Enhancing Low-Temperature Syngas Production via Surface Tailoring of Supported Intermetallic Nanocatalysts

An active and coke-resistant silica-encapsulated intermetallic Ni3Zn nanoparticle catalyst was developed for low-temperature (450 °C) dry reforming of methane (DRM). The catalyst exhibited a remarkable 4-fold increase in activity (4.5 s–1) with over 99% CO selectivity and 3 orders of magnitude less carbonaceous species and demonstrated remarkable stability (70 h) compared to that of a monometallic Ni catalyst. The key is the combined effect of surface ensemble structure and electronic interaction modulation through the surface composition tailoring achieved by off-stoichiometric Ni and Zn loading in controlling surface chemistry for achieving different activities and H2/CO ratios. Characterized by ion spectroscopy, X-ray photoelectron spectroscopy, and the neutron pair distribution function, it was revealed that paired Niδ−–Znδ+ active sites are crucial for DRM. Transient infrared spectroscopy and isotopic analysis uncovered the synergistic effect of Niδ−–Znδ+ sites in activating C–H bonds and dissociating CO2 to prevent coke formation under low-temperature conditions.