Attenuating metal-substrate conjugation in atomically dispersed nickel catalysts for electroreduction of CO2 to CO.

Atomically dispersed transition metals on carbon-based aromatic substrates are an emerging class of electrocatalysts for the electroreduction of CO2. However, electron delocalization of the metal site with the carbon support via d-π conjugation strongly hinders CO2 activation at the active metal centers. Herein, we introduce a strategy to attenuate the d-π conjugation at single Ni atomic sites by functionalizing the support with cyano moieties. In situ attenuated total reflection infrared spectroscopy and theoretical calculations demonstrate that this strategy increases the electron density around the metal centers and facilitates CO2 activation. As a result, for the electroreduction of CO2 to CO in aqueous KHCO3 electrolyte, the cyano-modified catalyst exhibits a turnover frequency of ~22,000 per hour at -1.178 V versus the reversible hydrogen electrode (RHE) and maintains a Faradaic efficiency (FE) above 90% even with a CO2 concentration of only 30% in an H-type cell. In a flow cell under pure CO2 at -0.93 V versus RHE the cyano-modified catalyst enables a current density of -300 mA/cm2 with a FE above 90%.

Iron phthalocyanine with coordination induced electronic localization to boost oxygen reduction reaction.

Iron phthalocyanine (FePc) is a promising non-precious catalyst for the oxygen reduction reaction (ORR). Unfortunately, FePc with plane-symmetric FeN4 site usually exhibits an unsatisfactory ORR activity due to its poor O2 adsorption and activation. Here, we report an axial Fe-O coordination induced electronic localization strategy to improve its O2 adsorption, activation and thus the ORR performance. Theoretical calculations indicate that the Fe-O coordination evokes the electronic localization among the axial direction of O-FeN4 sites to enhance O2 adsorption and activation. To realize this speculation, FePc is coordinated with an oxidized carbon. Synchrotron X-ray absorption and Mössbauer spectra validate Fe-O coordination between FePc and carbon. The obtained catalyst exhibits fast kinetics for O2 adsorption and activation with an ultralow Tafel slope of 27.5 mV dec-1 and a remarkable half-wave potential of 0.90 V. This work offers a new strategy to regulate catalytic sites for better performance.