联吡啶铁铜双金属负载PAN纤维的制备及其可见光催化性能研究

通过配位作用将Cu~(2+)引入到负载2’2联吡啶铁络合物(Fe(bpy)~(2+)3)的偕胺肟改性聚丙烯腈(PAN)纤维上,制备了联吡啶铁铜双金属负载改性PAN纤维催化材料,分别使用FT-IR、DRS和XPS技术对其进行表征,并考察了其作为非均相Fenton催化剂在有机染料罗丹明B氧化降解过程中的光催化性能。结果显示,该催化剂中Cu~(2+)能够通过羟基和Fe~(2+)发生相互作用,并将催化剂光响应范围拓展至整个可见光区。当催化剂中m(Cu)/m(Fe)为1.07时,催化剂显示出最高的光催化活性,而且Cu~(2+)的引入也显著提升了该催化剂的p H值适用性和可见光利用率。     

改性PAN纳米纤维铁配合物的制备及其催化降解染料性能的比较研究

分别以聚丙烯腈(PAN)纳米纤维和普通PAN纤维为原料,经偕胺肟改性和Fe3+配位反应制备了两种改性PAN纤维铁配合物。考察和比较了偕胺肟改性和Fe3+配位反应中两种纤维的腈基转化率及其配合物中铁含量的变化。然后在表征的基础上分别将两种改性PAN纤维铁配合物作为非均相Fenton反应催化剂应用于偶氮染料活性红195的氧化降解反应中,研究了两者在暗态和可见光辐射条件下的催化降解性能。结果表明,PAN纳米纤维比普通PAN纤维更容易发生偕胺肟改性和Fe3+配位反应。PAN纳米纤维铁配合物对可见光吸收性能略低于普通PAN纤维铁配合物。在染料的氧化降解反应中,PAN纳米纤维铁配合物具有更好的催化活性和稳定性,尤其在暗态时表现得更为突出。     

AOPAN/RC纳米纤维膜的制备及对金属离子吸附性能

采用静电纺丝技术制备聚丙烯腈/醋酸纤维素(PAN/CA)纳米纤维膜,通过化学改性制备偕胺肟化聚丙烯腈/再生纤维素(AOPAN/RC)纳米纤维膜,研究了纳米纤维膜对单一金属离子(Fe~(3+))和混合金属离子(Cu~(2+)、Cd~(2+)、Fe~(3+))的吸附性能。通过扫描电镜、红外光谱、X射线能谱仪等测试对纳米纤维膜进行了表征,并通过静态接触角测定纳米纤维膜亲水性能。研究表明,改性后制备的AOPAN/RC纳米纤维膜的亲水性能得到较大改善,同时纳米纤维膜能够高效吸附溶液中的金属离子,纳米纤维膜对单一组分Fe~(3+)的饱和吸附可达411.21mg/g,对于混合金属离子溶液,纳米纤维膜对其吸附能力顺序为Fe~(3+)Cu~(2+)Cd~(2+),而且纳米纤维膜具备优良的重复使用能力。     

柠檬酸改性棉纤维铁配合物的制备及其对染料的光催化降解作用

使用工业化的轧-烘-焙工艺对棉织物进行柠檬酸改性以引入羧基,然后与Fe~(3+)进行配位反应制备柠檬酸改性棉纤维铁配合物。在经过SEM、FT-IR、DRS和TGA表征的基础上,将柠檬酸改性棉纤维铁配合物作为非均相Fenton反应催化剂应用于偶氮染料的降解反应中,重点考察了其催化性能。结果表明,Fe~(3+)初始浓度和反应温度的提高均有利于柠檬酸改性棉织物与Fe~(3+)之间的配位反应,并能够显著增加配合物的铁离子含量。柠檬酸改性棉纤维铁配合物作为非均相Fenton反应催化剂在暗态时能够促进偶氮染料的降解反应,辐射光能明显加强其催化活性,而增加其铁离子含量或引入Cu~(2+)具有进一步改善其催化活性的作用。     

Fe-AO-PAN纳米纤维催化剂的制备及其对活性橙K-GN染料降解的催化

采用静电纺制备聚丙烯腈纳米纤维,将其浸泡在盐酸羟胺溶液中进行改性,获得偕胺肟改性聚丙烯腈纳米纤维(AO-PAN),再将AO-PAN与三氯化铁溶液在室温下反应,得到聚丙烯腈铁的配合物(Fe-AO-PAN),并采用SEM、FT-IR和EDAX能谱分析方法对其进行表征。然后将其作为非均相Fenton反应催化剂用于活性橙K-GN染料的氧化降解反应中,同时研究了吸附不同Fe3+量的聚丙烯腈纳米纤维对脱色率的影响,并用可见光分光光度计测量不同降解程度的染料吸光度。结果表明,偕胺肟改性聚丙烯腈纳米纤维与Fe3+发生了配位反应,从而制成了Fe-AO-PAN纳米催化剂,而且催化剂中Fe3+含量的增加会促进活性橙K-GN染料的氧化降解。     

固定漆酶对对苯二酚的降解研究

以静电纺制备的PAN纳米纤维为原料,用盐酸羟胺水溶液对其进行化学改性后得到偕胺肟基PAN螯合纳米纤维(AOPAN),将其与Cu~(2+)配位得到金属配合纳米纤维为载体固定漆酶,并研究了固定漆酶对对苯二酚的降解。分别采用红外光谱仪(FT-IR)、扫描电子显微镜(SEM)和能谱仪(EDAX)对不同处理阶段的PAN纳米纤维进行了观察分析,并对固定漆酶的性能进行了研究,通过测定不同降解阶段对苯二酚的吸光度变化来分析其降解情况。结果表明:改性后的PAN纳米纤维表面没有出现严重的裂痕或降解现象。固定漆酶的最适pH值为4,最适温度为50℃。铜离子配合螯合PAN纳米纤维膜(Cu-AOPAN)固定的漆酶,3次重复利用后,对对苯二酚的降解率分别为55.18%、50.75%、50.65%。     

交联型偕胺肟型凝胶的制备及对镓离子的吸附性能

以水合联胺为交联剂,利用"热致相分离"原理制备了聚丙烯腈/二甲亚砜(PAN/DMSO)交联(C-PAN)凝胶,将其进一步与羟胺(NH2OH)反应后得到交联型偕胺肟(C-PAO)凝胶,交联型偕胺肟凝胶可用于吸附强碱性模拟拜耳溶液中的镓离子(Ga~(3+))。文中采用了超临界CO_2萃取干燥法取代真空干燥,并探讨了不同溶度参数的交换溶剂对凝胶孔径的影响。红外测试结果表明,凝胶成功偕胺肟化且偕胺肟基团与镓离子发生了螯合作用;扫描电镜照片显示,当交换溶剂的溶度参数与PAN基体的差值(Δδ)增加,得到的凝胶孔径减小;吸附测试结果显示,偕胺肟凝胶对模拟拜耳溶液中镓离子的饱和吸附量为15.8 mg/g,平衡时间为140 min。     

纳米TiO_2/偕胺肟纤维制备的研究

采用配位-水解法制备出负载于偕胺肟纤维的纳米TiO2光催化剂,并用甲基橙溶液的光催化降解反应对所制得的光催化剂进行活性评价。利用SEM,EDS,XRD等手段对该催化纤维表面的TiO2粒子的形貌、成分、晶型进行了表征。实验表明催化剂的最佳制备条件:Ti 4+溶液的浓度为0.1198mol/L,室温下配位时间60min,在温度为55℃的水浴锅中水解7h。所制得的催化剂结合牢固,易于分离。研究还发现以偕胺肟纤维为配体对TiO2的催化性能有较大的增强作用。     

偕胺肟基螯合纳米纤维的制备

以静电纺聚丙烯腈(PAN)纳米纤维为原料,与盐酸羟胺的水溶液反应,将腈基转化为偕胺肟基团,从而制备出偕胺肟基螯合纤维。探讨了盐酸羟胺浓度、pH值、反应时间及温度对转化率的影响,并分别采用扫描电子显微镜和傅里叶变换红外光谱(FT-IR)对PAN纳米纤维膜反应前后的形貌和分子基团进行分析。结果表明:PAN在pH值为7时,腈基转化率最高;-CN转化率随着浓度、反应时间及温度的增大而提高。红外光谱分析表明,PAN分子中有部分腈基转化为偕胺肟基团。     

Fe~(3+)/N共改性TiO_2可见光催化剂的制备及其对染料光催化降解性能研究

以偕胺肟纤维(AOCF)为载体,与TiCl_4进行配位后再水解,制得TiO_2/纤维复合物(N-TiO_2)。再将NTiO_2与FeCl_3反应,获得Fe、N共改性纳米TiO_2/纤维复合材料(Fe3+/N-TiO_2)。采用SEM、XRD、EDS等对复合物的形貌、晶态结构、表面元素进行表征。以染料降解率为指标,优化制备条件:Fe~(3+)初始浓度5.0mmol/L、pH=2.0、改性反应时间为20min。考察了Fe~(3+)/N-TiO_2对活性黄、活性红和甲基橙三种染料溶液的光催化降解性能,结果显示:在可见光下其对3种染料表现出良好的光催化性能,且可多次重复使用与再生,光催化反应过程符合一级反应动力学特征。PL和UV-Vis分析表明:Fe、N共改性使TiO_2禁带宽度窄化,吸收带边红移,其光谱响应范围变宽。     

In situ incorporation of well-dispersed Cu–Fe oxides in the mesochannels of AMS and their utilization as catalysts towards the Fenton-like degradation of methylene blue

Multi-components active metal oxide-supported catalysts are highly promising in heterogeneous catalysis due to some special promoting effects. In this study, by the controllable amount of Cu, Cu–Fe decorated anionic surfactant-templated mesoporous silica (Cu _x Fe/AMS) was directly prepared. The obtained catalysts were characterized by X-ray diffraction, N₂ adsorption–desorption, inductively coupling plasma emission spectroscopy, scanning electron microscopy, transmission electron microscopy, UV–visible, hydrogen temperature-programmed reduction, and X-ray photoelectron spectroscopy techniques. The results revealed that bimetallic Cu–Fe oxides were directly formed and highly dispersed in the mesochannels during the calcinations and the introduction of Cu²⁺ and Fe²⁺ on the micelles has influence on the structure properties. As compared to the monometallic Fe-modified AMS, the presence of Cu promotes the effects between Fe species and silica wall, leading to the better dispersion of Fe in the mesochannels of AMS. Finally, a series of Cu–Fe-modified AMS were used as Fenton-like catalysts and exhibited good catalytic activity in the degradation of methylene blue (MB), which resulted from high dispersion of Fe species and synergetic effect between Cu and Fe active sites. 1.0 was the optimum molar ratio of Cu²⁺ to Fe²⁺ ions to achieve the best catalytic activity and stability.     

Synthesis and characterization of Co–Fe nanoparticles supported on mesoporous silicas

Co–Fe bimetallic samples containing 25 wt% total of metal content were prepared by incipient wetness impregnation of cobalt nitrate and iron nitrate salts over hexagonal mesoporous silica (HMS) and SBA-15 supports. Changes in the textural properties and reduction behavior were compared with monometallic cobalt/iron-based samples. The samples were characterized by N₂ physisorption, X-ray diffraction (XRD), H₂-temperature programmed reduction (TPR), transmission electron microscopy (TEM) and H₂ chemisorption. The amount of incorporated metal was estimated by atomic absorption spectroscopy (AAS). Morphological properties revealed that after introduction of the metal to the SBA-15 support, the specific area, pore volume and pore diameter decreased to a lesser extent for bimetallic samples. XRD measurements detected the formation of Co₃O₄ and CoFe₂O₄ phases for both bimetallic samples. TPR profiles indicated similar behavior for both the bimetallic and monometallic samples. Higher temperatures were observed for the reducibility of Co–Fe/HMS as compared to Co–Fe/SBA-15. Dispersion values of the bimetallic samples were higher than Fe monometallic samples and lower than Co monometallic samples according to hydrogen chemisorption. The particle size distribution of the bimetallic samples estimated by TEM microphotographs showed a smaller fraction of larger size particles for Co–Fe/SBA-15.     

Fe(III)/rGO/Bi2MoO6复合光催化剂制备及光催化芬顿协同降解苯酚

光催化-芬顿技术耦合可高效降解有机污染物。本研究采用溶剂热法制备了Fe(III)掺杂rGO/Bi₂MoO₆复合催化剂(Fe(III)/rGO/Bi₂MoO₆), 通过外加H₂O₂构建了光催化-芬顿协同体系, 可见光照射3 h后对苯酚的降解率(82%)远高于单独光催化(18%)或芬顿反应(48%), 进一步优化条件对苯酚可实现完全降解。这主要是通过Fe得失电子实现价态的转变, 并以此作为桥梁实现光催化-芬顿的协同作用。同时石墨烯的优异导电性能不仅克服了光催化中光生电子空穴难以分离的问题, 而且促进了Fe³⁺/Fe²⁺的循环反应, 促使芬顿反应产生更多的羟基自由基(?OH), 进一步提高了苯酚的降解效率。实验考察了Fe(III)含量、催化剂投加量、H₂O₂含量以及pH等因素对协同降解效果的影响。淬灭实验证明?OH是协同降解体系中最主要的活性物种, ?O₂^-和h⁺对降解活性也会产生一定的影响, 结合实验结果提出了Fe(III)/rGO/Bi₂MoO₆光催化-芬顿协同降解苯酚的机理。     

Enhanced CO Affinity on Cu Facilitates CO2 Electroreduction toward Multi-Carbon Products

Electrochemical CO₂ reduction reaction (CO₂RR) is a promising strategy for waste CO₂ utilization and intermittent electricity storage. Herein, it is reported that bimetallic Cu/Pd catalysts with enhanced *CO affinity show a promoted CO₂RR performance for multi-carbon (C2+) production under industry-relevant high current density. Especially, bimetallic Cu/Pd-1% catalyst shows an outstanding CO₂-to-C2+ conversion with 66.2% in Faradaic efficiency (FE) and 463.2 mA cm⁻² in partial current density. An increment in the FE ratios of C2+ products to CO  for Cu/Pd-1% catalyst further illuminates a preferable C2+ production. In situ Raman spectra reveal that the atop-bounded CO is dominated by low-frequency band CO on Cu/Pd-1% that leads to C2+ products on bimetallic catalysts, in contrast to the majority of high-frequency band CO on Cu that favors the formation of CO. Density function theory calculation confirms that bimetallic Cu/Pd catalyst enhances the *CO adsorption and reduces the Gibbs free energy of the C C coupling process, thereby favoring the formation of C2+ products.     

Studies on nanosized iron based modified catalyst for Fischer-Tropsch synthesis application

To improve catalytic performance iron based catalyst, the effects of some metal promoters, especially potassium, copper and other transition metal oxides as well as different supports have been reported. A series of Fe/K/Cu catalysts promoted with magnesium and ceria by precipitation method, followed by impregnation method; keeping Cu and K content same. The catalysts were characterized by XRD, N2 physisorption, TPR and TEM techniques. From XRD, the presence of hematite (Fe2O3) phase was detected in all precipitated iron catalysts and CFe2.5 phase in all used catalysts. TPR results showed that addition of Mg facilitated the reduction of Fe2O3 and decrease in reduction temperature. The catalytic performance was investigated in a fixed-bed reactor at 250 degrees C, 2 MPa pressure and H2/CO molar ratio of 2. Concentration of Mg was found to affect the CO conversion and product distribution. It was found that precipitated iron catalyst Fe/Mg/Cu/K with Mg/Fe ratio of 0.1 showed highest conversion (60.6%) and C5(+) selectivity (92.4%) among all catalysts tested.     

一种新的过渡金属层状材料Na4Cu3TaAs4的结构和物理性质(英文)

我们报道了一种新的过渡金属层状砷化物Na4Cu3TaAs4的合成、结构和物理性质.这种材料采用Ⅰ√2 m空间群,晶胞参数为a=5.9101(3)?,c=13.8867(12)?.这个材料的结构中包含两层Na,而Na夹在反氧化铅型(Cu/Ta)As层之间,类似于"111"型铁基超导体NaFeAs.过渡金属位由75%的Cu和25%的Ta占据,Ta形成了明确的√2超结构.Cu和Ta分别为+1和+5价.角分辨光电子能谱测得的Na4Cu3TaAs4能带结构能够和DFT计算结果良好地吻合.角分辨光电子能谱和输运测量均表明该材料表现为金属行为,具有p型载流子.磁化率测量表明该材料表现为几乎不依赖温度的抗磁性.这种新材料扩展了含有反氧化铅型层的材料系统,并为进一步研究该材料系统提供了一个很好的平台.     

Study on photocatalytic degradation of several volatile organic compounds

The gas-phase photolytic and photocatalytic reactions of several aromatics and chlorohydrocarbons were investigated. The experimental results revealed that chlorohydrocarbons like trichloroethylene, dichloromethane and chloroform could be degraded through either photolysis or photocatalysis under irradiation of germicidal lamp, and the elimination rate of chlorohydrocarbons through photolysis was quicker than that through photocatalysis. UV light from a germicidal lamp could directly lead to degradation of toluene but could hardly act on benzene. The photodegradation rate for these volatile organic compounds (VOCs) through photolysis followed an order: trichloroethylene>chloroform>dichloromethane>toluene>benzene>carbon tetrachloride, and through photocatalysis followed: trichloroethylene>chloroform>toluene>dichloromethane>benzene>carbon tetrachloride. Besides, a series of modified TiO2 photocatalysts were prepared by depositing noble metal, doping with transition metal ion, recombining with metal oxides and modifying with super strong acid. Activity of these catalysts was examined upon photocatalytic degradation of benzene as a typical compound that was hard to be degraded. It indicated that these modification methods could promote the activity of TiO2 catalyst to different extent. The apparent zero-order reaction rate constant for degrading benzene over SnO2/TiO2 catalyst had the highest value, which was nearly three times as that over P25 TiO2. But it simultaneously had the lowest rate for mineralizing the objective compound. In spite that Fe3+/TiO2 catalyst behaved slightly less active than SnO2/TiO2 for degradation of benzene, the mineralization rate over Fe3+/TiO2 was the highest one among the prepared catalysts.     

Electronic structure studies of nanoferrite Cu(x)Co(1-x)Fe2O4 by X-ray absorption spectroscopy

Pure and mixed cobalt copper ferrites are of great interest due to their widespread application in electronics and medicine. We report on the electronic structure of a nanoferrite Cu(x)Co(1-x)Fe2O4 (0.0 < or = x < or = 1.0) system studied by X-ray absorption spectroscopy. These magnetic nanoferrites (average crystallite size approximately 31-43 nm) were synthesized by an auto combustion method and are characterized by high resolution X-ray diffraction and near edge X-ray absorption fine structure measurements at the O K and Co, Cu, and Fe L-edges. The O K-edge spectra suggest that there is a strong hybridization between O 2p and 3d electrons of Co, Cu and Fe cations and Fe L3,2-edge spectra indicate that Fe ions coexist in mixed valence states (Fe3+ and Fe2+) at tetrahedral and octahedral sites of the spinel structure. Copper and cobalt ions are distributed in the divalent state in octahedral sites of the spinel structure. The origin of high saturation magnetization and coercivity in cobalt-copper ferrites are explained in light of these results.     

Self-assembling behaviour of Pt nanoparticles onto surface of TiO2 and their resulting photocatalytic activity

In the present study, self-assembling behaviour of guest nanoparticles (platinum) onto the surface of host support (titanium dioxide) during photodeposition process as a function of solution pH has been explored in detail by means of transmission electron microscope (TEM). The photocatalytic activity of the resulting bimetallic nanoassembly (Pt/TiO₂) was evaluated by studying the degradation of two organic pollutants viz. triclopyr and methyl orange. Microscopic studies revealed that the deposition and/or distribution of Pt nanoparticles onto the surface of TiO₂ were strongly guided by the ionization state of support which in turn was regulated by the solution pH of photodeposition process. A direct relationship between the solution pH of deposition process and the photocatalytic activity of resulting bimetallic catalyst has been observed. A mechanism based on the interparticle interaction between TiO₂ and hydrolytic products of metal ions has been proposed for the differences in the photocatalytic activity of the resulting nanocomposite.