Highly Efficient CO₂ Electroreduction on ZnN₄‐based Single‐Atom Catalyst

Abstract

The electrochemical reduction reaction of carbon dioxide (CO2RR) to carbon monoxide (CO) is the basis for the further synthesis of more complex carbon‐based fuels or attractive feedstock. Single‐atom catalysts have unique electronic and geometric structures with respect to their bulk counterparts, thus exhibiting unexpected catalytic activities. A nitrogen‐anchored Zn single‐atom catalyst is presented for CO formation from CO2RR with high catalytic activity (onset overpotential down to 24 mV), high selectivity (Faradaic efficiency for CO (FECO) up to 95 % at −0.43 V), remarkable durability (>75 h without decay of FECO), and large turnover frequency (TOF, up to 9969 h−1). Further experimental and DFT results indicate that the four‐nitrogen‐anchored Zn single atom (Zn‐N4) is the main active site for CO2RR with low free energy barrier for the formation of *COOH as the rate‐limiting step.

Engineering Local Coordination Environments of Atomically Dispersed and Heteroatom‐Coordinated Single Metal Site Electrocatalysts for Clean Energy‐Conversion

“…Other transition metal‐based SACs have also been developed for the CO 2 RR including ZnN 4 and MnN 4 Cl sites. Zhang et al demonstrated that the CO 2 RR activity of the MnN 4 moiety could be significantly improved through the introduction of external Cl ligands ( Figure 14 ).…”

Achieving tolerant CO2 electro-reduction catalyst in real water matrix

“…To date, many kinds of the state-of-the-art catalysts have been developed showing outstanding activities and selectivities, but their stabilities have been reported to be within hours or a maximum of hundred hours (Table S1). [5][6][7][8][9][10][11][12][17][18][19][22][23][24][25][26][27][28] To achieve high durability for practical application, the issue of deactivation of the metal catalyst should be first considered. However, no study has yet extensively focused on this issue.…”

Recent Advances in Atomic‐Level Engineering of Nanostructured Catalysts for Electrochemical CO2 Reduction

“…For the formation of CO, four‐nitrogen‐anchored Zn single atom is reported to display a low overpotential down to 24 mV and a FE up to 95% at −0.43 V due to the decreased free energy barrier of the formation of *COOH on Zn‐N 4 sites. [ 100 ] Very recently, Zhang et al developed halogen and nitrogen dual‐coordinated single Mn atom for ECR with a CO FE of 97% and current density of around 10 mA cm −2 at a low overpotential of 0.49 V. [ 101 ] Meanwhile, the (Cl, N)‐Mn/G catalyst exhibited an extremely high TOF of 38 347 h −1 at the overpotential of 0.49 V. The currently developed SACs mostly reduce CO 2 into formate and CO with high FEs over 90%, while the production of hydrocarbons is relatively difficult. Cu metal has been reported to be more active for hydrocarbon production than other metals.…”