ZIF‐67 Derived Co/NC Nanoparticles Enable Catalytic Leuckart‐type Reductive Amination of Bio‐based Carbonyls to N‐Formyl Compounds

Abstract

It is of great significance to develop non‐precious metal catalysts with excellent catalytic activity, stability, and acid resistance for biomass valorization. Herein, catalytic amination of biomass carbonyl compounds was achieved via a Leuckart‐type reaction over Co nanoparticles (NPs) embedded N‐doped carbon catalyst, which was prepared by thermolysis of ZIF‐67 precursor at different temperatures in the N2 atmosphere. The Co/NC‐800 catalyst exhibited excellent catalytic activity and recyclability in furfural reductive amination to mono‐substituted formamide, which was attributed to the synergistic catalytic action of Co NPs and nitrogen base sites of the catalyst. The reductive amination mechanisms were elucidated by theoretical calculations, and showed that the initial formation of C−N bond was derived from the condensation of furfural and formamide, followed by dehydration to form C=N double bond, which was then reduced by hydrogen species Co−H− and NH+. The developed catalytic system was applicable to different carbonyls for the synthesis of corresponding N‐formyl compounds with up to 99 % yield.

MOF-Derived Cobalt@Mesoporous Carbon as Electrocatalysts for Oxygen Evolution Reaction: Impact of Organic Linker

“…They revealed an average size of 14.7, 10.3, 8.1, and 7.1 nm for Co/NMC-2MeIM (Figure a), Co/NMC-PDCA (Figure b), Co/NMC-BDC-NH 2 (Figure c), and Co/MC-DHTA (Figure d), respectively. Figure e shows the high-resolution TEM (HR-TEM) image of the two adjacent lattice fringes between the rose arrows were ∼0.205 nm, which corresponds to (111) of the face-centered cubic metallic cobalt, while the two adjacent yellow lattice stripes were ∼0.356 nm corresponding to (002) of carbon. − The polycrystallinity of cobalt into Co/NMC-2MeIM was confirmed by selected area electron diffraction (SAED), showing the diffraction rings of (002) plane of carbon and (111), (200), (220), and (311) planes of Co 0 (Figure f).…”

Highly Efficient and Recyclable Nitrogen-Doped Mesoporous Carbon-Supported Ru Catalyst for the Reductive Amination of Levulinic Acid/Esters to Pyrrolidones

“…N-doped mesoporous carbon (NMC) has attracted a lot of attention and is used as a catalyst carrier due to its adjustable pore size and functionalization, high surface area, good hydrothermal stability, and electron conduction. Moreover, the replacement of the C atom by a N atom can lower the valence band, increase the chemical stability of the material, and increase the electron density at the Fermi energy level. ,− According to our previous study, NMC-embedded Ru showed excellent catalytic performance for the hydrogenolysis of LA to GVL, where the weak basicity of the N dopant may promote the adsorption of acidic LA and consequently accelerate the following hydrogenolysis reaction. This inspired us to design and develop a novel NMC-supported Ru multifunctional catalyst for the reductive amination of LA/esters with amines.…”

Activation of Molecular Oxygen and Peroxodisulfate for Removal of Water‐Soluble Antibiotics Using Metal‐Organic Framework‐Derived CoNx@NC Catalyst

“…The obtained precipitate was dried at 60 °C in a hot air oven over night. [63] 200 mg of CoÀ Co PBA@C was ground in a mortar pestle to get a fine powder. The powder was placed in a crucible boat and heated at 800 °C in the presence of N 2 for 3 h (in a tubular furnace with a heating rate: of 5 °C/min from 35 °C).…”