In situ encapsulated Co/MnOx nanoparticles inside quasi-MOF-74 for the higher alcohols synthesis from syngas

[Display omitted] •The Co/MnOx nanoparticles were in situ encapsulated within quasi-MOF-74 by controlled deligandation of CoMn-MOF-74.•Co/MnOx@quasi-MOF-74 core-shell catalyst showed 48.7 wt% of ROH selectivity, where of 93.2 wt% is C2+OH.•Very low CH4 and indetectable CO2 were produced during the reaction.•Co0, Co2+ and Co2C collaborate with each other to enhance C2+OH formation during the reaction. Selective conversion of syngas (CO/H2) to higher alcohols (C2+OH) is of great interest but presents a significant challenge in keeping an appropriate balance between the carbon chain growth and CO insertion to achieve a high C2+OH selectivity. Herein we found that a core-shell Co/MnOx@quasi-MOF-74 catalyst can be easily constructed through controlled deligandation of a bimetallic CoMn-MOF-74 by partial pyrolysis strategy. The as-obtained Co/MnOx@quasi-MOF-74 catalyst produces three types of synergistic active sites (Co°, coordinatively unsaturated sites (CUSs) of Co2+ and Co2C) that collaborate with each other to enhance C2+OH formation during the reaction. The Co° nanoparticles within the framework of quasi-MOF-74 enable CO dissociation and significant CHx-CHy coupling to occur while the uniformly distributed CUSs of Co2+ working with Co2C strengthen CO insertion process, leading an outstanding catalytic performance in the process of CO hydrogenation. The total selectivity of alcohols (ROH) reached 48.7 wt%, where of 93.2 wt% can be C2+OH, and very low CH4 and indetectable CO2 were produced at 200 °C, 3.0 MPa (CO/H2 = 1/2) and a gaseous hourly space velocity (GHSV) of 4500 mL g−1 h−1, reaching the catalytic performance comparable to that of the optimal level of multifunctional catalyst operated at much higher pressure (6.0 MPa). This work highlights the potential of using MOF-derived quasi-MOF materials as a tunable platform to explore highly efficient catalysts for syngas conversion.