NiFe LDH/Fe2O3/Ni3S2 Heterostructure with a Superhydrophilic/Superaerophobic Surface for Solar-Driven Electrolytic Water Splitting.

The development of a bifunctional electrocatalyst with high efficiency, high stability, and low cost is of great significance in practical applications of electrocatalytic water splitting. Herein, a self-supporting bifunctional electrocatalyst with a NiFe layered double hydroxide/Fe2O3/Ni3S2 heterostructure (NiFe LDH/Fe2O3/Ni3S2/IF) for hydrogen evolution and oxygen evolution reactions (HER/OER) is synthesized by the self-corrosion of iron foam (IF) and hydrothermal strategies. The constructed NiFe LDH/Fe2O3/Ni3S2/IF hierarchical heterostructure was not only beneficial to expose active sites and promote charge/mass transfer but also generate a superhydrophilic/superaerophobic surface, thereby accelerating the reaction kinetics to improve the HER/OER activity. Therefore, NiFe LDH/Fe2O3/Ni3S2/IF exhibited superior overpotentials of 226.2 and 162.8 mV for the OER and HER at 100 mA cm-2, respectively. NiFe LDH/Fe2O3/Ni3S2/IF was employed as both the cathode and the anode to assemble a device for overall water splitting and displayed a voltage of 1.55 V at 10 mA cm-2. The overall water splitting device was coupled with a solar cell to simulate a solar-powered water splitting system, resulting in a superior solar-to-hydrogen conversion efficiency of 15.16%. This work can promote the development of clean energy sources such as solar hydrogen production.

P-Orbital Bismuth Single-Atom Catalyst for Highly Effective Oxygen Electroreduction in Quasi-Solid Zinc-Air Batteries.

P-block metals have gradually been utilized to synthesize non-noble-metal catalysts for oxygen reduction reaction (ORR) due to the easily tunable localized p-orbitals and resulted versatile electronic structures. The high-density single-atom bismuth sites (Bi-NC) anchored onto nitrogen-doped three-dimensional porous carbon are proved to possess significant electrocatalytic ORR performance. Theoretical calculations unveil positively charged bismuth centers prominently improved the adsorption capacity of N-doped carbon to O2 . The p orbitals of Bi sites within Bi-NC easily generate hybrid states with p orbitals of O2 , thus promoting charge transfer and ultimately reducing the energy barrier of ORR. Benefiting from p-orbital electrons regulation of bismuth atoms, Bi-NC exhibit ORR half-wave potential of 0.86 V (vs RHE). Additionally, both liquid and quasi-solid zinc-air batteries with Bi-NC as air-cathodes achieve higher power density and specific capacity than 20 wt% Pt/C, and comparable stability and round-trip efficiency with 20 wt% Pt/C. The discovery sheds light on the theoretical and practical guidance for p-block metallic single-atom catalysts.

N-doped WO3 anchored on porous carbon as boosted oxygen reduction catalyst for zinc-air batteries.

N-doped WO3 anchored on porous carbon (N-WO3/PNC) was synthesized as an efficient oxygen reduction catalyst. The N doping reduced the overpotential of WO3 during oxygen reduction. N-WO3/PNC displayed a half-wave potential of 0.85 V. An N-WO3/PNC-based zinc-air battery displayed a high power density of 209.7 mW cm-2.

Deep eutectic solvent and molten salt-assisted construction of wheat straw-derived N/O co-doped porous carbon for flexible zinc-air batteries.

As a common biomass resource, wheat straw is gradually being derived as carbon materials for oxygen reduction reaction (ORR) in zinc-air batteries (ZABs). Herein, the wheat straw-derived carbon was prepared by ball milling and pyrolysis using deep eutectic solvent (DES) as the medium, which avoided the cumbersome procedures. The hydrogen bond of DES was utilized to reconstructed into a hydrogen bond network structure between DES and lignin/cellulose/hemicellulose of wheat straw. The hydrogen bond network structure was converted into N/O co-doped porous carbon (N/O-WSPC) with abundant N/O co-doped sites after high-temperature pyrolysis. Meanwhile, KHCO3 was employed to further generate hierarchical pore structures and increase the specific surface area of the N/O-WSPC. The N/O co-doped sites provided intrinsic ORR activity, while the porous structure facilitates the mass transfer effect. Therefore, the N/O-WSPC exhibited a half-wave potential of 0.87 V (vs. RHE) and a limiting current density of 5.98 mA cm-2 for ORR.The N/O-WSPC-based flexible ZAB displayed an energy density of 652.23 Wh kg-1 and a charging-discharging cycle duration for over 19 h. The DES-assisted strategy facilitates the sustainable and efficient application of wheat straw-derived carbon materials in energy storage and conversion devices.

Strategies for Sustainable Production of Hydrogen Peroxide via Oxygen Reduction Reaction: From Catalyst Design to Device Setup.

An environmentally benign, sustainable, and cost-effective supply of H2O2 as a rapidly expanding consumption raw material is highly desired for chemical industries, medical treatment, and household disinfection. The electrocatalytic production route via electrochemical oxygen reduction reaction (ORR) offers a sustainable avenue for the on-site production of H2O2 from O2 and H2O. The most crucial and innovative part of such technology lies in the availability of suitable electrocatalysts that promote two-electron (2e-) ORR. In recent years, tremendous progress has been achieved in designing efficient, robust, and cost-effective catalyst materials, including noble metals and their alloys, metal-free carbon-based materials, single-atom catalysts, and molecular catalysts. Meanwhile, innovative cell designs have significantly advanced electrochemical applications at the industrial level. This review summarizes fundamental basics and recent advances in H2O2 production via 2e--ORR, including catalyst design, mechanistic explorations, theoretical computations, experimental evaluations, and electrochemical cell designs. Perspectives on addressing remaining challenges are also presented with an emphasis on the large-scale synthesis of H2O2 via the electrochemical route.

Engineering Mn atomic sites in multi-dimensional nitrogen-doped carbon for highly efficient oxygen reduction reaction.

Nitrogen-coordinated single-atom manganese in multi-dimensional nitrogen-doped carbon electrocatalysts (Mn-NC) were successfully constructed by combining two-dimensional nanosheets and one-dimensional nanofibers. The Mn-NC exhibited excellent oxygen reduction reaction catalytic activity with a half-wave potential of 0.88 V, which is higher than the 0.85 V of Pt/C.

Cu Nanoclusters/FeN4 Amorphous Composites with Dual Active Sites in N-Doped Graphene for High-Performance Zn-Air Batteries.

Exploring inexpensive and earth-abundant transition metal-nitrogen-based carbon (MNC) catalysts to substitute the scarce and costly Pt-based electrocatalysts for the oxygen reduction reaction (ORR) is quite anticipated in metal-air batteries (MABs). Here, we demonstrate a facile vacuum-annealing method to synthesize Cu nanoclusters/FeN4 amorphous composites embedded in N-doped graphene (Cu/Fe-NG). This approach avoids the long-term pyrolysis procedure and the use of an inert atmosphere in the conventional procedure for fabricating MNC catalysts. Interestingly, we discovered that the amorphous structure of Cu/FeN4 composites can provide high-activity bimetallic M-Nx sites (M = Cu, Fe), because of which the Cu/FeN4 composites exhibit boosted electrocatalytic activity with a positive half-wave potential of 0.88 V (vs RHE), long-term durability, and low hydrogen peroxide for the ORR. The origin of this enhancement was assigned to the concomitance of Fe-N4 and Cu-Nx moieties in Cu/Fe-NG, favoring adsorption and activation of the O2 molecule as suggested by X-ray absorption fine structure (XAFS) analyses and density functional theory (DFT) calculations. Moreover, examinations of Cu/Fe-NG in both liquid and quasi-solid-state Zn-air batteries (ZABs) can exhibit remarkable performances. This work may offer facile fabrication of enhanced performance MNC catalysts as well as a profound insight into the use of amorphous materials in the ORR and ZABs.