Designing a highly active electrocatalyst with optimal stability at low cost is must and non-negotiable if large-scale implementations of fuel cells are to be fully realized. Zeolitic-imidazolate frameworks (ZIFs) offer rich platforms to design multifunctional materials due to their flexibility and ultrahigh surface area. Herein, an advanced Co-N x /C nanorod array derived from 3D ZIF nanocrystals with superior electrocatalytic activity and stability toward oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) compared to commercial Pt/C and IrO 2 , respectively, is synthesized. Remarkably, as a bifunctional catalyst (E j = 10 (OER) − E 1/2 (ORR) ≈ 0.65 V), it further displays high performance of Zn-air batteries with high cycling stability even at a high current density. Such supercatalytic properties are largely attributed to the synergistic effect of the chemical composition, high surface area, and abundant active sites of the nanorods. The activity origin is clarified through post oxygen reduction X-ray photoelectron spectroscopy analysis and density functional theory studies. Undoubtedly, this approach opens a new avenue to strategically design highly active and performance-oriented electrocatalytic materials for wider electrochemical energy applications.

Replacement of noble‐metal platinum catalysts with cheaper, operationally stable, and highly efficient electrocatalysts holds huge potential for large‐scale implementation of clean energy devices. Metal–organic frameworks (MOFs) and metal dichalcogenides (MDs) offer rich platforms for design of highly active electrocatalysts owing to their flexibility, ultrahigh surface area, hierarchical pore structures, and high catalytic activity. Herein, an advanced electrocatalyst based on a vertically aligned MoS2 nanosheet encapsulated Mo–N/C framework with interfacial Mo–N coupling centers is reported. The hybrid structure exhibits robust multifunctional electrocatalytic activity and stability toward the hydrogen evolution reaction, oxygen evolution reaction, and oxygen reduction reaction. Interestingly, it further displays high‐performance of Zn–air batteries as a cathode electrocatalyst with a high power density of ≈196.4 mW cm−2 and a voltaic efficiency of ≈63 % at 5 mA cm−2, as well as excellent cycling stability even after 48 h at 25 mA cm−2. Such outstanding electrocatalytic properties stem from the synergistic effect of the distinct chemical composition, the unique three‐phase active sites, and the hierarchical pore framework for fast mass transport. This work is expected to inspire the design of advanced and performance‐oriented MOF/MD hybrid‐based electrocatalysts for wider application in electrochemical energy devices.

Highly active, stable, and cheap Pt-free catalysts for the hydrogen evolution reaction (HER) are under increasing demand for future energy conversion systems. However, developing HER electrocatalysts with Pt-like activity that can function at all pH values still remains as a great challenge. Herein, based on our theoretical predictions, we design and synthesize a novel N,P dual-doped carbon-encapsulated ruthenium diphosphide (RuP @NPC) nanoparticle electrocatalyst for HER. Electrochemical tests reveal that, compared with the Pt/C catalyst, RuP @NPC not only has Pt-like HER activity with small overpotentials at 10 mA cm (38 mV in 0.5 m H SO , 57 mV in 1.0 m PBS and 52 mV in 1.0 m KOH), but demonstrates superior stability at all pH values, as well as 100 % Faradaic yields. Therefore, this work adds to the growing family of transition-metal phosphides/heteroatom-doped carbon heterostructures with advanced performance in HER.

Structural and compositional engineering of atomic-scaled metal-N-C catalysts is important yet challenging in boosting their performance for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Here, boron (B)-doped Co-N-C active sites confined in hierarchical porous carbon sheets (denoted as Co-N,B-CSs) were obtained by a soft template self-assembly pyrolysis method. Significantly, the introduced B element gives an electron-deficient site that can activate the electron transfer around the Co-N-C sites, strengthen the interaction with oxygenated species, and thus accelerate reaction kinetics in the 4e processed ORR and OER. As a result, the catalyst showed Pt-like ORR performance with a half-wave potential (E) of 0.83 V versus (vs) RHE, a limiting current density of about 5.66 mA cm, and higher durability (almost no decay after 5000 cycles) than Pt/C catalysts. Moreover, a rechargeable Zn-air battery device comprising this Co-N,B-CSs catalyst shows superior performance with an open-circuit potential of ∼1.4 V, a peak power density of ∼100.4 mW cm, as well as excellent durability (128 cycles for 14 h of operation). DFT calculations further demonstrated that the coupling of Co-N active sites with B atoms prefers to adsorb an O molecule in side-on mode and accelerates ORR kinetics.

A series of noble metal diphosphides (IrP2@NC, RhP2@NC and Pd5P2@NC) have been designed and fabricated, and among which IrP2@NC exhibits ultrahigh hydrogen evolution reaction performance.