Oxygen reduction reaction (ORR), oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) are three key reactions for the development of green and sustainable energy systems. Efficient electrocatalysts for these reactions are highly desired to lower their overpotentials and promote practical applications of related energy devices. Metal–organic frameworks (MOFs) have recently emerged as precursors to fabricate carbon-based electrocatalysts with high electrical conductivity and uniformly distributed active sites. In this review, the current progress of MOF-derived carbon-based materials for ORR/OER/HER electrocatalysis is presented. Materials design strategies of MOF-derived carbon-based materials are firstly summarized to show the rich possibilities of the morphology and composition of MOF-derived carbon-based materials. A wide range of applications based on these materials for ORR, OER, HER and multifunctional electrocatalysis are discussed, with an emphasis on the required features of MOF-derived carbon-based materials for the electrocatalysis of corresponding reactions. Finally, perspectives on the development of MOF-derived carbon-based materials for ORR, OER and HER electrocatalysis are provided.

MOF-derived electrocatalysts for oxygen reduction, oxygen evolution and hydrogen evolution reactions

Rationally designing an efficient and stable multifunctional electrocatalyst to replace the noble metal catalysts is extremely demanding but challenging. Herein, we develop a facile method to synthesis the defective nitrogen-doped graphene encapsulated metal nanoparticles by pyrolysis of graphene-supermolecule complexes. The obtained catalyst exhibits superior activities toward ORR (E1/2 = 0.864 V), OER (η =383 mV@10 mA/cm2) and HER (η = 193 mV@10 mA/cm2) in 0.1 M KOH solution. Equipping the materials into a rechargeable zinc-air battery produces a peak power density of 205 mW/cm2 and a cycle life of 667 h. It is found that formative M–Nx and defective N-doped graphene are the main origins of ORR activity while OER and HER activities are attributed to the defect-rich N-doped C and Co core. This finding provides insights to design electrocatalyst with both multifunctional catalytic activities and high stability.

Trifunctional Co nanoparticle confined in defect-rich nitrogen-doped graphene for rechargeable Zn-air battery with a long lifetime

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

Topological defects, with an asymmetric local electronic redistribution, are expected to locally tune the intrinsic catalytic activity of carbon materials. However, it is still challenging to deliberately create high-density homogeneous topological defects in carbon networks due to the high formation energy. Toward this end, an efficient NH3 thermal-treatment strategy is presented for thoroughly removing pyrrolic-N and pyridinic-N dopants from N-enriched porous carbon particles, to create high-density topological defects. The resultant topological defects are systematically investigated by near-edge X-ray absorption fine structure measurements and local density of states analysis, and the defect formation mechanism is revealed by reactive molecular dynamics simulations. Notably, the as-prepared porous carbon materials possess an enhanced electrocatalytic CO2 reduction performance, yielding a current density of 2.84 mA cm-2 with Faradaic efficiency of 95.2% for CO generation. Such a result is among the best performances reported for metal-free CO2 reduction electrocatalysts. Density functional theory calculations suggest that the edge pentagonal sites are the dominating active centers with the lowest free energy (ΔG) for CO2 reduction. This work not only presents deep insights for the defect engineering of carbon-based materials but also improves the understanding of electrocatalytic CO2 reduction on carbon defects.

Ammonia Thermal Treatment toward Topological Defects in Porous Carbon for Enhanced Carbon Dioxide Electroreduction.

Interface engineering is promising but still challenging for developing highly efficient and stable non-noble-metal-based electrocatalysts for water splitting. Herein, partially phosphidated core@shell Co@Co-P nanoparticles encapsulated in bamboo-like N, P co-doped carbon nanotubes (denoted as Part-Ph Co@Co-P@NPCNTs) are prepared through a pyrolysis-oxidation-phosphidation strategy. In this structure, each Co nanoparticle is covered with a thin Co-P layer to form a special core@shell heterojunction interface, and the core@shell structure is further encapsulated by N, P co-doped CNTs that not only protect the Co from corrosion but also guarantee an effective and fast electron transfer on cobalt phosphide. As a bifunctional catalyst for both the hydrogen evolution reaction and oxygen evolution reaction, it exhibits an excellent activity for overall water splitting, and enables long-term operation without significant degradation. Density functional theory calculations demonstrate that the interface of the Co/Co2 P heterojunction could lower the values of ΔGH * (hydrogen adsorption) and ΔGB (water dissociation), which are negatively correlated to the j10 , because of the electronic structures of up-shifted d-band center. This study not only presents an efficient and stable electrocatalyst for overall water splitting but also provides a special route for the interface engineering of heterostructures.

Interface Engineering of Partially Phosphidated Co@Co–P@NPCNTs for Highly Enhanced Electrochemical Overall Water Splitting

Graphene-based materials still exhibit poor electrocatalytic activities for the hydrogen evolution reaction (HER) although they are considered to be the most promising electrocatalysts. We fabricated a graphene-analogous material displaying exceptional activity towards the HER under acidic conditions with an overpotential (57 mV at 10 mA cm-2 ) and Tafel slope (44.6 mV dec-1 ) superior to previously reported graphene-based materials, and even comparable to the state-of-the art Pt/C catalyst. X-ray absorption near-edge structure (XANES) and solid-state NMR studies reveal that the distinct feature of its structure is dual graphitic-N doping in a six-membered carbon ring. Density functional theory (DFT) calculations show that the unique doped structure is beneficial for the activation of C-H bonds and to make the carbon atom bonded to two graphitic N atoms an active site for the HER.

Dual Graphitic-N Doping in a Six-Membered C-Ring of Graphene-Analogous Particles Enables an Efficient Electrocatalyst for the Hydrogen Evolution Reaction.

Wei Hu

Papers

Dual Graphitic-N Doping in a Six-Membered C-Ring of Graphene-Analogous Particles Enables an Efficient Electrocatalyst for the Hydrogen Evolution Reaction.