Abstract
The selective gas-phase oxidation of γ-picoline (γ-P) to isonicotinic acid (INA)—a key precursor for the anti-tuberculosis drug isoniazid—was investigated over a V–Mn oxide catalyst as a solvent-free, waste-minimizing alternative to conventional liquid-phase synthesis routes. XRD and Raman spectroscopy confirmed the formation of a stable manganese vanadate crystalline phase with a high concentration of terminal vanadyl groups (V=O), providing well-defined redox-active sites. Water vapour proved essential for sustainable process performance: at an optimal H2O/substrate molar ratio of 98, γ-picoline conversion reached 94.8% with INA selectivity of 86.5%, eliminating the need for hazardous solvents or additives. NH3-TPD and kinetic analysis revealed that water vapour acts as a competitive adsorbent at vanadium Lewis acid sites, accelerating target product desorption and suppressing deep oxidation to COx—directly reducing carbon waste. Long-term stability was assessed over 96 h of continuous operation: the 23.4% decline in specific surface area correlated with an equivalent reduction in total acidity, while pore diameter expansion from 2.07 to 3.25 nm mitigated diffusion limitations, partially compensating for deactivation. These findings establish the V–Mn oxide system as a promising green catalytic platform for upgrading petrochemical fractions into high-value pharmaceutical intermediates with reduced environmental impact.