An Efficient and Practical System for the Synthesis of N , N ‐Dimethylformamide by CO 2 Hydrogenation using a Heterogeneous Ru Catalyst: From Batch to Continuous Flow

In the context of CO 2 utilization, a number of CO 2 conversion methods have been identified in laboratory‐scale research; however, only a very few transformations have been successfully scaled up and implemented industrially. The main bottleneck in realizing industrial application of these CO 2 conversions is the lack of industrially viable catalytic systems and the need for practically implementable process developments. In this study, a simple, highly efficient and recyclable ruthenium‐grafted bisphosphine‐based porous organic polymer (Ru@PP‐POP) catalyst has been developed for the hydrogenation of CO 2 to N , N ‐dimethylformamide, which affords a highest ever turnover number of 160 000 and an initial turnover frequency of 29 000 h −1 in a batch process. The catalyst is successfully applied in a trickle‐bed reactor and utilized in an industrially feasible continuous‐flow process with an excellent durability and productivity of 915 mmol h −1  g Ru −1 .