Lu Hua Li

Toward Design of Synergistically Active Carbon-Based Catalysts for Electrocatalytic Hydrogen Evolution

Replacement of precious Pt catalyst with cost-effective alternatives would be significantly beneficial for hydrogen production via electrocatalytic hydrogen evolution reaction (HER). All candidates thus far are exclusively metallic catalysts, which suffer inherent corrosion and oxidation susceptibility during acidic proton-exchange membrane electrolysis. Herein, based on theoretical predictions, we designed and synthesized nitrogen (N) and phosphorus (P) dual-doped graphene as a nonmetallic electrocatalyst for sustainable and efficient hydrogen production. The N and P heteroatoms could coactivate the adjacent C atom in the graphene matrix by affecting its valence orbital energy levels to induce a synergistically enhanced reactivity toward HER. As a result, the dual-doped graphene showed higher electrocatalytic HER activity than single-doped ones and comparable performance to some of the traditional metallic catalysts.

Strong Oxidation Resistance of Atomically Thin Boron Nitride Nanosheets

Investigation of oxidation resistance of two-dimensional (2D) materials is critical for many of their applications because 2D materials could have higher oxidation kinetics than their bulk counterparts due to predominant surface atoms and structural distortions. In this study, the oxidation behavior of high-quality boron nitride (BN) nanosheets of 1-4 layers thick has been examined by heating in air. Atomic force microscopy and Raman spectroscopy analyses reveal that monolayer BN nanosheets can sustain up to 850 °C, and the starting temperature of oxygen doping/oxidation of BN nanosheets only slightly increases with the increase of nanosheet layer and depends on heating conditions. Elongated etch lines are found on the oxidized monolayer BN nanosheets, suggesting that the BN nanosheets are first cut along the chemisorbed oxygen chains and then the oxidative etching grows perpendicularly to these cut lines. The stronger oxidation resistance of BN nanosheets makes them more preferable for high-temperature applications than graphene.

Molecule-level g-C3N4 coordinated transition metals as a new class of electrocatalysts for oxygen electrode reactions

Organometallic complexes with metal-nitrogen/carbon (M-N/C) coordination are the most important alternatives to precious metal catalysts for oxygen reduction and evolution reactions (ORR and OER) in energy conversion devices. Here, we designed and developed a range of molecule-level graphitic carbon nitride (g-C3N4) coordinated transition metals (M-C3N4) as a new generation of M-N/C catalysts for these oxygen electrode reactions. As a proof-of-concept example, we conducted theoretical evaluation and experimental validation on a cobalt-C3N4 catalyst with a desired molecular configuration, which possesses comparable electrocatalytic activity to that of precious metal benchmarks for the ORR and OER in alkaline media. The correlation of experimental and computational results confirms that this high activity originates from the precise M-N2 coordination in the g-C3N4 matrix. Moreover, the reversible ORR/OER activity trend for a wide variety of M-C3N4 complexes has been constructed to provide guidance for the molecular design of this promising class of catalysts.

Large-scale mechanical peeling of boron nitride nanosheets by low-energy ball milling

Mechanical cleavage by Scotch tape was the first method to produce graphene and is still widely used in laboratories. However, a critical problem of this method is the extremely low yield. We have tailored ball milling conditions to produce gentle shear forces that produce high quality boron nitride (BN) nanosheets in high yield and efficiency. The in-plane structure of the BN nanosheets has not been damaged as shown by near edge X-ray absorption fine structure measurements. The benzyl benzoate acts as the milling agent to reduce the ball impacts and milling contamination. This method is applicable to any layered materials for producing nanosheets.

Superhydrophobic properties of nonaligned boron nitride nanotube films

Superhydrophobicity is highly desirable for numerous applications. Here, we report that a semierect but nonaligned boron nitride nanotube (BNNT) film showed superhydrophobicity with contact angle above 170 degrees and a small contact angle hysteresis. This superhydrophobicity was stable over a large range of drop sizes, and the measured critical transition pressure was about 10 kPa. However, the prostrate BNNT films only showed hydrophobicity. The drop retraction behavior during evaporation, the pressure effect on contact angle, the critical transition pressure, the drop impact behavior, and the self-cleaning efficiency between these two kinds of films were systematically investigated and compared.

Dielectric screening in atomically thin boron nitride nanosheets

Two-dimensional (2D) hexagonal boron nitride (BN) nanosheets are excellent dielectric substrate for graphene, molybdenum disulfide, and many other 2D nanomaterial-based electronic and photonic devices. To optimize the performance of these 2D devices, it is essential to understand the dielectric screening properties of BN nanosheets as a function of the thickness. Here, electric force microscopy along with theoretical calculations based on both state-of-the-art first-principles calculations with van der Waals interactions under consideration, and nonlinear Thomas-Fermi theory models are used to investigate the dielectric screening in high-quality BN nanosheets of different thicknesses. It is found that atomically thin BN nanosheets are less effective in electric field screening, but the screening capability of BN shows a relatively weak dependence on the layer thickness.

Photoluminescence of boron nitride nanosheets exfoliated by ball milling

The photoluminescence of boron nitride (BN) nanosheets exfoliated by ball milling method has been investigated. At room temperature, the nanosheets have strong deep ultraviolet (DUV) light emission at 224 nm and weak defect-related UV (∼300 nm) emission. The DUV peak profile slightly changes with the increase of milling time due to the increase of stacking faults caused by the shear force during milling. The decreased ∼300 nm emission after milling treatments has been attributed to the preferential orientation of the BN nanosheets on substrate and the strong polarization anisotropy of BN materials in luminescence.

Ball milling: a green mechanochemical approach for synthesis of nitrogen doped carbon nanoparticles

Technological and scientific challenges coupled with environmental considerations have attracted a search for robust, green and energy-efficient synthesis and processing routes for advanced functional nanomaterials. In this article, we demonstrate a high-energy ball milling technique for large-scale synthesis of nitrogen doped carbon nanoparticles, which can be used as an electro-catalyst for oxygen reduction reactions after a structural refinement with controlled thermal annealing. The resulting carbon nanoparticles exhibited competitive catalytic activity (5.2 mA cm(-2) kinetic-limiting current density compared with 7.6 mA cm(-2) on Pt/C reference) and excellent methanol tolerance compared to a commercial Pt/C catalyst. The proposed synthesis route by ball milling and annealing is an effective process for carbon nanoparticle production and efficient nitrogen doping, providing a large-scale production method for the development of highly efficient and practical electrocatalysts.

Structure and properties of biomedical films prepared from aqueous and acidic silk fibroin solutions

Silk fibroin films are promising materials for a range of biomedical applications. To understand the effects of casting solvents on film properties, we used water (W), formic acid (FA), and trifluoroacetic acid (TFA) as solvents. We characterized molecular weight, secondary structure, mechanical properties, and degradation behavior of cast films. Significant degradation of fibroin was observed for TFA-based film compared to W and TA-based films when analyzed by SDS-PAGE. Fibroin degradation resulted in a significant reduction in tensile strength and modulus of TFA-based films. Compared to water, TFA-based films demonstrated lower water solubility (19.6% vs. 62.5% in 12 h) despite having only a marginal increase in their β-sheet content (26.9% vs. 23.7%). On the other hand, FA-based films with 34.3% β-sheet were virtually water insoluble. Following solubility treatment, β-sheet content in FA-based films increased to 50.9%. On exposure to protease XIV, water-annealed FA-based films lost 74% mass in 22 days compared to only 30% mass loss by ethanol annealed FA films. This study demonstrated that a small variation in the β-sheet percentage and random coil conformations resulted in a significant change in the rates of enzymatic degradation without alteration to their tensile properties. The film surface roughness changed with the extent of enzymatic hydrolysis.

Synthesis of boron nitride nanotubes by boron ink annealing

Ball-milling and annealing is one effective method for the mass production of boron nitride nanotubes (BNNTs). We report that the method has been modified to a boron (B) ink annealing method. In this new process, the nanosize ball-milled B particles are mixed with metal nitrate in ethanol to form an ink-like solution, and then the ink is annealed in nitrogen-containing gas to form nanotubes. The new method greatly enhances the yield of BNNTs, giving a higher density of nanotubes. These improvements are caused by the addition of metal nitrate and ethanol, both of which can strongly boost the nitriding reaction, as revealed by thermogravimetric analysis. The size and structure of BNNTs can be controlled by varying the annealing conditions. This high-yield production of BNNTs in large quantities enables the large-scale application of BNNTs.