materials, [2] and their coupled composites. [3] Among them, TM singleatom catalysts (SACs) have recently emerged as a new type of frontier materials with high activity, stability, and selectivity, rendering the great potential for diverse catalytic systems. [4] The unique electronic structure, maximized atomutilization efficiency, and unsaturated coordination bonds of the active centers in SACs contribute to the enhanced performance. [5] Moreover, recent investigations have demonstrated that the introduction of secondary metal atoms can further enhance the activity of SACs, indicating the promising development of dual-metal SACs. [6] Nevertheless, on the one hand, there is a serious lack of effective strategies to achieve the atomic control of targeted reactive sites comprising binary metal atoms; on the other hand, the identification of the diatomic structure in dual-metal SACs and the deeper functional mechanism of bimetallic atoms for synergistic catalysis are still in their infancy.Owing to the increasing concerns from energy and environmental issues, growing attention has been paid on developing sustainable energy conversion and storage technologies, such as water-splitting electrolyzers, fuel cells, metal-air batteries, etc. [7] However, the sluggish kinetics of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) on the electrodes has been proven to With the inspiration of developing bifunctional electrode materials for reversible oxygen electrocatalysis, one strategy of heteroatom doping is proposed to fabricate dual metal single-atom catalysts. However, the identification and mechanism functions of polynary single-atom structures remain elusive. Atomically dispersed binary Co-Ni sites embedded in N-doped hollow carbon nanocubes (denoted as CoNi-SAs/NC) are synthesized via proposed pyrolysis of dopamine-coated metalorganic frameworks. The atomically isolated bimetallic configuration in CoNi-SAs/NC is identified by combining microscopic and spectroscopic techniques. When employing as oxygen electrocatalysts in alkaline medium, the resultant CoNi-SAs/NC hybrid manifests outstanding catalytic performance for bifunctional oxygen reduction/evolution reactions, boosting the realistic rechargeable zinc-air batteries with high efficiency, low overpotential, and robust reversibility, superior to other counterparts and state-of-the-art precious-metal catalysts. Theoretical computations based on density functional theory demonstrate that the homogenously dispersed single atoms and the synergistic effect of neighboring Co-Ni dual metal center can optimize the adsorption/desorption features and decrease the overall reaction barriers, eventually promoting the reversible oxygen electrocatalysis. This work not only sheds light on the controlled synthesis of atomically isolated advanced materials, but also provides deeper understanding on the structure-performance relationships of nanocatalysts with multiple active sites for various catalytic applications.To date, large numbers of low cost and efficie...

The size effect of transition‐metal nanoparticles on electrocatalytic performance remains ambiguous especially when decreasing the size to the atomic level. Herein, we report the spatial isolation of cobalt species on the atomic scale, which was achieved by tuning the zinc dopant content in predesigned bimetallic Zn/Co zeolitic imidazole frameworks (ZnCo‐ZIFs), and led to the synthesis of nanoparticles, atomic clusters, and single atoms of Co catalysts on N‐doped porous carbon. This synthetic strategy allowed an investigation of the size effect on electrochemical behavior from nanometer to Ångström dimensions. Single‐atom Co catalysts showed superior bifunctional ORR/OER activity, durability, and reversibility in Zn–air batteries compared with the other derivatives and noble‐metal Pt/C+RuO2, which was attributed to the high reactivity and stability of isolated single Co atoms. Our findings open up a new avenue to regulate the metal particle size and catalytic performance of MOF derivatives.

The size effect of transition‐metal nanoparticles on electrocatalytic performance remains ambiguous especially when decreasing the size to the atomic level. Herein, we report the spatial isolation of cobalt species on the atomic scale, which was achieved by tuning the zinc dopant content in predesigned bimetallic Zn/Co zeolitic imidazole frameworks (ZnCo‐ZIFs), and led to the synthesis of nanoparticles, atomic clusters, and single atoms of Co catalysts on N‐doped porous carbon. This synthetic strategy allowed an investigation of the size effect on electrochemical behavior from nanometer to Ångström dimensions. Single‐atom Co catalysts showed superior bifunctional ORR/OER activity, durability, and reversibility in Zn–air batteries compared with the other derivatives and noble‐metal Pt/C+RuO2, which was attributed to the high reactivity and stability of isolated single Co atoms. Our findings open up a new avenue to regulate the metal particle size and catalytic performance of MOF derivatives.

Nanosheets assembled into nickel sulfide nanospheres were synthesized in a controlled manner, and exhibited superior tri-functional activities owing to optimized binding with hydrogen/oxygen intermediates.

Zinc-air battery has drawn increasing attention from the whole world owing to its large energy capacity, stable working voltage, environmentally friendship, and low price. A special porous Zn with three-dimensional (3D) network frame structure, whose multistage average pore sizes can be tuned from 300 to 8 um, is synthesized in this work. It is found that there is a competition between Zn2+ and NH4+ for their reduction on the supports. And the decrease of Zn2+ concentration and increase of NH4+ concentration can facilitate the decrease of pore size. Potential-dynamic polarization was tested with 3-electrodes cell, aiming to characterize the electrochemical activity and corrosion properties of porous Zn and commercial Zn foil electrodes. After optimization, the porous Zn prepared with the parameters of 3 M NaBr, 1 M C2H3O2NH4, and 0.01 M C4H6O4Zn shows the most negative corrosion potential of −1.45 V among all the samples, indicating the remarkable anti-corrosion property. Its discharge specific capacity is up to 812 mAh g−1. And discharge-charge test of the porous Zn shows an initial discharge platform of 1.33 V and an initial charge platform of 1.96 V, performing a small overpotential. What's more, the porous Zn exhibits a much longer cycle life than commercial Zn foil. Our work will not only shed light on the design and synthesis of other porous metal materials, but also further promote the development of Zn-based battery electrochemistry.

Reasonable design and development of a low-cost and high-efficiency bifunctional electrocatalyst for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is essential for promoting the development of Zinc-air battery technology. Herein, we obtained an integrated catalytic electrode, NiFe nanoparticles supported on nitrogen-doped carbon (NC) directly grown on the carbon cloth (designated as Ni 3 Fe 2 @NC/CC), by pyrolysis of bimetallic NiFe metal-organic framework (MOF) precursor. There is a synergistic effect between nickel and iron component, which enhances the bifunctional catalytic activity. In addition, the underlying carbon cloth is conducive to the efficient electron transfer and also benefits the uniform loading of catalytically active materials. Thus, the integrated electrode shows good OER/ORR dual-functional catalytic performance, and the OER overpotential is much lower than that of the traditional drop-coating electrode and precious metal catalyst (IrO 2 ). Moreover, the Ni 3 Fe 2 @NC/CC integrated electrode used in zinc-air batteries shows good flexibility and cycle stability. Our findings provide a new avenue for the development of efficient and stable bifunctional oxygen electrocatalysts.

The development of high-efficiency,l ow-cost, and earth-abundant electrocatalysts for overall water splitting remains achallenge. In this work, Ni-modified MoS 2 hybrid catalysts are grown on carbon cloth (Ni-Mo-S@CC) through a one-step hydrothermalt reatment. The optimized Ni-Mo-S@CC catalyst shows excellent hydrogen evolution reaction (HER) activity with al ow overpotential of 168 mV at ac urrent density of 10 mA cm À2 in 1.0 m KOH, which is lower than those of Ni-Mo-S@CC( 1:1),N i-Mo-S@CC (3:1), and pure MoS 2 .S ignificantly,t he Ni-Mo-S@CC hybrid catalyst also displays outstanding oxygen evolutionr eaction( OER) activity with al ow overpotential of 320 mV at ac urrent density of 10 mA cm À2 ,a nd remarkable long-term stabilityf or 30 ha ta constant currentd ensity of 10 mA cm À2 .E xperimental results and theoretical analysis based on density functional theory demonstrate that the excellent electrocatalytic performance can be attributed mainlyt ot he remarkablec onductivity, abundant active sites, and synergistic effect of the Ni-doped MoS 2 .T his work sheds light on au nique strategy for the designo fh igh-performance and stable electrocatalysts for water-splitting electrolyzers.