蚕丝纤维/金属酞菁活化双氧水催化氧化酸性橙的研究

合成了四磺酸基钴酞菁(CoPcS),采用基质辅助激光解析电离飞行时间质谱(MALDI-TOF-MS)、紫外-可见光谱(UV-Vis)和傅里叶变换红外光谱(FT-IR)对其进行表征,然后通过三聚氯氰改性将其负载到蚕丝纤维(SF)上,制得了新型蚕丝纤维负载钴酞菁催化剂(CoPcS-SF)。以H2O2为氧化剂,考察了CoPcS-SF对酸性橙Ⅱ(AO2)的催化氧化性能,结果表明,在中性条件下,CoPcS-SF能高效催化氧化AO2,反应60min后AO2的去除率可达97%以上,并且具有较好的重复使用性。考察了pH值、电解质NaCl和温度对CoPcS-SF催化性能的影响,结果表明,CoPcS-SF在pH值3～9较宽范围内均具有较高催化活性;NaCl对催化AO2有促进作用;催化活性随反应温度升高而增强。FT-IR和气质联用(GC-MS)对AO2的降解产物分析表明,AO2的主要产物为顺丁烯二酸、反丁烯二酸和丁二酸等小分子可生物降解脂肪酸。     

催化湿式氧化高浓度对氯苯基异氰酸酯生产废水催化剂的研究

以过渡金属氧化物CuO为主活性组分,通过对ZrO2的复合和掺入电子助剂CeO2的考察,研制出适用于催化湿式氧化处理高浓度对氯苯基异氰酸酯生产废水的复合催化荆.在固定床鼓泡式反应器连续反应装置上对废水进行处理,考察了各组分浸渍液浓度、焙烧温度、焙烧时间等制备条件对催化剂的催化活性的影响,确定了最佳制备条件.结果表明:优化制备的CuO-ZrO2-CeO2/TiO2催化荆,用于处理高浓度对氯苯基异氰酸酯生产废水时具有较好的催化活性,在反应温度T=240℃,反应压力P=6.5MPa,空速=2.0h-1,V(气):V(水)=230:1,进水pH=8条件下CODcr去除率达到96.9%,而在相同反应条件下未加催化剂的湿式氧化CODcr去除率只有40.8%.     

不同结构形貌BiVO4的水热制备及可见光催化性能

采用水热法,无需添加剂,通过调控反应液pH值和反应温度制备了不同结构和形貌的BiVO4可见光催化剂.利用X射线衍射(XRD)、扫描电子显微镜(SEM)、紫外可见漫反射(DRS)和低温氮吸附等手段对样品进行表征,结果显示:水热温度与反应液pH值对晶体结构有很大影响,180℃水热温度和酸性条件有利于单斜相的生成.反应液pH值对形貌也有很大影响,不同条件下得到了片状、立方状、棒状等不同形貌的BiVO4.同时以亚甲基蓝为降解对象,考察了所制备BiVO4的可见光催化活性.其中,pH值为2,反应液中制备的片状单斜相BiVO4具有最高的光催化活性(4 h达92.0%).此外,还考察了光催化剂用量、亚甲基蓝浓度和电子受体的存在对光催化过程的影响,结果表明:当催化剂用量为1.0 g/L,亚甲基蓝浓度为10 mg/L,KBrO3为电子受体时光催化效果最佳.     

负载型纳米TiO2的制备及其催化活性研究

以硅胶为载体、钛酸丁酯为原料,通过微乳液法制得平均晶粒度为6.3nm的锐钛矿型纳米TiO2负载催化剂.研究了焙烧温度、m(TiO2):m(硅胶)、溶液pH对紫外光照射下纳米TiO2降解溶液中苯酚的光催化活性的影响.结果表明,焙烧温度从400℃提高到700℃时,TiO2晶粒度从6.3nm增加到的83.2nm,而催化活性先增大后降低,在450℃时催化活性最大,苯酚的去除率45.6%;随着m(TiO2):m(硅胶)的减小,催化剂活性先增加后降低,在TiO2:硅胶(质量比)为0.05/1000时催化剂活性达到最大;溶液pH值小于6时,苯酚去除率随pH值减小而增大,但变化并不太明显;pH值大于6时,苯酚去除率随pH值增大而增大.     

邻-酚羟基取代N-杂环卡宾[C，O]螯合烯丙基钯配合物／MAO催化降冰片烯的聚合

研究了以3种N-杂环卡宾[C,O]螯合烯丙基钯配合物(NHC-Pd)1、2和3为催化剂,甲苯为溶剂,甲基铝氧烷(MAO)为助催化剂催化降冰片烯(NBE)的聚合。考察了催化剂2在不同反应温度、n(Al)/n(Pd)以及n(NBE)/n(Pd)等因素影响下的催化活性和聚合物性能。结果表明,该催化体系对降冰片烯系具有高催化活性,最高活性可达到3.2×107gPNBE/(mol Pd.h)。聚合物具有很好的耐热性能,其热分解温度高于400℃。通过对聚合产物FT-IR分析判断,降冰片烯聚合反应以烯烃加成聚合方式进行。     

α-二亚胺合镍氯化物/MgCl2(THF)2负载催化剂合成支化聚乙烯

以MgCl2(THF)2负载 [C6H5-N=C (CH3)C(CH3)=N-C6H5]NiCl2和AlEt2Cl组成的催化体系进行乙烯聚合,庚烷为溶剂制备支化聚乙烯(w=24000～34000).聚合条件如助催化剂、铝镍摩尔比、聚合温度和金属镍浓度对催化活性有很大的影响.负载催化剂在AlEt2Cl为助催化剂、聚合温度14 ℃、铝镍摩尔比80、金属镍浓度0.18 mmol/L的条件下催化活性达到51 kg PE/mol Ni·h.聚乙烯的支化度随着聚合温度的升高而迅速增加,受铝镍摩尔比的影响不大.     

双组分α-二亚胺镍复式催化剂制备长支链聚乙烯

报道以两种后过渡金属催化剂二-(2,6-二甲基苯基)-丁二亚胺氯化镍和二-(2-甲基苯基)-丁二亚胺氯化镍所组成的复式催化体系,催化单一乙烯聚合可制备得到长支链(n≥6)的聚乙烯。在合适的聚合条件下此复式催化剂具有很好的协同作用,其催化活性比任一单一催化剂的催化活性都高。本文详细研究了两种催化荆的摩尔比、聚合温度等聚合条件对催化活性及产物结构的影响。用^13C—NMR、FT—IR、DSC对聚合物进行了表征。     

晶相可调TiO2多孔薄膜的低温制备及其性能

采用低温方法制备了金红石含量可调TiO2多孔薄膜,并用X射线衍射仪(XRD)、BET比表面积测量仪和透射电镜(TEM)对其进行了表征。以甲基橙(MO)为光催化反应的模型化合物,研究了TiO2多孔薄膜的光催化活性以及重复使用效果。结果表明:随金红石含量增加,TiO2薄膜的紫外光催化活性减小,而可见光催化活性增加;在金红石含量相近的条件下,水热合成TiO2薄膜的紫外和可见光催化活性均高于机械混合TiO2薄膜;TiO2薄膜的光催化重复使用性能良好。当其它实验条件相同时改变MO溶液的初始pH值,其最大降解效率发生在pH=3.00时。光电共同催化效果优于光催化。     

共沉淀法制备纳米Fe3O4及其对橙黄Ⅱ的降解

通过共沉淀法制备Fe3O4纳米颗粒,采用X射线衍射(XRD)、扫描电子显微镜(SEM)和比表面孔隙分析(BET)对样品进行表征。以合成的纳米Fe3O4催化H2O2氧化降解橙黄Ⅱ,考察了共沉淀法制备过程中的Fe2+/Fe3+的摩尔比、反应温度、pH值、Fe离子浓度等因素对Fe3O4催化性能的影响。结果表明在Fe2+/Fe3+的摩尔比为3∶4、反应温度80℃、pH值为10、Fe离子浓度为0.1mol·L-1的条件下制备出的Fe3O4纳米颗粒催化活性最高,其粒径为20nm左右。并且未干燥的磁流体对橙黄Ⅱ的降解效率明显高于Fe3O4粉体。     

二亚胺镍配合物/烷基铝催化4-乙烯基吡啶的聚合

制备了N,N-二(2,6-二异丙基苯基)苊二亚胺氯化镍,与A lE t2C l组成催化体系,催化4-乙烯基吡啶(4-VP)的聚合。研究表明,该催化体系可以有效地催化4-乙烯基吡啶聚合,并具有较高的活性,聚合条件如单体浓度、铝镍摩尔比、聚合温度和聚合时间等对4-乙烯基吡啶的聚合反应活性有较大的影响。最佳反应条件是单体浓度为0.6 m o l/L、n(A l)/n(N i)为800、温度为30℃,这时催化活性达到47.2 kg P(4-VP)/m o l N i.h。     

Catalytic conversion of 1,2-dichlorobenzene over mesoporous V2O5/TiO2 prepared from spray pyrolysis

Mesoporous V2O5/TiO2 particles were prepared by spray pyrolysis and applied to the catalytic oxidation of 1,2-dichlorobenzene (1,2-DCB). Two different precursors (alkoxide and nanoparticles) for the TiO2 support were used to determine the effects on the texture properties and the catalytic activity of the mesoporous V2O5/TiO2 particles. The 5 wt% V2O5/TiO2 particles had the largest surface area (173 m2/g) and 4.7 nm in average pore size. The catalytic activity of the V2O5/TiO2 particles depended strongly on the loading quantity of vanadium, whereas the P25-derived samples showed no significant change in catalytic activity with weight% of vanadium. The surface area of the V2O5/TiO2 particles prepared using the alkoxide precursor was larger than that of the particles prepared using P25 nanoparticles. The P25-derived V2O5/TiO2 particles, however, showed a higher catalytic activity compared with those alkoxide-derived, which is due to the difference in the vanadium quantity exposed to the pore surface. It was confirmed that the 10 wt% V2O5/TiO2 particles prepared by spray pyrolysis had an excellent activity for the oxidation of 1,2-DCB, particularly at temperatures below 300 degrees C.     

催化乳酸铵酯化的改性树脂的制备与表征

为降低酯化催化剂的制备成本,提高催化酯化反应的性能,以磺酸型阳离子交换树脂和FeCl3·6H2O为原料,采用液固溶剂法制备了固体酸催化剂.利用XRF,FTIR,XRD,NH3-FTIR对催化剂进行表面酸性、元素含量等性质的测试表征.研究表明,FeCl3与阳离子交换树脂的Bronsted酸中心(SO3H)发生化学反应形成了新的Lewis酸中心,络合到树脂上的Fe3+量为11.8%.测试了催化剂促进乳酸铵和正丁醇酯化反应的催化活性,当催化剂用量为1.5%时,酯化率高达96.1%.     

用腐植酸树脂分离富集-火焰原子吸收法测定电镀液中痕量铅

采用酚醛树脂对天然腐植酸交联固化,制备成腐植酸酚醛树脂.采用火焰原子吸收分光光度法(FAAS)研究了腐植酸酚醛树脂对铅的吸附性能.结果表明,腐植酸酚醛树脂对铅有较强的吸附能力,吸附量受介质pH值的影响,当pH值大于3.0时,铅可被定量吸附,最大吸附量可达17.28 mg/g.吸附于树脂上的铅可以用0.1 mol/L的HNO3溶液完全解脱.以FAAS法为检测手段,对镀铬液中痕量铅进行分离富集,建立了电镀液中痕量铅的测定新方法,应用于实际样品的测定,结果满意.     

Effect of elevated annealing temperature on the morphology, microstructure, conductivity and microwave absorption properties of phthalocyanine polymer

An aromatic, diether-linked phthalocyanine resin (Pc) was prepared from 4,4′-bis (3,4-dicyanophenoxy) biphenyl (BPh) and investigated for morphology, microstructure, dielectric, conductivity and microwave absorption properties at different annealing temperatures from 300 to 800 °C. The results showed that the annealing temperature could significantly change the morphology and microstructure of the Pc polymer, leading to the generation of carbon-Pc polymer composites, and enhance the microwave absorbing and electrical properties of the Pc polymer. The dramatic electrical and dielectric transition happened when the annealing condition was 550 °C 24 h. The conductivity of the samples exhibited a transition of electrical behavior from an insulator to semiconductor of approximately 10⁺² S/cm. Pc polymer exhibited excellent microwave absorption properties in the frequency range of 0.5–18.0 GHz after sintering process. The microwave absorption of the annealing Pc polymer can be mainly attributed to the dielectric loss rather than magnetic loss. The sample annealed at 500 °C 24 h had two strong microwave absorbing peaks and achieved a maximum absorbing value of ?44 dB around 10.7 and 17.5 GHz when the thickness was 3.0 mm. The novel carbon-Pc polymer composites were believed to have potential applications in the microwave absorbing area.     

Simultaneous preconcentration of Co(II), Ni(II), Cu(II), and Cd(II) from environmental samples on Amberlite XAD-2000 column and determination by FAAS

A new method for the preconcentration of some trace metals (Co, Ni, Cu, and Cd) as complexed with ammonium pyrrolidynedithiocarbamate (APDC) was developed using a mini-column filled with Amberlite XAD-2000 resin. Metal contents were determined by flame atomic absorption spectrometry (FAAS) after the metal complexes accumulated on the resin were eluted with 1M HNO(3) in acetone. The effects of the analytical parameters such as sample pH, quantity of complexing agent, eluent type, resin quantity, sample volume, sample flow rate, and matrix ions were investigated on the recovery of the metals from aqueous solutions. The relative standard deviation (R.S.D.) of the method was <6%. The validation of the method was confirmed using two certified reference materials (CRM TMDW-500 Drinking Water and CRM SA-C Sandy Soil C). The method was successfully applied to some stream waters and mushroom samples from Eastern Black Sea Region (Trabzon city) of Turkey.     

密胺餐具中三聚氰胺单体的迁移研究

采用高效液相色谱法(HPLC)测定了密胺餐具中三聚氰胺单体的迁移量。研究了2种不同材质(脲醛表面覆密胺的制品、密胺树脂模塑制品)中三聚氰胺单体的迁移行为,以及浸泡温度和浸泡时间对密胺餐具中三聚氰胺迁移量的影响。实验结果表明:随着浸泡温度的升高,三聚氰胺单体的迁出量呈上升的趋势;特定温度下,三聚氰胺的迁出量随着浸泡时间的延长而增大。市面购得密胺餐具96份,其中密胺树脂模塑制品51份,脲醛表面覆密胺制品45份,脲醛表面覆密胺制品中三聚氰胺单体迁移量的合格率低于密胺树脂模塑制品。     

酞菁钴负载镁铝水滑石对甲基橙的氧化脱色

通过共沉淀法制备了Mg/Al物质的量比为3∶1的镁铝水滑石,并将其作为载体负载磺化酞菁钴制得新型功能材料酞菁钴负载水滑石(CoPcTs-LDH)。通过红外和热重分析表征了CoPcTs-LDH,研究了CoPcTs-LDH/H2O2对100mL 10mg/L甲基橙的氧化脱色。实验结果表明,在25～37℃、pH值为3～9、反应7h后甲基橙的剩余率均低于30%;反应过程符合一级动力学模型,阿伦尼乌斯活化能Ea=57.64kJ/mol;反应过程中羟基自由基发挥了重要作用;CoPcTs-LDH在重复使用5次后对甲基橙仍有很好的氧化脱色能力,具有较高的重复使用性能。     

氧化石墨烯负载铁酞菁涂层的制备及其防腐蚀性能

目前,鲜见将石墨烯用于防腐蚀涂料的研究报道。以氧化石墨烯负载铁酞菁复合材料(GO-Fe Pc)为填料、环氧树脂E-44和107胶为成膜剂、T-31为固化剂,采用共混法制备了双组分涂料,并涂覆于Q235钢基片制备防腐蚀涂层,通过中性盐雾试验、抗老化和电化学等手段研究并评价了填料含量对涂层防腐蚀性能的影响。结果表明:添加GO-Fe Pc填料的涂层具有较好的防腐蚀性能,且E-44与GO-Fe Pc的质量比为100∶1时效果最佳,涂层附着力为0级,氙灯老化30 d和中性盐雾试验15 d后,涂层无腐蚀现象,3.5%Na Cl浸泡15 d后的电极腐蚀电位最高,为-0.258 V,防腐蚀性能最佳。     

TiO2纳米棒光催化降解甲基橙的研究

本文以甲基橙为目标降解物考察了催化剂的添加量、甲基橙溶液的pH值、晶化时间、热处理温度等因素对用"软模板"制备的TiO2纳米棒光催化活性的影响.研究表明:当催化剂添加量为0.08g、甲基橙溶液的pH=4、晶化时间为24h、热处理温度为500℃时,TiO2光催化剂的催化效果最佳,达到了85.96%.     

Single Layer of Polymeric Cobalt Phthalocyanine: Promising Low‐Cost and High‐Activity Nanocatalysts for CO Oxidation

The catalytic behavior of transition metals (Sc to Zn) combined in polymeric phthalocyanine (Pc) is investigated systematically by using first‐principles calculations. The results indicate that CoPc exhibits the highest catalytic activity for CO oxidation at room temperature with low energy barriers. By exploring the two well‐established mechanisms for CO oxidation with O₂, namely, the Langmuir–Hinshelwood (LH) and the Eley–Rideal (ER) mechanisms, it is found that the first step of CO oxidation catalyzed by CoPc is the LH mechanism (CO + O₂ → CO₂ + O) with energy barrier as low as 0.65 eV. The second step proceeds via both ER and LH mechanisms (CO + O → CO₂) with small energy barriers of 0.10 and 0.12 eV, respectively. The electronic resonance among Co‐3d, CO‐2π*, and O₂‐2π* orbitals is responsible for the high activity of CoPc. These results have significant implications for a novel avenue to fabricate organometallic sheet nanocatalysts for CO oxidation with low cost and high activity.