The Active Center of Co–N–C Electrocatalysts for the Selective Reduction of CO(2) to CO Using a Nafion-H Electrolyte in the Gas Phase

[Image: see text] To contribute a solution for the global warming problem, the selective electrochemical reduction of CO(2) to CO was studied in the gas phase using a [CO(2)(g), Co–N–C cathode | Nafion-H | Pt/C anode, H(2)/water] system without using carbonate solutions. The Co–N–C electrocatalysts were synthesized by partial pyrolysis of precursors in inert gas, which were prepared from various N-bidentate ligands, Co(NO(3))(2), and Ketjenblack (KB). The most active electrocatalyst was Co–(4,4′-dimethyl-2,2′-bipyridine)/KB pyrolyzed at 673 K, denoted Co–4,4′-dmbpy/KB(673K). A high performance of CO formation (331 μmol h(–1) cm(–2), 217 TOF h(–1)) at 0.020 A cm(–2) with 78% current efficiency was obtained at −0.75 V (SHE) and 273 K under strong acidic conditions of Nafion-H. Characterization studies using extended X-ray absorption fine structure (EXAFS), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy–energy-dispersive X-ray (TEM-EDX), X-ray diffraction (XRD), and temperature-programmed desorption with mass spectrometry (TPD-MS) indicated the active site as Co coordinated with four N atoms bonding the surface of KB, abbreviated Co–N(4)–C(x) structure. A model of the reduction mechanism of CO(2) on the active site was proposed.