Partial Hydrogenation of 2-Methyl-3-butyn-2-ol over Pd/ZnO: Effect of Reduction Temperature on Alloy Formation and Catalytic Response

We have investigated the catalytic effect of the β-phase PdZn alloy on selective gas-phase hydrogenation of 2-methyl-3-butyn-2-ol over Pd/ZnO using Pd/Al₂O₃ as a benchmark. Activation (in H₂) of Pd/ZnO to 973 K generated a β-phase PdZn alloy (from X-ray diffraction). Five intermediate samples with a modified surface PdZn/Pdᵟ⁻ mole ratio (based on X-ray photoelectron spectroscopy) but similar metal nanoparticle size (mean size = 6 nm from high-resolution scanning electron microscopy/scanning transmission electron microscopy) were generated by changing the final activation temperature between 403 and 973 K. Activation over the same temperature range increased metal nanoparticle size (6 → 10 nm) and lowered the surface Pdᵟ⁻ content in the Pd/Al₂O₃ samples. In each case, regardless of the activation temperature, greater selectivity to target 2-methyl-3-buten-2-ol (MBE) was observed over Pd/ZnO relative to Pd/Al₂O₃. Both catalysts delivered a similar activity/selectivity trend characterized by enhanced MBE selectivity and lower activity over the systems activated at a higher temperature. We associate this response with the formation of β-PdZn alloy and metal encapsulation that impacts on surface Pdᵟ⁻ in Pd/ZnO. Pd/ZnO outperformed an industrial Lindlar catalyst, Pd/CuO, and Au/Al₂O₃ in terms of selective transformation to MBE. Our results establish the beneficial effect of the PdZn alloy phase to promote the continuous production of commercially important alkenols.