Aluminum modulation of cobalt states in perovskite for higher alcohols synthesis from syngas

The catalytic synthesis of higher alcohols (HAS) from syngas is of great significance but remains profoundly challenging due to the difficulty in balancing C O cleavage, C C coupling and CO insertion. Herein, we integrate perovskite and spinel structures by doping Al into Ca 0.7 La 0.3 Ti 0.7 Co 0.3 O 3 , yielding catalysts with high selectivity for higher alcohols. The obtained Ca 0.7 La 0.3 Ti 0.7 Co 0.3 O 3 -Al x catalysts exhibit three synergistic active sites (Co 0 , Co δ+ , and oxygen vacancies) that promote C 2+ OH formation during the reaction process. Specifically, Co 0 active sites promote the dissociation of adsorbed CO and facilitate C C coupling, while Co δ+ active sites are closely associated with CO insertion. In addition, Al doping generates oxygen vacancies, and the Co Al interaction regulates both the electronic state of Co 0 surfaces and the relative abundance of Co δ+ active sites. Among the tested catalysts, Ca 0.7 La 0.3 Ti 0.7 Co 0.3 O 3 -Al 1.5 exhibited the best performance, achieving a total alcohol selectivity of 58.8%, C 2+ OH selectivity of 76.6 wt% and space-time yield (STY) of 4.3 mmol·g cat −1 ·h −1 . This work provides a potential strategy for designing catalysts for the synthesis of higher alcohols from syngas.