Core–shell Co@CoO catalysts for the hydroformylation of olefins

Hou, Zhenshan; Xu, Wen; Ma, Yue; Wei, Xinjia; Gong, Honghui; Zhao, Xiuge; Qin, Yuxi; Peng, Qingpo

doi:10.1039/d2nj02797f

Cited by 10 publications

(13 citation statements)

References 58 publications

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Section: Research Progress For Heterogeneous Hydroformylation By Coba...mentioning

confidence: 99%

“…On the basis of the above studies, it can be found that the high specific surface area of the support may also promote the dispersion of Co. Xu et al used deep eutectic solvents (DESs) as structural guides to synthesize Co@CoO core–shell NPs with a higher specific surface area compared to aqueous media (Figure a). The catalyst enables the exposure of more active sites, which promotes the efficient utilization of the active species.…”

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

confidence: 99%

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

confidence: 99%

“…Schematic diagram of strategies to enhance the activity and stability of cobalt-based catalysts in heterogeneous hydroformylation. CoO core–shell NPs were reproduced with permission from ref . Copyright 2022 Royal Society of Chemistry.…”

Section: Introductionmentioning

confidence: 99%

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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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Section: Research Progress For Heterogeneous Hydroformylation By Coba...mentioning

confidence: 99%

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

confidence: 99%

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

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

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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“…Stabilization of the Co complexes with phosphine ligands can improve the stability at the expense of the activity. , In this case, homogeneous Co-based catalysts which were initially applied in the hydroformylation industry have been fastly replaced by homogeneous Rh-based catalysts. − , Moreover, approaches of recycling Co are less effective than the mature methods of recycling Rh . To this end, great efforts have been made to directly develop efficient heterogeneous Co-based catalysts. − For instance, the Co–Co 2 C interface where Co and Co 2 C adsorbed olefins and CO, respectively, worked in synergy to catalyze the hydroformylation of 1-hexene . Mo 6 C 2 -bonded Co species served as active sites for propene hydroformylation.…”

mentioning

confidence: 99%

Efficient Interfacial Sites between Metallic and Oxidized Cobalt for Propene Hydroformylation

Pu,

Zhao,

Yin

et al. 2023

Nano Lett.

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Currently, the hydroformylation of short olefins is operated almost exclusively by using Rh catalysts. Considering the high cost and scarcity of rhodium resources, it is important to develop non-noble metal catalysts toward hydroformylation. Herein, we report an efficient cobalt-based catalyst rich in interfacial sites between metallic and oxidized cobalt species for the hydroformylation of short olefin, propene, under a moderate syngas pressure. The catalyst exhibited a high specific activity of 252 mol mol Co −1 h −1 in toluene under 2 bar of propene and 40 bar of CO/H 2 mixed gas (CO/H 2 = 1:1) at 160 °C. According to mechanistic studies, the interface of metallic and oxidized cobalt species promoted the adsorption of CO and propene. Moreover, the interfacial sites lowered the energy barrier for CO* hydrogenation and C−C coupling compared with metallic cobalt.

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ZIF‐67 Derived Cobalt Catalysts for the Hydroformylation of Liquid Olefins

Almeida,

Patiño,

Cerrillo

et al. 2024

ChemCatChem

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Herein, we describe a general monometallic cobalt heterogeneous catalyst for the hydroformylation of olefins, achieving good yields and recyclability up to five times with no loss in catalytic activity. These catalysts were prepared through the pyrolysis of the well‐defined metal‐organic framework ZIF‐67. The addition of steam during the pyrolysis did not affect the final phase composition of the cobalt particles; nonetheless, it resulted in an increase of the cobalt particle size and the partial removal of the carbonaceous matrix. The materials were extensively characterized by several techniques, and it was observed that the N‐doped carbon matrix played a crucial role in terms of activity and stability. Different liquid olefins, including internal, terminal, and cyclic were successfully tested in our hydroformylation protocol. Aldehydes yields of 48‐77% for different liquid olefins were achieved with the optimal catalyst. No leaching of the active sites was observed over five catalytic cycles. The high stability of the catalyst is attributed to the presence of stabilizing nitrogen atoms bearing the cobalt sites.

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Core–shell Co@CoO catalysts for the hydroformylation of olefins

Abstract: A new strategy has been proposed for synthesizing Co@CoO core-shell nanoparticles with a core-shell structure, which involves a facile solvent-thermal process in deep eutectic solvents (DESs). In contrast to irregular...

Cited by 10 publications

References 58 publications

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

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

Efficient Interfacial Sites between Metallic and Oxidized Cobalt for Propene Hydroformylation

ZIF‐67 Derived Cobalt Catalysts for the Hydroformylation of Liquid Olefins

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