Predictive chemical kinetic modeling of CO2 conversion via Pt-catalyzed dry methane reforming

Dry reforming of methane (DRM) over Pt enables CO 2 conversion to syngas (H 2 /CO). We develop a fully automated, rule-based microkinetic model for Pt-catalyzed DRM (600–1300 K) and validate it against published fixed-bed reactor datasets spanning a wide range of temperatures (700–1100 K) and feed ratios. Sensitivity, flux, and surface-speciation analyses identify OCX, denoting CO adsorbed on a Pt surface site X, as a bottleneck intermediate mediating cooperative CH 4 /CO 2 activation. CO desorption ( ) has the largest negative sensitivity coefficient with respect to CH 4 concentration, i.e. faster CO removal most strongly promotes methane conversion, while OCX regeneration ( ) sustains surface saturation and suppresses conversion. Methane activates via sequential C − H scissions ( ); CO 2 proceeds predominantly via a hydrogen-mediated carboxyl route ( ). Three regimes emerge: (i) desorption-limited, OCX-saturated kinetics (790–980 K), (ii) site-liberating pathway activation (980–1100 K), and (iii) distributed control with carbon-management challenges (1100–1300 K). The predictive model reproduces conversions and syngas yields and offers design guidelines: promote CO removal without excessive OCX buildup and apply temperature-specific strategies to balance conversion and stability. To our knowledge, this is the first experimentally benchmarked, fully automated, rule-generated microkinetic model for Pt-catalyzed DRM, complementing prior DFT-based microkinetic studies. • Predictive microkinetic model for Pt-catalyzed dry reforming of methane (DRM). • Key surface intermediate (OCX) limits CH 4 and CO 2 activation and H 2 yield. • Hydrogen production trends explained across 700–1100 K with sensitivity analysis. • Three kinetic regimes identified, guiding energy-efficient reactor operation. • Mechanistic insights support catalyst design for clean H 2 and syngas generation.