Aerobically Autoxidized Self-Charge Concept Derived from Synergistic Pyrrolic Nitrogen and Catechol Configurations in N, O Co-Doped Carbon Cathode Material.

Aerobically autoxidized self-charging concept has drawn significant attraction due to its promising chemical charge features without external power supply. Particularly, heteroatom-doped carbon materials with abundant oxidizable sites and good conductivity are expected to be ideal cathode materials. However, there is no well-defined aerobically autoxidized self-charging concept based on heteroatom-doped carbon materials, significantly hindering the design of related carbon cathodes. An aerobically autoxidized self-chargeable concept derived from synergistic effect of pyrrolic nitrogen and catechol configuration in carbon cathode using model single pyrrolic nitrogen and oxygen (N-5, O) co-doped carbon and O-enriched carbon is proposed. First, self-charging of N-5, O co-doped carbon cathode can be achieved by aerobic oxidation of pyrrolic nitrogen and catechol to oxidized pyrrolic nitrogen and ortho-quinone configurations, respectively. Second, introducing a single pyrrolic nitrogen configuration enhanced acidic wettability of N-5, O co-doped carbon facilitating air self-charge/galvanic discharge involving proton removal/introduction. Third, synergistic effect of pyrrolic nitrogen and hydroxyl species with the strong electron-donating ability to conjugated carbon-based backbone endows N-5, O co-doped carbon with a higher highest occupied molecular orbital (HOMO) energy level more susceptible to oxidation charging. The assembled Cu/Carbon batteries can drive a timer after every air-charging run. This promising aerobically autoxidized self-charging concept can inspire exploring high-efficiency self-charging devices.

Yolk-Shell Fe3 O4 @Void@N-Carbon Nanostructures Based on One-Step Deposition of SiO2 and Resorcinol-3-Aminophenol-Formaldehyde (R-APF) Cocondensed Resin Dual Layers onto Fe3 O4 Nanoclusters.

Yolk-shell magnetic nanoparticles@nitrogen-enriched Carbon nanostructures with a magnetic core and a hollow nitrogen-enriched carbon shell exhibit considerable promise in various applications, such as drug delivery, heterogenous catalysts, removal of metal ions and organic pollutants, and screening of biomolecules, due to their strong magnetic response, unique cavities, and the selective absorption ability of nitrogen-enriched groups. However, their complicated synthesis always involves possible surface modification, layer-by-layer deposition of a sacrificial middle layer and an outer nitrogen-enriched layer on magnetic nanoparticles, subsequent carbonization, and final removal of the sacrificial middle layer. Herein, yolk-shell Fe3 O4 @nitrogen-enriched carbon nanostructures are constructed based on NH4 + ion-induced one-step deposition of SiO2 and Resorcinol-3-aminophenol-formaldehyde cocondensed resin (R-APF) dual layers onto poly acrylic acid-modified Fe3 O4 nanoclusters without any extra surface modification. The N-Carbon shell thickness of the yolk-shell Fe3 O4 @Void@N-Carbon nanostructure can be finely tailored though tailoring the feeding amount of aminophenol and resorcinol to tune the thickness of the outer R-APF resin shell onto Fe3 O4 @SiO2 intermediate particles. This NH4 + ion-induced one-pot deposition of double layers can effectively promote synthesis efficiency of this kind of yolk-shell nanostructure.

Monomer Protonation-Dependent Surface Polymerization to Achieve One-Step Grafting Cross-Linked Poly(4-Vinylpyridine) Onto Core-Shell Fe3 O4 @SiO2 Nanoparticles.

Functional polymer-grafting silica nanoparticles hold great promise in diverse applications such as molecule recognition, drug delivery, and heterogeneous catalysis due to high density and uniform distribution of functional groups and their tunable spatial distance. However, conventional grafting methods from monomers mainly consist of one or more extra surface modification steps and a subsequent surface polymerization step. A monomer protonation-dependent surface polymerization strategy is proposed to achieve one-step uniform surface grafting of cross-linked poly(4-vinylpyridine) (P4VP) onto core-shell Fe3 O4 @SiO2 nanostructures. At an approximate pH, partially protonated 4VP sites in aqueous solution can be strongly adsorbed onto deprotonated silanol groups (SiO- ) onto Fe3 O4 @SiO2 nanospheres to ensure prior polymerization of these protonated 4VP sites exclusively onto Fe3 O4 @SiO2 nanoparticles and subsequent polymerization of other 4VP and divinylbenzene monomers harvested by these protonated 4VP monomers onto Fe3 O4 @SiO2 nanoparticles, thereby achieving direct grafting of cross-linked P4VP macromolecules onto Fe3 O4 @SiO2 nanoparticles.

Unprecedented 100% conversion from pyridinic to pyrrolic nitrogen configuration for electrochemically active nitrogen-doped carbon materials.

Nitrogen-doped carbons with promising electrochemical performance exhibit a strong dependence on nitrogen configuration. Therefore, accurate control of nitrogen configurations is crucial to clarify their influence. Unfortunately, there is still no well-defined conversion route to finely control nitrogen configuration. Herein, we proposed the concept of 100% conversion from pyridinic to pyrrolic nitrogen in carbon materials through low-temperature pyrolysis and alkali activation of hydroxypyridine-3-halophenol-formaldehyde resins. Their dehalogenation pyrolysis promotes formation of carbon intermediates and conversion of tautomeric pyridone and hydroxypyridine into pyrrolic and pyridinic nitrogen through eliminating carbonyl and hydroxyl functionalities, respectively. Continuous thermal alkali activation introduces hydroxyl groups into carbon materials, converting pyridinic species to intermediate hydroxypyridine and pyridone; subsequently, these configurations transform to pyridinic and pyrrolic nitrogen, respectively, and finally, an excessive alkali ensures 100% conversion from pyridinic to pyrrolic nitrogen. NaOH activation for pyrrolic and pyridinic nitrogen co-doped carbon and KOH activation for model nitrogen-containing compounds including acridine, phenanthridine, and acridone further confirm that alkali activation plays an indispensable role in 100% conversion from pyridinic to pyrrolic units through the tautomeric hydroxypyridine and pyridone intermediates. Low-temperature alkali-induced controllable conversion of nitrogen configuration in carbon materials is suitable modulating nitrogen configurations for almost all nitrogen-doped carbon materials in electrochemical applications.

Proof of Aerobically Autoxidized Self-Charge Concept Based on Single Catechol-Enriched Carbon Cathode Material.

HIGHLIGHTS: An air-breathing chemical self-charge concept of oxygen-enriched carbon cathode. The oxygen-enriched carbon material with abundant catechol groups. Rapid air-oxidation chemical self-charge of catechol groups. The self-charging concept has drawn considerable attention due to its excellent ability to achieve environmental energy harvesting, conversion and storage without an external power supply. However, most self-charging designs assembled by multiple energy harvesting, conversion and storage materials increase the energy transfer loss; the environmental energy supply is generally limited by climate and meteorological conditions, hindering the potential application of these self-powered devices to be available at all times. Based on aerobic autoxidation of catechol, which is similar to the electrochemical oxidation of the catechol groups on the carbon materials under an electrical charge, we proposed an air-breathing chemical self-charge concept based on the aerobic autoxidation of catechol groups on oxygen-enriched carbon materials to ortho-quinone groups. Energy harvesting, conversion and storage functions could be integrated on a single carbon material to avoid the energy transfer loss among the different materials. Moreover, the assembled Cu/oxygen-enriched carbon battery confirmed the feasibility of the air-oxidation self-charging/electrical discharging mechanism for potential applications. This air-breathing chemical self-charge concept could facilitate the exploration of high-efficiency sustainable air self-charging devices.

Architecture inspired structure engineering toward carbon nanotube hybrid for microwave absorption promotion.

Constructing sophisticated 3D structure has been shown to be fruitful in developing carbon nanotubes (CNTs) microwave absorbers (MAs). However, issues with the unclear electromagnetic (EM) responding synergy of CNTs toward substrate and the limited dissipation property caused by the large dense CNTs networks throughout the reported models still need to be resolved. Inspired by the creeper-window-room-structured architecture, an analogous conformal nanostructure of amorphous carbon/CNTs (N-AC/CNTs) hybrid is constructed through an in situ autocatalytic planting approach. By this model, not only the inheritance of frequency dependence characteristic but the co-inheritance of lossy behavior and impedance matching is demonstrated. Moreover, by virtue of the unique structure, a synergistic reinforcing dielectric loss from conductive loss and dielectric polarization was introduced. Therefore, N-AC/CNTs-750 shows impressive EM performance. This work hereby unveils the synergy of EM response from CNTs toward substrate, and provides a pioneering insight into developing architecture-inspired structure engineering to construct high-performance MAs.

2D FeOCl: A Highly In-Plane Anisotropic Antiferromagnetic Semiconductor Synthesized via Temperature-Oscillation Chemical Vapor Transport.

2D van der Waals (vdW) transition-metal oxyhalides with low symmetry, novel magnetism, and good stability provide a versatile platform for conducting fundamental research and developing spintronics. Antiferromagnetic FeOCl has attracted significant interest owing to its unique semiconductor properties and relatively high Néel temperature. Herein, good-quality centimeter-scale FeOCl single crystals are controllably synthesized using the universal temperature-oscillation chemical vapor transport (TO-CVT) method. The crystal structure, bandgap, and anisotropic behavior of the 2D FeOCl are explored in detail. The absorption spectrum and electrical measurements reveal that 2D FeOCl is a semiconductor with an optical bandgap of ≈2.1 eV and a resistivity of ≈10-1  Ω m at 295 K, and the bandgap increases with decreasing thickness. Strong in-plane optical and electrical anisotropies are observed in 2D FeOCl flakes, and the maximum resistance anisotropic ratio reaches 2.66 at 295 K. Additionally, the lattice vibration modes are studied through temperature-dependent Raman spectra and first-principles density functional calculations. A significant decrease in the Raman frequencies below the Néel temperature is observed, which results from the strong spin-phonon coupling effect in 2D FeOCl. This study provides a high-quality low-symmetry vdW magnetic candidate for miniaturized spintronics.

Insight into the Property Enhancement Mechanism of Chemically Prepared Multi-Main-Phase (Nd,Ce)2Fe14B.

Nd2Fe14B has attracted intensive attention because of its excellent magnetic properties since 1980s. However, large demands for the expensive rare earth (mainly refers to Nd/Pr/Dy) limit its wider applications. Investigations of Ce-doped Nd2Fe14B have been attempted recently and multi-main-phase (MMP) (Nd,Ce)2Fe14B provides a promising way for the preparation of high-performance Ce-doped permanent magnets even though the inner mechanism has not been absolutely understood. We synthesized Ce-doped Nd2Fe14B nanostructures by the chemical method and successfully realized the obvious property enhancement of the MMP sample compared with that of the single-main-phase one. The coercivity of the MMP nanostructures is nearly 4.5 kOe with a remanence ratio of 0.36 before magnetic orientation, which is much larger than that of the SMP sample (1.7 kOe and 0.21), respectively. The property enhancement mechanism of the MMP sample analyzed mainly by first-order reversal curves could be concluded in three aspects: first, the content of α-Fe will be decreased; hence, the difficulty of the magnetic nucleation is increased. Second, the exchange coupling effect between the adjacent magnetic structures will be strengthened significantly. Last, the grain boundary phases with various magnetic features are formed, enhancing the magnetic pinning effect and specially tuning the inner interactions. This work is helpful for the deeper understanding of the property enhancement mechanism in MMP nanomagnets and provides an instructive way for the effective design and preparation of high-performance MMP Ce-doped Nd2Fe14B nanomagnets.

Molten-Salt-Assisted Chemical Vapor Deposition Process for Substitutional Doping of Monolayer MoS2 and Effectively Altering the Electronic Structure and Phononic Properties.

Substitutional doping of layered transition metal dichalcogenides (TMDs) has been proved to be an effective route to alter their intrinsic properties and achieve tunable bandgap, electrical conductivity and magnetism, thus greatly broadening their applications. However, achieving valid substitutional doping of TMDs remains a great challenge to date. Herein, a distinctive molten-salt-assisted chemical vapor deposition (MACVD) method is developed to match the volatilization of the dopants perfectly with the growth process of monolayer MoS2, realizing the substitutional doping of transition metal Fe, Co, and Mn. This doping strategy effectively alters the electronic structure and phononic properties of the pristine MoS2. In addition, a temperature-dependent Raman spectrum is employed to explore the effect of dopants on the lattice dynamics and first-order temperature coefficient of monolayer MoS2, and this doping effect is illustrated in depth combined with the theoretical calculation. This work provides an intriguing and powerful doping strategy for TMDs through employing molten salt in the CVD system, paving the way for exploring new properties of 2D TMDs and extending their applications into spintronics, catalytic chemistry and photoelectric devices.

Single-site pyrrolic-nitrogen-doped sp2-hybridized carbon materials and their pseudocapacitance.

Integrating nitrogen species into sp2-hybridized carbon materials has proved an efficient means to improve their electrochemical performance. Nevertheless, an inevitable mixture of nitrogen species in carbon materials, due to the uncontrolled conversion among different nitrogen configurations involved in synthesizing nitrogen-doped carbon materials, largely retards the precise identification of electrochemically active nitrogen configurations for specific reactions. Here, we report the preparation of single pyrrolic N-doped carbon materials (SPNCMs) with a tunable nitrogen content from 0 to 4.22 at.% based on a strategy of low-temperature dehalogenation-induced and subsequent alkaline-activated pyrolysis of 3-halogenated phenol-3-aminophenol-formaldehyde (X-APF) co-condensed resins. Additionally, considering that the pseudocapacitance of SPNCMs is positively dependent on the pyrrolic nitrogen content, it could be inferred that pyrrolic nitrogen species are highly active pseudocapacitive sites for nitrogen-doped carbon materials. This work gives an ideal model for understanding the contribution of pyrrolic nitrogen species in N-doped carbon materials.

UV-Triggered Self-Healing of a Single Robust SiO2 Microcapsule Based on Cationic Polymerization for Potential Application in Aerospace Coatings.

UV-triggered self-healing of single microcapsules has been a good candidate to enhance the life of polymer-based aerospace coatings because of its rapid healing process and healing chemistry based on an accurate stoichiometric ratio. However, free radical photoinitiators used in single microcapsules commonly suffer from possible deactivation due to the presence of oxygen in the space environment. Moreover, entrapment of polymeric microcapsules into coatings often involves elevated temperature or a strong solvent, probably leading to swelling or degradation of polymer shell, and ultimately the loss of active healing species into the host matrix. We herein describe the first single robust SiO2 microcapsule self-healing system based on UV-triggered cationic polymerization for potential application in aerospace coatings. On the basis of the similarity of solubility parameters of the active healing species and the SiO2 precursor, the epoxy resin and cationic photoinitiator are successfully encapsulated into a single SiO2 microcapsule via a combined interfacial/in situ polymerization. The single SiO2 microcapsule shows solvent resistance and thermal stability, especially a strong resistance for thermal cycling in a simulated space environment. In addition, the up to 89% curing efficiency of the epoxy resin in 30 min, and the obvious filling of scratches in the epoxy matrix demonstrate the excellent UV-induced healing performance of SiO2 microcapsules, attributed to a high load of healing species within the capsule (up to 87 wt %) and healing chemistry based on an accurate stoichiometric ratio of the photoinitiator and epoxy resin at 9/100. More importantly, healing chemistry based on a UV-triggered cationic polymerization mechanism is not sensitive to oxygen, extremely facilitating future embedment of this single SiO2 microcapsule in spacecraft coatings to achieve self-healing in a space environment with abundant UV radiation and oxygen.

In Situ Confined Growth Based on a Self-Templating Reduction Strategy of Highly Dispersed Ni Nanoparticles in Hierarchical Yolk-Shell Fe@SiO2 Structures as Efficient Catalysts.

Ni-based magnetic catalysts exhibit moderate activity, low cost, and magnetic reusability in hydrogenation reactions. However, Ni nanoparticles anchored on magnetic supports commonly suffer from undesirable agglomeration during catalytic reactions due to the relatively weak affinity of the magnetic support for the Ni nanoparticles. A hierarchical yolk-shell Fe@SiO2 /Ni catalyst, with an inner movable Fe core and an ultrathin SiO2 /Ni shell composed of nanosheets, was synthesized in a self-templating reduction strategy with a hierarchical yolk-shell Fe3 O4 @nickel silicate nanocomposite as the precursor. The spatial confinement of highly dispersed Ni nanoparticles with a mean size of 4 nm within ultrathin SiO2 nanosheets with a thickness of 2.6 nm not only prevented their agglomeration during catalytic transformations but also exposed the abundant active Ni sites to reactants. Moreover, the large inner cavities and interlayer spaces between the assembled ultrathin SiO2 /Ni nanosheets provided suitable mesoporous channels for diffusion of the reactants towards the active sites. As expected, the Fe@SiO2 /Ni catalyst displayed high activity, high stability, and magnetic recoverability for the reduction of nitroaromatic compounds. In particular, the Ni-based catalyst in the conversion of 4-nitroamine maintained a rate of over 98 % and preserved the initial yolk-shell structure without any obvious aggregation of Ni nanoparticles after ten catalytic cycles, which confirmed the high structural stability of the Ni-based catalyst.

Nitrogen-Enriched Fe3O4@Carbon Nanospheres Derived from Fe3O4@3-Aminophenol/Formaldehyde Resin Nanospheres Based on a Facile Hydrothermal Strategy: Towards a Robust Catalyst Scaffold for Platinum Nanocrystals.

Robust nitrogen-enriched Fe3O4@carbon nanospheres have been fabricated as a catalyst scaffold for Pt nanoparticles. In this work, core-shell Fe3O4@3-aminophenol/formaldehyde (APF) nanocomposites were first synthesized by a simple hydrothermal method, and subsequently carbonized to Fe3O4@N-Carbon nanospheres for in situ growth of Pt nanocrystals. Abundant amine groups were distributed uniformly onto Fe3O4@N-Carbon nanospheres, which not only improved the dispersity and stability of the Pt nanocrystals, but also endowed the Pt-based catalysts with good compatibility in organic solvents. The dense three-dimensional cross-linked carbon shell protects the Fe3O4 cores against damage from harsh chemical environments, even in aqueous HCl (up to 1.0 M) or NaOH (up to 1.0 M) solutions under ultrasonication for 24 hours, which indicates that it can be used as a robust catalyst scaffold. In the reduction of nitrobenzene compounds, the Fe3O4@N-Carbon@Pt nanocatalysts show outstanding catalytic activity, stability, and recoverability.