In recent years, there are more and more researches on nitrogen-containing catalysts at home and abroad, and the application of nitrogen-containing catalysts in industry has become more and more mature. Currently, nitrogen-containing catalysts are mainly used as cathodic REDOX catalysts for direct methanol fuel cells (DMFC), or for oxygen reduction reactions (ORR) in electrochemistry. In the organic synthesis industry, amide catalysts are used for asymmetric synthesis.
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Common nitrogen-containing catalysts and their applications are listed below:
- Nitrogen doped carbon material: Similar to the atomic radius of C, N can be doped as an electron donor into the carbon material by substitution, which is helpful to improve the conductivity of carbon material, and can also increase the activity potential of adsorbing metal particles on the surface of carbon material, thus enhancing the interaction between metal particles and the material. Generally, nitrogen has three chemical forms in nitrogen-doped carbon materials: pyridinic-N；pyrrolic-N；and graphitic-N. The application of nitrogen-doped carbon materials in fuel cell electrocatalysis has two main aspects: as a non-noble metal oxygen reduction catalyst and as a carrier of noble metal catalyst.
Figure 1. Nitrogen doped carbon materials are used for ORR and OER
- New type of non-metal photocatalyst: In recent years, carbon nitride (C3N4) has been found to be a new type of visible light response catalyst. The g-C3N4 can be modified by morphological regulation and element doping, and a new type of non-metal photocatalyst with unique electronic structure and appropriate valence band position can be obtained. At the same time it has the advantages of high thermal stability and chemical stability as well as low cost and environmental protection. It has a broad prospect in the fields of photocatalytic decomposition of water and degradation of organic pollutants.
Figure 2.The g-C3N4 material can be used as a new type of non-metallic photocatalyst.
- Organic nitrogen containing small molecules: Organic nitrogen-containing small molecules have become a fast developing catalyst in recent years because they are easy to get raw materials, convenient to synthesize and environmentally friendly. Asymmetric Michael addition reaction is one of the classical methods to form c-c and c-n bonds. The asymmetric Michael addition reaction catalyzed by organic nitrogen-containing small molecules has become an effective method for the preparation of various pharmaceutical intermediates due to its advantages such as easy operation and no harsh conditions.
The organic nitrogen-containing small molecular catalysts that catalyze the addition of Michael are mainly divided into four categories: 1.L-proline and its salts; 2.derivatives of L-proline; 3. imidazoles; 4.thiourea.
- Chiral amides: In recent years, chiral quadrylamide, as a new kind of bifunctional chiral catalyst with good catalytic activity, has been widely concerned by organic chemists and has been successfully applied in many asymmetric catalytic reactions with high enantioselectivity. More and more novel optically active quadrylamide catalysts have been discovered and successfully applied to the asymmetric synthesis of many organic molecules, showing their great potential and application prospects in the field of organic chemistry.
- Covalent organic framework materials (COFs): Covalent organic framework polymer (COFs) is a crystalline material with ordered porous structure formed by reversible polymerization of light elements C, O, N, B, etc., connected by covalent bonds and controlled by thermodynamics.
COFs material has the advantages of high thermal stability and large specific surface area, and has a great application prospect in catalysis. It can introduce the catalytic site through the coordination metal of skeleton heteroatom, introduce the catalytic site through the derivation of a skeleton functional group, or introduce monomer into a functional group as the catalytic site.
Figure 3. Nitrogen containing covalent organic framework materials