Intermetallic PdZn Nanoparticles Catalyze the Continuous-flow Hydrogenation of Alkynols to Cis-enols
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Designing highly active and stable lead-free palladium-based catalysts without introducing surfactants and stabilizers is vital for large-scale and high-efficiency manufacturing of cis-enols via continuous-flow semi-hydrogenation of alkynols. Herein, we report an intermetallic PdZn/ZnO catalyst, designed by using the coupling strategy of strong electrostatic adsorption and reactive metal-support interaction, which can be used as a credible alternative to the commercial PdAg/AlO and Lindlar catalysts. Intermetallic PdZn nanoparticles with electron-poor active sites on a Pd/ZnO catalyst significantly boost the thermodynamic selectivity with respect to the mechanistic selectivity and therefore enhance the selectivity towards cis-enols. Based on in situ diffuse reflectance infrared Fourier-transform spectra as well as simulations, we identify that the preferential adsorption of alkynol over enol on PdZn nanoparticles suppresses the over-hydrogenation of enols. These results suggest the application of fine surface engineering technology in oxide-supported metal (particles) could tune the ensemble and ligand effects of metallic active sites and achieve directional hydrogenation in fine chemical synthesis.
Application of Metal-Based Catalysts for Semi-Hydrogenation of Alkynol: A Review.
Wang P, Ma Y, Shi Y, Duan F, Wang M Materials (Basel). 2023; 16(23).
PMID: 38068153 PMC: 10707398. DOI: 10.3390/ma16237409.