The effects of molecular configuration on the photochromism and decolorization of two bipyridinium-based coordination polymers

Two layer-like coordination polymers, {[Cd(Bpyen)_0.5(m-BDC)(H₂O)Br]·4H₂O}(1) and {[Cd(Bpyen)_0.5(o-BDC)Br]·H₂O}(2), have been solvothermally synthesized and structurally characterized. The two compounds own common rapid photochromic response but different decolorization behaviors. The photoproduct of compound 2 is more stable in air. The relationship between structure and photoresponsive behavior has been studied in detail.     

A fluorescence chemosensor for benzonitrile derived from in-situ synthesis of azolate–carboxylic acid and zinc(II) ions

A new zinc(II) homometallic coordination polymer (CP), {[Zn(TAA-OH)₂] · 1.5H₂O}_n (1) (HTAA-OH = 2-(5-hydroxy-1H-1,2,4-triazole-1-yl) acetic acid) has been synthesized via an in-situ synthetic approach and structurally characterized in detail. In 1, the HTAA-OH ligand is generated in-situ by the nucleophilic addition of 2-(1H-1,2,4-triazole-1-yl) acetic acid. CP 1 features a 2D structure with sql topology, where the neighboring Zn(II) ions are bridged through two oxygen atoms of carboxyl group and two nitrogen atoms of triazole from the HTAA-OH ligands. Luminescence study shows that 1 dispersed in acetonitrile performs a distinct luminescence enhancing effect upon addition of benzonitrile, indicating that 1 is a promising fluorescence chemosensor for benzonitrile.     

Polymers of phenylenediamines

The chemical or electrochemical oxidation of phenylenediamines in acidic aqueous media yields the corresponding oligomers or polymers. Their structures and properties are discussed in relation to a closely-related conducting polymer, polyaniline. Depending on the reaction conditions, polyphenylenediamines are produced as powders, colloidal dispersions, thin films, or composites. In contrast to polyaniline, polyphenylenediamines are rated as non-conductors and their conductivities are low. Similarly to polyaniline, these polymers display a salt–base transition and they are redox-active. They act as reductants of noble-metal compounds to the corresponding metals or as precursors in the carbonization to nitrogen-rich carbons. Applications proposed in the literature are outlined; they include the corrosion protection of metals, catalysis, electrorheology, sensors, energy-conversion devices, electrochromism, noble-metal recovery, and water treatment.     

K–I co-doped crystalline carbon nitride with outstanding visible light photocatalytic activity for H2 evolution

Heteroatomic doping is an effective way to optimize the electronic structure of carbon nitride to boost photocatalytic performance. However, the extra introduced defects could result in the decrease of its crystallinity. In this work, crystalline K–I co-doped carbon nitride (K–I–CCN) was simply synthesized from molten salt ionthermal post-calcination in nitrogen atmosphere. Structure characterization results indicate that compared to K–CCN synthesized from conventional molten salt heat treatment in air, nitrogen heating atmosphere is more conductive for the formation of homogeneous pore structure of the catalyst, which has larger surface area and pore volume, while could repairing some defects and resulting in better polymerization crystallization. In addition, except the implanting of K, I doping is still retained after nitrogen heat treatment, thus forming K–I co-doping structure. Due to the positive charge effect of K–I co-doping, K–I–CCN has a narrower band gap, higher surface charge density and stronger charge transport, so it performs significantly enhanced photocatalytic H₂ evolution activity from water splitting.     

基于功能参数的渐进成形件表面质量表征研究

目的 以圆锥台成形件为例，基于粗糙表面的区域支承率曲线，进行了用功能参数表征表面几何形貌的研究，以全面、准确、定量地表征渐进成形件的表面质量，预测表面性能。方法 用渐进成形工艺加工成形角分别为35°、45°和55°的圆锥台件，将各圆锥台的成形面分为顶部、中部和底部三个区域，并使用三维表面轮廓仪，在上述三个区域中随机测量各4个样本。根据ISO 25178-2:2012，将各样本表面的区域支承率曲线分为峰区、核心区和谷区，选用部分功能参数——核心区高度Sk、峰区材料体积Vmp、核心区材料体积Vmc和谷区空隙体积Vvv表征表面，并与常用的高度表征参数——Sa、Sq、Ssk和Sku进行比较。结果 成形件表面的Ssk和Sku的计算值极不稳定，变异系数（标准偏差与均值之比）最高值分别可达127.67%和39.11%，Sa、Sq的最大变异系数分别为4.41%和4.26%，虽然它们的参数计算值较为稳定，但常无法体现表面形貌的实际差异。功能参数独立表征不同功能区，Sk和Vmc的最大变异系数分别为9.32%和7.73%，说明同一表面各处，在长期工作阶段具有较为一致的表面性能，Vmp和Vvv的最大变异系数分别为60.53%和31.25%，说明表面各处峰、谷区的形貌有所不同，因而在磨合时间、磨粒存储等方面会有不同的表现。结论 粗糙表面的三维本质要求用三维表征参数才能全面表征其几何形貌。高度参数虽然计算简单，但常难以解读它们的物理意义，无法定量评价表面性能；功能参数具有明确的物理意义，可为表征表面质量、预测表面性能提供定量、实用的方法。     

A pricing-based location model for deploying a hydrogen fueling station network

We propose an innovative two-step Pricing-Based Location strategy for the rollout of new hydrogen fueling stations. A first model maximizes the profit of a new station with a price p¹ which corresponds to a design capacity supplying a given market share (n¹ customers). According to these findings and with the objective of deploying an extensive network, a second model searches for a suitable location as remote as possible from existing competitors, but as close as possible to just n¹ demand locations. This problem is solved by an agent-based model integrating the Particle Swarm Optimization metaheuristic and a Geographic Information System representing the geospatial distribution of customer demand. We apply this model to the city of Paris by locating additional stations across the city one by one to supply a growing captive fleet of taxis and other transport operators in the future.     

Fabricating NixCo1−xO@C cocatalysts sensitized by CdS through electrostatic interaction for efficient photocatalytic H2 evolution

Exploiting efficient and stable noble metal-free hydrogen evolution catalysts for water splitting is of great importance. In this work, Ni_xCo_1-xO@C/CdS hybrid is successfully fabricated through an electrostatic interaction of oppositely charged nanoparticles on their surfaces. The resulting Ni_xCo_1-xO@C nanoboxes cocatalysts which were derived from NiCo-LDH@ZIF-67 with Ni–Co layered double hydroxides (LDH) decorated with ZIF-67 precursor exhibited improved hydrogen production rate compared with bare CdS semiconductor from 0.7 mmol g⁻¹ h⁻¹ to 56 mmol g⁻¹ h⁻¹. It is demonstrated that the electrostatic interaction between the two surface charged nanoparticles of Ni_xCo_1-xO@C and CdS play an important role in migrating and separating of photogenerated charge carriers. The synthesized Ni_xCo_1-xO@C as excellent candidates for cost-effective cocatalysts is aimed to substitute for noble metals in photocatalytic H₂ evolution.     

铍铜合金断续切削后刀面磨损机理研究

目的研究断续切削过程温度变化对刀具粘结现象、涂层剥落和刀具磨损的影响。方法搭建了仿铣削加工的断续车削实验平台,采用热电偶法测量了断续切削过程中刀具后刀面在不同速度下的切削温度,利用带有能谱仪(EDS)的扫描电镜(SEM)观察后刀面随速度变化的磨损形貌并分析后刀面磨损区域的元素组成,阐述了后刀面温度和刀具磨损之间的联系,研究了Ti AlN涂层硬质合金刀具断续切削铍铜合金C17200时的后刀面磨损机理。结果随着切削速度的增加,刀具温度在v=500 m/min出现峰值,温度越高,后刀面的涂层剥落和粘结磨损现象越严重,涂层剥落和粘结磨损现象在切削速度为500 m/min时最严重,而后随着刀具温度的降低而减缓,切削速度600 m/min时的涂层剥落和粘结磨损现象相比500 m/min时有所减轻。结论断续切削过程中,刀具持续性地经受"负载-卸载"、"升温-降温"产生的高温、冲击和加工环境的不稳定性,是引起粘结现象、涂层剥落和刀具磨损的主要原因。涂层剥落和粘结磨损是导致铍铜合金断续切削刀具失效的主要磨损形式。     

Numerical simulation of liquid water emerging and transport in the flow channel of PEMFC using the volume of fluid method

Three-dimensional numerical simulation of liquid water emerging from the gas diffusion layer (GDL) surface to the gas flow channel in the proton exchange membrane (PEM) fuel cell (PEMFC) is carried out using the volume of fluid (VOF) method. The effects of the water velocity in the GDL hole, the airflow velocity and the wettability of the channel surfaces on the water emerging process and transport in the flow channel are investigated. It is found that at low water velocity, the water detaches from the water hole, forming discrete water droplets on the GDL surface, and is transported downstream on the GDL surface until removed from the GDL surface by the U-turn part of the flow channel; whereas at high water velocity, the continuous water column impinges the hydrophilic channel surface counter to the GDL surface, being directly removed from the GDL surface. The airflow velocity affects water detachment and impact process in the channel corner, and water droplet breakup is observed under high airflow velocity. The channel surface wettability influences water droplet shape and its transport in the channel. Rather than forming corner water films at the U-turn for hydrophilic channel surface, water maintains the droplet shape and smoothly passes through the U-turn for hydrophobic channel surface. The importance of the U-turn to the water removal is also discussed. The U-turn promotes water removal from the GDL surface at low water velocity and water breakup at high airflow velocity.     

Modification of the ultrasonication derived-g-C3N4 nanosheets/quantum dots by MoS2 nanostructures to improve electrocatalytic hydrogen evolution reaction

In this work, graphitic carbon nitride (g-C₃N₄) nanosheets/quantum dots (NS/QD) was prepared using a simple and low-cost procedure. By two steps exfoliation in a bath and tip sonicator, the g-C₃N₄ (NS/QD) was produced from bulk g-C₃N₄. To improve electrocatalytic hydrogen evolution reaction (HER), the g-C₃N₄ (NS/QD) were modified by the MoS₂ nanostructures. Nanocomposite of the g-C₃N₄ (NS/QD) with MoS₂ nanostructures was deposited on a flexible, conductive and three dimensional carbon cloth by a facile and binder-free electrophoretic technique. This electrode exhibited a Tafel slope of 88 mV/dec and an overpotential of 0.28 V vs RHE at −2 mA/cm², lower than that of the g-C₃N₄, and good stability after 1000 cycles and 100 days for HER. The enhanced electrocatalytic performance was attributed to the MoS₂ and g-C₃N₄ nanostructures on three dimensional carbon cloth, leading to high surface area and more number of the exposed active sites for HER. This heterostructure improved charge transport, proton adsorption and hydrogen evolution on the electrode. This work proposes cost-effective, stable and three dimensional g-C₃N₄ based electrode for hydrogen evolution reaction.