The oxygen evolution reaction (OER) is a critical electrochemical reaction in water splitting and rechargeable metal–air batteries. It plays a pivotal role in achieving high-efficiency clean-energy production and energy storage in these devices. Transition metal-based bimetallic MOFs (TMB MOFs) with two different metal ions possess specific synergistic effects, which could exhibit OER performance and stability superior to those of the corresponding monometallic MOFs for water oxidation. Benefiting from the diversity of chemical composition and structural type, TMB MOFs can also serve as precursors and templates to obtain alloy-particle-decorated carbon materials with high surface area, or metal compounds such as bimetallic sulfides, phosphides, and hydroxides with atomic-level mixing of heterometallic elements. These materials with high-density active sites exhibit much improved catalytic activity in the water oxidation reaction. This article aims to review the recent progress with TMB MOFs and their derivatives in relation to applications as electrocatalysts in OER, including analysis of the mechanism of the OER process with the assistance of DFT calculations and in situ or operando techniques.

Transition metal-based bimetallic MOFs and MOF-derived catalysts for electrochemical oxygen evolution reaction

Rechargeable Zn-air batteries are under intensive studies because of their high-energy density, low cost, and safety. However, their wide application is prevented by several remaining technical issues, one of which is the lack of suitable bifunctional cathodic catalysts for oxygen reduction reaction (ORR) during discharging and oxygen evolution reaction (OER) during charging. Due to low material cost and wide distribution, carbon-based materials may serve as promising electrocatalysts, while doping heteroatoms such as nitrogen or boron can effectively enhance their catalytic activity. Herein, we pyrolyze a metal-organic framework containing Zn, N, and B as the precursor to synthesize dual-doped and metal-free porous carbon materials as efficient ORR/OER bifunctional electrocatalysts. The surface area of obtained carbon materials can be greatly enhanced by pyrolysis under H 2 -containing atmosphere. In addition, N and B are evenly distributed within the carbon materials due to the crystalline MOF precursor. The resultant carbon materials exhibit high ORR and OER catalytic activities in both half-cell and single-cell battery measurements. Our study has demonstrated for the first time that MOFs can be used as precursors to synthesize metal-free ORR/OER bifunctional cathodic electrocatalysts with great potential in rechargeable Zn-air batteries.

A metal-free ORR/OER bifunctional electrocatalyst derived from metal-organic frameworks for rechargeable Zn-Air batteries

Applications of metal–organic framework-derived materials in fuel cells and metal-air batteries

Hierarchical magnetic-dielectric composites are promising functional materials with prospective applications in microwave absorption (MA) field. Herein, a three-dimension hierarchical “nanotubes on microrods,” core–shell magnetic metal–carbon composite is rationally constructed for the first time via a fast metal–organic frameworks-based ligand exchange strategy followed by a carbonization treatment with melamine. Abundant magnetic CoFe nanoparticles are embedded within one-dimensional graphitized carbon/carbon nanotubes supported on micro-scale Mo2N rod (Mo2N@CoFe@C/CNT), constructing a special multi-dimension hierarchical MA material. Ligand exchange reaction is found to determine the formation of hierarchical magnetic-dielectric composite, which is assembled by dielectric Mo2N as core and spatially dispersed CoFe nanoparticles within C/CNTs as shell. Mo2N@CoFe@C/CNT composites exhibit superior MA performance with maximum reflection loss of − 53.5 dB at 2 mm thickness and show a broad effective absorption bandwidth of 5.0 GHz. The Mo2N@CoFe@C/CNT composites hold the following advantages: (1) hierarchical core–shell structure offers plentiful of heterojunction interfaces and triggers interfacial polarization, (2) unique electronic migration/hop paths in the graphitized C/CNTs and Mo2N rod facilitate conductive loss, (3) highly dispersed magnetic CoFe nanoparticles within “tubes on rods” matrix build multi-scale magnetic coupling network and reinforce magnetic response capability, confirmed by the off-axis electron holography.

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Hierarchical Magnetic Network Constructed by CoFe Nanoparticles Suspended Within "Tubes on Rods" Matrix Toward Enhanced Microwave Absorption.

Since the discovery of N-doped carbon nanotubes as the first carbon-based metal-free electrocatalyst (C-MFEC) for oxygen reduction reaction (ORR) in 2009, C-MFECs have shown multifunctional electrocatalytic activities for many reactions beyond ORR, such as oxygen evolution reaction (OER), hydrogen evolution reaction (HER), carbon dioxide reduction reaction (CO2RR), nitrogen reduction reaction (NRR), and hydrogen peroxide production reaction (H2O2PR). Consequently, C-MFECs have attracted a great deal of interest for various applications, including metal–air batteries, water splitting devices, regenerative fuel cells, solar cells, fuel and chemical production, water purification, to mention a few. By altering the electronic configuration and/or modulating their spin angular momentum, both heteroatom(s) doping and structural defects (e.g., atomic vacancy, edge) have been demonstrated to create catalytic active sites in the skeleton of graphitic carbon materials. Although certain C-MFECs have been made to be comparable to or even better than their counterparts based on noble metals, transition metals and/or their hybrids, further research and development are necessary in order to translate C-MFECs for practical applications. In this article, we present a timely and comprehensive, but critical, review on recent advancements in the field of C-MFECs within the past five years or so by discussing various types of electrocatalytic reactions catalyzed by C-MFECs. An emphasis is given to potential applications of C-MFECs for energy conversion and storage. The structure–property relationship for and mechanistic understanding of C-MFECs will also be discussed, along with the current challenges and future perspectives.

Carbon-based metal-free electrocatalysts: from oxygen reduction to multifunctional electrocatalysis

Low-price, high-performance and strong-stability electrocatalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are highly significant in the application of clean energy d...

Electrospun MOF-Based FeCo Nanoparticles Embedded in Nitrogen-Doped Mesoporous Carbon Nanofibers as an Efficient Bifunctional Catalyst for Oxygen Reduction and Oxygen Evolution Reactions in Zinc-Air Batteries

Nitrogen-doped carbon materials are promising oxygen reduction reaction (ORR) electrocatalysts owing to high performance and stability. Herein, a three-dimensional porous bio-MOF-1, Zn8(Ad)4(Bpdc)6O·2Me2NH2 (Ad = adeninate; Bpdc = biphenyldicarboxylate), was used as precursor to fabricate N-doped porous carbon materials (NPC-1000-ts, where 1000 stands for the carbonization temperature and t represents the carbonization time, t = 2, 3 and 4 h) by simple carbonization under Ar atmosphere. The porous carbon materials had different contents of graphitic N and graphitization degrees of carbon. The catalytic activities of NPCs as metal-free ORR electrocatalysts were studied. The obtained NPC-1000-4 (pyrolysis under 1000 °C for 4 h) displayed outstanding ORR performance, with a positive onset potential (−0.012 V), a higher half-wave potential (E1/2) (−0.13 V) and a larger limiting current density (−5.76 mA/cm2) at −0.8 V (vs. Ag/AgCl) in KOH solution (0.1 M) than those of commercial Pt/C (20 wt%) catalyst (Eonset = −0.014 V, E1/2 = −0.14 V and −5.08 mA/cm2 at −0.8 V vs. Ag/AgCl). Obviously, the onset potential of NPC-1000-4 surpassed that of Pt/C, which was rare among currently available studies on metal-free nitrogen-doped porous carbon materials. Graphitic N significantly affected ORR catalytic performance besides graphitization degree of carbon. Meanwhile, NPC-1000-4 allowed an effective 4e−-dominant ORR process, and most importantly, coupled with much higher long-term stability (89.5%) than that of commercial Pt/C (20 wt%, 65.8%) catalyst and higher resistance to methanol poisoning. The remarkable ORR activity of NPC-1000-4 can be ascribed to large surface area, considerable hierarchical porosity, high graphitization degree and synergism between enriched active sites and high portion of graphitic N. Overall, the findings guide the development of MOF-derived metal-free N-doped carbon materials as high-activity non-precious electrocatalysts for ORR.

Metal-organic framework-derived metal-free highly graphitized nitrogen-doped porous carbon with a hierarchical porous structure as an efficient and stable electrocatalyst for oxygen reduction reaction.

Lijuan Yang

Papers

Electrospun MOF-Based FeCo Nanoparticles Embedded in Nitrogen-Doped Mesoporous Carbon Nanofibers as an Efficient Bifunctional Catalyst for Oxygen Reduction and Oxygen Evolution Reactions in Zinc-Air Batteries

Metal-organic framework-derived metal-free highly graphitized nitrogen-doped porous carbon with a hierarchical porous structure as an efficient and stable electrocatalyst for oxygen reduction reaction.

Efficient ORR activity of N-doped porous carbon encapsulated cobalt electrocatalyst derived from a novel bimetal-organic framework