Sonochemical synthesis of PANI-BiVO4-GO semiconductor nanocomposite highly efficient visible-light photocatalytic performance

Abstract

Polyaniline/Bismuth Vanadate/Graphene Oxide (PANI-BiVO₄-GO) or BGPA composite was prepared by sonochemical deposition of bismuth vanadate-graphene oxide (BiVO₄) nanoparticles on the surface of polyaniline (PANI). The best photocatalytic degradation performance was obtained by 5wt% BGPA composites for MB, RhB, and SO dyes, which is approximately 4 times higher than that of 1% BGPA. Meanwhile, the photocatalytic stability of BiVO₄ was significantly improved by introducing PANI into the PANI-BiVO₄-GO composite. The dramatic promotion of the photocatalytic degradation performance and the photocatalytic stability can be attributed to the formation of a heterojunction free electron between PANI and BiVO₄-GO. The existence of those extra free electrons can dramatically enhance the efficiency of the photogenerated electrons, which accelerate the transfer of photogenerated holes from BiVO₄-GO to PANI, and therefore inhibit the self-oxidation of BiVO₄.     

基于光刀图像的机器人示教纠偏方法

为了解决机器人辅助在线检测系统示教过程中效率低、人为干预多的问题,针对孔类特征,提出一种通过处理光刀图像获取机器人位姿纠正参数的方法。在该方法中,纠偏过程按照将图像光刀线调整为水平方向、将被测特征调整至图像中央、根据不同特征调整最优扫描方向3个步骤进行。根据光刀图像可以求出测量坐标系与被测特征的位姿关系,并得到该位姿与理想测量位姿的偏差。经过坐标变换即可得到在机器人基坐标系下的调整参数。另外,可利用电脑控制机器人运动,从而实现了纠偏过程的自动化。实验结果表明,该方法可将初始的示教位姿修正为理想位姿,且比传统方式效率更高。     

煤基高能量密度燃料的合成及表征

高能量密度燃料是为新型高性能飞行器提供动力保障的关键,其合成及应用研究具有重要的前瞻性和重大战略意义。煤炭是我国的主体能源和重要原料,通过煤直接转化获取的煤基油,充分保留了煤中特有的环状分子化学结构,具有良好的热安定性和较高的能量密度,被认为是高超音速飞行器的优选燃料。以煤直接液化工艺生产的煤液化石脑油馏分为起始原料,通过富集轻质芳烃、化学合成、催化加氢稳定和产物分离提纯等方法制备煤基高能量密度燃料,并对其产物进行分子结构表征和性能评价。结果表明,煤直接液化生产的石脑油馏分是一种优异的催化重整原料,经催化重整富集轻质芳烃后,其轻质芳烃质量分数高达71.05%。Diels-Alder化学合成主产物是由多个封闭环平面组成且具有空间立体构型的二环或三环烃类物质,质量分数为46.18%,因分子内存在较大的张力能,结构紧凑,其拥有更大的密度和体积热值。煤基高能量密度燃料的密度和体积热值分别为0.8990 g/cm3与38.06 MJ/L,均大大超过现行的国内石油基喷气燃料(RP-3和RP-6)、煤基大比重喷气燃料、美国和俄罗斯军用标准。与单一纯物质合成高能量密度燃料(JP-10和T-10)比较,其密度与体积热值偏小。究其原因主要是轻质芳烃的富集度仅为71.05%,需进一步提高其轻质芳烃质量分数。另外,制备的煤基高能量密度燃料种类复杂,其主产物质量分数仅46.18%,下一步可重点调控合成产物的分子构型和纯化分离。     

Probing Protein Folding with Sequence-Reversed α-Helical Bundles

Recurrent protein folding motifs include various types of helical bundles formed by α-helices that supercoil around each other. While specific patterns of amino acid residues (heptad repeats) characterize the highly versatile folding motif of four-α-helical bundles, the significance of the polypeptide chain directionality is not sufficiently understood, although it determines sequence patterns, helical dipoles, and other parameters for the folding and oligomerization processes of bundles. To investigate directionality aspects in sequence-structure relationships, we reversed the amino acid sequences of two well-characterized, highly regular four-α-helical bundle proteins and studied the folding, oligomerization, and structural properties of the retro-proteins, using Circular Dichroism Spectroscopy (CD), Size Exclusion Chromatography combined with Multi-Angle Laser Light Scattering (SEC-MALS), and Small Angle X-ray Scattering (SAXS). The comparison of the parent proteins with their retro-counterparts reveals that while the α-helical character of the parents is affected to varying degrees by sequence reversal, the folding states, oligomerization propensities, structural stabilities, and shapes of the new molecules strongly depend on the characteristics of the heptad repeat patterns. The highest similarities between parent and retro-proteins are associated with the presence of uninterrupted heptad patterns in helical bundles sequences.     

Characteristics of reaction and product microstructure during light calcination of magnesite in transport bed

A gas-heating laboratory transport bed was adopted to simulate the industrial transportbed reactor for flash calcination of magnesite, and a method based on TG analysis of a reacted sample was further developed to calculate the decomposition rate or conversion of its containing MgCO₃. The study investigated how the conversion and product reactivity as well as microstructure vary with reaction conditions including temperature, particle size and times of re-calcination for powder magnesite. Magnesite powder (<150 μm) calcination is a quick reaction that reaches 98% decomposition of its containing MgCO₃ in 1—2 s,corroborating the feasibility of magnesite flash-calcination in transport bed reactors. The coloration time given by the citric acid chromogenic method was 17—55 s and 294 s for the obtained products from transport and fixed beds, respectively. This proves the obviously higher activity and thus improved microstructure of the product from transport bed. During the calcination process, the MgO grain size of the product gradually increases, and the surface structure changes from loose and porous to dense and smooth. This structural change can be completed within a few seconds.     

CuO-SiO2气凝胶@TiO2纳米纤维无牺牲剂光催化还原CO2

采用溶胶-凝胶法制备CuO-SiO2复合气凝胶,通过在气凝胶孔道内填充TiCl4,然后将其气相水解,得到了在CuO-SiO2气凝胶表面生长了高结晶度的TiO2纳米纤维(CuO-SiO2@TiO2),纤维直径～16 nm.通过XPS、UPS、UV-Vis DRS、荧光光谱(PL)等表征了材料的结构及光电性能.结果表明,制备的CuO-SiO2@TiO2对可见光有明显吸收,且荧光强度较商用TiO2(P25)大幅降低,光生电子-空穴对更加稳定.再在纳米纤维上负载CuO,所得CuO-SiO2@TiO2/CuO在可见光区的荧光强度进一步增强.以300 W氙灯为光源,分别以CuO-SiO2@TiO2及CuO-SiO2@TiO2/CuO为催化剂,无牺牲剂条件下光催化还原CO2,4 h后甲醇产率分别为1304.0及1589.0μmol/g-cat,转换频率(TOF)分别为0.038及0.046 h–1.循环实验表明,纳米纤维具有较好的光催化稳定性,经过4次光催化循环实验后,CuO-SiO2@TiO2/CuO的保留率～94％,甲醇产率可达1472.0μmol/g-cat,TOF为0.042 h–1.     

Highly efficient photocatalytic activity and mechanism of novel Er3+ and Tb3+ co-doped BiOBr/ g-C3N5 towards sulfamethoxazole degradation

Bismuth oxyhalides (BiOX (X = Cl, Br, I) are considered to be an important p-type semiconductors in the photocatalysis applications. In particular, tetragonal BiOBr is considered as a stable photocatalyst due to its resilient absorption in the visible region with an band gap energy of 2.8 eV. In the meantime, lanthanide ions (with 3+ oxidation state) implies as conversion catalyst gained huge impact and remain a serious topic in materials chemistry. Here we synthesized upconversion photocatalyst mainly consists of BiOBr with the Er ³⁺ and Tb ³⁺ ions along with low band gap g-C₃N₅ for the improved photocatalytic performances. The synthesized Er³⁺/Tb³⁺@BiOBr-g-C₃N₅ heterojunction was systematically characterized by XRD, and FT-IR for the confirmation of the composite and their morphology were analysed with FESEM and HR-TEM analysis which revealed that the sheets of g-C₃N₅ were decorated by Er³⁺/Tb³⁺ loaded BiOBr microspheres. The XPS analysis confirmed the suitable oxidation state of all the individual elements existing in the composite. As the UV-DRS analysis showed that the band gap of the Er³⁺/Tb³⁺ BiOBr-gC₃N₅ heterojunction was narrowed to 2.64 eV. To evaluate the photocatalytic efficiency of the synthesized g-C₃N₅, Er³⁺/Tb³⁺@BiOBr and Er³⁺/Tb³⁺@BiOBr-gC₃N₅ heterojunction under the simulated visible light irradiation source towards the aqueous sulfamethoxazole degradation. The Er³⁺/Tb³⁺@BiOBr-gC₃N₅ heterojunction shows maximum degradation efficiency of 94.2% after 60 min of visible light irradiation whereas the pure g-C₃N₅ provided about 43.8% and Er³⁺/Tb³⁺@BiOBr implies 55.2% degradation efficiency. The plausible degradation mechanism of pollutant removal was proposed.     

Three-dimensional complex construct fabrication of illite by digital light processing-based additive manufacturing technology

Illite is a group of clay minerals that are expected to be widely used in catalyst fabrication, radioactive element adsorption, and so forth, due to its excellent adsorption properties. However, the shape control limitation of the illite product should be overcome to maximize its utilization and properties. We herein propose additive manufacturing (AM) as one of the best solutions to solve this structural drawback. Digital light processing (DLP) technology with the film-type of the material supplying system was adapted instead of the general vat-type DLP system to increase illite printability. The photo-curability and printability of illite-contained photocurable suspension were optimized. The color effect due to different ferric oxide content in yellow- and white-illite which influence the photopolymerization process also adjusted thoroughly. White illite showed better photo-curability and could be increased solid loading than yellow illite. The defect-free illite products with three-dimensional complex structures, which cannot be produced by typical ceramic processes, were obtained by DLP technology for both yellow- and white-illite after sintering at 1100°C. The overcoming of shape control limitation of illites by ceramic AM proved in this study has excellent potential for expanding illite utilities in various applications.     

High-temperature sulfurized synthesis of MnxCd1-xS composites for enhancing solar-light driven H2 evolution

In recent years, tremendous efforts have been devoted to develop new photocatalyst with wide spectrum response for H₂ generation from water or aqueous solution. In this paper, Mn_xCd_1-xS composites were in-situ fabricated via the high-temperature sulfurization to enhance the solar-light photocatalytic capacity of H₂ evolution. Benefiting from the S defects and junction interface between MnS and CdS, Mn_xCd_1-xS composites exhibited the better H₂ evolution rate than pure MnS. The H₂ evolution rate of optimal Mn_0.5Cd_0.5S with a Mn(II) content of 22.52% and a Mn/Cd mole ratio of 0.95:1 was 9.27 mmol g^?1 h^?1, which was 35.65 and 2.38 times higher than pure MnS (0.26 mmol g^?1 h^?1) and CdS (3.89 mmol g^?1 h^?1), respectively. In addition, H₂ evolution capacity of Mn_0.5Cd_0.5S decreased from 44.83 to 41.66 mmol g^?1 after three cycles. Mn_0.5Cd_0.5S prepared via the high-temperature sulfurization was thus a potential material for solar-light induced H₂ generation.