Activity and Stability of Two Polymer-Supported Rhodium-Based Catalysts for the Vapour Phase Carbonylation of Methanol

Blasio, Nicola De; Tempesti, E.; Kaddouri, A.; Mazzocchia, C.; Cole‐Hamilton, David J.

doi:10.1006/jcat.1998.2030

Cited by 29 publications

(16 citation statements)

References 17 publications

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“…Methanol carbonylation with polymer-supported Rh complex catalysts dates back to the infancy of the field of heterogenized homogeneous catalysts, for example with early publications by Gates [13,29]. Over 33 years, only a few publications of polymer-supported Rh catalysts for methanol carbonylation have appeared [30][31][32][33][34][35][36][37][38][39], but extensive research in industry has allowed Chiyoda-UOP to overcome the typical catalyst stability, deactivation and leaching issues that often plague supported metal complex catalysts, leading to the commercially practiced Acetica TM process. The commercial process [25,26,28] uses a Rh complex ionically immobilized [40] on a poly(vinylpyridine) resin, which has proven to be more stable than previous supported catalysts, for example those using polymer-tethered phosphine ligands.…”

Section: Introductionmentioning

confidence: 99%

On the Stability and Recyclability of Supported Metal–Ligand Complex Catalysts: Myths, Misconceptions and Critical Research Needs

2010

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Research on heterogenized metal complex catalysts has been carried out for 40 years. Despite thousands of published catalysts, there are only two significant commercial processes that utilize supported metal complex catalysts. Most academic papers are simply ''demonstration of concept'' studies reporting myriad ways to support various metal complex catalysts. Too few papers focus on rigorous studies of reaction kinetics, catalyst recycle, catalyst stability and deactivation pathways. Here, preliminary stability and deactivation studies of supported enantioselective Co-salen epoxide ring-opening catalysts and enantioselective Ru-salen olefin cyclopropanation catalysts are summarized. Insights with regard to catalyst deactivation suggest methodologies for catalyst stabilization, allowing for more effective catalyst recycle and enhanced catalyst turnover. Further examples where supported metal complex catalysts are applied in commercial processes will require the field to shift focus from ''demonstration of concept'' studies to more detailed investigations of catalyst stability and recyclability.

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Section: Introductionmentioning

confidence: 99%

On the Stability and Recyclability of Supported Metal–Ligand Complex Catalysts: Myths, Misconceptions and Critical Research Needs

2010

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“…However, such‐derived materials are inferior for the insufficient bonding with metals due to the absence of strong interactions with the polymer. Later, modified polymer with pendant ligands was developed to coordinate with metal species but still suffered from the low surface concentration of ligands in the polymer to effectively grasp metal species for catalytic processes. Enlighted by these seminal works, Ding et al pioneered on the design and fabrication of a series of polymers coined as porous organic ligands (POLs), which are synthesized by the self‐ or copolymerization of vinyl‐functionalized ligands.…”

Section: Pops Polymerized By Vinyl‐based Monomersmentioning

confidence: 99%

“…The key lies in developing a catalyst with sufficient activity, selectivity, and stability. Many efforts have been done to anchor active sites on different supports, such as inorganic porous materials, SiO 2 supported with 1‐butyl‐3‐methylimidazolium iodide, quaternary polyvinyl pyridine polymer, and the modified polymer with pendant P(III) species . The activity was usually unsatisfied, and the stability need to be improved in these heterogeneous systems, originating from the coordination environments of rhodium of heterogeneous system, which is different from that of homogenous catalysis.…”

Section: Pip‐based Single‐site Metal Catalystsmentioning

confidence: 99%

Dual‐Ionically Bound Single‐Site Rhodium on Porous Ionic Polymer Rivals Commercial Methanol Carbonylation Catalysts

et al. 2019

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porous organic polymers (POPs) connected through strong autologous covalent bonds from vinyl-polymerization are emerging as a family of advanced materials advantageous to MOFs, because of a relatively high thermal stability of the skeleton, a hierarchical porosity, as well as the structural diversity. [4] In addition, the ligands [4] or the functional sites [5] in POPs can serve as strong anchoring sites for different metals with great tunability of the metal properties via different preparation methods, being more suitable for cataly sis. It has been believed that the chemical bond between metal species and POPs can be a coordination or an ionic bond, and the latter is generally more stable particularly under harsh reaction conditions. In this context, an effective method to create strong ionic bond is by the immobilization of the ionic active sites onto a new type of POPs with charged skeleton balanced by counterions, coined herein as porous ionic polymers (PIPs). [5] Thanks to the strong bonding and the ionic nature, the resultant single-site metal catalysts can well inherit both the advantages of homo-and heterogeneous processes, i.e., the high activity of the former and the catalyst robustness of the latter. Herein, we first briefly introduce the preparation approaches for porous organic polymers and the corresponding strategies for heterogenization of homogeneous metallic catalysts, and then exemplify a PIP hosted single-site rhodium catalyst (Rh 1 /PIP) for vapor-phase methanol carbonylation, and its excellent performance shows a promising prospect in this exciting field. POPs Polymerized by Vinyl-Based MonomersDifferent synthetic strategies have been developed to prepare POPs. [3,6] The widely used hard or soft-templates are supposed to be removed completely, requiring a highly complicated and energy-consuming procedure. [3] Moreover, the residual metals (Cu, Ni, etc.) as polymerization catalysts for Sonogashira, [7,8] Click, [9] and Yamamoto reactions [10] usually show negative impacts on the catalytic performance of POPs. Contrarily, the polymerization process of vinyl-based monomers is an exception, which can not only avoid the residue of templates and metals, but also offer excellent yields (near 100%) and simple operation. [11] Novel porous polymers can serve as self-supporting solid carriers and provide abundant coordination or charged sites for single-site metals, and thus are emerging as advanced functional materials in heterogeneous catalysis for various transformations traditionally catalyzed by homogeneous systems. A brief overview of the development of this heterogenization given, including the recent advances regarding electrovalent bonds by employing charged supports represented by porous ionic polymers (PIPs), which is exemplified herein with a novel single-site Rh 1 /PIP catalyst, featuring a new active site [Rh(CO)I 3 ] 2− dual-ionically bound onto a quaternary phosphonium cationic framework polymer, different from the single-ionically bound [Rh(CO) 2 I 2 ] − in previous studies. Such a u...

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“…The activity of the catalyst depends on the properties of the support; polymeric supports give better results [20] because of the flexibility of the polymer backbone [21,22], and because of their compatibility with reaction media. The anchoring of catalysts on polymer supports improves the loading of metal ions and controls the interactions between catalysts and substrates; it also enhances the activity and selectivity of the catalysts [23,24]. A polymer support prevents the aggrega- tion of active sites and increases the activity of the catalyst.…”

Section: Phenol Oxidationmentioning

confidence: 99%

Novel polystyrene-anchored zinc complex: Efficient catalyst for phenol oxidation

Sutar

Das

Pattnaik

et al. 2014

Chinese Journal of Catalysis

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Activity and Stability of Two Polymer-Supported Rhodium-Based Catalysts for the Vapour Phase Carbonylation of Methanol

Cited by 29 publications

References 17 publications

On the Stability and Recyclability of Supported Metal–Ligand Complex Catalysts: Myths, Misconceptions and Critical Research Needs

On the Stability and Recyclability of Supported Metal–Ligand Complex Catalysts: Myths, Misconceptions and Critical Research Needs

Dual‐Ionically Bound Single‐Site Rhodium on Porous Ionic Polymer Rivals Commercial Methanol Carbonylation Catalysts

Novel polystyrene-anchored zinc complex: Efficient catalyst for phenol oxidation

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