Construction of a (NNN)Ru-Incorporated Porous Organic Polymer with High Catalytic Activity for β-Alkylation of Secondary Alcohols with Primary Alcohols

Cui, Yao; Wang, Jixian; Yu, Lei; Xu, Ying; Young, David J.; Li, Hong Xi

doi:10.3390/polym14020231

“…The utilization of alcohols as alkylating agents has gained significant research attention due to their environmentally friendly nature and high atom efficiency. This is because they generate only water as a byproduct. − Numerous expensive precious metal catalysts (e.g., Pt, Ru, and Pd) were employed in this reaction. ,− However, their high cost hinders their extensive application. Consequently, the development of highly efficient nonprecious metals (e.g., Co, Ni, and Fe)-based catalysts for this reaction has emerged as the most urgent priority at present.…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Insights into a Co(II)-Coordinated “Free” Metal Site of 2D Zinc-Based MOFs for β-Alkylation of Secondary Alcohols with Primary Alcohols

Li,

Fu,

Shi

et al. 2023

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Through in-depth study of the properties and reaction mechanisms of catalysts, it is possible to better optimize catalytic systems and improve reaction efficiency and selectivity. This remains one of the challenges in the field of catalysis. Therefore, the research and design of catalysts play crucial roles in understanding and optimizing catalytic reaction mechanisms. A robust 2D zinc-based MOFs (Zn-HA) supported Co(II) ion catalyst (Zn-HA@Co) has been designed and synthesized via a coordination-assisted strategy for β-alkylation of secondary alcohols with primary alcohols. The characterization demonstrated that the anchoring of Co(II) on Zn-HA via coordination could efficiently enhance the Co(II) ion dispersity and interaction between Co(II) and Zn-HA MOFs. Importantly, the density functional theory results have provided mechanistic insights into the energy of the HOMO and LUMO of the Zn-HA@Co catalyst as well as the energy change of the entire process after interacting with the reactants and the specific energy changes of each orbital. The synthesized Zn-HA@Co MOFs effectively lower the energy barrier of the catalytic reaction process. We expect that our research and design of catalysts will serve as valuable guideline for understanding and optimizing catalytic reaction mechanisms.

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Palladium and Ruthenium Dual‐Single‐Atom Sites on Porous Ionic Polymers for Acetylene Dialkoxycarbonylation: Synergetic Effects Stabilize the Active Site and Increase CO Adsorption

Li

¹

,

Wang

²

,

Qiao

³

et al. 2023

Angewandte Chemie

0

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Heterogeneous single‐metal‐site catalysts usually suffer from poor stability, thereby limiting industrial applications. Dual Pd1−Ru1 single‐atom‐sites supported on porous ionic polymers (Pd1−Ru1/PIPs) were constructed using a wetness impregnation method. The two isolated metal species in the form of a binuclear complex were immobilized on the cationic framework of PIPs through ionic bonds. Compared to the single Pd‐ or Ru‐site catalyst, the dual single‐atom system exhibits higher activity with 98 % acetylene conversion and near 100 % selectivity to dialkoxycarbonylation products, as well as better cycling stability for ten cycles without obvious decay. Based on DFT calculations, it was found that the single‐Ru site exhibited a strong CO adsorption energy of −1.6 eV, leading to an increase in the local CO concentration of the catalyst. Notably, the Pd1−Ru1/PIPs catalyst had a much lower energy barrier of 2.49 eV compared to 3.87 eV of Pd1/PIPs for the rate‐determining step. The synergetic effect between neighboring single sites Pd1 and Ru1 not only enhanced the overall activity, but also stabilized PdII active sites. The discovery of synergetic effects between single sites can deepen our understanding of single‐site catalysts at the molecular level.

show abstract

Palladium and Ruthenium Dual‐Single‐Atom Sites on Porous Ionic Polymers for Acetylene Dialkoxycarbonylation: Synergetic Effects Stabilize the Active Site and Increase CO Adsorption

Li

¹

,

Wang

²

,

Qiao

³

et al. 2023

View full text Add to dashboard Cite

Heterogeneous single‐metal‐site catalysts usually suffer from poor stability, thereby limiting industrial applications. Dual Pd1−Ru1 single‐atom‐sites supported on porous ionic polymers (Pd1−Ru1/PIPs) were constructed using a wetness impregnation method. The two isolated metal species in the form of a binuclear complex were immobilized on the cationic framework of PIPs through ionic bonds. Compared to the single Pd‐ or Ru‐site catalyst, the dual single‐atom system exhibits higher activity with 98 % acetylene conversion and near 100 % selectivity to dialkoxycarbonylation products, as well as better cycling stability for ten cycles without obvious decay. Based on DFT calculations, it was found that the single‐Ru site exhibited a strong CO adsorption energy of −1.6 eV, leading to an increase in the local CO concentration of the catalyst. Notably, the Pd1−Ru1/PIPs catalyst had a much lower energy barrier of 2.49 eV compared to 3.87 eV of Pd1/PIPs for the rate‐determining step. The synergetic effect between neighboring single sites Pd1 and Ru1 not only enhanced the overall activity, but also stabilized PdII active sites. The discovery of synergetic effects between single sites can deepen our understanding of single‐site catalysts at the molecular level.

show abstract

Construction of a (NNN)Ru-Incorporated Porous Organic Polymer with High Catalytic Activity for β-Alkylation of Secondary Alcohols with Primary Alcohols

Cited by 4 publications

References 73 publications

Mechanistic Insights into a Co(II)-Coordinated “Free” Metal Site of 2D Zinc-Based MOFs for β-Alkylation of Secondary Alcohols with Primary Alcohols

Mechanistic Insights into a Co(II)-Coordinated “Free” Metal Site of 2D Zinc-Based MOFs for β-Alkylation of Secondary Alcohols with Primary Alcohols

Palladium and Ruthenium Dual‐Single‐Atom Sites on Porous Ionic Polymers for Acetylene Dialkoxycarbonylation: Synergetic Effects Stabilize the Active Site and Increase CO Adsorption

Palladium and Ruthenium Dual‐Single‐Atom Sites on Porous Ionic Polymers for Acetylene Dialkoxycarbonylation: Synergetic Effects Stabilize the Active Site and Increase CO Adsorption

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