Efficient Reduction of CO(2) to CO with High Current Density Using in Situ or ex Situ Prepared Bi-Based Materials

[Image: see text] The development of inexpensive electrocatalysts that can promote the reduction of CO(2) to CO with high selectivity, efficiency, and large current densities is an important step on the path to renewable production of liquid carbon-based fuels. While precious metals such as gold and silver have historically been the most active cathode materials for CO(2) reduction, the price of these materials precludes their use on the scale required for fuel production. Bismuth, by comparison, is an affordable and environmentally benign metal that shows promise for CO(2) conversion applications. In this work, we show that a bismuth–carbon monoxide evolving catalyst (Bi-CMEC) can be formed under either aqueous or nonaqueous conditions using versatile electrodeposition methods. In situ formation of this thin-film catalyst on an inexpensive carbon electrode using an organic soluble Bi(3+) precursor streamlines preparation of this material and generates a robust catalyst for CO(2) reduction. In the presence of appropriate imidazolium based ionic liquid promoters, the Bi-CMEC platform can selectively catalyze conversion of CO(2) to CO without the need for a costly supporting electrolyte. This inexpensive system can catalyze evolution of CO with current densities as high as j(CO) = 25–30 mA/cm(2) and attendant energy efficiencies of Φ(CO) ≈ 80% for the cathodic half reaction. These metrics highlight the efficiency of Bi-CMEC, since only noble metals have been previously shown to promote this fuel forming half reaction with such high energy efficiency. Moreover, the rate of CO production by Bi-CMEC ranges from approximately 0.1–0.5 mmol·cm(–2)·h(–1) at an applied overpotential of η ≈ 250 mV for a cathode with surface area equal to 1.0 cm(2). This CO evolution activity is much higher than that afforded by other non-noble metal cathode materials and distinguishes Bi-CMEC as a superior and inexpensive platform for electrochemical conversion of CO(2) to fuel.