MOF-derived CuZn/NaY@C catalysts based on zeolite induced growth: construction of multi-defect centers in ethynylation of formaldehyde for 1,4-butynediol synthesis

Cu-based catalysts have attracted significant attention in the synthesis of highly valuable 1,4-butynediol via the coupling reaction between acetylene and formaldehyde, yet the development of highly stable catalysts remains a challenge. In this study, a novel carbon-zeolite hybrid-supported copper-based catalyst (CuZn/NaY@C) was successfully synthesized by a zeolite-induced one-pot homogeneous self-assembly method. By optimizing a series of preparation conditions, 5Cu5Zn/NaY@C-400 achieved a high yield of 86% and excellent selectivity of 96% for 1,4-butynediol (BYD). Furthermore, the catalyst maintained a yield of 73% and a selectivity of 90% after 100 h of continuous operation, with stability exceeding that of commercial catalysts. The apparent activation energy of 5Cu5Zn/NaY@C-400 is 27.5 kJ/mol equivalent to 28.6 kJ/mol of commercial catalysts, indicating its comparable reaction efficiency. Structural analysis of the catalyst, characterized by various techniques, shows that abundant carbon defects and oxygen vacancies in 5Cu5Zn/NaY@C-400 indirectly enhance C 2 H 2 adsorption and promote the formation of active Cu 2 C 2 intermediates. And the appropriate amount of acidic sites in the catalyst facilitates formaldehyde activation. Moreover, highly dispersed Cu 2+ located in the supercages of the NaY zeolite and the strong Cu-Zn interaction formed at the CuO-ZnO interface effectively stabilize Cu 2 C 2 during the reaction. This study provides novel strategies for the rational design of high-performance Cu-based catalysts applied in ethynylation of formaldehyde for 1,4-butynediol synthesis.