Preparation of an Unsupported Copper-Based Catalyst for Selective Hydrogenation of Acetylene from Cu2O Nanocubes

Designing cheap, earth-abundant, and nontoxic metal catalysts for acetylene hydrogenation is of pivotal importance, but challenging. Here, a nonprecious metal catalyst for selective hydrogenation of acetylene in excess ethylene was prepared from Cu₂O nanocubes. The preparation includes two steps: (1) thermal treatment in acetylene-containing gas at 160 °C and (2) hydrogen reduction at 180 °C. The resultant catalyst showed outstanding performance at low temperature (80-100 °C) and 0.1-0.5 MPa pressure, completely converting acetylene with a low selectivity to undesired ethane (<20%). The characterization results of high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy corroborated that the formation of an interstitial copper carbide (Cu_xC) might give rise to significantly enhanced hydrogenation activity. Preliminary density functional theory calculation demonstrated that the lattice spacing of Cu₃C was nearly identical to that of the new Cu_xC crystallite measured in HRTEM and determined by XRD. The calculated dissociation energy of hydrogen on Cu₃C(0001) was considerably lower than that on Cu(111), suggesting superior hydrogenation activity of Cu₃C(0001). It is experimentally verified that copper(I) acetylide (Cu₂C₂) might be the precursor of Cu_xC. Cu₂C₂ underwent partial hydrogenation to fabricate Cu_xC crystallites and the thermal decomposition to Cu and carbon materials in parallel.