Mechanism of ethanol partial oxidation into syngas over catalysts based on mesoporous MgAl₂O₄ spinel loaded with fluorite PrCeZrO or spinel MnCr₂O₄ oxides and promoted by Ru + Ni was studied by in situ FTIRS and ¹⁸O SSITKA. Surface species (ethoxy, adsorbed ethanol, acetaldehyde, acetate, etc.) were identified and their thermal stability and reactivity were estimated. Analysis of kinetics of the ¹⁸O transfer into reaction products (CO, CO₂, CH₃CHO) allowed to estimate the rates of steps and present a scheme of the reaction mechanism including (1) fast CH₃CHO formation on mixed metal oxide sites; (2) rate-limiting stage of surface oxygen species incorporation into acetaldehyde or ethoxy species with C–C bond rupture yielding CO and CO₂ along with H₂ and H₂O; (3) water gas shift reaction by redox mechanism affecting CO/CO₂ ratio and their oxygen isotope fraction. Strong interaction of PrCeZrO or MnCr₂O₄ oxides with MgAl₂O₄ support results in decreasing constants of main reaction steps in comparison with those for catalysts based on bulk fluorite and spinel oxides, correlating with a higher surface oxygen bonding strength and its low coverage revealed by pulse microcalorimetry. DFT analysis confirmed a low energy barrier of the step of Ru–O oxygen incorporation into C–C bond of ethoxy species with its rupture explaining a higher syngas selectivity for Ru-doped catalysts.

通过原位FTIRS和¹⁸ O SSITKA研究了以Ru + Ni为助剂的萤石PrCeZrO或尖晶石MnCr ₂ O ₄氧化物负载介孔MgAl ₂ O ₄尖晶石在催化剂上乙醇部分氧化为合成气的机理。鉴定表面种类（乙氧基，吸附的乙醇，乙醛，乙酸盐等），并评估其热稳定性和反应性。分析¹⁸ O转移至反应产物（CO，CO ₂，CH ₃ CHO）的动力学，可以估算步骤的速率，并提出反应机理的方案，其中包括（1）快速CH ₃在混合金属氧化物位点上形成CHO；（2）表面氧物种掺入乙醛或乙氧基中的限速阶段，CC键断裂，产生CO和CO ₂以及H ₂和H ₂ O；（3）通过氧化还原机理的水煤气变换反应影响CO / CO ₂比及其氧同位素分数。PrCeZrO或MnCr ₂ O ₄氧化物与MgAl ₂ O _4的强相互作用与基于块状萤石和尖晶石氧化物的催化剂相比，该载体可降低主要反应步骤的常数，这与较高的表面氧键合强度和由脉冲量热法显示的低覆盖率有关。DFT分析证实了Ru–O氧掺入乙氧基的C–C键中的步骤具有较低的能垒，其破裂说明了掺Ru催化剂的合成气选择性更高。