Assessment of kinetics of photoinduced Fe‐based atom transfer radical polymerization under conditions using modeling approach

Kinetic insight into photoinduced Fe‐based atom transfer radical polymerization (ATRP) involving monomer‐mediated photoreduction was performed by modeling approach for the first time. Preliminary numerical analysis of number‐average molar mass (M_n) derivation in this specific system was given. Simulation results provided a full picture of reactant concentration and reaction rate throughout the entire polymerization. Methyl 2,3‐dibromoisobutyrate (MibBr₂) generated from methyl methacrylate (MMA)‐mediated photoreduction as the leading factor for the deviation of M_n from theoretical value was confirmed by reaction contributions in α‐bromophenylacetate (EBPA) containing system. Reasonable predictions were made with respect to the polymerizations under a variety of initial conditions. Results show that increasing light intensity will shorten transition period and increase steady state polymerization rate; decreasing catalyst loading will cause the decrease in polymerization rate and M_n deviation; varying initiation activity will slightly increase the time to attain steady state of dispersity (M_w/M_n) evolution and enormously change the fraction of reaction contributions; increasing targeted chain length will extend transition period, decrease steady state polymerization rate, increase M_n deviation degree with same reaction contributions, and decrease the time to attain the steady state of M_w/M_n. The numerical analysis presented in this work clearly demonstrates the unique ability of our modeling approach in describing the kinetics of photoinduced Fe‐based ATRP of MMA. © 2017 American Institute of Chemical Engineers AIChE J, 2017     

一种新型罗丹明类双通道荧光探针及其对Fe~(3+)和Cu~(2+)的选择性识别研究

以罗丹明B、水合肼和吡啶-2-甲醛为反应物,合成了一种新型的罗丹明类Fe~(3+)和Cu~(2+)双通道分子探针(Fluorescent probe,FP),并用核磁和质谱对其分子结构进行了表征。利用荧光分光光度计和紫外可见分光光度计研究了FP对Fe~(3+)、Cu~(2+)等14种金属离子的识别性能。研究结果表明,在V(CH_3OH)∶V(H_2O)=1∶1体系中,当选用荧光光谱分析时,探针FP对Fe~(3+)具有良好的选择性响应,且Fe~(3+)浓度在2~30μmol/L时,探针荧光强度与Fe~(3+)浓度呈线性关系,线性相关系数为0.998。当选用紫外可见光谱分析时,探针FP对Cu~(2+)具有很好的选择性响应,且当Cu~(2+)浓度为0~9μmol/L时,探针FP的吸光度与Cu~(2+)浓度呈线性关系,线性相关系数为0.999。     

反渗透浓水中难降解有机物的去除技术研究进展

有机污染物是阻碍反渗透RO浓水达标排放或资源化利用的关键因素之一。对RO浓水难降解有机物的去除方法进行概括总结,阐述了生物法、铁炭微电解法和高级氧化法的研究现状,尤其对高级氧化法的研究进展和存在问题进行了详细的分析。在此基础上,提出高级氧化-活性炭吸附、高级氧化-生物等联合技术是今后研究的主要方向。     

MIL-53(Fe)金属有机骨架材料对刚果红的高效吸附

通过水热法制备规则外形的MIL-53(Fe)金属有机骨架材料(MOF),并通过傅里叶红外光谱(FT-IR)、X射线衍射(XRD)、扫描电镜(SEM)和透射电镜(TEM)对材料进行表征。以刚果红作为目标物,研究所制得的MOF材料对其的吸附行为。结果表明,MIL-53(Fe)对刚果红的吸附动力学符合准二级动力学,吸附模型符合Langmuir吸附模型。MIL-53(Fe)材料对刚果红的最大吸附量为1 482 mg/g,是可望用于去除染料废水刚果红的高效吸附材料。     

锻烧温度对Fe_2O_3光催化降解偏二甲肼废水的影响

以NH_3·H_2O and Fe(NO_3)_3·9H_2O为原料,采用共沉淀法得到前驱体,分别在150、250、350、450、550℃锻烧前驱体制备了Fe_2O_3,借助拉曼光谱、热重分析仪、X射线衍射、透射电子显微镜和紫外-可见光谱对其进行了表征。通过降解偏二甲肼废水,比较了不同锻烧温度下所得催化剂光催化的活性。结果表明,Fe_2O_3的结晶性和粒径大小同时决定光催化性能,锻烧温度小于450℃时,结晶性起决定作用,锻烧温度大于450℃时,粒径大小起决定作用,450℃锻烧的Fe_2O_3光催化降解偏二甲肼废水的效果最好。     

Zero Thermal Expansion Achieved by an Electrolytic Hydriding Method in La(Fe,Si)13 Compounds

The La(Fe,Si)₁₃‐based compounds have been recently developed as promising negative thermal expansion (NTE) materials by elemental substitution, which show large, isotropic and nonhysteretic NTE properties as well as relatively high electrical and thermal conductivities. In this paper, the La(Fe,Si)₁₃ hydrides are prepared by a novel electrolytic hydriding method. Furthermore, the thermal expansion and magnetic properties of La(Fe,Si)₁₃ hydrides are investigated by the variable‐temperature X‐ray diffraction and physical property measurement system. Fascinatingly, it is found that room‐temperature NTE properties and zero thermal expansion (ZTE) properties with broad operation‐temperature window (20–275 K) have been achieved after electrolytic hydriding. The further magnetic properties combined with theoretical analysis reveal that the improvements of NTE and ZTE properties in the La(Fe,Si)₁₃ hydrides are ascribed to the variations of magnetic exchange couplings after hydrogenation. The present results highlight the potential applications of La(Fe,Si)₁₃ hydrides with room‐temperature NTE and broad operation‐temperature window ZTE properties.     

Gas Phase Synthesis of Multifunctional Fe‐Based Nanocubes

Magnetron‐sputtering inert‐gas condensation is an emerging technique offering single‐step, chemical‐free synthesis of nanoparticles with well‐defined morphologies optimized for specific applications. In this study, the authors report a flexible approach to produce Fe nanocubes as building blocks for high‐performance NO₂ gas sensor devices, and hybrid FeAu nanocubes with magneto‐plasmonic properties. Considering that nucleation happens within a short distance from the sputtering target, the authors utilize the high‐permeability and resultant screening effect induced by magnetic Fe targets of various thicknesses to manipulate the magnetic field configuration and plasma confinement. The authors thus readily switch from bimodal to single‐Gaussian size distributions of Fe nanocubes by modifying their primordial thermal environments, as explained by a combination of modeling methods. Simultaneously, the authors obtain a material yield increase of more than one order of magnitude compared to experiments using postgrowth mass filtration. The effectiveness of the method is demonstrated by the deposition of Fe nanocubes on microhotplate devices, leading to unprecedented NO₂ detection performance for Fe‐based chemoresistive gas sensors. The exceedingly low detection limit down to 3 ppb is attributed to a morphological change in operando from Fe/Fe‐oxide core/shell to specific hollow‐nanocube structures, as revealed by in situ environmental transmission electron microscopy.     

3D Self‐Supported Fe‐Doped Ni2P Nanosheet Arrays as Bifunctional Catalysts for Overall Water Splitting

The development of highly efficient bifunctional electrocatalysts for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is crucial for improving the efficiency of overall water splitting, but still remains challenging issue. Herein, 3D self‐supported Fe‐doped Ni₂P nanosheet arrays are synthesized on Ni foam by hydrothermal method followed by in situ phosphorization, which serve as bifunctional electrocatalysts for overall water splitting. The as‐synthesized (Ni_0.33Fe_0.67)₂P with moderate Fe doping shows an outstanding OER performance, which only requires an overpotential of ≈230 mV to reach 50 mA cm^?2 and is more efficient than the other Fe incorporated Ni₂P electrodes. In addition, the (Ni_0.33Fe_0.67)₂P exhibits excellent activity toward HER with a small overpotential of ≈214 mV to reach 50 mA cm^?2. Furthermore, an alkaline electrolyzer is measured using (Ni_0.33Fe_0.67)₂P electrodes as cathode and anode, respectively, which requires cell voltage of 1.49 V to reach 10 mA cm^?2 as well as shows excellent stability with good nanoarray construction. Such good performance is attributed to the high intrinsic activity and superaerophobic surface property.     

PDA/RGO复合材料对水中Fe（Ⅲ）的吸附行为

将多巴胺与氧化石墨烯纳米片层接枝复合制备了聚多巴胺/还原氧化石墨烯（PDA/RGO）复合材料,通过XRD、FTIR、FESEM和XPS等对该复合材料的结构和表面性质进行表征,并研究了其对水中Fe（Ⅲ）的吸附性能,考察了pH、吸附剂用量、吸附时间、Fe（Ⅲ）浓度和温度对其吸附性能的影响。结果表明：通过多巴胺与氧化石墨烯的仿生复合成功制备出具有优良吸附性能的PDA/RGO复合材料。pH为2,293 K时,该吸附材料对水中Fe（Ⅲ）的最大吸附量为59.1 mg·g^-1,其吸附等温线符合Freundlich方程,吸附动力学可用准二级动力学方程来描述。吸附热力学研究表明该复合材料对Fe（Ⅲ）的吸附过程为自发吸热过程,呈现非均质吸附特性。作为一种新型吸附材料,该复合材料在Fe（Ⅲ）等金属污染废水处理中将具有潜在的应用前景。