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A new, self-assembled and self-healing class of recyclable heterogeneous Brønsted acid catalysts have been developed by mixing an aqueous solution of tetrasodium salt of tetraphenylmethane-tetrasulphonate (TPSM) and a salt of tetrakis(4-aminophenyl)methane. As a result, three-dimensional crystalline organic framework (F-2) was obtained, linked by hydrogen bonds and additionally stabilized by the opposite charges of the components (Fig. 1). The materials functioned as a new type of catalytically active Brønsted acid in a series of reactions, including the ring opening of epoxides and acetal formation reactions in organc solvents. F-2 was also proved to be an efficient media for stabilizing metal nanoparticles.