Research Progress in Enzyme Biofuel Cells Modified Using Nanomaterials and Their Implementation as Self-Powered Sensors.

Enzyme biofuel cells (EBFCs) can convert chemical or biochemical energy in fuel into electrical energy, and therefore have received widespread attention. EBFCs have advantages that traditional fuel cells cannot match, such as a wide range of fuel sources, environmental friendliness, and mild reaction conditions. At present, research on EBFCs mainly focuses on two aspects: one is the use of nanomaterials with excellent properties to construct high-performance EBFCs, and the other is self-powered sensors based on EBFCs. This article reviews the applied nanomaterials based on the working principle of EBFCs, analyzes the design ideas of self-powered sensors based on enzyme biofuel cells, and looks forward to their future research directions and application prospects. This article also points out the key properties of nanomaterials in EBFCs, such as electronic conductivity, biocompatibility, and catalytic activity. And the research on EBFCs is classified according to different research goals, such as improving battery efficiency, expanding the fuel range, and achieving self-powered sensors.

Design and Synthesis of Amphiphilic Catalyst [C16mim]5VW12O40Br and Its Application in Deep Desulfurization with Superior Cyclability at Room Temperature.

Achieving long-term stable deep desulfurization at room temperature and recovering high value-added sulfone products is a challenge at present. Herein, a series of catalysts [Cnmim]5VW12O40Br (CnVW12, 1-alkyl-3-methylimidazolium bromide tungstovanadate, n = 4, 8, 16) were presented for the room temperature catalytic oxidation of dibenzothiophene (DBT) and its derivatives. Factors affecting the reaction process, such as the amount of catalyst, oxidant, and temperature, were systematically discussed. C16VW12 showed higher catalytic performance, and 100% conversion and selectivity could be achieved in 50 min with only 10 mg. The mechanism study showed that the hydroxyl radical was the active radical in the reaction. Benefiting from the "polarity strategy", the sulfone product accumulated after 23 cycles in a C16VW12 system, and the yield and purity were about 84% and 100%, respectively.

Molecular Cytological Analysis and Specific Marker Development in Wheat-Psathyrostachys huashanica Keng 3Ns Additional Line with Elongated Glume.

Psathyrostachys huashanica Keng (2n = 2x = 14, NsNs) is an excellent gene resource for wheat breeding, which is characterized by early maturity, low plant height, and disease resistance. The wheat-P. huashanica derivatives were created by the elite genes of P. huashanica and permeate into common wheat through hybridization. Among them, a long-glume material 20JH1155 was identified, with larger grains and longer spike than its parents. In the present study, the methods of cytological observation, GISH, and sequential FISH analysis showed that 20JH1155 contained 21 pairs of wheat chromosomes and a pair of P. huashanica. There were some differences in 5A and 7B chromosomes between 20JH1155 and parental wheat 7182. Molecular marker, FISH, and sequence cloning indicated 20JH1155 alien chromosomes were 3Ns of P. huashanica. In addition, differentially expressed genes during immature spikelet development of 20JH1155 and 7182 and predicted transcription factors were obtained by transcriptome sequencing. Moreover, a total of 7 makers derived from Ph#3Ns were developed from transcriptome data. Taken together, the wheat-P. huashanica derived line 20JH1155 provides a new horizon on distant hybridization of wheat and accelerates the utilization of genes of P. huashanica.

Construction of Water-Stable Rare-Earth Organic Frameworks with Ambient High Proton Conductivity Based on Zirconium Sandwiched Heteropolytungstate.

Water-stable proton-conducting materials owning excellent performances at ambient temperatures are currently one of the crucial challenges. Herein, four water-stable three-dimensional polyoxometalate-based rare-earth organic frameworks have been successfully synthesized and formulated as H{Ln4(L)2(H2O)21[Zr3(OH)3(PW9O34)2]}·15H2O (1-3) (Ln = La (1), Ce (2), Pr (3); L = 3,5-pyridine dicarboxylic acid), which are the first examples of MOFs constructed by a zirconium sandwiched polyoxoanion. There are abundant coordinated water molecules functionalizing the PrIII centers, and simultaneously, plenty of lattice water molecules are fitted into the channel of the framework. A continuous H-bonding network is found between the architectures and plays an important role in stabilizing the structure. Benefiting from the consecutive H-bonding networks, compounds 1-3 showed high proton conductivities at ambient temperature (up to 1.05 × 10-3 S·cm-1 under 98% RH) by a synergistic effect of the combined components.

The Microstructures, Mechanical Properties, and Deformation Mechanism of B2-Hardened NbTiAlZr-Based Refractory High-Entropy Alloys.

The NbTiAlZrHfTaMoW refractory high-entropy alloy (RHEA) system with the structure of the B2 matrix (antiphase domains) and antiphase domain boundaries was firstly developed. We conducted the mechanical properties of the RHEAs at 298 K, 1023 K, 1123 K, and 1223 K, as well as typical deformation characteristics. The RHEAs with low density (7.41~7.51 g/cm3) have excellent compressive-specific yield strength (σYS/ρ) at 1023 K (~131 MPa·cm3/g) and 1123 K (~104.2 MPa·cm3/g), respectively, which are far superior to most typical RHEAs. And, they still keep appropriate plastic deformability at room temperature (ε > 0.35). The superior specific yield strengths are mainly attributed to the solid solution strengthening induced by the Zr element. The formation of the dislocation slip bands with [111](101_) and [111](112_) directions and their interaction provide considerable plastic deformation capability. Meanwhile, dynamic recrystallization and dislocation annihilation accelerate the continuous softening after yielding at 1123 K.

Portable smartphone-integrated AuAg nanoclusters electrospun membranes for multivariate fluorescent sensing of Hg2+, Cu2+ and l-histidine in water and food samples.

Detection of heavy metals have been pivotal due to their non-biodegradability and food chain accumulation. Herein, a multivariate ratiometric sensor was developed by in situ integrating AuAg nanoclusters (NCs) into electrospun cellulose acetate nanofibrous membranes (AuAg-ENM) for visual detection of Hg2+, Cu2+ and consecutive sensing of l-histidine (His), which was integrated into a smartphone platform for quantitative on-site detection. AuAg-ENM achieved multivariate detection of Hg2+ and Cu2+ by fluorescence quenching, and subsequent selective recovery of the Cu2+-quenched fluorescence by His, which distinguished Hg2+ and Cu2+ and fulfilled determination of His simultaneously. Notably, AuAg-ENM achieved selective monitoring of Hg2+, Cu2+ and His in water, food and serum samples with high accuracy comparable to ICP and HPLC tests. A logic gate circuit was devised to further explain and promote the application of AuAg-ENM detection by smartphone App. This portable AuAg-ENM provides a promising reference for fabricating intelligent visual sensors for multiple detection.

Cu-Doped Boron Nitride Nanosheets for Solid-Phase Extraction and Determination of Rhodamine B in Foods Matrix.

Cu-doped boron nitride nanosheets (Cu-BNNS) were first reported as promising adsorbents for the solid-phase extraction and determination of rhodamine B (RhB) dye in a food matrix. Different characterizations, including XRD, FTIR, XPS, SEM, and TEM, were performed to confirm the formation of the adsorbent. Then, the adsorption performance of Cu-BNNS was investigated by adsorption kinetics, isotherms, and thermodynamics. Multiple extraction parameters were optimized by single-factor experiments. Under optimized conditions, the recoveries in the food matrix were in the range of 89.8-95.4%, with the spiked levels of 100 ng/mL and 500 ng/mL, respectively. This novel system was expected to have great potential to detect RhB in a wide variety of real samples.

Two three-dimensional Fe(II) frameworks based on {P4Mo6} tetrameric clusters exhibiting efficient visible-light photocatalytic properties for the degradation of Cr(VI) and methylene blue.

Two three-dimensional frameworks based on the {P4Mo6} unit, H(4,4'-bipy)2[Fe4(PO4)(H2O)4Na6][Fe6(H2O)4][(Mo6O12)(HPO4)3(PO4)(OH)3]4·5H2O (4,4'-bipy = 4,4'-bipyridine) (1) and H3(C12H14N2)4[Fe4(PO4)(H2O)4Na4][Fe2(Mo6O12(HPO4)3(PO4)(OH)3)4]·6H2O (2) were successfully synthesized by varying the solvent. The extended structures of the two compounds were formed by transition metal Fe(II) ions bridging the {P4Mo6}-based tetrameric clusters around [NaXFe4(PO4)] (X = 6 (1), or X = 4 (2)) core. The 4,4'-bipy molecules and in situ generated methyl viologen cations as templates induce the formation of two three-dimensional structures, an 8-connected bcu topology framework for 1 and a 4-connected 2-fold interpenetrating diamond-like topological network for 2, respectively. Additionally, multiform hydrogen bonds are found in the framework and also play an important role in stabilizing the structure. The proton conduction mechanism of the two compounds can be mainly classified as the Grotthuss mechanism; the proton conductivity values are 1.06 × 10-3 S cm-1 for 1 and 3.13 × 10-3 S cm-1 for 2 at 75 °C under 98% relative humidity. The visible-light photocatalytic activity was evaluated by photocatalytic decomposition of Cr(VI) and MB dye, and the removal ratios can reach 95.6% (1) and 82% (2) for Cr(VI), and 98% (1) and 99% (2) for MB.

Preparation of fluorescent bimetallic silver/copper nanoparticles and their utility of dual-mode fluorimetric and colorimetric probe for Hg2.

A dual-mode colorimetric and fluorimetric probe was successfully established based on silver/copper bimetallic nanoparticles (AgCu-BNPs). The AgCu-BNPs were confirmed as individually bimetallic nanoparticles with a mean size of 7.7 ± 0.2 nm, as characterized by high resolution transmission electron microscopy. Intriguingly, the AgCu-BNPs possess both surface plasmon resonances (SPR) and fluorescence emission. AgCu-BNPs emanate bright blue fluorescence with optical emission centered at 442 nm with high quantum yield of 30.3%, and AgCu-BNPs were attenuated or even quenched by Hg2+ via both static and dynamic quenching, coincidently accompanied by a visible color change, which endow AgCu-BNPs a unique utility as dual-mode colorimetric and fluorimetric probes. The detection limits as low as 89 nM and 9 nM were determined by dual-mode of AgCu-BNPs, respectively. The recovery rates in real samples were found to be 97.3-118.8%, and 89.5-112.7% by colorimetric and fluorescent methods separately, demonstrates the good environmental tolerance of the dual-mode probe.

Quasi-Situ Characterization of Retained Austenite Orientation in Quenching and Partitioning Steel via Uniaxial Tensile Tests.

As a representative of the third generation of advanced high strength steel, the quenching and partitioning steel has excellent potential in automobile manufacturing. The characterization and analysis of the mechanical properties and microstructure of the quenching and partitioning steel during deformation is an effective way to explore the microstructure evolution and transformation-induced plasticity effects of complex phase steels. The relationship between the microstructure morphology and mechanical properties of a 1180 MPa-grade quenching and partitioning steel was investigated through interrupted uniaxial tensile tests plus quasi-situ electron backscatter diffraction measurements. A mixture of ferrite, martensite, and retained austenite was observed in the microstructure. It was found that the volume fraction of global retained austenite decreased linearly with the increase of displacement (0 mm-1.05 mm). The evolution of the retained austenite with typical crystal direction ranges with deformation was characterized. Results show that the orientation (111) and (311) account for the highest proportion of retained austenite grains in the undeformed sample and the mechanical stability of the (311) retained austenite grains is the best. Moreover, the retained austenite grains rotated significantly in the early stage of the specimen deformation process (around yielding), and the work hardening of the specimen was weak at this stage, simultaneously.

Enhanced Photocatalytic Hydrogen Production of the Polyoxoniobate Modified with RGO and PPy.

The development of high-efficiency, recyclable, and inexpensive photocatalysts for water splitting for hydrogen production is of great significance to the application of solar energy. Herein, a series of graphene-decorated polyoxoniobate photocatalysts Nb6/PPy-RGO (Nb6 = K7Nb6O19, RGO = reduced graphene oxide, PPy = polypyrrole), with the bridging effect of polypyrrole were prepared through a simple one-step solvothermal method, which is the first example of polyoxoniobate-graphene-based nanocomposites. The as-fabricated photocatalyst showed a photocatalytic H2 evolution activity without any co-catalyst. The rate of 1038 µmol g-1 in 5 h under optimal condition is almost 43 times higher than that of pure K7HNb6O19·13H2O. The influencing factors for photocatalysts in photocatalytic hydrogen production under simulated sunlight were studied in detail and the feasible mechanism is presented in this paper. These results demonstrate that Nb6O19 acts as the main catalyst and electron donor, RGO provides active sites, and PPy acted as an electronic bridge to extend the lifetime of photo-generated carriers, which are crucial factors for photocatalytic H2 production.

Graphene-like BN@SiO2 nanocomposites as efficient sorbents for solid-phase extraction of Rhodamine B and Rhodamine 6G from food samples.

A novel dendritic silicon dioxide nanocomposite coated with a highly dispersed graphene-like boron nitride nanosheet (g-BN(x)@SiO2) was in-situ synthesized and employed as a solid-phase extraction material for the Rhodamine B (RhB) and Rhodamine 6G (R6G) enrichment in food samples prior to their quantitation by HPLC. The structures and morphologies of g-BN(x)@SiO2 were characterized by XRD, FTIR, BET and TEM. The adsorption performance and mechanism were investigated and showed an enhanced maximum adsorption capacity of 625 mg/g for RhB on the nanocomposite loaded with 1% of g-BN via a fast, spontaneous process. Under optimal extraction conditions, this method showed low detection and quantification limits (2.8 µg/L for RhB, 2.1 µg/L for R6G and 9.2 µg/L for RhB, 6.9 µg/L for R6G, respectively), good repeatability (RSD% <3.7%), and satisfactory spiked recoveries of 94.8%-103.1% for RhB and R6G in real chili powder and beverage. Therefore, the g-BN(1%)@SiO2-based materials possess significant potential.

Interface Effects on He Ion Irradiation in Nanostructured Materials.

In advanced fission and fusion reactors, structural materials suffer from high dose irradiation by energetic particles and are subject to severe microstructure damage. He atoms, as a byproduct of the (n, α) transmutation reaction, could accumulate to form deleterious cavities, which accelerate radiation-induced embrittlement, swelling and surface deterioration, ultimately degrade the service lifetime of reactor materials. Extensive studies have been performed to explore the strategies that can mitigate He ion irradiation damage. Recently, nanostructured materials have received broad attention because they contain abundant interfaces that are efficient sinks for radiation-induced defects. In this review, we summarize and analyze the current understandings on interface effects on He ion irradiation in nanostructured materials. Some key challenges and research directions are highlighted for studying the interface effects on radiation damage in nanostructured materials.

Tuning electronic properties of boron nitride nanoplate via doping carbon for enhanced adsorptive performance.

In this paper, the carbon-doped boron nitride nanoplate (C-BNNP) was prepared by pyrolyzing the precursor under N2 and served as an excellent adsorbent for removal of Rhodamine B (RhB). The structure and composition of C-BNNP were characterized and its adsorption behavior for RhB was investigated. Compared with boron nitride nanoplate (BNNP) which was synthesized under NH3, C-BNNP displayed an enhancement of the adsorption capacity for RhB (833mg/g). The adsorption activity was comprehensibly studied by kinetics, isotherm and thermodynamics. The adsorption kinetics followed pseudo-second-order model. The equilibrium adsorption data agreed well with the Langmuir isotherm. And the thermodynamics indicated that the adsorption process was a spontaneous, exothermic and physisorption process. In addition, the density functional theory was proposed that doping carbon in the BNNP decreased the chemical hardness of the adsorbent and enhanced the adsorption capacity of C-BNNP for RhB.

Tuning the Chemical Hardness of Boron Nitride Nanosheets by Doping Carbon for Enhanced Adsorption Capacity.

The chemical hardness of adsorbents is an important physicochemical property in the process of adsorption based on the hard and soft acids and bases (HSAB) theory. Tuning chemical hardness of adsorbents modulated by their concomitants is a promising approach to enhance the adsorptive capacity in principle. In the present work, we report an efficient strategy that the adsorption capacity for aromatic sulfocompounds can be enhanced by tuning the chemical hardness. This strategy is first theoretically explored by introducing C element into the network of hexagonal boron nitride (h-BN) based on a series of model materials (model_xC, x = 1-5). Computational results show that the chemical hardness is reduced after gradually C-doping, which may lead to an enhancement of adsorption capacity according to the HSAB theory. Then, a series of C-doped h-BN materials (BCN-x, x = 10-50) were controlled synthesized. All of the as-prepared materials show better adsorption capacities (e.g., 27.43 mg g-1 for BCN-50) than pure h-BN. Experiment results show that the adsorption capacity correlates well with the C content in the BCN-x, which is consistent with the results predicted by theoretical calculation. This strategy may be helpful to rationally design highly efficient adsorbents in separation engineering and may be expanded to similar two-dimensional materials, where the π-π interaction is the dominant driven force.