Cobalt Nanoparticles and Atomic Sites in Nitrogen‐Doped Carbon Frameworks for Highly Sensitive Sensing of Hydrogen Peroxide

In situ monitoring of hydrogen peroxide (H₂O₂) during its production process is needed. Here, an electrochemical H₂O₂ sensor with a wide linear current response range (concentration: 5 × 10^?8 to 5 × 10^?2 m ), a low detection limit (32.4 × 10^?9 m ), and a high sensitivity (568.47 µA mm ^?1 cm^?2) is developed. The electrocatalyst of the sensor consists of cobalt nanoparticles and atomic Co‐N_x moieties anchored on nitrogen doped carbon nanotube arrays (Co‐N/CNT), which is obtained through the pyrolysis of the sandwich‐like urea@ZIF‐67 complex. More cobalt nanoparticles and atomic Co‐N_x as active sites are exposed during pyrolysis, contributing to higher electrocatalytic activity. Moreover, a portable screen‐printed electrode sensor is constructed and demonstrated for rapidly detecting (cost ≈40 s) H₂O₂ produced in microbial fuel cells with only 50 µL solution. Both the synthesis strategy and sensor design can be applied to other energy and environmental fields.     

Interface Modulation of MoS2/Metal Oxide Heterostructures for Efficient Hydrogen Evolution Electrocatalysis

Developing efficient earth‐abundant MoS₂ based hydrogen evolution reaction (HER) electrocatalysts is important but challenging due to the sluggish kinetics in alkaline media. Herein, a strategy to fabricate a high‐performance MoS₂ based HER electrocatalyst by modulating interface electronic structure via metal oxides is developed. All the heterostructure catalysts present significant improvement of HER electrocatalytic activities, demonstrating a positive role of metal oxides decoration in promoting the rate‐limited water dissociation step for the HER mechanism in alkaline media. The as‐obtained MoS₂/Ni₂O₃H catalyst exhibits a low overpotential of 84 mV at 10 mA cm^?2 and small charge‐transfer resistance of 1.5 Ω in 1 m KOH solution. The current density (217 mA cm^?2) at the overpotential of 200 mV is about 2 and 24 times higher than that of commercial Pt/C and bare MoS₂, respectively. Additionally, these MoS₂/metal oxides heterostructure catalysts show outstanding long‐term stability under a harsh chronopotentiometry test. Theoretical calculations reveal the varied sensitivity of 3d‐band in different transition oxides, in which Ni‐3d of Ni₂O₃H is evidently activated to achieve fast electron transfer for HER as the electron‐depletion center. Both electronic properties and energetic reaction trends confirm the high electroactivity of MoS₂/Ni₂O₃H in the adsorption and dissociation of H₂O for highly efficient HER in alkaline media.     

Designing Metallic and Insulating Nanocrystal Heterostructures to Fabricate Highly Sensitive and Solution Processed Strain Gauges for Wearable Sensors

All‐solution processed, high‐performance wearable strain sensors are demonstrated using heterostructure nanocrystal (NC) solids. By incorporating insulating artificial atoms of CdSe quantum dot NCs into metallic artificial atoms of Au NC thin film matrix, metal–insulator heterostructures are designed. This hybrid structure results in a shift close to the percolation threshold, modifying the charge transport mechanism and enhancing sensitivity in accordance with the site percolation theory. The number of electrical pathways is also manipulated by creating nanocracks to further increase its sensitivity, inspired from the bond percolation theory. The combination of the two strategies achieves gauge factor up to 5045, the highest sensitivity recorded among NC‐based strain gauges. These strain sensors show high reliability, durability, frequency stability, and negligible hysteresis. The fundamental charge transport behavior of these NC solids is investigated and the combined site and bond percolation theory is developed to illuminate the origin of their enhanced sensitivity. Finally, all NC‐based and solution‐processed strain gauge sensor arrays are fabricated, which effectively measure the motion of each finger joint, the pulse of heart rate, and the movement of vocal cords of human. This work provides a pathway for designing low‐cost and high‐performance electronic skin or wearable devices.     

Interfacial Engineering of W2N/WC Heterostructures Derived from Solid-State Synthesis: A Highly Efficient Trifunctional Electrocatalyst for ORR,OER, and HER

To meet the practical demand of overall water splitting and regenerative metal–air batteries, highly efficient, low-cost, and durable electrocatalysts for the oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER) are required to displace noble metal catalysts. In this work, a facile solid-state synthesis strategy is developed to construct the interfacial engineering of W₂N/WC heterostructures, in which abundant interfaces are formed. Under high temperature (800 °C), volatile CN_x species from dicyanodiamide are trapped by WO₃ nanorods, followed by simultaneous nitridation and carbonization, to form W₂N/WC heterostructure catalysts. The resultant W₂N/WC heterostructure catalysts exhibit an efficient and stable electrocatalytic performance toward the ORR, OER, and HER, including a half-wave potential of 0.81 V (ORR) and a low overpotential at 10 mA cm⁻² for the OER (320 mV) and HER (148.5 mV). Furthermore, a W₂N/WC-based Zn–air battery shows outstanding high power density (172 mW cm⁻²). Density functional theory and X-ray absorption fine structure analysis computations reveal that W₂N/WC interfaces synergistically facilitate transport and separation of charge, thus accelerating the electrochemical ORR, OER, and HER. This work paves a novel avenue for constructing efficient and low-cost electrocatalysts for electrochemical energy devices.     

Recent Progress in CVD Growth of 2D Transition Metal Dichalcogenides and Related Heterostructures

In recent years, 2D layered materials have received considerable research interest on account of their substantial material systems and unique physicochemical properties. Among them, 2D layered transition metal dichalcogenides (TMDs), a star family member, have already been explored over the last few years and have exhibited excellent performance in electronics, catalysis, and other related fields. However, to fulfill the requirement for practical application, the batch production of 2D TMDs is essential. Recently, the chemical vapor deposition (CVD) technique was considered as an elegant alternative for successfully growing 2D TMDs and their heterostructures. The latest research advances in the controllable synthesis of 2D TMDs and related heterostructures/superlattices via the CVD approach are illustrated here. The controlled growth behavior, preparation strategies, and breakthroughs on the synthesis of new 2D TMDs and their heterostructures, as well as their unique physical phenomena, are also discussed. Recent progress on the application of CVD‐grown 2D materials is revealed with particular attention to electronics/optoelectronic devices and catalysts. Finally, the challenges and future prospects are considered regarding the current development of 2D TMDs and related heterostructures.     

Enhanced Photocatalytic Performances of CeO2/TiO2 Nanobelt Heterostructures

CeO₂/TiO₂ nanobelt heterostructures are synthesized via a cost‐effective hydrothermal method. The as‐prepared nanocomposites consist of CeO₂ nanoparticles assembled on the rough surface of TiO₂ nanobelts. In comparison with P25 TiO₂ colloids, surface‐coarsened TiO₂ nanobelts, and CeO₂ nanoparticles, the CeO₂/TiO₂ nanobelt heterostructures exhibit a markedly enhanced photocatalytic activity in the degradation of organic pollutants such as methyl orange (MO) under either UV or visible light irradiation. The enhanced photocatalytic performance is attributed to a novel capture–photodegradation–release mechanism. During the photocatalytic process, MO molecules are captured by CeO₂ nanoparticles, degraded by photogenerated free radicals, and then released to the solution. With its high degradation efficiency, broad active light wavelength, and good stability, the CeO₂/TiO₂ nanobelt heterostructures represent a new effective photocatalyst that is low‐cost, recyclable, and will have wide application in photodegradation of various organic pollutants. The new capture–photodegradation–release mechanism for improved photocatalysis properties is of importance in the rational design and synthesis of new photocatalysts.     

Oxygen‐Tolerant Hydrogen Peroxide Reduction Catalysts for Reliable Noninvasive Bioassays

Noninvasive bioassays based on the principle of a hydrogen peroxide (H₂O₂) cathodic reaction are highly desirable for low concentration analyte detection within biofluids since the reaction is immune to interference from oxidizable species. However, the inability to selectively reduce H₂O₂ over O₂ for commonly used stable catalysts (carbon or noble metals) is one of the key factors limiting their development and practical applications. Herein, catalysts that enable selective H₂O₂ reduction in the presence of oxygen with fluctuating concentrations are reported. These catalysts consist of noble metal nanoparticles underneath an amorphous chromium oxide nanolayer, which inhibits O₂ diffusion to the metal/oxide interface and suppresses its reduction reaction. Using these catalysts, analytes of low concentration in biofluids, including but not limited to glucose and lactate, are detected within the presence of various interferents. This work enables wide application of the cathodic detection principle and the development of reliable noninvasive bioassays.     

On‐Electrode Synthesis of Shape‐Controlled Hierarchical Flower‐Like Gold Nanostructures for Efficient Interfacial DNA Assembly and Sensitive Electrochemical Sensing of MicroRNA

The performance for biomolecular detection is closely associated with the interfacial structure of a biosensor, which profoundly affects both thermodynamics and kinetics of the assembly, binding and signal transduction of biomolecules. Herein, it is reported on a one‐step and template‐free on‐electrode synthesis method for making shape‐controlled gold nanostructures on indium tin oxide substrates, which provide an electrochemical sensing platform for ultrasensitive detection of nucleic acids. Thus‐prepared hierarchical flower‐like gold nanostructures (HFGNs) possess large surface area that can readily accommodate the assembly of DNA probes for subsequent hybridization detection. It is found that the sensitivity for electrochemical DNA sensing is critically dependent on the morphology of HFGNs. By using this new strategy, a highly sensitive electrochemical biosensor is developed for label‐free detection of microRNA‐21 (miRNA‐21), a biomarker for lung cancers. Importantly, it is demonstrated that this biosensor can be employed to measure the miRNA‐21 expression level from human lung cancer cell (A549) lysates and worked well in 100% serum, suggesting its potential for applications in clinical diagnosis and a wide range of bioanalysis.     

Enhancement of Ferromagnetism in Nonmagnetic Metal Oxide Nanoparticles by Facet Engineering

Ferromagnetism in semiconducting metal oxide nanoparticles has been intensively investigated due to their potential applications in spintronics, information storage, and biomedicine. Ferromagnetism can be produced in nonmagnetic metal oxide nanoparticles by a variety of methods or factors, but the saturated magnetization is typically of the order of 10^?4 emu g^?1 and too small to be useful in practice. In this work, it is demonstrated theoretically and experimentally that stronger ferromagnetism can be achieved in undoped nonmagnetic metal oxide semiconductors by exposing some specific polar crystal facets with carvings of special bonds via the interaction with underlying vacancies. In₂O₃ microcubes with completely enclosed {001} polar facets show two orders of magnitude enhancement at room temperature compared to nanoparticles with an irregular morphology. The surface magnetic domains on the {001} facets account for the significantly enhanced ferromagnetism. The technique and concept described here can be extended to other types of metal oxide nanostructures to spur their application to spintronics.     

Highly Selective Photoreduction of CO2 with Suppressing H2 Evolution by Plasmonic Au/CdSe–Cu2O Hierarchical Nanostructures under Visible Light

Here, the photocatalytic CO₂ reduction reaction (CO₂RR) with the selectivity of carbon products up to 100% is realized by completely suppressing the H₂ evolution reaction under visible light (λ > 420 nm) irradiation. To target this, plasmonic Au/CdSe dumbbell nanorods enhance light harvesting and produce a plasmon‐enhanced charge‐rich environment; peripheral Cu₂O provides rich active sites for CO₂ reduction and suppresses the hydrogen generation to improve the selectivity of carbon products. The middle CdSe serves as a bridge to transfer the photocharges. Based on synthesizing these Au/CdSe–Cu₂O hierarchical nanostructures (HNSs), efficient photoinduced electron/hole (e^?/h⁺) separation and 100% of CO selectivity can be realized. Also, the 2e^?/2H⁺ products of CO can be further enhanced and hydrogenated to effectively complete 8e^?/8H⁺ reduction of CO₂ to methane (CH₄), where a sufficient CO concentration and the proton provided by H₂O reduction are indispensable. Under the optimum condition, the Au/CdSe–Cu₂O HNSs display high photocatalytic activity and stability, where the stable gas generation rates are 254 and 123 µmol g^?1 h^?1 for CO and CH₄ over a 60 h period.     

A Hydrangea‐Like Superstructure of Open Carbon Cages with Hierarchical Porosity and Highly Active Metal Sites

Carbon micro‐/nanocages have attracted great attention owing to their wide potential applications. Herein, a self‐templated strategy is presented for the synthesis of a hydrangea‐like superstructure of open carbon cages through morphology‐controlled thermal transformation of core@shell metal–organic frameworks (MOFs). Direct pyrolysis of core@shell zinc (Zn)@cobalt (Co)‐MOFs produces well‐defined open‐wall nitrogen‐doped carbon cages. By introducing guest iron (Fe) ions into the core@shell MOF precursor, the open carbon cages are self‐assembled into a hydrangea‐like 3D superstructure interconnected by carbon nanotubes, which are grown in situ on the Fe–Co alloy nanoparticles formed during the pyrolysis of Fe‐introduced Zn@Co‐MOFs. Taking advantage of such hierarchically porous superstructures with excellent accessibility, synergetic effects between the Fe and the Co, and the presence of catalytically active sites of both metal nanoparticles and metal–N_x species, this superstructure of open carbon cages exhibits efficient bifunctional catalysis for both oxygen evolution reaction and oxygen reduction reaction, achieving a great performance in Zn–air batteries.     

过氧化氢浓度、载荷和滑动速度对1Cr18Ni9Ti不锈钢摩擦学行为的影响

未来的航空航天运载火箭需要使用绿色的燃料,使运动件有好的摩擦学性能,当前对其研究的公开报道较少.利用环-块式摩擦磨损试验机对1Cr18Ni9Ti不锈钢与ZrO2陶瓷摩擦副在质量分数25%,50%和75%的H2O2介质中,于3种滑动速度和3种载荷条件下的摩擦磨损行为进行了研究.通过三维白光共焦显微镜分析了试样磨损表面的形貌和粗糙度.结果表明:在H2O2质中,1Cr18Ni9Ti/ZrO2摩擦的总的趋势是H2O2浓度越高、载荷越大,摩擦系数越小;1Cr18Ni9Ti的磨损随着H2O2浓度的提高、载荷的增大而增大;在高浓度H2O2中1Cr18Ni9Ti与ZrO2摩擦副之间的主要磨损机制是较严重的犁沟型磨损和黏着磨损.     

Amine Functionalized Metal–Organic Framework Coordinated with Transition Metal Ions: d–d Transition Enhanced Optical Absorption and Role of Transition Metal Sites on Solar Light Driven H2 Production

Design and development of efficient photocatalysts for H₂ production from water and sunlight have gained significant attention as the solar assisted approach is considered to be a promising approach for the generation of clean fuel. However, the poor charge carrier separation and light harvesting ability of existing photocatalysts limits the efficiency of photoconversion of water. In this work, the synthesis of transition metal ions (M²⁺ = Co²⁺, Cu²⁺, and Ni²⁺) coordinated with Ti‐metal organic frameworks (Ti‐MOFs) through a simple post‐synthetic coordination method for efficient solar light‐driven H₂ production is reported. Notably, coordination of M²⁺ ions with Ti‐MOF significantly improves the optical absorption by d–d transitions and the multimetal sites facilitate the fast charge carrier separation, thereby enhancing the solar light‐driven H₂ production activity. Very interestingly, the rate of solar light‐driven H₂ production is varied with respect to different metal ions coordination due to the position of d–d bands absorption in the solar spectrum, and the complexing tendency of M²⁺ ions with sacrificial electron donors. A maximum solar H₂ production rate of 1583.55 µmol h^?1 g^?1 is achieved with a Cu²⁺ coordinated Ti‐MOF, which is ≈13 fold higher than that of the pristine Ti‐MOF.     

Oxygen Vacancy–Rich In‐Doped CoO/CoP Heterostructure as an Effective Air Cathode for Rechargeable Zn–Air Batteries

An efficient and low‐cost electrocatalyst for reversible oxygen electrocatalysis is crucial for improving the performance of rechargeable metal?air batteries. Herein, a novel oxygen vacancy–rich 2D porous In‐doped CoO/CoP heterostructure (In‐CoO/CoP FNS) is designed and developed by a facile free radicals–induced strategy as an effective bifunctional electrocatalyst for rechargeable Zn–air batteries. The electron spin resonance and X‐ray absorption near edge spectroscopy provide clear evidence that abundant oxygen vacancies are formed in the interface of In‐CoO/CoP FNS. Owing to abundant oxygen vacancies, porous heterostructure, and multiple components, In‐CoO/CoP FNS exhibits excellent oxygen reduction reaction activity with a positive half‐wave potential of 0.81 V and superior oxygen evolution reaction activity with a low overpotential of 365 mV at 10 mA cm^?2. Moreover, a home‐made Zn–air battery with In‐CoO/CoP FNS as an air cathode delivers a large power density of 139.4 mW cm^?2, a high energy density of 938 Wh kg_Zn^?1, and can be steadily cycled over 130 h at 10 mA cm^?2, demonstrating great application potential in rechargeable metal–air batteries.