Electrocatalysts play critical roles in electrochemical energy storage and conversion technologies such as fuel cells, metal–air batteries, and H₂O/CO₂/N₂ electrolysis. Recently, metal–organic framework (MOF)-derived electrocatalysts have been extensively explored not only because of their superior electrocatalytic activities but also their well-defined active sites, particularly those of single-atom active sites, which have been recognized as role-model electrocatalysts for fundamental understanding of the catalytic mechanisms at both the molecular and electronic levels. In this paper, we have reviewed the recent progress in MOF-derived electrocatalysts with focus on the characterization of the catalytically active sites, their functional mechanisms and performance validation/optimization of the oxygen reduction reaction (ORR), oxygen evolution reaction (OER), hydrogen evolution reaction (HER), carbon dioxide reduction reaction (CO₂RR), and nitrogen reduction reaction (NRR). Regarding the synthesis of the electrocatalysts with active sites, the alloy and composite formation and the edge-defect/oxygen vacancy engineering are discussed. Regarding the characterization for fundamental understanding, some advanced in situ/ex situ characterization and theoretical calculations using first-principles Density Functional Theory (DFT) are summarized. Some technical challenges are analyzed and the corresponding further research directions for overcoming the challenges are also proposed for future research and development of practicable MOF-derived electrocatalysts.

Although lithium (Li) and sodium (Na) metals can be selected as the promising anode materials for next‐generation rechargeable batteries of high energy density, their practical applications are greatly restricted by the uncontrollable dendrite growth. Herein, a platinum (Pt)–copper (Cu) alloy‐coated Cu foam (Pt–Cu foam) is prepared and then used as the substrate for Li and Na metal anodes. Owing to the ultrarough morphology with a three‐dimensional porous structure and the quite large surface area as well as lithiophilicity and sodiophilicity, both Li and Na dendrite growths are significantly suppressed on the substrate. Moreover, during Li plating, the lithiated Pt atoms can dissolve into Li phase, leaving a lot of microsized holes on the substrate. During Na plating, although the sodiated Pt atoms cannot dissolve into Na phase, the sodiation of Pt atoms elevates many microsized blocks above the current collector. Either the holes or the voids on the surface of Pt–Cu foam what can be extra place for deposited alkali metal, what effectively relaxes the internal stress caused by the volume exchange during Li and Na plating/stripping. Therefore, the symmetric batteries of Li@Pt–Cu foam and Na@Pt–Cu foam have both achieved long‐term cycling stability even at ultrahigh areal capacity at 20 mAh cm⁻².

In this work, a trace amount of acid-treated multi-walled carbon nanotubes (a-MWCNTs) is introduced into the negative active materials (NAMs) of a lead acid battery (LAB) by simply dispersing a-MWCNTs in the water, which is then added into the dry mixture of lead oxide powder, expanders and carbon black for lead paste preparation. The abundant oxygen-containing groups on the a-MWCNTs show significant influence on the chemical reactions happening during the curing process, leading to the improved properties of NAMs. Specifically, after formation, the NAMs containing 100 ppm a-MWCNTs display a spongy-like structure comprised of interconnected domino-like Pb slices, giving favorable porosity and electroactive surface area of the NAMs. Moreover, the quasi-rod structure of Pb slices provides the channels for fast electron transfer. These two features greatly accelerate the electrochemical reaction between Pb and PbSO₄, and hence hinder the accumulation of PbSO₄ crystals. As a result, the high-rate partial-state-of-charge (HRPSoC) cycle-life of the simulated cell constructed from the a-MWCNTs-containing negative plate achieves a HRPSoC cycle-life more than 1.5 times longer than the cell constructed when the negative plate contains only carbon black. Since our method is of great convenience and low-cost, it is expected to have a great feasibility in the LAB industry.

Layered double hydroxide (LDH) catalysts provide promising OER activity which can be employed in overall water splitting for hydrogen production. However, their weak surface hydrogen adsorption (H_ad) and high water dissociation energy can result in the inferior hydrogen evolution reactions (HER) activity. In this paper, a highly efficient HER catalyst of F-doped NiCoMo LDH is successfully designed and synthesized through in situ growing on nickel foam (F-NiCoMo LDH/NF) for overall water splitting. DFT calculations demonstrate that the introduction of Mo and F atoms in NiCo LDH can induce the generation of anisotropic lattice strain, resulting in the generation of high-energy active interface and shifting the d-band centers. Therefore, the adsorption energy of H_ad is optimized and the water dissociation energy barrier is decreased. As a result, this F-NiCoMo LDH/NF catalyst electrode displays a low overpotential of 107.5 mV at 10 mA cm⁻² and a small Tafel slope of 67.2 mV dec⁻¹ for HER. The assembled electrolyzer by employing this catalyst electrode requires only 1.83 V to deliver 300 mA cm⁻² and operates stably for 100 h.

Graphene-based composites have been widely explored for electrode and electrocatalyst materials for electrochemical energy systems. In this paper, a novel composite material of the reduced graphene oxide nanosheets (rGON) with gold nanoparticles (NPs) (rGON-AuNP) is synthesized, and its morphology, structure, and composition are characterized by scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), energy dispersive X-ray (EDX), Fourier transform infrared spectroscopic (FTIR), Raman, and UV-Vis techniques. To confirm this material’s electrochemical activity, a glucose oxidase (GOD) is chosen as the target reagent to modify the rGON-AuNP layer to form GOD/rGON-AuNP/glassy carbon (GC) electrode. Two pairs of distinguishable redox peaks, corresponding to the redox processes of two different conformational GOD on AuNP, are observed on the cyclic voltammograms of GOD/rGON-AuNP/GC electrode. Both cyclic voltammetry and electrochemical impedance spectroscopy are employed to study the mechanism of direct electron transfer from GOD to GC electrode on the rGON-AuNP layer. In addition, this GOD/rGON-AuNP/GC electrode shows catalytic activity toward glucose oxidation reaction.