Nitrogen-bridged Fe-Cu Atomic Pair Sites for Efficient Electrochemical Ammonia Production and Electricity Generation with Zn-NO2 Batteries.

The development of environmentally sustainable and highly efficient technologies for ammonia production is crucial for the future advancement of carbon-neutral energy systems. The nitrite reduction reaction (NO2 RR) for generating NH3 is a promising alternative to the low-efficiency nitrogen reduction reaction (NRR), owing to the low N=O bond energy and high solubility of nitrite. In this study, we designed a highly efficient dual-atom catalyst with Fe-Cu atomic pair sites (termed FeCu DAC), and the as-developed FeCu DAC was able to afford a remarkable NH3 yield of 24,526 µg h-1 mgcat. -1 at -0.6 V, with a Faradaic Efficiency (FE) for NH3 production of 99.88 %. The FeCu DAC also exhibited exceptional catalytic activity and selectivity in a Zn-NO2 battery, achieving a record-breaking power density of 23.6 mW cm-2 and maximum NH3 FE of 92.23 % at 20 mA cm-2 . Theoretical simulation demonstrated that the incorporation of the Cu atom changed the energy of the Fe 3d orbital and lowered the energy barrier, thereby accelerating the NO2 RR. This study not only demonstrates the potential of galvanic nitrite-based cells for expanding the field of Zn-based batteries, but also provides fundamental interpretation for the synergistic effect in highly dispersed dual-atom catalysts.

Double-Confinement Construction of Atomically-Dispersed-Fe Bifunctional Oxygen Electrocatalyst for High-Performance Zinc-Air Battery.

Simultaneously achieving high activity for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is the key to constructing rechargeable Zn-air batteries (ZABs). Here the complexation of 1,10-phenanthroline and the spatial confinement effect of closo-[B12 H12 ]2- are used to solidify metal-boron-cluster-organic-polymers on the surface of SiO2 microspheres to construct a bifunctional oxygen electrocatalyst (FeBCN/NHCS). Driven by FeBCN/NHCS, the half-wave-potential of ORR surpasses that of the Pt/C catalyst, reaching 0.893 V versus RHE, and the overpotential (η10 ) of OER is as low as 361 mV. The ZABs of FeBCN/NHCS as an air cathode not only have high power density and specific capacity, but also have charge-discharge durability. The FeBCN/NHCS is not only related to the high specific surface area, but also the high exposure rate of single-atom Fe and the doping of heteroatom B. This study provides an efficient oxygen electrocatalyst and also contributes wisdom to the acquisition of highly active oxygen electrocatalyst.

Self-supported iron-doped cobalt-copper oxide heterostructures for efficient electrocatalytic denitrification.

The electrocatalytic reduction of nitrate ions (NO3-) to nitrogen gas (N2) has emerged as an effective approach for mitigating nitrate pollution in water bodies. However, the development of efficient and highly selective cathode materials remains challenging. Conventional copper-based catalysts often exhibit low selectivity because they strongly adsorb oxygen. In this study, a straightforward solvothermal and pyrolysis method was used to grow iron-doped cobalt-copper oxide heterogeneous structures on copper foam surfaces (Fe-CoO/CuO@CF). Then, the effects of the applied potential, initial NO3- concentration, Cl- concentration, electrolyte pH, and different catalysts on the catalyst performance were investigated. Compared with recently reported congeners, Fe-CoO/CuO@CF is less expensive and exhibits outstanding activity for NO3- reduction. Meanwhile, under a cathode potential of - 1.31 V vs. Ag/AgCl, Fe-CoO/CuO@CF degrades 98.6 % of NO3- in 200 min. In addition, when employing a method inspired by NH4+ removal by breakpoint chlorination, N2 selectivity over Fe-CoO/CuO@CF was raised from 10 % without Cl- to 99.7 % when supplemented with Cl-. The catalyst demonstrated excellent cyclic stability, maintaining a high electrocatalytic activity for the conversion of NO3- to N2 gas over eleven cycles. Moreover, Fe-CoO/CuO@CF enabled 63.7 % removal of NO3- from wastewater (50 mg/L NO3--N) prepared from natural water, with 100 % conversion to N2. Computational studies showed that iron doping decreased the free energy change of the intermediate of NO3- reduction reaction. This study provides an effective strategy for the electrochemical reduction of nitrate to nitrogen gas and offers good prospects for addressing nitrate pollution.

Electron Modulation and Morphology Engineering Jointly Accelerate Oxygen Reaction to Enhance Zn-Air Battery Performance.

Combining morphological control engineering and diatomic coupling strategies, heteronuclear FeCo bimetals are efficiently intercalated into nitrogen-doped carbon materials with star-like to simultaneously accelerate oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The half-wave potential and kinetic current density of the ORR driven by FeCoNC/SL surpass the commercial Pt/C catalyst. The overpotential of OER is as low as 316 mV (η10 ), and the mass activity is at least 3.2 and 9.4 times that of mononuclear CoNC/SL and FeNC/SL, respectively. The power density and specific capacity of the Zn-air battery with FeCoNC/SL as air cathode are as high as 224.8 mW cm-2 and 803 mAh g-1 , respectively. Morphologically, FeCoNC/SL endows more reactive sites and accelerates the process of oxygen reaction. Density functional theory reveals the active site of the heteronuclear diatomic, and the formation of FeCoN5C configuration can effectively tune the d-band center and electronic structure. The redistribution of electrons provides conditions for fast electron exchange, and the change of the center of the d-band avoids the strong adsorption of intermediate species to simultaneously take into account both ORR and OER and thus achieve high-performance Zn-air batteries.

MOF-on-MOF-Derived Ultrafine Fe2P-Co2P Heterostructures for High-Efficiency and Durable Anion Exchange Membrane Water Electrolyzers.

The alkaline hydrogen evolution reaction (HER) in an anion exchange membrane water electrolyzer (AEMWE) is considered to be a promising approach for large-scale industrial hydrogen production. Nevertheless, it is severely hampered by the inability to operate tolerable HER catalysts consistently under low overpotentials at ampere-level current densities. Here, we develop a universal ligand-exchange (MOF-on-MOF) modulation strategy to synthesize ultrafine Fe2P and Co2P nanoparticles, which are well anchored on N and P dual-doped carbon porous nanosheets (Fe2P-Co2P/NPC). In addition, benefiting from the downshift of the d-band center and the interfacial Co-P-Fe bridging, the electron-rich P site is triggered, which induces the redistribution of electron density and the swapping of active centers, lowering the energy barrier of the HER. As a result, the Fe2P-Co2P/NPC catalyst only requires a low overpotential of 175 mV to achieve a current density of 1000 mA cm-2. The solar-driven water electrolysis system presents a record-setting and stable solar-to-hydrogen conversion efficiency of 20.36%. Crucially, the catalyst could stably operate at 1000 mA cm-2 over 1000 h in a practical AEMWE at an estimated cost of US$0.79 per kilogram of H2, which achieves the target (US$2 per kg of H2) set by the U.S. Department of Energy (DOE).

Dense Crystalline/Amorphous Phosphides/Oxides Interfacial Sites for Enhanced Industrial-Level Large Current Density Seawater Oxidation.

Designing high-efficiency and low-cost catalysts with high current densities for the oxygen evolution reaction (OER) is critical for commercial seawater electrolysis. Here, we present a heterophase synthetic strategy for constructing an electrocatalyst with dense heterogeneous interfacial sites among crystalline Ni2P, Fe2P, CeO2, and amorphous NiFeCe oxides on nickel foam (NF). The synergistic effect of high-density crystalline and amorphous heterogeneous interfaces effectively promotes the redistribution of the charge density and optimizes the adsorbed oxygen intermediates, lowering the energy barrier and promoting the O2 desorption, thus enhancing the OER performance. The obtained NiFeO-CeO2/NF catalyst exhibited outstanding OER catalytic activity, with low overpotentials of 338 and 408 mV required to attain high current densities of 500 and 1000 mA cm-2, respectively, in alkaline natural seawater electrolytes. The solar-driven seawater electrolysis system presents a record-setting and stable solar-to-hydrogen conversion efficiency of 20.10%. This work provides directives for developing highly effective and stable catalysts for large-scale clean energy production.

Co/MoC Nanoparticles Embedded in Carbon Nanoboxes as Robust Trifunctional Electrocatalysts for a Zn-Air Battery and Water Electrocatalysis.

To meet the application needs of rechargeable Zn-air battery and electrocatalytic overall water splitting (EOWS), developing high-efficiency, cost-effective, and durable trifunctional catalysts for the hydrogen evolution reaction (HER), oxygen evolution, and reduction reaction (OER and ORR) is extremely paramount yet challenging. Herein, the interface engineering concept and nanoscale hollowing design were proposed to fabricate N-doping carbon nanoboxes confined with Co/MoC nanoparticles. Uniform zeolitic imidazolate framework nanocube was employed as the starting material to construct the trifunctional electrocatalyst through the conformal polydopamine-Mo layer coating and the subsequent pyrolysis treatment. The Co@IC/MoC@PC catalyst displayed superior electrochemical ORR performances with a positive half-wave potential of 0.875 V and a high limiting current density of 5.89 mA/cm2. When practically employed as an electrocatalyst in regenerative Zn-air battery, a high specific capacity of 728 mAh/g, a large peak power density of 221 mW/cm2, a high open-circuit voltage of 1.482 V, and a low charge/discharge voltage gap of 0.41 V were obtained. Moreover, its practicability was further exploited by overall water splitting, affording low overpotentials of 277 and 68 mV at 10 mA/cm2 for the OER and HER in 1 M KOH solution, respectively, and a decent operating potential of 1.57 V for EOWS. Ultraviolet photoelectron spectroscopy and density functional theory calculation revealed that the Co/MoC interface synergistically facilitated the charge-transfer, thereby contributing to the enhancements of electrocatalytic ORR/OER/HER processes. More importantly, this catalyst design concept can offer some interesting prospects for the construction of outstanding trifunctional catalysts toward various energy conversion and storage devices.