Constructing hierarchical sulfur-doped nitrogenous carbon nanosheets for sodium-ion storage.

Hierarchical sulfur-doped nitrogenous carbon (S/NC) and nitrogenous carbon (NC) nanosheets are successfully fabricated by carbonization of their corresponding precursor polymers which are synthesized through the polymerization reaction of dianhydride and multi-amine compounds. Hierarchical S/NC nanosheets deliver greatly enhanced reversible capacity, compared with hierarchical NC nanosheets, of 280 mAh g-1 at a current density of 100 mA g-1 after 300 cycles. It is found that the introduction of sulfur species in carbon skeleton results in increasing the turbostratic structures, rather than enlarging the interlayer distances, for boosting the specific capacity of sodium-ion storage. The turbostratic structures and sulfur dopant existed in the carbon can offer more active sites for the sodium-ion storage. Carbon-based materials doped with sulfur are capable of improving the sodium-ion storage property, which can broaden the horizon of designing a string of outstanding carbon materials for the future energy storage technologies.

Dispersing molecular cobalt in graphitic carbon nitride frameworks for photocatalytic water oxidation.

The development of water oxidation catalysts (WOCs) to cooperate with light-energy transducers for solar energy conversion by water splitting and CO2 fixation is a demanding challenge. The key measure is to develop efficient and sustainable WOCs that can support a sustainable photocatalyst to reduce over-potentials and thus to enhance reaction rate of water oxidation reaction. Cobalt has been indentified as active component of WOCs for photo/electrochemical water oxidation, and its performance relies strongly on the contact and adhesion of the cobalt species with photoactive substrates. Here, cobalt is homogeneously engineered into the framework of pristine graphitic carbon nitride (g-C3 N4 ) via chemical interaction, establishing surface junctions on the polymeric photocatalyst for the water oxidation reaction. This modification promotes the surface kinetics of oxygen evolution reaction by the g-C3 N4 -based photocatalytic system made of inexpensive substances, and further optimizations in the optical and textural structure of Co-g-C3 N4 is envisaged by considering ample choice of modification schemes for carbon nitride materials.

Transient Metal Centers at the Covalent Heterointerface Favor Photocatalytic Hydrogen Evolution.

Semiconductor heterostructures effectively promote the transfer and separation of interfacial photoinduced charges for the photocatalytic process. Herein, we constructed a direct Z-scheme SnSe2/CdS heterojunction photocatalyst. N-type SnSe2 semiconductors are suitable candidate materials for oxidation half-reactions in Z-scheme heterojunctions. The intimate atomic-level interfacial contact through Cd-Se bonds provides a better interfacial charge transport channel for the photoinduced charges. Moreover, the transient Sn4+/Sn0 centers caused by the photoredox process boost the interfacial charge transport/separation at the interface. Besides, the presence of S vacancies acting as electron enrichment centers further enhances the redox ability for hydrogen production. Therefore, the SnSe2/CdS heterostructure showed a superior visible-light photocatalytic H2-production activity of 13.6 mmol·g-1·h-1 using ascorbic acid as a sacrificial agent, which is 9.7 times higher than that of pristine CdS. The apparent quantum yield reaches 10.5% at λ = 420 nm. This work provides a useful way to improve charge transfer in the Z-scheme heterojunction photocatalyst for hydrogen production.

Tuning of an optical dimer nanoantenna by electrically controlling its load impedance.

Optical antennas are elementary units used to direct optical radiation to the nanoscale. Here we demonstrate an active control over individual antenna performances by an external electrical trigger. We find that by an in-plane command of an anisotropic load medium, the electromagnetic interaction between individual elements constituting an optical antenna can be controlled, resulting in a strong polarization and tuning response. An active command of the antenna is a prerequisite for directing light wave through the utilization of such a device.

[Statistical comparison of independent validation results for near infrared spectroscopy models predicting calorific value of straw].

Two hundred and twenty-two straw samples, consisting of 170 rice straw samples and 50 wheat straw samples, were collected from 24 provinces of China. Near infrared spectroscopy (NIRS)was applied to build quantitative models for calorific value of straw combining the use of principal component regression (PCR), partial least square regression (PLS)and modified partial least square regression (MPLS). Different scatter correction methods and derivative treatments were adopted to help improve the accuracy of NIRS models. A total of 54 NIRS models were obtained and independent validations were conducted using the same validation set of samples. A statistical comparison of independent validation results was then introduced to evaluate whether the models perform significantly. Bias and bias corrected standard error of prediction (SEP(C)), which are the mean and the standard deviation of the prediction residuals respectively, were compared by the proposed statistical procedures. It was concluded that near infrared spectroscopy was able to predict the calorific value of straw samples rapidly and accurately, with resulting SEP(C)s between 134 and 178 J x g(-1); statistical comparison of biases and SEP(C)s was a reasonable and efficient way to compare spectral pre-processing methods, and select NIRS models predicting calorific value of straw.

[Proximate analysis of straw by near infrared spectroscopy (NIRS)].

Proximate analysis is one of the routine analysis procedures in utilization of straw for biomass energy use. The present paper studied the applicability of rapid proximate analysis of straw by near infrared spectroscopy (NIRS) technology, in which the authors constructed the first NIRS models to predict volatile matter and fixed carbon contents of straw. NIRS models were developed using Foss 6500 spectrometer with spectra in the range of 1,108-2,492 nm to predict the contents of moisture, ash, volatile matter and fixed carbon in the directly cut straw samples; to predict ash, volatile matter and fixed carbon in the dried milled straw samples. For the models based on directly cut straw samples, the determination coefficient of independent validation (R2v) and standard error of prediction (SEP) were 0.92% and 0.76% for moisture, 0.94% and 0.84% for ash, 0.88% and 0.82% for volatile matter, and 0.75% and 0.65% for fixed carbon, respectively. For the models based on dried milled straw samples, the determination coefficient of independent validation (R2v) and standard error of prediction (SEP) were 0.98% and 0.54% for ash, 0.95% and 0.57% for volatile matter, and 0.78% and 0.61% for fixed carbon, respectively. It was concluded that NIRS models can predict accurately as an alternative analysis method, therefore rapid and simultaneous analysis of multicomponents can be achieved by NIRS technology, decreasing the cost of proximate analysis for straw.

Enhancing Visible-Light Hydrogen Evolution Performance of Crystalline Carbon Nitride by Defect Engineering.

Crystalline carbon nitride (CCN)-based semiconductors have recently attracted widespread attention in solar energy conversion. However, further modifying the photocatalytic ability of CCN always results in a trade-off between high crystallinity and good photocatalytic performance. Herein, a facile defect engineering strategy was demonstrated to modify the CCN photocatalysts. Results confirmed that the obtained D-CCN maintained the high crystallinity; additionally, the hydrogen production rate of D-CCN was approximately 8 times higher than that of CCN. Particularly, it could produce H2 even if the incident light wavelength extended to 610 nm. The significantly improved photocatalytic activity could be ascribed to the introduction of defects into the CCN polymer network to form the midgap states, which significantly broadened the visible-light absorption range and accelerated the charge separation for photoredox catalysis.

Structure-Mediated Charge Separation in Boron Carbon Nitride for Enhanced Photocatalytic Oxidation of Alcohol.

Boron carbon nitride (BCN) is a promising earth-abundant photocatalyst for solar energy conversion. However, the photocatalytic activities of BCN materials remain moderate because of the fast electron-hole recombination. Herein, an ordered BCN structure is fabricated by a facile one-step thermal treatment strategy. The ordered structure of BCN is directly evident from powder X-ray diffraction and high-resolution transmission electron microscopy. Importantly, it is found that the long-period ordered structure can intrinsically accelerate the separation and transfer kinetics of photogenerated charge carriers. Benefiting from these advantages, the ordered BCN structure exhibits remarkable performance for photoinduced selective oxidation of benzyl alcohol compared with the pristine BCN counterpart. This work highlights the important role of the crystal structure of light-harvesting materials in affecting electron-hole separation and at the same time points to the ample potential for improving the photocatalytic performance.

Hydrogenation of nitroarenes into aromatic amines over Ag@BCN colloidal catalysts.

The present work reports that two-dimension layered ternary boron carbon nitrogen nanosheets can serve as good carriers to support and disperse noble metal nanoparticles. The Ag@BCN colloids have thus been prepared by attaching Ag nanoparticles on the surfaces of BCN nanosheets. The detailed structures of the Ag@BCN samples were investigated by X-ray diffraction, transmission electron microscopy, atomic force microscope, infrared, and X-ray photoelectron spectroscopy. It is found that the surface NH groups of BCN nanosheets are beneficial for the attachment of Ag nanopaprticles. Compared with the conventional organic capping compounds, the two dimensional planar BCN nanosheets endow the attached nanoparticle with the high active surfaces. Moreover, the hydrogenation of nitroarenes into the corresponding aromatic amines can be highly achieved over Ag@BCN colloids by NaBH4. In particular, the apparent activation energy of the conversion reaction of p-nitroaniline to p-phenylenediamine was found to be 76.0kJ/mol over the Ag@BCN colloids with 3wt% Ag content. Our results may provide a new approach for the design noble metal based composites and find the practical application for the hydrogenation of nitroarenes.

Hexagonal boron nitride nanoplates as emerging biological nanovectors and their potential applications in biomedicine.

The application of nanomaterials in the biological and medical areas has attracted great attention. Cytotoxicity, stability and solubility are the prerequisites for a nanomaterial to be considered for application in the field of biomedicine. Here, we suggest a simple method to produce highly dispersed water-soluble ultrathin h-BN nanoplates whose size measures ca. 30-60 nm in diameter and 1.6 nm in thickness. Moreover, we demonstrate that h-BN nanoplates can act as a reliable biological nanovector to carry proteins by cross-linking immobilization. Furthermore, the biocompatibility of h-BN nanoplates has also been explored via an apoptosis assay. In addition, a successful attempt has been made to investigate the potency of h-BN nanoplates as an immunostimulating adjuvant in a mouse immunization experiment. Preliminary results show that the level of antibody response stimulated by an antigen protein (bovine serum albumin) linked with h-BN is ca. 4 times higher than that by the antigen protein alone. This work gives evidence that water-soluble h-BN nanoplates are of high biocompatibility and low reactogenicity and therefore they can serve as an excellent biomedical platform for nanoparticle-biomolecular interactions. They preserve and even enhance the bioacitivities of the cross-linked antigen proteins, which strongly suggests their use in nanoparticle vaccine design.

Boron nitride encapsulated copper nanoparticles: a facile one-step synthesis and their effect on thermal decomposition of ammonium perchlorate.

Reactivity is of great importance for metal nanoparticles used as catalysts, biomaterials and advanced sensors, but seeking for high reactivity seems to be conflict with high chemical stability required for metal nanoparticles. There is a subtle balance between reactivity and stability. This could be reached for colloidal metal nanoparticles using organic capping reagents, whereas it is challenging for powder metal nanoparticles. Here, we developed an alternative approach to encapsulate copper nanoparticles with a chemical inertness material--hexagonal boron nitride. The wrapped copper nanoparticles not only exhibit high oxidation resistance under air atmosphere, but also keep excellent promoting effect on thermal decomposition of ammonium perchlorate. This approach opens the way to design metal nanoparticles with both high stability and reactivity for nanocatalysts and their technological application.

Carbon-doped BN nanosheets for metal-free photoredox catalysis.

The generation of sustainable and stable semiconductors for solar energy conversion by photoredox catalysis, for example, light-induced water splitting and carbon dioxide reduction, is a key challenge of modern materials chemistry. Here we present a simple synthesis of a ternary semiconductor, boron carbon nitride, and show that it can catalyse hydrogen or oxygen evolution from water as well as carbon dioxide reduction under visible light illumination. The ternary B-C-N alloy features a delocalized two-dimensional electron system with sp(2) carbon incorporated in the h-BN lattice where the bandgap can be adjusted by the amount of incorporated carbon to produce unique functions. Such sustainable photocatalysts made of lightweight elements facilitate the innovative construction of photoredox cascades to utilize solar energy for chemical conversion.

Dispersed Cu2O octahedrons on h-BN nanosheets for p-nitrophenol reduction.

We demonstrate here that two-dimensional boron nitride (h-BN) nanosheets can be employed as a robust supporting substrate to incorporate function metal oxides. The Cu2O@h-BN composites are thus obtained by dispersing Cu2O octahedrons on the surfaces of h-BN nanosheets. The -OH and -NH groups on the surfaces of h-BN nanosheets are found to be beneficial for anchoring Cu2O octahedrons. Moreover, the Cu2O@h-BN composites exhibit superior activity for the reduction of p-nitrophenol to pure Cu2O crystals and h-BN nanosheets. The h-BN component in the composites plays a critical role in the formation and adsorbing of the p-nitrophenolate ions, and, at the same time, Cu2O components react with brohydride ions and transfer a surface hydrogen species and electrons, resulting in the reduction of p-nitrophenol into p-aminophenol. Our results provide a new approach for the rational design and development of metal oxides composites and open the way to a range of important applications of h-BN-based materials.