Oxide‐Encapsulated Silver Electrocatalysts for Selective and Stable Syngas Production from Reactive Carbon Capture Solutions

Electrolysis of bicarbonate‐containing CO2 capture solutions is a promising approach towards achieving low‐cost carbon‐neutral chemicals production. However, the parasitic bicarbonate‐mediated hydrogen evolution reaction (HER) and electrode instability in the presence of trace impurities remain major obstacles to overcome. This work demonstrates that the combined use of titanium dioxide (TiO2) overlayers with the chelating agent ethylene diamine tetra‐acetic acid (EDTA) significantly enhances the selectivity and stability of Ag‐based electrocatalysts for bicarbonate electrolysis. The amorphous TiO2 overlayers suppress the HER by over 50 % at potentials more negative than −0.7 V vs. RHE, increasing the CO faradaic efficiency (FE) by 33 % (relative). In situ surface‐enhanced Raman spectroscopy (SERS) measurements reveal the absence of near‐surface bicarbonate species and an abundance of CO2 reduction intermediates at the Ag|TiO2 buried interface, suggesting that the overlayers suppress HER by blocking bicarbonate ions from reaching the buried active sites. In accelerated degradation tests with 5 ppm of Fe(III) impurity, the addition of EDTA allows stable CO production with >47 % FE, while the electrodes rapidly deactivate in the absence of EDTA. This work highlights the use of TiO2 overlayers for enhancing the CO : H2 ratio while simultaneously protecting electrocatalysts from impurities likely to be present in “open” carbon capture systems. This work demonstrates a simple yet effect strategy to enhance CO selectivity and electrode stability using a titanium dioxide (TiO2) overlayer and a chelating agent ethylene diamine tetra‐acetic acid (EDTA). This strategy is ideally suited for the direct electrolysis of reactive CO2 capture solution towards carbon‐neutral chemicals production.