片状煤焦颗粒CO2气化过程中形态及结构演变特性研究

采用高温热台显微镜观测了片状煤焦颗粒CO₂气化过程中的形态演变,并通过拉曼光谱分析了气化半焦的碳微晶结构,同时研究了气化温度（1000-1200℃）和煤焦初始当量直径（1.00-1.60 mm）对其CO₂气化过程中的形态及结构演变的影响规律。结果表明,与反应前期相比,反应后期的颗粒收缩（面积、体积、当量直径）更加剧烈。在所研究的气化温度范围内,随着气化温度的升高,煤焦颗粒的面积收缩率和体积收缩率逐渐减小。煤焦初始粒径显著影响颗粒收缩,1100℃气化温度下,颗粒的收缩趋势在初始粒径1.30 mm处出现转折。煤焦气化过程中碳消耗主导着表观密度的变化,在所研究的温度和粒径范围内,当碳转化率达到80%时,表观密度比线性减小到0.4以下。在相同气化温度下,随着碳转化率的增加,煤焦的石墨化程度先减小后增加,无定形碳含量先增加再减小。     

Silver microspheres coated with a molecularly imprinted polymer as a SERS substrate for sensitive detection of bisphenol A

An efficient approach is demonstrated for preparing particles consisting of a silver core and a shell of molecularly imprinted polymer (Ag@MIP). The MIP is prepared by using bisphenol A (BPA) as the template and 4-vinylpyridine as the functional monomer. The Ag@MIP fulfills a dual function in that the silver core acts as a SERS substrate, while the MIP allows for selective recognition of BPA. The Ag@MIP is characterized by scanning electron microscopy, transmission electron microscopy, X-ray powder diffraction, thermogravimetric analysis and Raman spectroscopy. The Raman intensity of Ag@MIP is higher than that of bare silver microspheres. The detection limit for BPA is as low as 10^?9 mol·L^?1.

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Graphical abstract Schematic illustration of the preparation of silver microspheres coated with a molecularly imprinted polymer (Ag@MIPs) for detecting bisphenol A (BPA) by surface enhanced Raman scattering (SERS).

     

Heterogeneous liquid phase oxidation of ethylbenzene to acetophenone with graphene carbon-based catalyst

The series of graphene materials and N-doped graphene materials were successfully synthesized and improved by high-temperature treatment with trace iron oxide. XRD, Raman, FT-IR, TEM and XPS were employed for these catalysts. The catalytic performance of these catalysts was investigated in the selective oxidation of ethylbenzene with tert-butyl hydroperoxide as oxidant. The impacts of temperature, mass of catalysts, reaction time and oxidants on the selective oxidation of ethylbenzene were also investigated. The N-doped graphene materials exhibit greatly remarkable catalytic performance than others. The conversion of ethylbenzene is more than 90% and the selectivity of acetophenone is more than 95% at 353 K. Graphene can be used as catalyst owing to its unique structures and chemical properties. The characterization tests show that the doping of N atoms can create more defects and more active sites in the N-doped graphene materials which could greatly improve the catalytic performance. Furthermore, such cost-effective graphene-based catalysts possess good stability and could be reused at least five times without remarkable loss of the catalytic activity.     

铜钱状二硫化钒的制备及储钠性能研究

钠离子电池因地壳中丰富的钠资源以及金属钠与金属锂之间具有相似的物化性质等特点,成为后锂时代电池的候选者之一,然而较大的钠离子半径影响了其体系的动力学性能及离子迁移速率,因此寻找合适的电极材料成为其发展的关键.二硫化钒作为过渡金属硫属化合物,具有类石墨烯的层状结构,为钠离子的储存提供了足够的空间,同时其出色的导电性能也为其作为高性能钠离子电池的电极材料提供了保证.利用水热法与超声剥离法,可控制备出三种堆叠密度不同的铜钱状二硫化钒（VS₂-Long、VS₂-Middle、VS₂-Short）,并将其用于储钠性能研究.结果表明,堆叠程度最低的VS₂-Short因其形貌结构特点而拥有较多的活性位点及较高结构稳定性,在100 mA·g^－1的电流密度下,循环300圈后容量高达410 mAh·g^－1;电流密度为2000 mA·g^－1,可逆容量仍高达333 mAh·g^－1.此外,还研究了二硫化钒作为钠离子电池电极材料的储能机制,通过非原位X射线粉末衍射（XRD）及透射电子显微镜（TEM）观测发现：放电过程中,电压在2.5～1.0 V发生嵌钠反应生成Na_xVS₂,之后逐渐开始转化反应生成Na₂S和V;充电时Na₂S和V转化生成Na_xVS₂,并最终脱钠生成VS₂,即在0.2～2.5 V间VS₂表现为嵌入转化的储钠机制.     

The coupling effect of slow-rate mechanical motion on the confined etching process in electrochemical mechanical micromachining

By introducing the mechanical motion into the confined etchant layer technique (CELT), we have developed a promising ultra-precision machining method, termed as electrochemical mechanical micromachining (ECMM), for producing both regular and irregular three dimensional (3D) microstructures. It was found that there was a dramatic coupling effect between the confined etching process and the slow-rate mechanical motion because of the concentration distribution of electrogenerated etchant caused by the latter. In this article, the coupling effect was investigated systemically by comparing the etchant diffusion, etching depths and profiles in the non-confined and confined machining modes. A two-dimensional (2D) numerical simulation model was proposed to analyze the diffusion variations during the ECMM process, which is well verified by the machining experiments. The results showed that, in the confined machining mode, both the machining resolution and the perpendicularity tolerance of side faces were improved effectively. Furthermore, the theoretical modeling and numerical simulations were proved valuable to optimize the technical parameters of the ECMM process.     

Specific detection and effective inhibition of a single bacterial species <Emphasis Type="Italic">in situ</Emphasis> using peptide mineralized Au cluster probes

Increasingly serious microbial infections call for the development of new simpler methods for the precise diagnosis and specific inhibition of such pathogens. In this work, a peptide mineralized Au cluster probe was applied as a new simplified strategy to both recognize and inhibit a single bacteria species of Staphylococcus aureus (S. aureus) simultaneously. The probes are composed of peptides and Au clusters. Moreover, the peptides specifically target S. aureus cells and the Au clusters provide fluorescent imaging and have an antibacterial effect. These new probes enable the simultaneous specific detection and effective destruction S. aureus cells in situ.     

Enhance the performance of polymer solar cells via extension of the flanking end groups of fused ring acceptors

Two new fused ring electron acceptors(FREAs)IDT-IC-T and IDT-IC-B with thienyl or phenyl substituents at the terminal INCN unit are synthesized.Theoretical calculations indicate that the two acceptors dominantly favor an intermolecularπ-πstacking between the flanking terminal groups.The twist angle between the aryl substituent and INCN unit has a significant influence on theπ-πstacking distance of terminal unit.IDT-IC-T with a smaller twist angle has a shorterπ-πstacking distance than that of IDT-IC-B with a larger twist angle.In addition,extending the conjugation also affects the blend film morphology.IDT-IC-T and IDT-IC-B based photoactive films show appropriate nanoscale phase separations;whereas,blend films based on the parent compound IDT-IC show large-size acceptor domains.As expected,PBDB-T:IDT-IC-T blend films show higher and more balanced electron and hole mobilities.Moreover,these two acceptors present a good charge-transport connectivity arising from the extended conjugation and the increased intermolecular overlapping.Ultimately,IDT-IC-T demonstrates the highest electron mobility(1.47×10~(-4)cm~2V~(-1)s~(-1))and the best power conversion efficiency(PCE)of 9.43%.As for IDT-IC,which only shows an electron mobility of 7.33×10~(-5)cm~2V~(-1)s~(-1)and a PCE of 5.82%.These findings provide a facile and effective way to improve the photovoltaic performance.     

White-light emission and tunable room temperature phosphorescence of dibenzothiophene

Molecular materials exhibiting room temperature phosphorescence(RTP) have received much attention during last few years. It has been known that different stacking fashions(e.g., formation of polymorph) and aggregation/crystal states could largely influence the RTP efficiency. However, whether the crystal morphology or shape could play a key role in modulation of the RTP has not been detected yet. In this work, we report that the dibenzothiophene(DBT) with the same molecular stacking fashion but different crystal morphologies can present alternated RTP performances. By modulation of the fluorescence and phosphorescence dual emission, a direct warm-white color light-emitting has also been successfully achieved. Moreover, the RTP emission can be further tuned through hybridization with β-cyclodextrin in different ratios, with the longest lifetime of 0.43 s.     

Photooxidation of a Twisted Isoquinolinone

Understanding the oxidation mechanism and positions of twistacenes and twistheteroacenes under ambient conditions is very important because such knowledge can guide us to design and synthesize novel, larger stable analogues. Herein, we demonstrated for the first time that a twisted isoquinolinone can decompose under oxygen and light at room temperature. The as‐decomposed product 1 was fully characterized through conventional methods as well as single‐crystal structure analysis. Moreover, the physical properties of the as‐obtained product were carefully investigated and the possible formation mechanism was proposed.     

Hierarchical MoS2@TiO2 Heterojunctions for Enhanced Photocatalytic Performance and Electrocatalytic Hydrogen Evolution

Hierarchical MoS₂@TiO₂ heterojunctions were synthesized through a one‐step hydrothermal method by using protonic titanate nanosheets as the precursor. The TiO₂ nanosheets prevent the aggregation of MoS₂ and promote the carrier transfer efficiency, and thus enhance the photocatalytic and electrocatalytic activity of the nanostructured MoS₂. The obtained MoS₂@TiO₂ has significantly enhanced photocatalytic activity in the degradation of rhodamine B (over 5.2 times compared with pure MoS₂) and acetone (over 2.8 times compared with pure MoS₂). MoS₂@TiO₂ is also beneficial for electrocatalytic hydrogen evolution (26 times compared with pure MoS₂, based on the cathodic current density). This work offers a promising way to prevent the self‐aggregation of MoS₂ and provides a new insight for the design of heterojunctions for materials with lattice mismatches.