RESUMO
Regulating the local environment and structure of metal center coordinated by nitrogen ligands (M-N4 ) to accelerate overall reaction dynamics of the electrochemical CO2 reduction reaction (CO2 RR) has attracted extensive attention. Herein, we develop an axial traction strategy to optimize the electronic structure of the M-N4 moiety and construct atomically dispersed nickel sites coordinated with four nitrogen atoms and one axial oxygen atom, which are embedded within the carbon matrix (Ni-N4 -O/C). The Ni-N4 -O/C electrocatalyst exhibited excellent CO2 RR performance with a maximum CO Faradic efficiency (FE) close to 100 % at -0.9â V. The CO FE could be maintained above 90 % in a wide range of potential window from -0.5 to -1.1â V. The superior CO2 RR activity is due to the Ni-N4 -O active moiety composed of a Ni-N4 site with an additional oxygen atom that induces an axial traction effect.
RESUMO
Sn-based materials are identified as promising catalysts for the CO2 electroreduction (CO2RR) to formate (HCOO- ). However, their insufficient selectivity and activity remain grand challenges. A new type of SnO2 nanosheet with simultaneous N dopants and oxygen vacancies (VO -rich N-SnO2 NS) for promoting CO2 conversion to HCOO- is reported. Due to the likely synergistic effect of N dopant and VO , the VO -rich N-SnO2 NS exhibits high catalytic selectivity featured by an HCOO- Faradaic efficiency (FE) of 83% at -0.9 V and an FE of > 90% for all C1 products (HCOO- and CO) at a wide potential range from -0.9 to -1.2 V. Low coordination Sn-N moieties are the active sites with optimal electronic and geometric structures regulated by VO and N dopants. Theoretical calculations elucidate that the reaction free energy of HCOO* protonation is decreased on the VO -rich N-SnO2 NS, thus enhancing HCOO- selectivity. The weakened H* adsorption energy also inhibits the hydrogen evolution reaction, a dominant side reaction during the CO2RR. Furthermore, using the catalyst as the cathode, a spontaneous Galvanic Zn-CO2 cell and a solar-powered electrolysis process successfully demonstrated the efficient HCOO- generation through CO2 conversion and storage.