Thermodynamically and Kinetically Stabilized Pt Clusters Against Sintering on CeO2 Nanofibers Through Enclosing CeO2 Nanocubes.

Sintering is a major concern for the deactivation of supported metals catalysts, which is driven by the force of decreasing the total surface energy of the entire catalytic system. In this work, a double-confinement strategy is demonstrated to stabilize 2.6 nm-Pt clusters against sintering on electrospun CeO2 nanofibers decorated by CeO2 nanocubes (m-CeO2 ). Thermodynamically, with the aid of CeO2 -nanocubes, the intrinsically irregular surface of polycrystalline CeO2 nanofibers becomes smooth, offering adjacent Pt clusters with decreased chemical potential differences on a relatively uniform surface. Kinetically, the Pt clusters are physically restricted on each facet of CeO2 nanocubes in a nanosized region. In situ high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) observation reveals that the Pt clusters can be stabilized up to 800 °C even in a high density, which is far beyond their Tammann temperature, without observable size growth or migration. Such a sinter-resistant catalytic system is endowed with boosted catalytic activity toward both the hydrogenation of p-nitrophenol after being aged at 500 °C and the sinter-promoting exothermic oxidation reactions (e.g., soot oxidation) at high temperatures over 700 °C. This work offers new opportunities for exploring sinter-resistant nanocatalysts, starting from the rational design of whole catalytic system in terms of thermodynamic and kinetic aspects.

Electronic textiles based on aligned electrospun belt-like cellulose acetate nanofibers and graphene sheets: portable, scalable and eco-friendly strain sensor.

Recently, there has been strong interest in flexible and wearable electronics to meet the technological demands of modern society. Environmentally-friendly and scalable electronic textiles is a key area that is still significantly underdeveloped. Here, we describe a novel strain sensor composed of aligned cellulose acetate (CA) nanofibers with belt-like morphology and a reduced graphene oxide (RGO) layer. The unique spatial alignment, microstructure and wettability of CA nanofibrous membranes facilitate their close contact with deposited GO colloids. After a portable and fast hot-press process within 700 s at 150 °C, the GO on CA membrane can be facilely reduced to a conductive RGO layer. Moreover, the connection among contiguous CA nanofibers and the interaction between the GO and CA substrate were both highly enhanced, resulting in superior mechanical strength with Young's modulus of 1.3 GPa and small sheet resistance lower than 10 kΩ. Therefore, the conductive RGO/CA membrane was successfully utilized as a strain sensor in a broad deformation range and with versatile deformation types. Moreover, the distinctive mechanical strength under different stretch angles endowed the well-aligned RGO/CA film with intriguing sensitivity against stress direction. Such a cost-effective and environmentally-friendly method can be easily extended to the scalable production of graphene-based flexible electronic textiles.

Novel photocatalyst gold nanoparticles with dumbbell-like structure and their superiorly photocatalytic performance for ammonia borane hydrolysis.

Gold nanoparticles (Au NPs) have attracted remarkable research interests in heterogeneous catalysis due to their unique physical and chemical properties. However, only small-size Au NPs (<7 nm) exhibit promising catalytic activity. In this work, dumbbell-like Au NPs (D-Au NPs) with average size of 37 × 11 nm were prepared by a secondary seed-mediated growth method to serve as novel photocatalyst for ammonia borane (AB) hydrolysis in the solution with specific pH value. Our results demonstrate that ⅰ) the strengthened LSPR compensation effect could effectively remedy the loss of catalytic activity resulting from the size enlarging of D-Au NPs, proven by that the heating power of a single Au nanoparticle (Ps) and turnover frequency of AB molecules within 10 minutes of D-Au NPs are 52.5 and 3.89 times higher than that of spherical Au NPs; ⅱ) the extinction coefficient and Ps of D-Au NPs are almost 2.72 and 2.42 times as high as that of rod-like Au NPs, demonstrating the promoting structure-property relationship of dumbbell-like structure.; ⅲ) when the pH value of AB solution was lower than 6.0, the hydrolysis rate was highly promoted, indicating that H+ ions play an active role in the hydrolysis process. This work greatly extends the application of noble metals and provides a new insight into AB hydrolysis.

In situ growth of hierarchical Al2O3 nanostructures onto TiO2 nanofibers surface: super-hydrophilicity, efficient oil/water separation and dye-removal.

Developing a facile strategy to synthesize template-free TiO2 membrane with stable super-hydrophilic surface is still a daunting challenge. In this work, super-hydrophilicity (close to 0°) and underwater super-oleophobicity (165°) have been successfully demonstrated on a hierarchical Al2O3/TiO2 membrane, which is prepared via a facile electrospinning method followed by simple calcination in air. The precisely-tuned Al2O3 heterojunctions grew in situ and dispersed uniformly on the TiO2 surface, resulting in an 'island in the sea' configuration. Such a unique feature allows not only achieving super-hydrophilicity by maximizing the surface roughness and enhancing the hydrogen bonding, but also improving the adsorption capacity toward different toxic dyes utilizing the abundant adsorption sites protected by the hierarchical nanostructure during sintering. The new Al2O3/TiO2 nanofibrous membrane can serve as a novel filter for gravity driven oil/water separation along with dye removal, achieving 97.7% of oil/water separation efficiency and 98% of dye capture, thanks to their superb wettability and the sophisticated adsorptive performance. Our presented fabrication strategy can be extended to a wide range of ceramic materials and inspires their advanced applications in water purification under harsh liquid-phase environments.

Visible-light promoted catalytic activity of dumbbell-like Au nanorods supported on graphene/TiO2 sheets towards hydrogenation reaction.

In this work, the rationally-designed sharp corners on Au nanorods tremendously improved the catalytic activity, particularly in the presence of visible light irradiation, towards the hydrogenation of 4-nitrophenol to 4-aminophenol. A strikingly increased rate constant of 50.6 g-1 s-1 L was achieved in M-Au-3, which was 41.8 times higher than that of parent Au nanorods under dark conditions. The enhanced activities were proportional to the extent of the protruding sharp corners. Furthermore, remarkably enhanced activities were achieved in novel ternary Au/RGO/TiO2 sheets, which were endowed with a 52.0 times higher rate constant than that of straight Au nanorods. These remarkably enhanced activities were even higher than those of previously reported 3-5 nm Au and 3 nm Pt nanoparticles. It was systematically observed that there are three aspects to the synergistic effects between Au and RGO sheets: (i) electron transfer from RGO to Au, (ii) a high concentration of p-nitrophenol close to dumbbell-like Au nanorods on RGO sheets, and (iii) increased local reaction temperature from the photothermal effect of both dumbbell-like Au nanorods and RGO sheets.

Self-assembly of defect-rich graphene oxide nanosheets with Na2Ti3O7 nanowires and their superior absorptive capacity to toxic dyes.

Graphene sheets, a flexible 2D material with excellent absorptive capacity, have great potential as absorbing materials. However, this material has always suffered from irreversible aggregation and thus loses the abundant active sites and large surface area. In this paper, large-scale graphene oxide (GO) sheets were cut and reduced to tiny reduced graphene oxide (RGO) sheets by a cell-break sonicator, for producing numerous defects, which are the center of chemisorption. Furthermore, sodium titanate nanowires functioned as a framework to help to disperse the tiny RGO sheets uniformly. And, in turn, the flexible tiny RGO sheets glued robust nanowires into a free-standing membrane. This novel composite membrane exhibited an ultra-high decoloration efficiency of 99.8% of rhodamine B in a continuous flow mode, and an outstanding absorptive capability of 1.30 × 10-2 mol g-1 correlated to RGO content in batch reaction, which is about two orders of magnitude higher than other reported graphene-based absorbents. In addition, an efficient and feasible method without any heat treatment for regenerating the membrane is illustrated, and the recycled membrane retains superior decoloration efficiency. The excellent absorptive performance indicates the framework-based disperse strategy has great potential for the construction and application of defect-rich graphene.

Flexible-in-rigid polycrystalline titanium nanofibers: a toughening strategy from a macro-scale to a molecular-scale.

TiO2 nanomaterials, especially one-dimensional TiO2 nanofibers fabricated by electrospinning, have received considerable attention in the past two decades, for a variety of basic applications. However, their safe use and easy recycling are still hampered by the inherently subpar mechanical performance. Here, we toughened polycrystalline TiO2 nanofibers by introducing Al3+-species at the very beginning of electrospinning. The resultant long-and-continuous TiO2 nanofibers achieved a Young's modulus of 653.8 MPa, which is ca. 25-fold higher than that of conventional TiO2 nanofibers. Within each nanofiber, amorphous Al2O3-based oxide effectively hindered the coalescence of TiO2 nanocrystals and potentially repaired the surface groves. The solid-state 17O-NMR spectra further revealed the toughening strategy on a molecular scale, where relatively flexible Ti-O-Al bonds replaced rigid O-Ti-O bonds at the interfaces of TiO2 and Al2O3. Moreover, the modified TiO2 nanofibers exhibited superb sinter-resistance, without cracking over 900 °C, which was dynamically monitored by TEM. Therefore, flexible-in-rigid TiO2 fibrous mats can be facilely folded into 3D sponges through origami art. As a potential showcase, the TiO2 sponges were demonstrated as a duarable and renewable filtrator with a high filtration efficiency of 99.97% toward PM2.5 and 99.99% toward PM10 after working for 300 min. This work provides a rational strategy to produce flexible oxide nanofibers and gives an in-depth understanding of the toughening mechanism from the macro-scale to the molecular-scale.

A Study on the Dynamic Tunning Range of CVD Graphene at Microwave Frequency: Determination, Prediction and Application.

In recent years, graphene has shown great application prospects in tunable microwave devices due to its tunable conductivity. However, the electromagnetic (EM) properties of graphene, especially the dynamic tunning characteristics, are largely dependent on experimental results, and thus are unable to be effectively predicted according to growth parameters, which causes great difficulties in the design of graphene-based tunable microwave devices. In this work, we systematically explored the impact of chemical vapor deposition (CVD) parameters on the dynamic tunning range of graphene. Firstly, through improving the existing waveguide method, the dynamic tunning range of graphene can be measured more accurately. Secondly, a direct mathematical model between growth parameters and the tunning range of graphene is established. Through this, one can easily obtain needed growth parameters for the desired tunning range of graphene. As a verification, a frequency tunable absorber prototype is designed and tested. The good agreement between simulation and experimental results shows the reliability of our mathematic model in the rapid design of graphene-based tunable microwave devices.

One stone two birds: a sinter-resistant TiO2 nanofiber-based unbroken mat enables PM capture and in situ elimination.

Airborne particulate matter (PM) primarily resulting from fossil fuel burning is an increasingly global issue. In this work, an intrinsically fragile TiO2 nanofibrous mat was facilely engineered with good structural integrity, flexibility, foldability, and high-temperature resistance (~1300 °C), by suppressing the sintering (i.e., growth) of nanocrystallites in each single nanofiber. Such functionalization enables self-regenerative air filtration for PM capture and in situ catalytic elimination in a "one-stone-two-birds" approach. Finite element analysis simulation revealed the retained nanopores in each anti-sintering nanofiber could facilitate the air flow during filtration. Without any chemical or physical modification, this self-standing and lightweight (7.1 g m-2) fibrous mat showed 96.05% filtration efficiency for 3-5 µm NaCl particles, with a low pressure drop of only 18 Pa and high quality factor of 0.179 Pa-1 under an airflow velocity of 32 L min-1. By utilizing its photocatalytic attribute, the nanofibrous mat in situ eliminated the captured particles from incense burning under one Sun irradiation in 4 h, and thereby spontaneously regenerated in an easy manner. The straightforward grafting of Au nanoparticles onto nanofibers could enable a quick degradation toward cigarette smoke, mainly due to the photothermally elevated local temperature by Au around the reactive sites. The plasmonic fibrous mat kept a high and stable filtration efficiency of PM0.3, PM2.5, and PM10 over 98.62%, 99.76%, and 99.99% during an outdoor long-term filtration test for 12 h under sunlight irradiation (Nanjing, China, September, 26th, 2020, 7:30 to 19:30). This work provides a solution for solving the airborne pollution from its source, prolonging the lifetime of the filter, and avoiding the risk of producing secondary pollution.

Unusual Hollow Al2O3 Nanofibers with Loofah-Like Skins: Intriguing Catalyst Supports for Thermal Stabilization of Pt Nanocrystals.

Recently, hollow nanofibers could be fabricated by coaxis electrospinning method or template method. However, they are limited to applications because of the hardship in actual preparation. In this work, hollow γ-Al2O3 nanofibers with loofah-like skins were first fabricated by using a single spinneret during electrospinning. These intriguing nanofibers were explored as new Pt supports with excellently sinter-resistant performance up to 500 °C, attributed to the unique loofah-like surface of γ-Al2O3 nanofibers and the strong metal-support interactions between Pt and γ-Al2O3. When applied in the catalytic reduction of p-nitrophenol, the Pt/γ-Al2O3 calcined at 500 °C exhibited 4-times higher reaction rate constant (6.8 s-1·mg-1) over free Pt nanocrystals.