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Nanostructured Cu-Sn Alloy for Actively and Selectively Converting CO2 to CO

Monday, 1 October 2018
Universal Ballroom (Expo Center)
W. Ju (Empa - Swiss Federal Laboratories for Materials Science), J. Zeng (Istituto Italiano di Tecnologia), D. Rentsch (Empa - Swiss Federal Laboratories for Materials Science), H. Ma (Empa – Swiss Federal Laboratories for Materials Science), M. Castellino, K. Bejtka, C. F. Pirri (Istituto Italiano di Tecnologia), U. F. Vogt (Empa – Swiss Federal Laboratories for Materials Science), and C. Battaglia (Empa - Swiss Federal Laboratories for Materials Science)
Many strategies have been proposed for carbon dioxide (CO2) reduction aiming to close the carbon cycle and compensate anthropogenic CO2 emissions. Electrochemical CO2 reduction has several advantages that it can be carried out under ambient conditions with water as the only additional feedstock, and electricity generated from renewable sources can be employed to achieve a fully sustainable route [1].

Copper (Cu) has unique features for electrochemically converting CO2 to a range of chemicals including hydrocarbons [2], but its selectivity for specific products is low. Especially, at a low or intermediate overpotential, the hydrogen evolution reaction (HER) dominates the overall process on polycrystalline Cu in aqueous solutions [3]. However, the selectivity of Cu can be tuned by introducing a secondary metal. Tin-modified nanostructured Cu (CuSn) electrocatalysts have been developed for electrochemically converting CO2 to carbon monoxide (CO). The doped Sn atoms in the topmost layer alloy with Cu, form a CuSn shell, and efficiently suppress the HER. By optimizing the Sn content in the CuSn layer and the nanostructure, the faradaic efficiency for CO reaches > 90 % at -0.7 V vs. RHE, and remains above 85 % in a wide potential range from -0.7 to -1.0 V [4]. However, the excellent selectivity for CO can be only observed at CuSn dendrites. When the CuSn catalyst has a particulate morphology, the selectivity for CO becomes much worse, even though the surface composition has the optimal Cu/Sn ratio. The CuSn particles are active for the HER at a low overpotential. Although the HER can be efficiently suppressed to a faradaic efficiency of less than 15 % at a high overpotential, the major products for CO2 reduction are both CO and formate (COOH-) [5]. This work highlights the importance of nanostructure and surface composition of CuSn catalysts for active and selective CO2 reduction.

Electrodes consisting of a three-dimensional porous architecture are prepared for a large active surface per unit geometric area. The CO production achieves a high partial current density of 4.9 mA·cm-2 at -0.8 V [4].

[1] Centi, G., et al. Energy Environ. Sci. 2013, 6, 1711-1731 [2] Qiao, J., et al., Chem. Soc. Rev. 2014, 43, 631-675 [3] Li, C., et al., J. Am. Chem. Soc. 2012, 134, 7231-4 [4] Zeng, J., et al., submitted [5] Ju, W., et al., in preparation