Metal‐Organic Framework‐Derived Non‐Precious Metal Nanocatalysts for Oxygen Reduction Reaction

Abstract

By virtue of diverse structures and tunable properties, metal‐organic frameworks (MOFs) have presented extensive applications including gas capture, energy storage, and catalysis. Recently, synthesis of MOFs and their derived nanomaterials provide an opportunity to obtain competent oxygen reduction reaction (ORR) electrocatalysts due to their large surface area, controllable composition and pore structure. This review starts with the introduction of MOFs and current challenges of ORR, followed by the discussion of MOF‐based non‐precious metal nanocatalysts (metal‐free and metal/metal oxide‐based carbonaceous materials) and their application in ORR electrocatalysis. Current issues in MOF‐derived ORR catalysts and some corresponding strategies in terms of composition and morphology to enhance their electrocatalytic performance are highlighted. In the last section, a perspective for future development of MOFs and their derivatives as catalysts for ORR is discussed.

Bimetallic Zeolitic Imidazolite Framework Derived Carbon Nanotubes Embedded with Co Nanoparticles for Efficient Bifunctional Oxygen Electrocatalyst

“…The current density in the CV (1.25-1.35 V vs RHE) potential window at different scan rates of 5-120 mV s −1 should be assigned to the charging of the double-layer ( Figure S18, Supporting Information). [23] Reasonably, the larger Cdl indicates more electroactive sites, which is in accordance with the introduction of carbon nanotubes and improved catalytic performance. The slope of the Cdl for Co@NC-3/1 was 5.09 mF cm −2 , which was much superior to that of the Co@NC-1/1 (3 mF cm −2 ), Co@NC-1/3 (1.17 mF cm −2 ), and Co@NC-1/0 (0.25 mF cm −2 ).…”

Porous Carbon‐Hosted Atomically Dispersed Iron–Nitrogen Moiety as Enhanced Electrocatalysts for Oxygen Reduction Reaction in a Wide Range of pH

“…The porous structures can not only provide more exposed active sites but facilitate mass‐transport for electrocatalytic reactions. As typical porous materials, metal–organic frameworks (MOFs), which are composed of well‐organized metal centers and organic ligands, are promising templates or precursors for porous nanomaterials in energy applications, including fuel cells, supercapacitors, and batteries . In addition to the large surface area, the composition of the resultant M–N–C catalysts can be easily controlled by substituting the metals or linkers.…”

N,P Co‐Coordinated Manganese Atoms in Mesoporous Carbon for Electrochemical Oxygen Reduction

“…However, the sluggish oxygen reduction reaction (ORR) has severely restrained the potential commercialization of fuel cells, which requires the usage of expensive and fuel‐vulnerable platinum (Pt) based catalysts. Therefore, numerous carbon‐based nanomaterials have been developed to replace the Pt based composites . Among them, the nitrogen species coordinated first‐row transition metal (e.g., Co, Ni, and Fe) atoms in carbons (M–N–C) are widely considered as promising electrocatalysts for ORR .…”

“…It has been reported previously that Fe–N–C and Co–N–C catalysts can exhibit comparable ORR activity to the commercial platinum‐supported carbon (Pt/C) catalyst in alkaline electrolytes . The remarkable ORR performance is generally resulted from the active N‐coupled metal centers, in which the N‐coordination tunes the electronic structure of metal atoms and thus modifies proper interaction with oxygen molecules adsorption as well as dissociation . Nevertheless, compared with Fe–N–C and Co–N–C, Mn–N–C materials have been less studied for cathodic ORR, due to their inferior activity .…”