Enhancing the activity, selectivity, and recyclability of Rh/PPh3 system-catalyzed hydroformylation reactions through the development of a PPh3-derived quasi-porous organic cage as a ligand

Wang, Wenlong; Li, Cunyao; Zhang, Heng; Lu, Lanlu; Jiang, Zheng; Cui, Lifeng; Liu, Hongguang; Li, Yan; Ding, Yunjie

doi:10.1016/s1872-2067(20)63746-9

Cited by 16 publications

(5 citation statements)

References 81 publications

(82 reference statements)

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“…[35] A vinylfunctionalized PPh 3 was used by Ding et al to fabricate a porous polymer supported single Rh catalyst (Rh/POLÀ PPh 3 ) which maintained the catalytic functionalities as that of the homogeneous HRh (CO)(PPh 3 ) 3 complex (Table 1, entry 21). [36][37][38] The Rh/POLÀ PPh 3 catalyst showed high activity and selectivity during ethylene hydroformylation while maintaining exceptional stability. The dual roles of the PPh 3 polymer as carriers and ligands were revealed by the QC method: the interaction between Rh and P in the monomer was the strongest, and vinyl enhanced the adsorption strength of RhÀ P. [39] Ethylene hydroformylation on Rh/POLÀ PPh 3 followed by reduction to npropanol has been industrialized in Hangzhou, China.…”

Section: Ethylene Carbonylation With H 2 Gasmentioning

confidence: 99%

Concepts of Ethylene Carbonylation with Hydrogen Gas and In‐Situ Generated Hydrogen

Zhang,

Guo,

Wang

2024

ChemCatChem

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The carbonylation reaction of olefins is one of the significant pathways for the synthesis of oxygen‐containing compounds such as aldehydes, esters, and amides. The ethylene carbonylation reactions have drawn much interest since they produce important chemicals such as propionaldehyde and methyl propionate, which are crucial intermediates for the synthesis of polymers. Moreover, ethylene carbonylation, coupled with C‐C bond formation, shows great promise for the synthesis of 3‐pentanone. However, due to the presence of various competing reactions, balancing the activity and selectivity of ethylene carbonylation reactions has remained a challenge. This concept article aims at describing the recent advances in the ethylene carbonylation with different hydrogen sources.

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Section: Ethylene Carbonylation With H 2 Gasmentioning

confidence: 99%

Concepts of Ethylene Carbonylation with Hydrogen Gas and In‐Situ Generated Hydrogen

Zhang,

Guo,

Wang

2024

ChemCatChem

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“…Hydroformylation of olefins exists in complexity, and the reaction process involves side reactions, such as olefin hydrogenation, olefin isomerization–hydroformylation, and hydroformylation–hydrogenation reduction. In homogeneous systems, ligand preference is one of the essential means to improve catalyst selectivity, − while heterogeneous catalysis mainly starts from the structure of the catalyst. − However, the activity of the heterogeneous hydroformylation has been difficult to approach that of the homogeneous system based on the inherent nature of both catalytic systems. This section reviews enhanced strategies to improve the activity of Co-based catalysts in terms of improving the dispersion of Co, regulating the reduction of Co, and improving the efficiency of the reaction process from the point of view of the pore structure, substrate, and solvent.…”

Section: Enhanced Strategies For the Activity Of Cobalt-based Catalys...mentioning

confidence: 99%

Outlook of Cobalt-Based Catalysts for Heterogeneous Hydroformylation of Olefins: From Nanostructures to Single Atoms

Gao,

Liu,

Wang

et al. 2023

Energy Fuels

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Hydroformylation of olefins, as a study of olefinic downstream derivative production, is of great relevance in chemical production. Heterogeneous hydroformylation is beneficial for catalyst separation and recycling compared to homogeneous systems. Cobalt is a cheap metal with excellent catalytic activity in hydroformylation as well as the precious metal rhodium. Therefore, the research on cobalt-based catalysts for heterogeneous hydroformylation has great value and significance. The nano or atomic structures of cobalt-based catalysts have significant impact on the catalytic behaviors of the hydroformylation process. There is rarely the design principles report on how to achieve significant improvement in hydroformylation performance by regulating the structure of the cobalt-based catalyst. Herein, we review the recent research progress on heterogeneous hydroformylation by cobalt-based catalysts with different metal sizes (from nanostructures to single atoms). On the basis of the difference in the catalytic mechanism between homogeneous and heterogeneous hydroformylation, we summarize and propose the regulation principles to enhance the activity and stability of cobalt-based catalysts in hydroformylation, where single-atom engineering is expected to achieve unity of high activity and stability of cobalt-based catalysts for hydroformylation applications. At the end of this review, we present an outlook on the opportunities and challenges in developing cobalt-based catalysts for heterogeneous hydroformylation.

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“…Since Cooper and co-workers proposed and reported the first case of crystalline POCs in 2009, the field has been vigorously developed. After more than one decade of development, POCs with different bonding modes, shapes and sizes have been synthesized and reported and have been widely used in separation, − sensing, proton conduction, , catalysis, , and so on. Benefiting from the inherent cavity and functionality of organic cages, the stabilization and storage of active material white phosphorus, the stabilization of metal nanoparticles, , and the storage of energy gas hydrogen have been achieved.…”

Section: Introductionmentioning

confidence: 99%

Porous Organic Cage as a Sulfur Host for Upgrading Capacity and Longevity of Li–S Batteries

Xie

Yang

El-Sayed

et al. 2023

ACS Appl. Nano Mater.

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Suffering from the severe shuttle effect, constructing high-performance lithium–sulfur (Li–S) batteries with high capacity and prolonged cycling life remains a great challenge. Developing porous host materials for sulfur loading remains a tendency. Porous organic cages (POCs), as a kind of porous material, exhibit potential in energy storage and conversion because of their inherent cavities and plentiful active sites. Herein, two POC materials of CPOC-301 and HPOC-401 with large octahedral cavities and abundant N and O heteroatoms were explored as host materials for loading a high sulfur content of 84 wt % in Li–S batteries. The resulting CPOC-301-S and HPOC-401-S cathodes exhibit improved electrochemical performances with high specific capacity (1302 and 1109 mA h g–1 at 0.05 C, respectively) and excellent cycling reversibility and stability (a low average capacity fading rate of 0.015% for 2500 cycles at 5 C for CPOC-301-S). Moreover, the interconversion of keto-enamine in CPOC-301 could accelerate the redox kinetics. This work provides the blueprint for POC families applied as promising host materials for advanced Li–S batteries.

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Enhancing the activity, selectivity, and recyclability of Rh/PPh3 system-catalyzed hydroformylation reactions through the development of a PPh3-derived quasi-porous organic cage as a ligand

Cited by 16 publications

References 81 publications

Concepts of Ethylene Carbonylation with Hydrogen Gas and In‐Situ Generated Hydrogen

Concepts of Ethylene Carbonylation with Hydrogen Gas and In‐Situ Generated Hydrogen

Outlook of Cobalt-Based Catalysts for Heterogeneous Hydroformylation of Olefins: From Nanostructures to Single Atoms

Porous Organic Cage as a Sulfur Host for Upgrading Capacity and Longevity of Li–S Batteries

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