Constructing FeNiPt@C Trifunctional Catalyst by High Spin-Induced Water Oxidation Activity for Zn-Air Battery and Anion Exchange Membrane Water Electrolyzer.

Developing cost-efficient trifunctional catalysts capable of facilitating hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR) activity is essential for the progression of energy devices. Engineering these catalysts to optimize their active sites and integrate them into a cohesive system presents a significant challenge. This study introduces a nanoflower (NFs)-like carbon-encapsulated FeNiPt nanoalloy catalyst (FeNiPt@C NFs), synthesized by substituting Co2+ ions with high-spin Fe2+ ions in Hofmann-type metal-organic framework, followed by carbonization and pickling processes. The FeNiPt@C NFs catalyst, characterized by its nitrogen-doped carbon-encapsulated metal alloy structure and phase-segregated FeNiPt alloy with slight surface oxidization, exhibits excellent trifunctional catalytic performance. This is evidenced by its activities in HER (-25 mV at 10 mA cm-2), ORR (half-wave potential of 0.93 V), and OER (294 mV at 10 mA cm-2), with the enhanced water oxidation activity attributed to the high-spin state of the Fe element. Consequently, the Zn-air battery and anion exchange membrane water electrolyzer assembled by FeNiPt@C NFs catalyst demonstrate remarkable power density (168 mW cm-2) and industrial-scale current density (698 mA cm-2 at 1.85 V), respectively. This innovative integration of multifunctional catalytic sites paves the way for the advancement of sustainable energy systems.

Engineering Metallic Alloy Electrode for Robust and Active Water Electrocatalysis with Large Current Density Exceeding 2000 mA cm-2.

The amelioration of brilliantly effective electrocatalysts working at high current density for the oxygen evolution reaction (OER) is imperative for cost-efficient electrochemical hydrogen production. Yet, the kinetically sluggish and unstable catalysts remain elusive to large-scale hydrogen (H2) generation for industrial applications. Herein, a new strategy is demonstrated to significantly enhance the intrinsic activity of Ni1-xFex nanochain arrays through a trace proportion of heteroatom phosphorus doping that permits robust water splitting at an extremely large current density of 1000 and 2000 mA cm-2 for 760 h. The in situ formation of Ni2P and Ni5P4 on Ni1-xFex nanochain arrays surface and hierarchical geometry of the electrode significantly promote the reaction kinetics and OER activity. The OER electrode provides exceptionally low overpotentials of 222 and 327 mV at current densities of 10 and 2000 mA cm-2 in alkaline media, dramatically lower than benchmark IrO2 and is among the most active catalysts yet reported. Remarkably, the alkaline electrolyzer renders a low voltage of 1.75 V at a large current density of 1000 mA cm-2, indicating outperformed overall water splitting. The electrochemical fingerprints demonstrate vital progress toward large-scale H2 production for industrial water electrolysis.

A hidden phase uncovered by ultrafast carrier dynamics in thin Bi2O2Se.

Bi2O2Se has attracted intensive attention due to its potential in electronics, optoelectronics, and ferroelectric applications. Despite that, there have only been a handful of experimental studies based on ultrafast spectroscopy to elucidate the carrier dynamics in Bi2O2Se thin films. Besides, different groups have reported various ultrafast timescales and associated mechanisms across films of different thicknesses. A comprehensive understanding in relation to thickness and fluence is still lacking. In this work, we have systematically explored the thickness-dependent Raman spectroscopy and ultrafast carrier dynamics in chemical vapor deposition (CVD)-grown Bi2O2Se thin films on a mica substrate with thicknesses varying from 22.44 nm down to 4.62 nm in both low and high pump fluence regions. Combining the thickness dependence and fluence dependence of the slow decay time, we demonstrate a hidden photoinduced ferroelectric transition in the thinner (<8 nm) Bi2O2Se films below the material damage thresholds, influenced by substrate-induced compressive strain and far-from-equilibrium excitation. Moreover, this transition can be manifested at high electronic excitation densities. Our results deepen the understanding of the interplay between the ferroelectric phase and semiconducting characteristics of Bi2O2Se thin films, offering potential applications in optoelectronic devices that benefit from the ferroelectric transition.

Unlocking the Potential of High Entropy Alloys in Electrochemical Water Splitting: A Review.

The global pursuit of sustainable energy is focused on producing hydrogen through electrocatalysis driven by renewable energy. Recently, High entropy alloys (HEAs) have taken the spotlight in electrolysis due to their intriguing cocktail effect, broad design space, customizable electronic structure, and entropy stabilization effect. The tunability and complexity of HEAs allow a diverse range of active sites, optimizing adsorption strength and activity for electrochemical water splitting. This review comprehensively covers contemporary advancements in synthesis technique, design framework, and physio-chemical evaluation approaches for HEA-based electrocatalysts. Additionally, it explores design principles and strategies aimed at optimizing the catalytic activity, stability, and effectiveness of HEAs in hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and overall water splitting. Through an in-depth investigation of these aspects, the complexity inherent in constituent element interactions, reaction processes, and active sites associated with HEAs is aimed to unravel. Eventually, an outlook regarding challenges and impending difficulties and an outline of the future direction of HEA in electrocatalysis is provided. The thorough knowledge offered in this review will assist in formulating and designing catalysts based on HEAs for the next generation of electrochemistry-related applications.

Constructing Nitrogen-Doped Carbon Hierarchy Structure Derived from Metal-Organic Framework as High-Performance ORR Cathode Material for Zn-Air Battery.

The development of efficient and low-cost catalysts for cathodic oxygen reduction reaction (ORR) in Zn-air battery (ZAB) is a key factor in reducing costs and achieving industrialization. Here, a novel segregated CoNiPt alloy embedded in N-doped porous carbon with a nanoflowers (NFs)-like hierarchy structure is synthesized through pyrolyzing Hofmann-type metal-organic frameworks (MOFs). The unique hierarchical NFs structure exposes more active sites and facilitates the transportation of reaction intermediates, thus accelerating the reaction kinetics. Impressively, the resulting 15% CoNiPt@C NFs catalyst exhibits outstanding alkaline ORR activity with a half-wave potential of 0.93 V, and its mass activity is 7.5 times higher than that of commercial Pt/C catalyst, surpassing state-of-the-art noble metal-based catalysts. Furthermore, the assembled CoNiPt@C+RuO2 ZAB demonstrates a maximum power density of 172 mW cm-2 , which is superior to that of commercial Pt/C+RuO2 ZAB. Experimental results reveal that the intrinsic ORR mass activity is attributed to the synergistic interaction between oxygen defects and pyrrolic/graphitic N species, which optimizes the adsorption energy of the intermediate species in the ORR process and greatly enhances catalytic activity. This work provides a practical and feasible strategy for synthesizing cost-effective alkaline ORR catalysts by optimizing the electronic structure of MOF-derived catalysts.

Monolithic Nickel Catalyst Featured with High-Density Crystalline Steps for Stable Hydrogen Evolution at Large Current Density.

Producing hydrogen via electrochemical water splitting with minimum environmental harm can help resolve the energy crisis in a sustainable way. Here, this work fabricates the pure nickel nanopyramid arrays (NNAs) with dense high-index crystalline steps as the cata electrode via a screw dislocation-dominated growth kinetic for long-term durable and large current density hydrogen evolution reaction. Such a monolithic NNAs electrode offers an ultralow overpotential of 469 mV at a current density of 5000 mA cm-2 in 1.0 m KOH electrolyte and shows a high stability up to 7000 h at a current density of 1000 mA cm-2 , which outperforms the reported catas and even the commercial platinum cata for long-term services under high current densities. Its unique structure can substantially stabilize the high-density surface crystalline steps on the catalytic electrode, which significantly elevates the catalytic activity and durability of nickel in an alkaline medium. In a typical commercial hydrogen gas generator, the total energy conversion rate of NNAs reaches 84.5% of that of a commercial Pt/Ti cata during a 60-day test of hydrogen production. This work approach can provide insights into the development of industry-compatible long-term durable, and high-performance non-noble metal catas for various applications.

Salt-Assisted Low-Temperature Growth of 2D Bi2 O2 Se with Controlled Thickness for Electronics.

Bi2 O2 Se is the most promising 2D material due to its semiconducting feature and high mobility, making it propitious channel material for high-performance electronics that demands highly crystalline Bi2 O2 Se at low-growth temperature. Here, a low-temperature salt-assisted chemical vapor deposition approach for growing single-domain Bi2 O2 Se on a millimeter scale with thicknesses of multilayer to monolayer is presented. Because of the advantage of thickness-dependent growth, systematical scrutiny of layer-dependent Raman spectroscopy of Bi2 O2 Se from monolayer to bulk is investigated, revealing a redshift of the A1g mode at 162.4 cm-1 . Moreover, the long-term environmental stability of ≈2.4 nm thick Bi2 O2 Se is confirmed after exposing the sample for 1.5 years to air. The backgated field effect transistor (FET) based on a few-layered Bi2 O2 Se flake represents decent carrier mobility (≈287 cm2  V-1 s-1 ) and an ON/OFF ratio of up to 107 . This report indicates a technique to grow large-domain thickness controlled Bi2 O2 Se single crystals for electronics.

Single step synthesis of highly conductive room-temperature stable cation-substituted mayenite electride target and thin film.

Novel approaches to synthesize efficient inorganic electride [Ca24Al28O64]4+(e-)4 (thereafter, C12A7:e-) at ambient pressure under nitrogen atmosphere, are actively sought out to reduce the cost of massive formation of nanosized powder as well as compact large size target production. It led to a new era in low cost industrial applications of this abundant material as Transparent Conducting Oxides (TCOs) and as a catalyst. Therefore, the present study about C12A7:e- electride is directed towards challenges of cation doping in C12A7:e- to enhance the conductivity and form target to deposit thin film. Our investigation for cation doping on structural and electrical properties of Sn- and Si-doped C12A7:e- (Si-C12A7:e, and Sn-C12A7:e-) reduced graphene oxide (rGO) composite shows the maximum achieved conductivities of 5.79 S·cm-1 and 1.75 S·cm-1 respectively. On the other hand when both samples melted, then rGO free Sn-C12A7:e- and Si-C12A7:e- were obtained, with conductivities ~280 S.cm-1 and 300 S·cm-1, respectively. Iodometry based measured electron concentration of rGO free Sn-C12A7:e- and Si-C12A7:e-, 3 inch electride targets were ~2.22 × 1021 cm-3, with relative 97 ± 0.5% density, and ~2.23 × 1021 cm-3 with relative 99 ± 0.5% density, respectively. Theoretical conductivity was already reported excluding any associated experimental support. Hence the above results manifested feasibility of this sol-gel method for different elements doping to further boost up the electrical properties.

Facile synthesis of tin-doped mayenite electride composite as a non-noble metal durable electrocatalyst for oxygen reduction reaction (ORR).

In this study, we synthesized nanosized Sn-doped C12A7:e- (C12Al7-xSnx:e-, where x = 0.20 to 1) composite with high surface area of 244 m2 g-1. An increasing trend in conductivity of Sn-doped C12A7:e- composites was observed at 300 K: 24 S cm-1, 68 S cm-1, 190 S cm-1 and 290 S cm-1, at doping levels of x = 0.20, 0.40, 0.80, and 1, respectively. Sn-doped C12A7:e-, with and without reduced graphene oxide (rGO), acts as a less expensive and highly active and durable electrocatalyst in the oxygen reduction reaction (ORR) for fuel cells. In the case of C12A7-xSnx:e- (where x = 1), calculated onset potential and current density were comparable to the commercially available 20% Pt/C electrode. Moreover, significant improvement was observed for Sn-doped C12A7:e- (doping level x = 1) with rGO composite. The ORR current density was about 5.9 mA cm-2, which was higher than that of Pt/C (5.2 mA cm-2). Our investigation of the effect of cation doping on structural and electrical properties of Sn-doped C12A7:e- composites shows that these results manifested the feasibility of this sol-gel method for different element doping. Furthermore, the as-prepared promising non-noble metal catalysts (NNMCs), viz., Sn-doped C12A7:e- composite materials, possess intrinsic long-time stability and excellent methanol resistance toward ORR in alkaline media and may serve as a promising alternative to Pt/C materials for ORR in its widespread implementation in fuel cells.

Lavender-like cobalt hydroxide nanoflakes deposited on nickel nanowire arrays for high-performance supercapacitors.

Hierarchical nanostructured electrodes with excellent electronic properties and high specific surface areas have promising applications in high-performance supercapacitors. However, high active mass loading and uniform structure are still crucial in fabricating such architectures. Herein, Co(OH)2 nanoflakes were homogeneously deposited on nickel nanowire arrays (NNA) through a hydrothermal approach to form an NNA@Co(OH)2 (NNACOH) composite electrode. The as-synthesized one dimensional (1D) system had a lavender-like structure with a high mass loading of 5.42 mg cm-2 and a high specific surface area of 74.5 m2 g-1. Due to the unique electrode structure characteristics, the electrode could deliver a high specific capacitance of 891.2 F g-1 at the current density of 1 A g-1 (corresponding to an areal capacitance of 4.83 F cm-2 at 5.42 mA cm-2). The capacitance could still maintain a high value of 721 F g-1 when the current density is increased to 50 A g-1. In addition, the electrode showed superior cycle stability with a capacitance retention of 89.3% after charging/discharging at the current density of 10 A g-1 for 20 000 cycles. A flexible asymmetric supercapacitor (ASC) was assembled by employing NNACOH as the positive electrode and activated carbon (AC) as the negative electrode. It delivered a maximum energy density of 23.1 W h kg-1 at the power density of 712 W kg-1 and an energy density of 13.5 W h kg-1 at the maximum power density of 14.7 kW kg-1 (based on the total mass of the electrodes), showing the state-of-the-art energy storage ability of the Co(OH)2 cathode material at device level.

Structural and Magnetic Response in Bimetallic Core/Shell Magnetic Nanoparticles.

Bimagnetic monodisperse CoFe2O4/Fe3O4 core/shell nanoparticles have been prepared by solution evaporation route. To demonstrate preferential coating of iron oxide onto the surface of ferrite nanoparticles X-ray diffraction (XRD), High resolution transmission electron microscope (HR-TEM) and Raman spectroscopy have been performed. XRD analysis using Rietveld refinement technique confirms single phase nanoparticles with average seed size of about 18 nm and thickness of shell is 3 nm, which corroborates with transmission electron microscopy (TEM) analysis. Low temperature magnetic hysteresis loops showed interesting behavior. We have observed large coercivity 15.8 kOe at T = 5 K, whereas maximum saturation magnetization (125 emu/g) is attained at T = 100 K for CoFe2O4/Fe3O4 core/shell nanoparticles. Saturation magnetization decreases due to structural distortions at the surface of shell below 100 K. Zero field cooled (ZFC) and Field cooled (FC) plots show that synthesized nanoparticles are ferromagnetic till room temperature and it has been noticed that core/shell sample possess high blocking temperature than Cobalt Ferrite. Results indicate that presence of iron oxide shell significantly increases magnetic parameters as compared to the simple cobalt ferrite.

Temperature-Dependent Magnetic Response of Antiferromagnetic Doping in Cobalt Ferrite Nanostructures.

In this work MnxCo1-xFe2O4 nanoparticles (NPs) were synthesized using a chemical co-precipitation method. Phase purity and structural analyses of synthesized NPs were performed by X-ray diffractometer (XRD). Transmission electron microscopy (TEM) reveals the presence of highly crystalline and narrowly-dispersed NPs with average diameter of 14 nm. The Fourier transform infrared (FTIR) spectrum was measured in the range of 400-4000 cm-1 which confirmed the formation of vibrational frequency bands associated with the entire spinel structure. Temperature-dependent magnetic properties in anti-ferromagnet (AFM) and ferromagnet (FM) structure were investigated with the aid of a physical property measurement system (PPMS). It was observed that magnetic interactions between the AFM (Mn) and FM (CoFe2O4) material arise below the Neel temperature of the dopant. Furthermore, hysteresis response was clearly pronounced for the enhancement in magnetic parameters by varying temperature towards absolute zero. It is shown that magnetic properties have been tuned as a function of temperature and an externally-applied field.