Regulating and Stabilizing Strong Metal‐Support Interactions on Ni/TiO₂ by Crystal Phase for Ultra‐Stable Ethanol Reforming

Abstract The regulation and stabilization of strong metal‐support interactions (SMSI) in high temperature hydrogen‐rich reaction condition remains a huge challenge due to its structural sensitivity. Herein, tunable SMSI is constructed and stabilized on TiO 2 supported Ni catalysts by TiO 2 crystal phase engineering strategy, and then a SMSI‐degree‐depended ethanol stream reforming (ESR) performance is demonstrated. Rutile supported Ni exhibited a weakened SMSI with 48.6% coverage, exposing more metallic Ni and Ni‐TiO 2 perimeter interface sites, and displayed exceptional H 2 yield of 4.7 mol H2 /mol ethanol and an ultra‐long stability of 420 h without deactivation at 500 °C. The low reaction energy and high resistance to carbon deposition (0.9 mg c /g cat ·h) and Ni 0 sintering on Ni/r‐TiO 2 catalyst explained its excellent catalytic performance. Furthermore, the effect of well‐defined SMSI structures on the reaction pathway and deactivation mechanism of the ESR is clarified. This work provides a precedent for the tailor and application of SMSI in high temperature hydrogen‐rich reaction conditions.