▎ 摘　　要

NOVELTY - A porous crystalline three dimensional covalent organic frameworks (COFs) hybrid composites comprises graphene or carbon nanotube incorporated into the covalent organic frameworks containing an aldehyde and an azo amine. USE - Porous crystalline three dimensional covalent organic frameworks (COFs) hybrid composites used for methane storage (claimed). ADVANTAGE - The three dimensional covalent organic frameworks hybrid composites has excellent high surface area for methane storage of 2400 m2/g or more at low cost, and has exceptional chemical stability. DETAILED DESCRIPTION - An INDEPENDENT CLAIM is included for synthesis of porous crystalline three dimensional COF hybrid composite, which involves mixing para-toluene sulfonic acid monohydrate (PTSAH20) with an aldehyde and an azo amine under moist free condition followed by grinding the mixture, adding graphene or carbon nanotubes to the mixture of and heating the mass at 70-100 degrees C obtaining porous composite covalent organic frameworks, and washing the porous composite covalent organic frameworks with water, nitrogen, N,N-dimethylacetamide, hot water, and finally with acetone, and drying the sample obtaining crystalline porous composite dimethyl acetamide, hot water, and finally with acetone, followed by drying the sample.