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

Abstract

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.

Cascade Performance of Nitroarenes with Alcohols Boosted by a Hollow Flying Saucer-Shaped Ni–Al2O3 Catalyst via a MOF-Templated Strategy Induced by the Kirkendall Effect

“…As for hydrogenation–alkylation cascade reaction, the N -methylation reaction takes advantage of the in situ generation of arylamines through the hydrogenation of corresponding nitroarenes. − Numerous heterogeneous catalysts have been specifically designed and optimized with a focus on their stability, ease of separation, and recyclability. − Recently, metal–organic framework (MOF) materials have attracted widespread interest among researchers in the field of catalysis, particularly in the area of organic catalysis reactions. − These crystalline porous materials possess the advantages of both homogeneous and heterogeneous catalysis, making them highly versatile and efficient catalysts. Importantly, the use of MOF materials as catalyst supports shows great potential, especially in the synthesis of highly dispersed nanostructured metal catalysts …”