Manganese acting as a high-performance heterogeneous electrocatalyst in carbon dioxide reduction

Abstract

Developing highly efficient electrocatalysts based on cheap and earth-abundant metals for CO 2 reduction is of great importance. Here we demonstrate that the electrocatalytic activity of manganese-based heterogeneous catalyst can be significantly improved through halogen and nitrogen dual-coordination to modulate the electronic structure of manganese atom. Such an electrocatalyst for CO 2 reduction exhibits a maximum CO faradaic efficiency of 97% and high current density of ~10 mA cm −2 at a low overpotential of 0.49 V. Moreover, the turnover frequency can reach 38347 h −1 at overpotential of 0.49 V, which is the highest among the reported heterogeneous electrocatalysts for CO 2 reduction. In situ X-ray absorption experiment and density-functional theory calculation reveal the modified electronic structure of the active manganese site, on which the free energy barrier for intermediate formation is greatly reduced, thus resulting in a great improvement of CO 2 reduction performance.

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 ).…”

“…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 ). Cl‐coordinated MnN 4 ((Cl, N)‐Mn/G) was synthesized by the pyrolysis of MnCl 2 and ethylenediamine at 800 °C and the Cl‐free control sample (N‐Mn/G) was obtained by using Mn(NO 3 ) 2 as the precursor. The (Cl, N)‐Mn/G exhibited a higher CO 2 RR activity than N‐Mn/G with a maximum CO FE of 97% and a low overpotential of 0.49 V at 10 mA cm −2 (Figure b–d).…”

“…The purple, green, blue, red, white, and gray reprents Mn, Cl, N, O, H, and C atoms, respectively. Reproduced with permission . Copyright 2019, Nature Publishing Group.…”

Gas Diffusion Strategy for Inserting Atomic Iron Sites into Graphitized Carbon Supports for Unusually High‐Efficient CO2 Electroreduction and High‐Performance Zn–CO2 Batteries

“…From the XPS data in Table S2 (Supporting Information), the N/C ratio for samples in the Fe 1 NC/S 1 -Y series is inversely proportional to the thermal activation temperature, which is in sharp contrast to the proportional correlation between the CO 2 ER activity of Fe 1 NC/S 1 -Y series and thermal activation temperature Figure 3. a) FE CO and b) J CO of Fe 1 NC/S 1 -Y series and NC/S 1 -1000. c) FE CO of Fe 1 NC/S 1 -1000, highlighted by the shaded region, compared to that of other reported state-of-the-art nonprecious metal/N-doped carbon-based SACs with FE CO over 90%: Fe-N 5 , [28] Fe-N-C, [29] Co-N 2 , [30] Ni-NG, [31] NiN-GS, [32] Ni-N-Gr, [33] A-Ni-NSG, [34] Co-N 5 /HNPCSs, [35] COF-367-Co, [36] ZnN x /C, [37] (Cl,N)-Mn/G, [38] and AD-Sn/N-C 1000. [26] d) TOFs of Fe 1 NC/S 1 -1000 compared to that of other reported nonprecious metal/N-doped carbon-based SACs: Fe-N-C, [29] Fe 3+ -N-C, [25] Fe-N 5 , [28] Fe 0.5 d, [39] Co-N 2 , [30] A-Ni-NSG, [34] AD-Sn/N-C, [26] and Co-N 5 /HNPCSs.…”

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.…”