Integration of Metal–Organic Frameworks and Metals: Synergy for Electrocatalysis

Abstract

Electrocatalysis is a highly promising technology widely used in clean energy conversion. There is a continuing need to develop advanced electrocatalysts to catalyze the critical electrochemical reactions. Integrating metal active species, including various metal nanostructures (NSs) and atomically dispersed metal sites (ADMSs), into metal–organic frameworks (MOFs) leads to the formation of promising heterogeneous electrocatalysts that take advantage of both components. Among them, MOFs can provide support and protection for the active sites on guest metals, and the resulting host‐guest interactions can synergistically enhance the electrocatalytic performance. In this review, three key concerns on MOF‐metal heterogeneous electrocatalysts regarding the catalytic sites, conductivity, and catalytic stability are first presented. Then, rational integration strategies of MOFs and metals, including the integration of metal NSs via surface anchoring, space confining, and MOF coating, as well as the integration of ADMSs either with the metal nodes/linkers or within the pores of MOFs, along with their recent progress on synergistic cooperation for specific electrochemical reactions are summarized. Finally, current challenges and possible solutions in applying these increasingly concerned electrocatalysts are also provided.

Unveiling the Electrocatalytic Activity of Cobaloxime Metallolinker in the UU-100(Co) Metal–Organic Framework toward the H2 Evolution Reaction: A DFT Study

“…Conversely, in our calculations, while we explained the Tafel slope using the Volmer–Tafel kinetic reaction pathway and a microkinetic model, it is crucial to acknowledge that the local environment of the active site in the linker may differ from that in the MOF. Also, the MOF structure may introduce cooperative effects or synergistic interactions among active sites that are not present in the isolated linker . Such cooperative effects can impact the overall catalytic activity and potentially lead to different kinetics.…”

“…Also, the MOF structure may introduce cooperative effects or synergistic interactions among active sites that are not present in the isolated linker. 84 Such cooperative effects can impact the overall catalytic activity and potentially lead to different kinetics. This led to the difference in the calculated values of the Tafel slope.…”

A review of metal–organic framework (MOF) materials as an effective photocatalyst for degradation of organic pollutants

“…Enhanced adsorption capacities result from the cooperative action of these forces, enabling the MOF–POM composite to capture and retain organic pollutants effectively. 219 Moreover, host–guest interactions influence the composite's photocatalytic activity by influencing charge transfer processes and the lifetime of photogenerated species. Therefore, a comprehensive understanding of these intricate interactions is paramount for harnessing the full potential of POM-based MOF hybrid materials in photocatalytic degradation and adsorption of organic pollutants.…”

(FeMnCe)-co-doped MOF-74 with significantly improved performance for overall water splitting

“…46 Thus, bimetallic or polymetallic catalysts usually show better catalytic performance than monometallic catalysts benefiting from the synergistic effect between different metals, 47,48 and the synergistic effect can achieve a catalytic effect of “1 + 1 > 2” due to the improved electron conductivity, reduced charge transfer resistance, and optimized surface adsorption capacity of reaction intermediates. 49,50 Previous results also have fully demonstrated that the synergistic effect of multiple metals can not only greatly boost their electrochemical performance due to their different coordination properties and preferences based on the hard–soft-acid–base (HSAB) theory, but also extend the application range of target materials.…”