Enhanced methanol production via selective hydrogen utilization during CO2 hydrogenation over Co containing dual-atom doped oxide catalyst

Capturing hydrogen with CO2 to produce methanol is becoming increasingly intriguing. Renewable H2 is expensive and is currently produced in a limited amount. Therefore, selective utilization of H2 towards methanol formation, which has been paid little attention to, is necessary without being wasted towards side product formation. Here, we show that using Co containing dual-atom doped oxide (Co-Zn-ZrO2) catalyst H2 utilization can be selectively directed towards methanol formation and at the same time, H2 wastage can be minimized by suppressing competitive CO formation. Co-Zn-ZrO2 produced methanol with space time yield of 1.5 gMeOH h-1 gcat-1, which is one of the highest ever reported under industrially relevant conditions. In this catalyst, Co was responsible for CO2 activation and formate stabilization and made Zn free of formate poisoning, which helped in easy H2 dissociation promoting formate hydrogenation to methanol. When Co was replaced with other metals (for example: Pd, Ni and Cu), H2 utilization was promoted more towards CO formation than towards methanol formation decreasing methanol selectivity. This work represents the potential of Co containing dual-atom doped oxide catalyst for selectively utilizing H2 for methanol formation while identifying the underlying factor for controlling H2 utilization towards methanol or CO formation.