Highly Selective Tandem Electrocatalytic and Thermocatalytic CO ₂ Reduction to Methanol Using Formic Acid as Intermediate

ABSTRACT Carbon capture and utilization (CCU) is a crucial strategy for mitigating emissions in industries that are challenging to defossilize. While methanol (MeOH) is a valuable chemical, its direct electroreduction from CO 2 (CO 2 RR) remains challenging due to low selectivity and Faradaic efficiency (FE). Here, we present a novel hybrid electro‐thermocatalytic tandem process that overcomes these limitations by coupling CO 2 electroreduction to formic acid (FA) with FA disproportionation to MeOH. The process employs a dendritic bismuth catalyst for highly selective CO 2 RR to FA (FE > 90%) in a flow cell, followed by FA disproportionation using an iridium‐based molecular catalyst under optimized acidic conditions (pH ≈ 0, 25 bar H 2 , 30°C). The thermocatalytic step achieves >90% selectivity and up to 80% yield of MeOH, even at low FA concentrations (1 M). Despite compatibility challenges between the alkaline CO 2 RR and acidic disproportionation steps, sequential coupling demonstrates an overall selectivity of ∼90% for CO 2 ‐to‐MeOH conversion. This work highlights the potential of hybrid processes for efficient CO 2 valorization; however, further optimization is necessary to enhance FA concentration and catalyst recyclability for industrial scalability.