• • The stoichiometric In2O3(110) surface (S-110) exhibits the optimal site for non-stoichiometric DMTM, with CH4 activation proceeding via polarization activation; this contrasts with reduced (R-110) and reoxidized (O2-R-110) surfaces that follow σ* and σ activation, respectively, directly impacting catalyst design by identifying S-110 as the most active phase for selective methanol synthesis.
• • The Mars-van Krevelen+Eley-Rideal route is kinetically favorable, as determined by energetic span model (ESM) analysis, with a low overoxidation tendency; this dual mechanism reduces the energy barrier for CH4 activation and minimizes CO2 formation, addressing the selectivity bottleneck that plagues conventional DMTM catalysts.
• • The binding ability of dual H atoms serves as a valid descriptor for reaction barriers and turnover frequency (TOF) on In2O3(110); this correlation enables predictive screening of catalyst modifications, as TOF values can be estimated from H binding energies, streamlining the optimization of In2O3-based catalysts for industrial DMTM.
• • Dynamic surface transformation S-110→R-110→O2-R-110 under reaction conditions leads to synchronous changes in CH4 activation mechanisms, with electron transfer patterns shifting from polarization to σ* to σ activation; this underscores the necessity of operando characterization to capture the active phase, as catalyst performance is highly sensitive to lattice oxygen availability and surface reduction state.