Catalytic ethynylation of formaldehyde for selective propargyl alcohol production using the copper metal organic framework HKUST-1

Abstract

HKUST-1 with high crystallinity has been successfully synthesized using a solvothermal method with Cu(NO₃)₂·3H₂O as the copper source, 1,3,5-benzenetricarboxylic acid as the organic ligand, and N,N-dimethylformamide as the solvent. HKUST-1 exhibited a typical octahedral shape with a large number of micropores as well as possessed a high specific area and large porosity of 1488.03 cm² g⁻¹ and 0.774 cm³ g⁻¹, respectively. The catalytic performance of HKUST-1 in the formaldehyde ethynylation reaction was evaluated in detail. The experimental results showed that HKUST-1 showed a good catalytic performance, achieving formaldehyde conversion, propargyl alcohol (PA) yield and 1,4-butynediol (BYD) yield of 95.1%, 60.2%, and 1.6%, respectively. The adsorption equilibrium constants K_C of the products PA and BYD on HKUST-1 were calculated via adsorption calculation experiments to be 2.26 and 56.65, respectively, which theoretically verified that HKUST-1 is more favourable for the reaction to produce PA. The results of the reaction kinetics showed that the reaction of catalytic ethynylation of formaldehyde for selective propargyl alcohol production is first order for both formaldehyde and acetylene.