三种基于2,4,6-三(3-吡啶基)-1,3,5-苯配体的Ni(Ⅱ)基配位聚合物的合成、结构及催化性能

通过调变溶剂热的反应条件,我们合成了3种Ni(Ⅱ)基的配位聚合物(CPs)[Ni (CH₃-BDC)(3-TBT)(H₂O)₂]·EtOH·2H₂O (CP1)、[Ni₃(CH₃-BDC)₃(3-TBT)₂(H₂O)₅]·2DMF·2H₂O (CP2)和[Ni₃(CH₃-BDC)₃(3-TBT)₂(H₂O)₆]·2DMF·4H2O (CP3),其中CH₃-H₂BDC=5-methyl isophthalic acid,3-TBT=2,4,6-tris (3-pyridyl)-1,3,5-benzene。X射线单晶衍射分析表明,3个CPs都是由相似的Ni₂(CH₃-BDC)₂的双核单元构建的,并分别呈现出从零维(0D)、2D到3D结构的网络骨架。反应条件的微小调变,导致了不同结构的配位聚合物。同时,催化实验表明,3在无溶剂的温和反应条件下,CP3对苄醇及其衍生物与苯胺的氧化-偶联反应表现出极好的催化活性和循环稳定性。     

Al-Decorated C2N Monolayer as a Potential Catalyst for NO Reduction with CO Molecules: A DFT Investigation

Developing efficient and economical catalysts for NO reduction is of great interest. Herein, the catalytic reduction of NO molecules on an Al-decorated C₂N monolayer (Al-C₂N) is systematically investigated using density functional theory (DFT) calculations. Our results reveal that the Al-C₂N catalyst is highly selective for NO, more so than CO, according to the values of the adsorption energy and charge transfer. The NO reduction reaction more preferably undergoes the (NO)₂ dimer reduction process instead of the NO direct decomposition process. For the (NO)₂ dimer reduction process, two NO molecules initially co-adsorb to form (NO)₂ dimers, followed by decomposition into N₂O and O_ads species. On this basis, five kinds of (NO)₂ dimer structures that initiate four reaction paths are explored on the Al-C₂N surface. Particularly, the cis-(NO)₂ dimer structures (D_cis-N and D_cis-O) are crucial intermediates for NO reduction, where the max energy barrier along the energetically most favorable pathway (path II) is as low as 3.6 kcal/mol. The remaining O_ads species on Al-C₂N are then easily reduced with CO molecules, being beneficial for a new catalytic cycle. These results, combined with its low-cost nature, render Al-C₂N a promising catalyst for NO reduction under mild conditions.     

Removal of Malachite Green Dye from Aqueous Solution by Catalytic Wet Oxidation Technique Using Ni/Kaolin as Catalyst

In this study, natural Algerian kaolin was used as a support and impregnated with nickel at different loading amounts (2 wt.%, 5 wt.%, and 7 wt.%) in order to prepare a supported catalyst. The wet impregnation technique was used in this preparation; nickel oxide (NiO) was the active phase precursor of the catalyst, and the catalysts were designated as follows: 2%, 5%, and 7% Ni/kaolin. These catalysts were put to the test in catalytic wet peroxide oxidation (CWPO) for degrading the organic contaminant malachite green dye (MG). Analytical techniques such as FTIR spectroscopy, X-ray diffraction, BET, and X-fluorescence were used to examine the structure, morphology, and chemical composition of the support and the produced catalysts. Several parameters, including temperature, catalytic dose, metal loading, hydrogen peroxide volume, and kinetic model were systematically investigated. The combination of improved parameters resulted in a significant increase in the catalytic activity, achieving a high removal rate of MG dye of 98.87%.     

Valorization of Fly Ashes and Sands Wastes from Biomass Boilers in One-Part Geopolymers

Fly ash (FA) and exhausted bed sands (sands wastes) that are generated in biomass burners for energy production are two of the wastes generated in the pulp and paper industry. The worldwide production of FA biomass is estimated at 10 million tons/year and is expected to increase. In this context, the present work aims to develop one-part alkali-activated materials with biomass FA (0–100 wt.% of the binder) and sands wastes (100 wt.% of the aggregate). FA from two different boilers, CA and CT, was characterized and the mortar’s properties, in the fresh and hardened conditions, were evaluated. Overall, the incorporation of FA decreases the compressive strength of the specimens. However, values higher than 30 MPa are reached with 50 wt.% of FA incorporation. For CA and CT, the compressive strength of mortars with 28 days of curing was 59.2 MPa (0 wt.%), 56.9 and 57.0 MPa (25 wt.%), 34.9 and 46.8 MPa (50 wt.%), 20.5 and 13.5 MPa (75 wt.%), and 9.2 and 0.2 MPa (100 wt.%), respectively. The other evaluated characteristics (density, water absorption, leached components and freeze–thaw resistance) showed no significant differences, except for the specimen with 100 wt.% of CA. Therefore, this work proved that one-part geopolymeric materials with up to 90 wt.% of pulp and paper industrial residues (FA and sand) can be produced, thus reducing the carbon footprint associated with the construction sector.     

利用激光诱导击穿光谱原位在线检测褐煤及煤烟

褐煤是我国现阶段的主要用煤,但因为其较低的煤化程度,使用时会产生污染环境的二氧化碳和黑灰,而且烟尘中含有的金属离子会危害人体健康,所以开展对褐煤烟尘的研究非常有意义.而激光诱导击穿光谱技术(L IBS)具有快速、多元素同时分析的特点,适合用于煤烟的原位在线探测.实验制备了含铅浓度不同的三种褐煤样本(O,H,L),其中O...     

Heterogeneous Catalysis of Ozone Using Iron–Manganese Silicate for Degradation of Acrylic Acid

Iron–manganese silicate (IMS) was synthesized by chemical coprecipitation and used as a catalyst for ozonating acrylic acid (AA) in semicontinuous flow mode. The Fe-O-Mn bond, Fe-Si, and Mn-Si binary oxide were formed in IMS on the basis of the results of XRD, FTIR, and XPS analysis. The removal efficiency of AA was highest in the IMS catalytic ozonation processes (98.9% in 15 min) compared with ozonation alone (62.7%), iron silicate (IS) catalytic ozonation (95.6%), and manganese silicate catalytic ozonation (94.8%). Meanwhile, the removal efficiencies of total organic carbon (TOC) were also improved in the IMS catalytic ozonation processes. The IMS showed high stability and ozone utilization. Additionally, H₂O₂ was formed in the process of IMS catalytic ozonation. Electron paramagnetic resonance (EPR) analysis and radical scavenger experiments confirmed that hydroxyl radicals (•OH) were the dominant oxidants. Cl⁻, HCO₃⁻, PO₄³⁻, Ca²⁺, and Mg²⁺ in aqueous solution could adversely affect AA degradation. In the IMS catalytic ozonation of AA, the surface hydroxyl groups and Lewis acid sites played an important role.     

林火中的阴燃现象:研究前沿与展望

森林中的植物腐殖质和有机泥炭土的阴燃是地球上尺度最大的燃烧与火灾现象,造成了巨大的经济损失及跨国界的雾霾,并严重破坏了生态系统.本文综述了阴燃林火的基础燃烧理论和化学反应机理,总结了其点火、火蔓延和熄火的行为特性.同时,归纳了近年来泥炭阴燃火的研究动态,包括如何通过小尺度的阴燃实验理解大尺度的阴燃林火,如何构建阴燃的数...     

煤粉燃烧过程中灰膜形成比例实验研究

煤焦颗粒燃烧过程中,灰膜形成显著影响其燃烧特性.因此,本文借助高温沉降炉研究了 61～75,75～90和90～125 μm三种粒径黄陵烟煤在1273和1673 K温度下的燃烧特性与灰膜形成比例;借助扫描电镜(SEM)详细观测空心微珠颗粒内部结构,提出灰膜比例计算公式,并分析温度,粒径和碳转化率对灰膜比例的影响.结果表明...     

碱活化多孔碳用于分离甲苯及活化/吸附机理

采用生物质木质素磺酸钠(SLS)为碳源,先与硬模板Na Cl混合预碳化,再加入活化剂Na OH在氮气保护下升温至850℃碳化,得到SLS基碱活化的多孔碳吸附剂(SPCN)。将SPCN用于吸附液体石蜡中芳香烃甲苯,对比研究了不同活化剂加入量对SPCN结构、性质及吸附效果的影响。结果表明,SPCN表面具有丰富的官能团和发达的微/介孔结构,活化剂加入量对比表面积的影响为先增大后减小,碱/碳质量比为1∶1时比表面积达到最大值(710. 4 m²/g);吸附量与比表面积呈正相关,样品SPCN-1的最大吸附量为2875. 17mg/g,远高于商业吸附剂,经5次吸附-解吸循环后仍保持92. 5%的吸附效率。探究了活化机理,NaOH、碳质和气体发生氧化还原反应释放气体留下孔隙,经充分酸洗、水洗后得到永久孔道。最后,结合扫描电子显微镜(SEM)、透射电子显微镜(TEM)、拉曼光谱(Raman)、X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)和比表面积分析等结果证明了吸附机理主要是孔隙填充效应、范德华力、π-π相互作用及电子供/受体作用的共同作用。首次报道了SPCN应用的新方向...     

煤油燃烧场主要组分浓度测量

利用自发振动拉曼散射技术测量了煤油燃烧场主要组分的摩尔分数。基于355 nm激光激发振动拉曼散射建立了自发拉曼散射实验系统,测量了空气中主要组分的摩尔分数,分析了该技术的测量精度;测量了煤油蒸气在355 nm激光激励下产生的荧光光谱,分析了荧光信号对拉曼信号的干扰;对不同燃烧条件下的煤油燃烧场进行了诊断,获得了贫油条件下煤油燃烧场主要组分（N2,O2,H2O,CO2等）的拉曼光谱,计算了组分摩尔分数及其随燃烧时间的变化规律。