A method for preparing a formamide compound via hydrogenation of carbon dioxide catalyzed by porous materials, wherein a catalyst that is a porous organometallic polymer as shown in formula (V), and an organic amine compound, as shown in general formula (I), are reacted with carbon dioxide and hydrogen gas under an air atmosphere to form the formamide compound as shown in general formula (II);
- the method comprises the following steps:
- under the air atmosphere, adding the organic amine compound (I) and the catalyst (V) to a 125 mL autoclave, sealing the 125 mL autoclave, and charging the carbon dioxide and the hydrogen gas with a predetermined pressure to obtain a reaction system;
- placing the reaction system in an oil bath, and then stirring and heating the reaction system to perform a reaction at a predetermined reaction temperature for a predetermined reaction time;
- slowly releasing the pressure from the autoclave after cooling down, and obtaining the formamide compound by a distillation or a column separation;
- wherein a reaction formula is:
- wherein:
- R1 is selected from the group consisting of hydrogen, optionally substituted C1-C20 alkyl, optionally substituted C4-C10 cycloalkyl, optionally substituted C6-C24 aryl, optionally substituted C6-C24 heteroaryl, optionally substituted C7-C25 aryl alkyl, optionally substituted C7-C25 heteroaryl alkyl, —(CH2)n—OR3, and —(CH2)n—NR4R5, wherein n=1-8;
- R2 is selected from the group consisting of optionally substituted C1-C20 alkyl, optionally substituted C4-C10 cycloalkyl, optionally substituted C6-C24 aryl, optionally substituted C6-C24 heteroaryl, optionally substituted C7-C25 aryl alkyl, optionally substituted C7-C25 heteroaryl alkyl, —(CH2)n—OR3, and —(CH2)n—NR4R5, wherein n=1-8 and R1 and R2 are connected into the optionally substituted C4-C10 cycloalkyl;
- wherein R3, R4 and R5 are separately selected from the group consisting of hydrogen, optionally substituted C1-C20 alkyl, optionally substituted C6-C24 aryl, optionally substituted C7-C25 aryl alkyl, and optionally substituted C7-C25 heteroaryl, wherein R4 and R5 are connected into optionally substituted C3-C10 cycloalkyl;
- wherein substituted is selected from the group consisting of one or more hydrogens in the group substituted by a substituent selected from the group consisting of halogen, C1-C4 alkyl, C1-C4 halogenated alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, hydroxyl, amino, and sulfhydryl;
- the porous organometallic polymer as shown in general formula (V) is:
- wherein:
- =(hetero)aryl and functional group substituted (hetero)aryl;
- the N-heterocyclic carbene ligands are benzimidazolylidene, phenanthromidazolylidene, acenaphthoimidazolylidene, pyrenoimidazolylidene, or bibenzimidazolylidene ligands;
- X is selected from the group consisting of halogen anion, tetrafluoroborate, hexafluorophosphate, and hexafluoroantimonate;
- L is an auxiliary ligand, and the auxiliary ligand is selected from the group consisting of halogen, carbonyl, benzene ring, cyclopentene ring, cyclooctadiene, hydroxyl, water, carbonate, acetate, acetylacetone anion, and phosphine ligand;
- R1 and R2 are separately selected from the group consisting of chain alkane groups with a carbon number of 1-12, a cyclic alkane group, benzyl, and aryl with a carbon number of 5-7;
- the organic amine compound (I) is an organic primary amine compound or an organic secondary amine compound.