NO和HSO偶联及其异构化反应机理

采用G2M（CC5）//MPW1PW91/6-311＋G（2df,p）方法,研究了HSO和NO偶联及其异构化反应机理,获得了各物种的几何构型和频率数据,并构建了标题反应的势能剖面。结果表明,该反应存在3条不同路径,优势路径为R（NO＋HSO）→IM1→TS1→IM2,其表观活化能为42.38 kJ· mol-1。此过程为NO中N原子与HSO中O原子偶合形成中间体IM1,接着IM1中SH基团从O（1）原子迁移到O（2）原子上后反应完成。     

微波协同离子液体催化合成富马酸二甲酯的工艺研究及应用

以离子液体[HSO3-pmim]+[HSO4]-为催化剂,马来酸酐和甲醇为原料,硫脲为异构化试剂,在微波条件下,通过酯化反应催化合成富马酸二甲酯。通过单因素实验和正交试验考察了马来酸酐与甲醇物质的量比、催化剂用量、微波功率和微波时间对富马酸二甲酯产率的影响。实验结果表明,合成富马酸二甲酯最佳条件为:马来酸酐与甲醇物质的量比为1∶6,催化剂离子液体[HSO3-pmim]+[HSO4]-用量为2.5g,微波功率为400 W,微波时间为7min,富马酸二甲酯的产率可达95.3%。在微波辐射下,催化剂离子液体[HSO3-pmim]+[HSO4]-重复使用7次后活性没有明显降低,富马酸二甲酯产率仍高于90%,表明该催化剂具有较好的反应活性和稳定性。     

基于8098单片机的步进电机控制系统

给出了利用8098单片机的高速输出单元HSO实现对步进电机的控制原理、硬件、软件设计。该系统与由复杂的电子线路或51系列单片机构成的步进电机控制系统相比,具有速度高、智能化、电路简单、工作可靠等特点。     

C+x*HSO-4插层化合物的水热法合成

通过水热法成功地合成了 C x · H SO- 4 石墨插层化合物 ,讨论了氧化剂、插入剂、反应时间、反应温度和原料配比等对插层反应的影响 ,以及热力学对插层反应的影响。与熔盐法相比 ,水热法优点显著 ,不仅反应温度低、操作简单 ,并且不需要抽真空 ,从而开辟了石墨插层化合物新的合成途径。     

热压烧结Fe_3Si-10%Cu复合材料在稀H_2SO_4中的腐蚀行为

采用机械合金化制粉/热压烧结制备了Fe3Si-10%Cu复合材料,研究了其在0.4,0.6和0.8 mol·L-1的稀H2SO4中的浸泡腐蚀行为.结果表明,Fe3Si-10%Cu复合材料在稀H2SO4中表现出腐蚀失重,且随H2SO4浓度增加材料的腐蚀速率降低;复合材料中Fe3Si和Cu两相在H2SO4溶液中形成了一个腐蚀电池,其中Fe3Si相为阳极,发生腐蚀,Cu为阴极,得到保护;电化学腐蚀测试表明,Fe3Si-10%Cu复合材料在0.4,0.6和0.8mol·L-1的H2SO4溶液中自腐蚀电位相当,且在0.4 mol·L-1溶液中具有最低的自腐蚀电流和维钝电流.在0.6和0.8 mol·L-1的H2SO4溶液中,阳极反应产物以SiO2形态附着在Fe3Si-10%Cu材料表面导致腐蚀速率下降.     

2-氯-1,3-二苯并噁唑啉环己烯对HSO_4~-的识别研究

利用紫外可见吸收光谱手段考察了2-氯-1,3-二苯并噁唑啉环己烯(化合物1)与F-,Cl-,Br-I,-,CH3COO-,HSO4-,H2PO4-等阴离子的作用.结果表明,该化合物对HSO4-具有选择性识别能力,可实现裸眼识别,有望成为HSO4-识别探针.     

离子液体[Hnmp]HSO_4催化菜籽油制备生物柴油

制备了具有酸性功能的离子液体[Hnmp]HSO4,并用其催化菜籽油酯交换制备生物柴油.该离子液体表现出良好的催化活性及稳定性.在醇油比为8∶1、反应温度(100±2)℃、反应时间5h和[Hnmp]HSO4的用量为菜籽油质量的8%时,生物柴油收率可达85.4%.并且该离子液体有较好的稳定性,循环使用4次后仍有较高的催化性能.     

基于苯并呋咱的HSO3-离子荧光探针

以4-氯-7-硝基苯并呋咱(NBD-Cl)和咪唑-4-甲醛为原料,设计合成了一种用于检测亚硫酸氢根离子(HSO₃-)的荧光探针,并通过核磁共振氢谱(1H-NMR)、质谱(MS)对其结构进行了表征.荧光测试结果表明:在二甲基亚砜(DMSO)水溶液中,该化合物能够对HSO₃-表现出荧光增强响应,而相同条件下该化合物对其他阴离子几乎没有类似的荧光识别现象,因此该荧光化合物对HSO₃-具有专一荧光识别作用,是一种有效的HSO₃-荧光探针.     

一种基于苯并噻唑的比色比率荧光探针识别检测HSO3-

合成了一种苯并噻唑衍生物荧光探针BDT，在中性水体系中，探针BDT与HSO₃^-发生迈克尔加成反应，破坏了探针分子的π-共轭体系，阻断了分子内电荷转移（ICT）过程，引起溶液颜色及荧光发射波长的显著改变，从而可实现在水体系中比色/比率检测HSO₃^-。探针BDT对HSO₃^-表现出高选择性、高灵敏度，检出限为2.86×10^-7mol·L^-1。实验结果表明，探针BDT能够用于白糖和白酒中一定浓度范围内HSO₃^-的检测及对HeLa细胞中外源及内源性HSO₃^-的荧光成像。     

[BMIM]HSO4/乙醇降解纤维素残渣的热解行为和产物分布

以微晶纤维素为原料，利用1-丁基-3甲基咪唑硫酸氢盐（[BMIM]HSO4）与乙醇二元溶剂体系在180 oC下进行催化降解制备得到纤维素固体残渣（SRE），并考察了[BMIM]HSO4质量浓度对SRE结构特征和热解过程的影响规律，为SRE的资源化利用提供理论基础。通过FTIR、Raman、XRD、SEM和激光粒度分析仪对样品进行结构表征，结果表明SRE保持了纤维素化学结构，但随着[BMIM]HSO4质量浓度的增加，SRE粒径显著降低，晶体结构不断被破环并转化为热不稳定的无定形结构。通过热重分析仪和管式反应器研究SRE的热解行为规律，结果表明：随着[BMIM]HSO4质量浓度的增加，SRE热失重起始温度显著降低，热失重曲线向低温区移动。同时，随[BMIM]HSO4浓度的增加，促进了可挥发分与残渣的气固作用，引起焦炭和气体产率增加，生物油产率降低；生物油成分中D-Allose的产率随[BMIM]HSO4浓度的增加大幅降低，而左旋葡萄糖酮和5-羟甲基糠醛、糠醛等含量升高，即[BMIM]HSO4浓度的增加有利于SRE转化生产糠醛等小分子生物质基平台化合物。     

[BPy][HSO4]离子液体催化合成3,4-二氢嘧啶-2-酮

经典的Biginelli反应用HCl作催化剂,通常产率较低(20%～50%).以[BPy][HSO4]离子液体为催化剂考察了Biginelli反应在不同温度和溶剂下的反应特点,合成了一系列3,4-二氢嘧啶-2-酮,产率70.7%～92.1%.该方法操作简单方便,产率、纯度较经典的Biginelli反应有较大的提高和改善,具有一定实用价值.     

具有良好可再生性的新型二氧化硅磁性氧化石墨烯纳米复合材料

Graphene oxide (GO) wrapped Fe₃O₄ nanoparticles (NPs) were prepared by coating the Fe₃O₄ NPs with a SiO₂ layer, and then modifying by amino groups, which interact with the GO nanosheets to form covalent bonding. The SiO₂ coating layer plays a key role in integrating the magnetic nanoparticles with the GO nanosheets. The effect of the amount of SiO₂ on the morphology, structure, adsorption, and regenerability of the composites was studied in detail. An appropriate SiO₂ layer can effectively induce the GO nanosheets to completely wrap the Fe₃O₄ NPs, forming a core-shell Fe₃O₄@SiO₂@GO composite where Fe₃O₄@SiO₂ NPs are firmly encapsulated by GO nanosheets. The optimized Fe₃O₄@SiO₂@GO sample exhibits a high saturated adsorption capacity of 253 mg·g?1 Pb(II) cations from wastewater, and the adsorption process is well fitted by Langmuir adsorption model. Notably, the composite displays excellent regeneration, maintaining a ~90% adsorption capacity for five cycles, while other samples decrease their adsorption capacity rapidly. This work provides a theoretical guidance to improve the regeneration of the GO-based adsorbents.     

微波预处理对复杂铜矿磨矿及浮选动力学的影响

The effect of CaCO₃, Na₂CO₃, and CaF₂ on the reduction roasting and magnetic separation of high-phosphorus iron ore containing phosphorus in the form of Fe₃PO₇ and apatite was investigated. The results revealed that Na₂CO₃ had the most significant effect on iron recovery and dephosphorization, followed by CaCO₃, the effect of CaF₂ was negligible. The mechanisms of CaCO₃, Na₂CO₃, and CaF₂ were investigated using X-ray diffraction (XRD), scanning electron microscopy and energy dispersive spectrometry (SEM–EDS). Without additives, Fe₃PO₇ was reduced to elemental phosphorus and formed an iron–phosphorus alloy with metallic iron. The addition of CaCO₃ reacted with Fe₃PO₇ to generate an enormous amount of Ca₃(PO₄)₂ and promoted the reduction of iron oxides. However, the growth of iron particles was inhibited. With the addition of Na₂CO₃, the phosphorus in Fe₃PO₇ migrated to nepheline and Na₂CO₃ improved the reduction of iron oxides and growth of iron particles. Therefore, the recovery of iron and the separation of iron and phosphorus were the best. In contrast, CaF₂ reacted with Fe₃PO₇ to form fine Ca₃(PO₄)₂ particles scattered around the iron particles, making the separation of iron and phosphorus difficult.     

不同硅饱和系数水榴石的碳酸化分解动力学

Carbonated decomposition of hydrogarnet is one of the vital reactions of the calcification–carbonation method, which is designed to dispose of low-grade bauxite and Bayer red mud and is a novel eco-friendly method. In this study, the effect of the silica saturation coefficient (x) on the carbonation of hydrogarnet was investigated from the kinetic perspective. The results indicated that the carbonation of hydrogarnets with different x values (x = 0.27, 0.36, 0.70, and 0.73) underwent two stages with significantly different rates, and the kinetic mechanisms of the two stages can be described by the kinetic functions R3 and D3. The apparent activation energies at Stages 1 and 2 were 41.96–81.64 and 14.80–34.84 kJ/mol, respectively. Moreover, the corresponding limiting steps of the two stages were interfacial chemical reaction and diffusion.     

一种超重力燃烧合成制备高性能高熵合金的新方法

A new method of high-gravity combustion synthesis (HGCS) followed by post-treatment (PT) is reported for preparing high-performance high-entropy alloys (HEAs), Cr_0.9FeNi_2.5V_0.2Al_0.5 alloy, whereby cheap thermite powder is used as the raw material. In this process, the HEA melt and the ceramic melt are rapidly formed by a strong exothermic combustion synthesis reaction and completely separated under a high-gravity field. Then, the master alloy is obtained after cooling. Subsequently, the master alloy is sequentially subjected to conventional vacuum arc melting (VAM), homogenization treatment, cold rolling, and annealing treatment to realize a tensile strength, yield strength, and elongation of 1250 MPa, 1075 MPa, and 2.9%, respectively. The present method is increasingly attractive due to its low cost of raw materials and the intermediate product obtained without high-temperature heating. Based on the calculation of phase separation kinetics in the high-temperature melt, it is expected that the final alloys with high performance can be prepared directly across master alloys with higher high-gravity coefficients.     

窄板坯结晶器内连铸工艺参数对钢液流场的影响

Computational simulations and high-temperature measurements of velocities near the surface of a mold were carried out by using the rod deflection method to study the effects of various operating parameters on the flow field in slab continuous casting (CC) molds with narrow widths for the production of automobile exposed panels. Reasonable agreement between the calculated results and measured subsurface velocities of liquid steel was obtained under different operating parameters of the CC process. The simulation results reveal that the flow field in the horizontal plane located 50 mm from the meniscus can be used as the characteristic flow field to optimize the flow field of molten steel in the mold. Increases in casting speed can increase the subsurface velocity of molten steel and shift the position of the vortex core downward in the downward circulation zone. The flow field of liquid steel in a 1040 mm-wide slab CC mold can be improved by an Ar gas flow rate of 7 L·min?1 and casting speed of 1.7 m·min?1. Under the present experimental conditions, the double-roll flow pattern is generally stable at a submerged entry nozzle immersion depth of 170 mm.     

电渣重熔脱硫技术研究进展

Electroslag remelting (ESR) gives a combination of liquid metal refining and solidification structure control. One of the typical aspects of liquid metal refining during ESR for the advanced steel and alloy production is desulfurization. It involves two patterns, i.e., slag–metal reaction and gas–slag reaction (gasifying desulfurization). In this paper, the advances in desulfurization practices of ESR are reviewed. The effects of processing parameters, including the initial sulfur level of consumable electrode, remelting atmosphere, deoxidation schemes of ESR, slag composition, melting rate, and electrical parameters on the desulfurization in ESR are assessed. The interrelation between desulfurization and sulfide inclusion evolution during ESR is discussed, and advancements in the production of sulfur-bearing steel at a high-sulfur level during ESR are described. The remaining challenges for future work are also proposed.     

利用皮秒激光烧蚀制备非球形铝纳米颗粒

We report the picosecond laser ablation of aluminum targets immersed in a polar organic liquid (chloroform, CHCl₃) with ~2 ps laser pulses at an input energy of ~350 μJ. The synthesized aluminum nanoparticles exhibited a surface plasmon resonance peak at ~340 nm. Scanning electron microscopy images of Al nanoparticles demonstrated the spherical morphology with an average size of (27 ± 3.6) nm. The formation of smaller spherical Al nanoparticles and the diminished growth could be from the formation of electric double layers on the Al nanoparticles. In addition to spherical aluminum nanoparticles, triangular/pentagonal/hexagonal nanoparticles were also observed in the colloidal solution. Field emission scanning electron microscopy images of ablated Al targets demonstrated laser induced periodic surface structures (LIPSSs), which were the high spatial frequency LIPSSs (HSF-LIPSSs) since their grating period was ~280 nm. Additionally, coarse structures with a period of ~700 nm were observed.     

Mineral transition and formation mechanism of calcium aluminate compounds in CaO?Al2O3?Na2O system during high-temperature sintering

The mineral transition and formation mechanism of calcium aluminate compounds in CaO?Al₂O₃?Na₂O system during the high-temperature sintering process were systematically investigated using DSC?TG, XRD, SEM?EDS, FTIR, and Raman spectra, and the crystal structure of Na₄Ca₃(AlO₂)₁₀ was also simulated by Material Studio software. The results indicated that the minerals formed during the sintering process included Na₄Ca₃(AlO₂)₁₀, CaO·Al₂O₃, and 12CaO·7Al₂O₃, and the content of Na₄Ca₃(AlO₂)₁₀ could reach 92wt% when sintered at 1200°C for 30 min. The main formation stage of Na₄Ca₃(AlO₂)₁₀ occurred at temperatures from 970 to 1100°C, and the content could reach 82wt% when the reaction temperature increased to 1100°C. The crystal system of Na₄Ca₃(AlO₂)₁₀ was tetragonal, and the cells preferred to grow along crystal planes (110) and (210). The formation of Na₄Ca₃(AlO₂)₁₀ was an exothermic reaction that followed a secondary reaction model, and its activation energy was 223.97 kJ/mol.