ICIQ

Abstract: The partial hydrogenation of propyne was studied over copper-based catalysts derived from Cu–Al hydrotalcite and malachite precursors and compared with supported systems (Cu/Al₂O₃ and Cu/SiO₂). The as-synthesized samples and the materials derived from calcination and reduction were characterized by XRF, XRD, TGA, TEM, N2 adsorption, H₂-TPR, XPS, and N₂O pulse chemisorption. Catalytic tests were carried out in a continuous flow-reactor at ambient pressure and 423–523 K using H₂:C₃H₄ ratios of 1–12 and were complemented by operando DRIFTS experiments. The propyne conversion and propene selectivity correlated with the copper dispersion, which varied with the type of precursor or support and the calcination and reduction temperatures. The highest exposed copper surface was attained on hydrotalcite-derived catalysts, which displayed C₃H₆ selectivity up to 80% at full C₃H₄ conversion and stable performance in long-run tests at T  473 K. Both activated Cu–Al hydrotalcites (this work) and Ni–Al hydrotalcites [S. Abelló, D. Verboekend, B. Bridier, J. Pérez-Ramírez, J. Catal. 259 (2008) 85] exhibited a relatively high alkene selectivity under optimal operation conditions, but they present a markedly distinctive catalytic behavior with respect to temperature and hydrogen-to-alkyne ratio. The product distribution was assigned through Density Functional Theory (DFT) simulations to the different stability of subsurface phases (carbides, hydrides) and the energies and barriers for the competing reaction mechanisms. The behavior of Cu in partial alkyne hydrogenation resembles that of Au nanoparticles, while Ni is closer to Pd.