Boosting electrocatalytic CO₂reduction reaction over viologen-functionalized metal–organic frameworks by enhancement of electron-transfer capacity

Abstract

Although the highly porous crystalline metal-organic frameworks (MOFs) are promising candidates to be active electrocatalysts for CO2 reduction reaction (CO2RR), but their poor electronic conductivities severely limited their applications. Viologen...

Robust {Cd2Zn}n–Organic Framework for Efficiently Catalyzing CO2 Cycloaddition and Knoevenagel Condensation

“…The found results summarized in Table exhibit that the combination of 0.3 mol % NUC-86a and 5 mol % n -Bu 4 NBr displays excellent catalytic efficiency for all selected epoxides with the reaction being nearly complete after 6 h. Overall, epoxides with non-hydrogen monoatomic groups and electron-absorbing groups (−CH 3 , −F, and −Cl) have higher reactivity than the ones with polyatomic substituents and electron-donating groups (−CHCH 2 , −CH 2 Cl, −CH 2 OCH 3 , and −Ph). Although the steric hindrance effect of the reactant molecules can be reduced due to the sufficiently large pore window, it can still be reflected in terms of the resulted yield, such as entries 8 and 9, which should be ascribed to the fact that the increased melting and boiling point due to large steric hindrance reduces the free vibration frequency of the epoxide molecules, which has a negative impact on the number of collisions at the active site. − In the meantime, the spectra of generated products are shown in Figures S10–S18. Taking the yield of styrene oxide as a reference, the catalytic activity of NUC-86a is comparable and even superior to that of most MOFs-based catalysts under normal or high-pressure conditions (Table S4), which should be ascribed to the fact that NUC-86a owns a satisfactory confined space environment such as enough pore window and sufficient active sites.…”

Ce/Zr-MOF with Dual Cycle Synergistic Catalysis Pathway Enabling Enhanced Peroxidase-like Performance for Wearable Hydrogel Patch Visualization Sensing Platform

“…The EIS plots of the as-prepared POD-like catalysts were obtained to elucidate the charge transfer process. With the incorporation of Ce, the Ce/Zr-MOF has a smaller radius than that of the Zr-MOF (Figure B), which means faster charge-transfer kinetics, indicating that the bimetallic MOF’s synergistic effect has increased conductivity and electron-transfer capability, both of which facilitate POD-like catalytic activity. , It is probable to suggest that the inherent and superior activity of Ce/Zr-MOF stems from its capacity to efficiently break down H 2 O 2 into ROS. To further comprehend the mechanism, the ROS has been investigated using an ESR with DMPO as the capture agent.…”

“…With the incorporation of Ce, the Ce/Zr-MOF has a smaller radius than that of the Zr-MOF (Figure 2B), which means faster chargetransfer kinetics, indicating that the bimetallic MOF's synergistic effect has increased conductivity and electrontransfer capability, both of which facilitate POD-like catalytic activity. 36,37 It is probable to suggest that the inherent and superior activity of Ce/Zr-MOF stems from its capacity to efficiently break down •− radicals. Ce/Zr-MOF's characteristic peak intensity is substantially higher than that of Ce-MOF, which means that the bimetallic synergistic effect expedites the Ce 3+ /Ce 4+ redox cycle and enhances catalytic activity.…”

Minireview and Perspectives of Bimetallic Metal–Organic Framework Electrocatalysts for Carbon Dioxide Reduction

“…To achieve CO 2 reduction at high current densities, unlike the above two reactors, a study has been conducted to achieve electrocatalytic CO 2 reduction at the amperometric level using the membrane electrode assembly (MEA) reactors, which is a breakthrough in the phase type. The MOF catalysts reported thus far have demonstrated the feasibility of being applied to MEA reactors, , but the optimal performance aspect remains an existing research gap for MOF catalysts.…”