Highly Efficient Cu‐Porphyrin‐Based Metal–Organic Framework Nanosheet as Cathode for High‐Rate Li‐CO₂ Battery

Abstract

The lithium‐carbon dioxide (Li‐CO2) battery as a novel metal‐air battery has a high specific energy density and unique CO2 conversion ability. However, its further development is limited by incomplete product decomposition resulting in poor cycling and rate performance. In this work, Cu‐tetra(4‐carboxyphenyl) porphyrin (Cu‐TCPP) nanosheets are prepared through the solvothermal method successfully. An efficient Li‐CO2 battery with Cu‐TCPP as catalyst achieves a high discharge capacity of 20393 mAh g−1 at 100 mA g−1, a long‐life cycle of 123 at 500 mA g−1, and a lower overpotential of 1.8 V at 2000 mA g−1. Density functional theory calculation reveals that Cu‐TCPP has higher adsorption energy of CO2 and Li2CO3 compared with TCPP, and a large number of electrons gather near the Cu‐N4 active sites in Cu‐TCPP. Therefore, the excellent CO2 capture ability of the porphyrin ligand and the synergic catalytic effect of Cu atom in Cu‐TCPP promote the thermodynamics and kinetics of CO2 reduction and evolution processes.

Recent Advances in Rechargeable Metal–CO2 Batteries with Nonaqueous Electrolytes

“…202 The dipole−quadrupole interaction between the metal sites in MOF and CO 2 provides active sites and reaction spaces for CO 2 chemical transformation. 203 Li et al studied transition metalbased eight porous MOFs (Mn 2 (bdc), Mn(dobdc), Mn-(C 2 H 2 N 3 ) 2 , Mn(HCOO) 2 , Cu(bdc), Co 2 (dobdc), Fe(bdc), and Ni 2 (dobdc); bdc = 1,4-benzenedicarboxylate, dobdc = 2,5dioxido-1,4-benzenedicarboxylate). However, they found that the Mn(II) metal centers are beneficial in reducing charging− discharging overpotential.…”

“…Although the stronger affinity toward CO 2 is good for CO 2 gas capture, endowing the Mn 2 (dobdc) MOF with higher maximum discharge capacity; but, at the same time, the stronger affinity hinders the CO 2 evolution during charging (following the equation: 2Li 2 CO 3 + C = 4Li + 3CO 2 ) from the Mn 2 (dobdc) MOF, abating Li 2 CO 3 decomposition and hence resulting in the increase in the charging voltage compared to its counterpart. 202 Xu et al 203 prepared Cu-tetra(4-carboxyphenyl) porphyrin (Cu-TCPP) MOF by solvothermal process and employed it as the catalytic cathode material for Li−CO 2 batteries. The active Cu sites in Copper-based porphyrin facilitate CO 2 reduction, and the π-conjugated bonds originating from the molecule structure of porphyrin are very conducive to CO 2 capture.…”

“…203 They prepared a slurry by mixing Cu-TCPP, PVDF, and super P in an 8:1:1 weight ratio and loaded the slurry on the carbon paper current collector, followed by vacuum drying at 70 °C (mass loading 0.2 mg). 203 TCPP and Cu-TCPP catalytic cathode-based Li−CO 2 batteries displayed deep discharge capacities of 15 979 mAh/g and 20 393 mAh/g, respectively, at 100 mA/g current density (Figure 16(i)). Regarding the discharging-charging overpotentials, the Cu-TCPP showed 1.21, 1.29, 1.41, 1.47, 1.61, 1.80, and 1.31 V at 100 mA/g, 200 mA/g, 400 mA/g, 500 mA/g, 1000 mA/g, 2000 mA/g, and again at 100 mA/g current densities, respectively.…”

A new honeycomb MOF for C2H4purification and C3H6enrichment by separating methanol to olefin products

“…[15][16][17][18][19] This specically leads to the unique pore shape/size and surface functionality in MOFs 20 and promotes their varied applications. [21][22][23][24][25][26][27][28] Typically, in gas adsorption and separation elds, many MOFs thus far have focused on separating C 2 or C 3 hydrocarbons from methane (C 1 ), which showed excellent performance and revealed promising application prospects. However, MOFs exhibiting efficient separation toward the MTO products of C 2 H 4 -C 3 H 6 mixtures have been reported only in a few MOFs.…”

Enhanced Photoassisted Li‐O2 Battery with Ce‐UiO‐66 Metal‐Organic Framework Based Photocathodes

“…Metal–organic frameworks (MOFs) have been considered as promising platforms for electrocatalytic reactions due to their hierarchical pore structures, tunable compositions, and well‐dispersed metal sites. [ 31–33 ] Various MOFs and their derivatives have been used to improve the kinetics of ORR and OER in the Li‐O 2 battery. [ 34,35 ] Very recently, Yu et al.…”