Zeolitic imidazolate frameworks derived Fe1-N-C catalysts with isolated single iron atoms have been synthesized and applied for selective ammoxidation reactions. For the preparation of the different Fe-based materials, benzylamine as an additive proved to be essential to tune the morphology and size of ZIFs resulting in uniform and smaller particles, which allow stable atomically dispersed Fe–N4 active sites. The optimal catalyst Fe1-N-C achieves an efficient synthesis of various aryl, heterocyclic, allylic, and aliphatic nitriles from alcohols in water under very mild conditions. With its chemoselectivity, recyclability, high efficiency under mild conditions this new system complements the toolbox of catalysts for nitrile synthesis, which are important intermediates with many applications in life sciences and industry.

A cobalt catalyst derived from a unique core–shell structure based on hollow ZIF-8 and ZIF-67 is prepared for the synthesis of nitriles from alcohols in water under mild conditions.

N‐Heterocycles, such as pyrroles, pyrimidines, quinazolines, and quinoxalines, are important building blocks for organic chemistry and the fine‐chemical industry. For their synthesis, catalytic borrowing hydrogen and acceptorless dehydrogenative coupling reactions of alcohols as sustainable reagents have received significant attention in recent years. To overcome the problems of product separation and catalyst reusability, several metal‐based heterogeneous catalysts have been reported to achieve these transformations with good yields and selectivity. In this Minireview, we summarize recent developments using both noble and non‐noble metal‐based heterogeneous catalysts to synthesize N‐heterocycles from alcohols and N‐nucleophiles via acceptorless dehydrogenation or borrowing hydrogen methodologies. Furthermore, this Minireview introduces strategies for the preparation and functionalization of the corresponding heterogeneous catalysts, discusses the reaction mechanisms and the roles of metal electronic states, and the influence of support Lewis acid–base properties on these reactions.

Recently, zeolitic imidazolate framework (ZIF)-derived metal/N-doped porous carbon nanocomposites (M@NCs) have emerged as a class of appealing heterogeneous catalysts applied in organic synthesis, and the striking features mainly involve low-cost...

A ZIF-derived hollow yolk–shell Co@CN catalyst is synthesized for the oxidative esterification of 5-hydroxymethylfurfural.

Cobalt nanoparticles embedded in N‐doped porous carbon (Co@CN) were prepared by the pyrolysis of bimetallic zeolitic imidazolate frameworks (BMZIFs) based on ZIF‐8 and ZIF‐67. The catalyst shows excellent catalytic efficiency in one‐pot selective oxidative cleavage of different linkages like β‐O‐4, a‐O‐4 and β‐1 in organosolv lignin and lignin model compounds in the presence of oxygen (ambient pressure) under mild conditions (383 K). Compared with traditional supported catalyst, the catalyst gives a highly hollow structure, which favored the adsorption of substrates and oxygen. The uniform cobalt nanoparticles surrounded by N‐doped graphitic structures and the strong electron transfer from graphitic nitrogen to Co NPs make it hard to be oxidized prior to use and higher catalytic reactivity. Moreover, the catalyst can be easily recovered by magnetic force after the reaction, and reused after reduction for five times without an obvious change in yields.

A metal-free oxidative dehydrogenation of N-heterocycles utilizing a nitrogen/phosphorus co-doped porous carbon (NPCH) catalyst is reported. The optimal material is robust against traditional poisoning agents and shows high antioxidant resistance....

A Co‐based heterogeneous catalyst supported on N,P co‐doped porous carbon (Co@NCP) is prepared via a facile in‐situ doping‐carbonization method. The Co@NCP composite features a large surface area, high pore volume, high‐density and strong basic sites. Furthermore, doping of P atoms can regulate the electronic density of Co. Therefore, Co@NCP exhibits good performance for the synthesis of quinoxalines from o‐nitroanilines and biomass‐derived diols under alkali‐free conditions.