Modulating the Active Sites of VS2 by Mn Doping for Highly Selective CO2 Electroreduction to Methanol in a Flow Cell

Methanol is a valuable liquid C₁ product in CO₂ electroreduction (CO₂ER); however, it is hard to achieve high selectivity and a large current density simultaneously. In this work, we construct Mn²⁺-doped VS₂ multilayer nanowafers applied in a flow cell to yield methanol as a single liquid product to tackle this challenge. Mn doping adjusts the electronic structure of VS₂ and concurrently introduces sulfur vacancies, forming a critical *CO_B intermediate and facilitating its sequential hydrogenation to methanol. The optimal Mn_4.8%-VS₂ exhibits methanol Faradic efficiencies of more than 60% over a wide potential range of -0.4 to -0.8 V in a flow cell, of which the maximal value is 72.5 ± 1.1% at -0.6 V along with a partial current density of 74.3 ± 1.1 mA cm^-2. This work opens an avenue to rationally design catalysts for engineering C₁ intermediates toward CO₂ER to a single liquid methanol in a flow cell.