Anionic Regulated NiFe (Oxy)Sulfide Electrocatalysts for Water Oxidation

The construction of active sites with intrinsic oxygen evolution reaction (OER) is of great significance to overcome the limited efficiency of abundant sustainable energy devices such as fuel cells, rechargeable metal–air batteries, and in water splitting. Anionic regulation of electrocatalysts by modulating the electronic structure of active sites significantly promotes OER performance. To prove the concept, NiFeS electrocatalysts are fabricated with gradual variation of atomic ratio of S:O. With the rise of S content, the overpotential for water oxidation exhibits a volcano plot under anionic regulation. The optimized NiFeS‐2 electrocatalyst under anionic regulation possesses the lowest OER overpotential of 286 mV at 10 mA cm^?2 and the fastest kinetics being 56.3 mV dec^?1 to date. The anionic regulation methodology not only serves as an effective strategy to construct superb OER electrocatalysts, but also enlightens a new point of view for the in‐depth understanding of electrocatalysis at the electronic and atomic level.     

The Genetic Heterogeneity among Different Mouse Strains Impacts the Lung Injury Potential of Multiwalled Carbon Nanotubes

Genetic variation constitutes an important variable impacting the susceptibility to inhalable toxic substances and air pollutants, as reflected by epidemiological studies in humans and differences among animal strains. While multiwalled carbon nanotubes (MWCNTs) are capable of causing lung fibrosis in rodents, it is unclear to what extent the genetic variation in different mouse strains influence the outcome. Four inbred mouse strains, including C57Bl/6, Balb/c, NOD/ShiLtJ, and A/J, to test the pro‐fibrogenic effects of a library of MWCNTs in vitro and in vivo are chosen. Ex vivo analysis of IL‐1β production in bone marrow‐derived macrophages (BMDMs) as molecular initiating event (MIE) is performed. The order of cytokine production (Balb/c > A/J > C57Bl/6 > NOD/ShiLtJ) in BMDMs is also duplicated during assessment of IL‐1β production in the bronchoalveolar lavage fluid of the same mouse strains 40 h after oropharyngeal instillation of a representative MWCNT. Animal test after 21 d also confirms a similar hierarchy in TGF‐β1 production and collagen deposition in the lung. Statistical analysis confirms a correlation between IL‐1β production in BMDM and the lung fibrosis. All considered, these data demonstrate that genetic background indeed plays a major role in determining the pro‐fibrogenic response to MWCNTs in the lung.     

Immobilization of Pt Nanoparticles via Rapid and Reusable Electropolymerization of Dopamine on TiO2 Nanotube Arrays for Reversible SERS Substrates and Nonenzymatic Glucose Sensors

Inspired by mussel‐adhesion phenomena in nature, polydopamine (PDA) coatings are a promising route to multifunctional platforms for decorating various materials. The typical self‐polymerization process of dopamine is time‐consuming and the coatings of PDA are not reusable. Herein, a reusable and time‐saving strategy for the electrochemical polymerization of dopamine (EPD) is reported. The PDA layer is deposited on vertically aligned TiO₂ nanotube arrays (NTAs). Owing to the abundant catechol and amine groups in the PDA layer, uniform Pt nanoparticles (NPs) are deposited onto the TiO₂ NTAs and can effectively prevent the recombination of electron–hole pairs generated from photo‐electrocatalysis and transfer the captured electrons to participate in the photo‐electrocatalytic reaction process. Compared with pristine TiO₂ NTAs, the as‐prepared Pt@TiO₂ NTA composites exhibit surface‐enhanced Raman scattering sensitivity for detecting rhodamine 6G and display excellent UV‐assisted self‐cleaning ability, and also show promise as a nonenzymatic glucose biosensor. Furthermore, the mussel‐inspired electropolymerization strategy and the fast EPD‐reduced nanoparticle decorating process presented herein can be readily extended to various functional substrates, such as conductive glass, metallic oxides, and semiconductors. It is the adaptation of the established PDA system for a selective, robust, and generalizable sensing system that is the emphasis of this work.     

Hybrid Nanoscopy of Hybrid Nanomaterials

The combination of complementary techniques to characterize materials at the nanoscale is crucial to gain a more complete picture of their structure, a key step to design and fabricate new materials with improved properties and diverse functions. Here it is shown that correlative atomic force microscopy (AFM) and localization‐based super‐resolution microscopy is a useful tool that provides insight into the structure and emissive properties of fluorescent β‐lactoglobulin (βLG) amyloid‐like fibrils. These hybrid materials are made by functionalization of βLG with organic fluorophores and quantum dots, the latter being relevant for the production of 1D inorganic nanostructures templated by self‐assembling peptides. Simultaneous functionalization of βLG fibers by QD655 and QD525 allows for correlative AFM and two‐color super‐resolution fluorescence imaging of these hybrid materials. These experiments allow the combination of information about the topography and number of filaments that compose a fibril, as well as the emissive properties and nanoscale spatial distribution of the attached fluorophores. This study represents an important step forward in the characterization of multifunctionalized hybrid materials, a key challenge in nanoscience.     

Sensitive Detection of Carcinoembryonic Antigen Using Stability‐Limited Few‐Layer Black Phosphorus as an Electron Donor and a Reservoir

The instability of few‐layer black phosphorus (FL‐BP) hampers its further applications. Here, it can be demonstrated that the instability of FL‐BP can also be the advantage for application in biosensor. First, gold nanoparticle/FL‐BP (BP‐Au) hybrid is facilely synthesized by mixing Au precursor with FL‐BP. BP‐Au shows outstanding catalytic activity (K = 1120 s^?1 g^?1) and low activation energy (17.53 kJ mol^?1) for reducing 4‐nitrophenol, which is attributed to the electron‐reservoir and electron‐donor properties of FL‐BP, and synergistic interaction of Au nanoparticles and FL‐BP. Oxidation of FL‐BP after catalytic reaction is further confirmed by transmission electron microscope, X‐ray photoelectron spectroscopy, and zeta potentials. Second, the catalytic activity of BP‐Au can be reversibly switched from “inactive” to “active” upon treatment with antibody and antigen in solution, thus providing a versatile platform for label‐free colorimetric detection of biomarkers. The sensor shows a wide detection range (1 pg mL^?1 to –10 µg mL^?1), high sensitivity (0.20 pg mL^?1), and selectivity for detecting carcinoembryonic antigen (CEA). Finally, the biosensor has been used to detect CEA in colon and breast cancer clinical samples with satisfactory results. Therefore, the instability of BP can also be the advantage for application in detecting cancer biomarker in clinic.     

Rational Design and Synthesis of Extremely Efficient Macroporous CoSe2–CNT Composite Microspheres for Hydrogen Evolution Reaction

Uniquely structured CoSe₂–carbon nanotube (CNT) composite microspheres with optimized morphology for the hydrogen‐evolution reaction (HER) are prepared by spray pyrolysis and subsequent selenization. The ultrafine CoSe₂ nanocrystals uniformly decorate the entire macroporous CNT backbone in CoSe₂–CNT composite microspheres. The macroporous CNT backbone strongly improves the electrocatalytic activity of CoSe₂ by improving the electrical conductivity and minimizing the growth of CoSe₂ nanocrystals during the synthesis process. In addition, the macroporous structure resulting from the CNT backbone improves the electrocatalytic activity of the CoSe₂–CNT microspheres by increasing the removal rate of generated H₂ and minimizing the polarization of the electrode during HER. The CoSe₂–CNT composite microspheres demonstrate excellent catalytic activity for HER in an acidic medium (10 mA cm^?2 at an overpotential of ≈174 mV). The bare CoSe₂ powders exhibit moderate HER activity, with an overpotential of 226 mV at 10 mA cm^?2. The Tafel slopes for the CoSe₂–CNT composite and bare CoSe₂ powders are 37.8 and 58.9 mV dec^?1, respectively. The CoSe₂–CNT composite microspheres have a slightly larger Tafel slope than that of commercial carbon‐supported platinum nanoparticles, which is 30.2 mV dec^–1.     

A Cost‐Efficient Bifunctional Ultrathin Nanosheets Array for Electrochemical Overall Water Splitting

The design of cost‐efficient earth‐abundant catalysts with superior performance for the electrochemical water splitting is highly desirable. Herein, a general strategy for fabricating superior bifunctional water splitting electrodes is reported, where cost‐efficient earth‐abundant ultrathin Ni‐based nanosheets arrays are directly grown on nickel foam (NF). The newly created Ni‐based nanosheets@NF exhibit unique features of ultrathin building block, 3D hierarchical structure, and alloy effect with the optimized Ni₅Fe layered double hydroxide@NF (Ni₅Fe LDH@NF) exhibiting low overpotentials of 210 and 133 mV toward both oxygen evolution reaction and hydrogen evolution reaction at 10 mA cm^?2 in alkaline condition, respectively. More significantly, when applying as the bifunctional overall water splitting electrocatalyst, the Ni₅Fe LDH@NF shows an appealing potential of 1.59 V at 10 mA cm^?2 and also superior durability at the very high current density of 50 mA cm^?2.     

A Novel and Facile Route to Synthesize Atomic‐Layered MoS2 Film for Large‐Area Electronics

High‐quality and large‐area molybdenum disulfide (MoS₂) thin film is highly desirable for applications in large‐area electronics. However, there remains a challenge in attaining MoS₂ film of reasonable crystallinity due to the absence of appropriate choice and control of precursors, as well as choice of suitable growth substrates. Herein, a novel and facile route is reported for synthesizing few‐layered MoS₂ film with new precursors via chemical vapor deposition. Prior to growth, an aqueous solution of sodium molybdate as the molybdenum precursor is spun onto the growth substrate and dimethyl disulfide as the liquid sulfur precursor is supplied with a bubbling system during growth. To supplement the limiting effect of Mo (sodium molybdate), a supplementary Mo is supplied by dissolving molybdenum hexacarbonyl (Mo(CO)₆) in the liquid sulfur precursor delivered by the bubbler. By precisely controlling the amounts of precursors and hydrogen flow, full coverage of MoS₂ film is readily achievable in 20 min. Large‐area MoS₂ field effect transistors (FETs) fabricated with a conventional photolithography have a carrier mobility as high as 18.9 cm² V^?1 s^?1, which is the highest reported for bottom‐gated MoS₂‐FETs fabricated via photolithography with an on/off ratio of ≈10⁵ at room temperature.     

Photonic Reactions Leading to Fluorescence in a Polymeric System Induced by the Photothermal Effect of Magnetite Nanoparticles Using a 780 nm Multiphoton Laser

Recently, polymer‐coated magnetite (Fe₃O₄) nanoparticles (NPs) are extensively studied for applications in therapeutics or diagnostics using photothermal effect. Therefore, it is essential to understand the interactions between Fe₃O₄ NPs and polymers when optical stimuli are applied. Herein, the photonic reactions of Fe₃O₄ NPs and polymer composites upon application of a 780 nm multiphoton laser are analyzed. The photonic reactions produce unique results including fluorescence from conformationally changed polymer and low‐temperature phase transformation of Fe₃O₄ NPs. Typically, π‐conjugated chains are formed, inducing fluorescence through a series of main and side‐chain cleavage reactions of polymers with the aliphatic chain. In addition, fluorescence is detected in the cellular system by photonic reactions between Fe₃O₄ NPs and biomolecules. After multiphoton laser irradiation, light emission is detected near the intracellular Fe₃O₄ NPs, and a stronger intensity is observed in large‐sized NPs.