Catalytic Role of Mg‐Al‐O Basic Centers in the Upgrade of Ethanol to n‐Butanol

The catalytic relevance of different surface functionalities present on hydrotalcite‐derived Mg−Al mixed metal oxides (MgAlO) are investigated in the context of ethanol upgrade to n‐butanol. The catalyst structure and active sites were altered through changes in the Mg/Al ratio and introduction of additional redox metal oxide functionalities. After performing a series of catalytic activity tests, operando FTIR characterization, TGA measurements and in situ active center titration; qualitative and quantitative relationships between catalyst structure and catalytic performance are obtained. We found the Mg−Al mixed metal oxides system can catalyze the ethanol to n‐butanol process through a Guerbet reaction pathway, though the process is kinetically limited. By introducing redox active metal oxides to the catalyst formulation, such as MoO 3 or V 2 O 5 , this problem can be partially solved, but at a cost of losing a significant fraction of high‐strength basic centers which are the most catalytically relevant function in the system, as they control enolate formation rates leading to the C−C coupling step required for n‐butanol formation.