃]^2-通过与两个[P]⁺的静电作用进行固载, 形成“双离子键”结构.
该催化剂在固定床乙醇羰基化过程中表现出优异的羰基化活性、选择性和稳定性. 在3.5 MPa、195^oC反应近1000 h后, Rh-TPISP催化剂TOF保持在约350 h^-1, 丙酰基选择性为95%以上, 高出所有文献报道的均相和多相乙醇羰基化活性. 其较高的活性主要是因为[Rh(CO)I₃]^2-比传统Rh活性相[Rh(CO)₂I₂]^-具有更强的富电子性, 而较高的稳定性主要是由于“双离子键”这种强静电作用比“Acetica^TM”工艺中“单离子键”更有利于Rh物种的固载. 故Rh-TPISP催化剂中的“双离子键”对其优异的催化性能具有极其重要的作用, 对后续多相乙醇羰基化的发展具有重要意义.

关键词: 多相乙醇羰基化, 单位点催化剂, 羰基化活性中心[Rh(CO)I₃]^2-, 超稳定双离子键固载, 多孔离子聚合物

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

任周, 刘洋, 吕元, 宋宪根, 郑长勇, 姜政, 丁云杰. 通过“双离子键”固载于季鏻盐聚合物的[Rh(CO)I₃]^2-物种在多相乙醇羰基化中的应用[J]. 催化学报, 2021, 42(4): 606-617.

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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图/表 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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通过“双离子键”固载于季鏻盐聚合物的[Rh(CO)I₃]^2-物种在多相乙醇羰基化中的应用

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

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