Mn3O4-MnOOH复合材料催化过硫酸氢钾降解罗丹明B

在碱性条件下，使用H₂O₂部分氧化Mn(OH)₂制备了Mn₃O₄-MnOOH复合材料，并将其作为过硫酸氢钾活化剂用于催化氧化降解水中难降解染料罗丹明B。采用X射线衍射仪(XRD)、X射线光电子能谱(XPS)、扫描电镜(SEM)、透射电镜(TEM)等多种手段表征了材料的物理化学性质，确定了其为内部Mn₃O₄、外部MnOOH的二元纳米片状核壳式结构。通过考察不同催化体系下罗丹明B的降解效果可得Mn₃O₄-MnOOH复合材料具有比单一锰氧化物更好的催化效能。在此基础上，进一步考察溶液初始pH、催化剂投加量、KHSO₅投加量、污染物浓度等因素对染料降解的影响，确定了适宜的反应条件，即pH为4，催化剂投加质量浓度为0.1 g/L,KHSO₅投加浓度为0.325 0 mmol/L，污染物初始质量浓度为50 mg/L，该条件下，反应30 min后，罗丹明B去除率...     

(NH4)2S吸收净化冶炼烟气中SO2回收硫资源的方法

采用(NH₄)₂S溶液吸收净化高浓度SO₂烟气,得到(NH₄)₂S₂O₃和NH₄HSO₃的混合溶液并转移至高压反应釜中,控制反应条件,两种物质发生自氧化还原反应,生成硫磺和(NH₄)₂SO₄.实验考察了吸收SO₂过程和自氧化还原过程的影响条件,结果表明:在pH=3～7,SO₂气体流速300 ml·min^-1,(NH₄)₂S浓度为0.2～1.2 mol·L^-1,常温条件下,烟气中二氧化硫的吸收率达到99.8%以上,且无H₂S生成;在pH=2.5～3.0,温度为130℃条件下,反应进行1 h,硫磺收率达到95%以上,溶液经过蒸发结晶得到(NH₄)₂SO₄.用X射线衍射(XRD)和X射线荧光光谱(XRF)对硫磺和硫酸铵进行表征分析,结果表明:硫磺的纯度为99.14%,硫酸铵中氮元素含量为23.6%.     

复合无机盐CuSO4/Fe2(SO4)3催化合成乙酸异戊酯

乙酸异戊酯通常在浓硫酸催化下由乙酸和异戊醇酯化制得,由于浓硫酸的氧化和脱水作用存在产品纯度低和色泽深等缺点,开发性能更加优良的酯化催化剂以代替硫酸成为研究热点。为考察复合无机盐催化剂CuSO₄/Fe₂(SO₄)₃合成乙酸异戊酯的催化性能,研究乙酸和异戊醇为原料在复合无机盐CuSO₄/Fe₂(SO₄)₃催化下的酯化反应,并考察催化剂用量、反应时间和乙酸与异戊醇物质的量比对乙酸酯化率的影响。结果表明,在乙酸用量0.1 mol、异戊醇用量0.2 mol、催化剂用量0.8 g、反应时间2.0 h和带水剂环己烷用量10 mL条件下,酯化率高于93%。催化剂具有催化活性高、操作简单和不污染环境等优点。     

乙酰丙酮钴(Ⅱ)对甲苯液相空气氧化反应的催化性能

以乙酰丙酮钴(Co(acac)₂)为催化剂,在1 L高压搅拌反应釜中研究了其对甲苯液相空气氧化反应的催化性能和反应产物分布,考察了催化剂用量对甲苯转化率和苯甲酸收率的影响,并考察了不同温度下不同催化剂用量时的催化剂寿命。结果表明,Co(acac)₂催化甲苯液相氧化是平行连串的复杂反应,Co(acac)₂的催化活性存在"催化-抑制转换"现象,适宜的催化剂用量为0.0044%(质量分数);催化剂的寿命随反应温度变化存在一个最大值,165℃时催化剂寿命最长,反应温度较低(<165℃)时催化剂更容易失活;在165℃、Co(acac)₂用量为0.0044%时,反应4 h,甲苯转化率为19%,苯甲酸收率为80%;与醋酸钴、环烷酸钴等钴盐催化剂相比,Co(acac)₂催化剂具有用量少、催化活性时间长的优点,可有效地减缓钴盐结垢现象,Co(acac)₂催化剂对甲苯液相空气氧化反应具有良好的催化性能。     

蔗糖在DMF-[BMIm]Cl溶剂中催化制备5-HMF

研究了在N,N-二甲基甲酰胺(DMF)-离子液体[BMIm]Cl混合溶剂中将蔗糖高效转化为5-羟甲基糠醛(5-HMF)的反应。运用紫外-可见分光光度计对水解液中5-HMF进行定量分析并计算其收率。考察了CrCl₃·6H₂O、AlCl₃·6H₂O、SnCl₄·5H₂O、FeCl₃、CoCl₂·6H₂O、ZnCl₂、CuCl₂·2H₂O、CaCl₂ 8种催化剂对反应的催化效果,结果表明AlCl₃·6H₂O催化效果最为明显。以AlCl₃·6H₂O为催化剂研究了不同反应条件如时间、温度、溶剂中DMF-[BMIm]Cl质量比、催化剂AlCl₃·6H₂O的用量对5-HMF收率的影响,得到的最佳条件为以0.5mmol蔗糖为反应物,0.4mmol AlCl₃·6H₂O为催化剂,反应时间2h,反应温度120℃,5g质量比为85:15的DMF-[BMIm]Cl混合溶剂,此条件下5-HMF收率最高可达63.4%。研究表明,DMF-[BMIm]Cl混合溶剂体系对蔗糖转化为5-HMF有一定的促进效果,在此溶剂体系中以AlCl₃·6H₂O为催化剂时可以得到较高的5-HMF产率。     

[Bmim]Cl中CrCl3-AlCl3催化纤维素降解制取5-羟甲基糠醛

5-羟甲基糠醛是一种具有很高利用价值的化学平台化合物。以离子液体1-丁基-3-甲基咪唑氯盐（[Bmim]Cl）为溶剂,以CrCl₃和AlCl₃为复合催化剂,在油浴加热条件下催化纤维素降解制取5-羟甲基糠醛,研究了催化剂种类、催化剂量、温度、纤维素浓度、气氛、纤维素聚合度、反应规模等不同因素对纤维素降解制取5-羟甲基糠醛的影响。结果表明,[Bmim]Cl用量为10 g,棉花添加量为0.5 g,x（CrCl₃）=25%（mol）,x（AlCl₃）=2.5%（mol）,反应温度为120℃,反应气氛为N₂（dry）气氛,反应时间为4 h时,HMF产率最高,达到59%。此外,反应过程中水的作用机理也被给予了相应解释。     

Zn(Ⅱ)配合物催化C—C键裂解和原位合成2-甲基-4(3H)-喹唑酮

在配合物的水热合成过程中往往可以发现新的化学反应和催化机理。本文通过[Zn(L)₂·(H₂O)₂·(NO₃)₂]（L=4(3H)-喹唑酮）配合物在130℃催化乙腈分子中的CC键断裂,原位合成化合物2-甲基-4(3H)-喹唑酮。利用红外、元素分析和X射线单晶衍射表征分析2-甲基-4(3H)-喹唑酮和[Zn(L)₂·(H₂O)₂·(NO₃)₂]的结构,结果表明[Zn(L)₂·(H₂O)₂·(NO₃)₂]和2-甲基-4(3H)-喹唑酮属于三斜晶系,P-1空间群。三组温度控制实验表明,温度对2-甲基-4(3H)-喹唑啉酮的形成有着重要的影响,并且温度高于130℃有利于该催化反应的进行。采取电喷雾质谱表征2-甲基-4(3H)-喹唑酮的形成机理发现,[Zn(L)₂·(H₂O)₂·(NO₃)₂]催化乙腈分子中的CC键断裂,生成(CN)₂和·CH₃。·CH₃有选择性地引入到4(3H)-喹唑酮中的C原子和N原子之间。本文对原位引入CH₃有着指导作用。     

Co3O4催化臭氧氧化降解水中酮基布洛芬的研究

以Co(NO₃)₂·6H₂O和尿素为原料制备了9种Co₃O₄催化材料，考察了其对水中酮基布洛芬(KTP)的催化臭氧氧化降解效能。结果表明，与单独臭氧氧化相比，所制备的Co₃O₄对水中KTP的催化臭氧氧化降解率提高了12.0%～63.8%，且在n[Co(NO₃)₂·6H₂O]:n(尿素)=4:1、煅烧温度400℃下制备得到的Co₃O₄催化剂催化活性最高。SEM、XRD、FTIR、XPS、BET等表征分析显示，该Co₃O₄催化剂表面呈覆盖细小微粒的球状颗粒，晶相为立方相，且表面含有丰富的羟基，表面羟基密度为1.075×10^-5 mol/m²。机理研究证实，Co₃O₄对水中KTP的非均相催化臭氧氧化降解...     

Ni/Si3N4催化剂在甲烷部分氧化反应中的应用

前期工作表明Ni/Si₃N₄催化剂在甲烷部分氧化反应中有较好的催化活性和很强的抗积炭能力。在前期工作的基础上考察了镍负载量和焙烧温度对Ni/Si₃N₄催化剂在甲烷部分氧化中催化性能的影响,并采用XRD、TPR、XPS等技术对催化剂进行了表征。结果表明,镍负载量和焙烧温度影响催化剂活性组分的表面分布和晶粒尺寸,并进一步影响催化剂的反应性能。在800℃反应条件下,活性组分负载量与CH₄转化率之间的关系为：C-10>C-15>C-5>C-1;而焙烧温度与CH₄转化率大小顺序为：S(400)> S(600)>S(800)。     

3-甲酰基-7β-苯乙酰胺基-3-头孢-4-羧酸二苯甲基的催化脱羰基反应

用常见膦配体与 ［IrCl(cod)］₂(cod为1,5-环辛四烯)、RuCl₂(cod)或RhCl₃形成的复合催化剂及以SBA-15、 MCM-41和MCM-48为载体所形成的负载型复合催化剂,对3-甲酰基-7β-苯乙酰胺-3-头孢-4-羧酸二苯甲基酯进行了催化脱羰基反应研究。结果发现,催化剂用量为底物物质的量的5%时,［IrCl(cod)］₂/SBA-15/亚磷酸三乙酯负载型复合催化剂脱羰基反应的产率最高,高效液相色谱产率为32%,柱色谱分离产率为23%,与文献报道的以化学计量RhCl(PPh₃)₃对该化合物进行脱羰基反应的产率相当,不但大大减少了贵金属的使用量,而且催化剂可以重复使用。     

Epoxidation of propylene by using [π-C5H5NC16H33]3[PW4O16] as catalyst and with hydrogen peroxide generated by 2-ethylanthrahydroquinone and molecular oxygen

The epoxidation of propylene catalyzed by a reaction-controlled phase transfer catalyst [π-C₅H₅NC₁₆H₃₃]₃[PW₄O₁₆] is investigated. The H₂O₂ is generated by the oxidation of 2-ethylanthrahydroquinone (EAHQ) with molecular oxygen in the organic solvent. Under mild conditions, the selectivity for propylene oxide, based on propylene, is 95%, and the yield, based on 2-ethylanthrahydroquinone, is 85%. During the epoxidation, the catalytic system is homogeneous. However, after the H₂O₂ is used up, the catalyst can be recovered as a precipitate and can be reused. After the epoxidation reaction, 2-ethylanthraquinone can be regenerated to 2-ethylanthrahydroquinone by catalytic hydrogenation, and no coproduct is produced.     

Dielectric dispersion in [N(C2H5)4]2ZnCl4 single crystal

Temperature dependence of the complex dielectric permittivity of [N(C₂H₅)₄]₂ZnCl₄ crystal was measured in the frequency range 300 Hz / MHz. Jump-wise changes in the real and imaginary components of ε* were observed for the three crystallographic directions at the phase transition temperature. The dielectric dispersion clearly apparent in the high-temperature phase, rapidly disappears at the phase transition. The anomalous changes in the dielectric permittivity are related to vibrations of the tetraethylammonium ion. The activation energy of these vibrations amounts to 40 kJ/mol.     

Phase transitions in R2 SnCl6-type crystals (R = NH3 C2H3, NH3C2H5 and N(CH3)4)

The thermal dilatation in (NH₃ ·CH₃) SnCl₆, (NH₃ · C₂H₅) SnCl₆ and [N(CH₃)] SnCl₆ was measured, and as the results it has turned out that (NH₃ ⁶·C₂H₅) SnCl₆ and [N(CH₃)₄]₂ SnCl₆ undergo the first order transitions at 128 K and 158 K, respectively. The low temperature phases of (NH · C₂H₅) SnCl₆ and [N(CH₃)₄]₂ SnC1₆ are found to be monoclinic and tetragonal, respectively, No phase transition was observed in (NH₃ ·CH₃)₂ SnCl₆ down to 77 K.     

In situ FTIR study on reaction pathways in Ni(CO)4/CH3OK catalytic system for low-temperature methanol synthesis in a liquid medium

An in situ infrared spectroscopic study was conducted to elucidate the reaction pathways for low-temperature methanol synthesis in a catalytic system composed of Ni(CO)₄ and CH₃OK (denoted as Ni(CO)₄/CH₃OK). The reaction was conducted in a liquid medium at 313–333 K with an initial pressure of 3.0 MPa. When CH₃OK was added to Ni(CO)₄ solution at 293 K, different carbonylnickelates, [Ni₅(CO)₁₂]²⁻, [Ni₆(CO)₁₂]²⁻ and [Ni(CO)₃(COOCH₃)]⁻, were immediately formed from Ni(CO)₄. The species and the composition of the carbonylnickel complexes varied with temperature. The variations in concentrations of methanol (MeOH) and methyl formate (MF) during the run, which were determined from their IR absorptions, indicated a pattern characteristic of consecutive reactions with MF as an intermediate. Thus, it was shown that methanol was produced through the carbonylation of MeOH to MF and the subsequent hydrogenation of MF to MeOH. Stable hydridocarbonylnickel anions, [HNi(CO)₃]⁻ and/or [HNi₂(CO)₆]⁻, were observed together with a small amount of Ni(CO)₄ throughout the methanol synthesis. Since Ni(CO)₄ alone showed no activity for the hydrogenation of MF, the hydridocarbonylnickel anions generated in the presence of CH₃OK must be responsible for the reaction. The dual role of CH₃OK in the catalytic system was stated.     

Towards recycling purpose: Converting PET plastic waste back to terephthalic acid using pH-responsive phase transfer catalyst

Converting polyethylene terephthalate (PET) wastes to its monomer and valuable chemicals via eco-friendly chemical method is still a challenge task. Previously, phase transfer catalysts used for alkaline hydrolysis were soluble in reaction media and hardly separated after reaction. Here, we reported several pH-responsive catalysts combined alkyl quaternary ammonium units with heteropolyacid anion for achieving stepwise product/catalyst separation and catalyst recycling. The properties of homogeneous/heterogeneous transfer behavior allow catalyst to be easily separated from reaction media by adjusting of pH value. Among them, [C₁₆H₃₃N(CH₃)₃]₃PW₁₂O₄₀ (abbreviated as [CTA]₃PW) exhibits the highest activity and the most suitable pH responsive values. Such a pH triggered switchable catalytic system not only shows good performance for depolymerization of pure PET, but also some real PET wastes such as coloured trays and PE/PET complex films could be completely degraded into terephthalic acid. Additionally, the reaction kinetics and activation energy of PET alkaline hydrolysis also studied with and without pH-responsive [CTA]₃PW.     

Accurate low-pressure kinetics for isobutane oxidation over phosphomolybdic acid and copper(II) phosphomolybdates

A low-pressure steady-state technique has been used to investigate the rates and mechanisms of the oxidation of isobutane over H₃[PMo₁₂O₄₀], CuH₄[PMo₁₂O₄₀]₂, Cu₂H₂[PMo₁₂O₄₀]₂, Cu_2.5H[PMo₁₂O₄₀]₂, and Cu₃[PMo₁₂O₄₀]₂. Observed oxidation products over all catalysts are methacrolein, 3-methyl-2-oxetanone, acetic acid, carbon dioxide and water. The most selective catalyst for methacrolein formation at low temperatures (<496 °C) is Cu_2.5H[PMo₁₂O₄₀]₂, where both Cu(II) reduction and acid sites play a role. The least active catalyst at low temperatures is phosphomolybdic acid followed by Cu₃[PMo₁₂O₄₀]₂. This activity is reversed at higher temperatures. The 3-methyl-2-oxetanone is a unique product and is likely to be the precursor to methacrylic acid. Acetic acid is also probably a precursor to complete oxidation. Catalyst deactivation or restructuring is significant only over H₃[PMo₁₂O₄₀].     

Calorimetric investigations of overcritical behaviour in (TEA)2CuCl4 crystals

The results of experimental investigation of molar heat capacity of [N(C₂H₅)₄]₂CuCl₄ - ferroelasto-ferroelectric crystals in a wide temperature range are presented. The typical anomaly for the first order phase transition of order-disorder type at 258 K and additional anomaly with maximum at 195 K has been observed. We suggest that the low temperature anomalies of physical properties of [N(C₂H₅)₄]₂CuCl₄ crystals can be attributed to over critical traces of isomorphous phase transitions (similar to that observed in liquid-gas system). Results of numerical analysis of phenomenological model of phase transition in [N(C₂H₅)₄]₂CuCl₄ crystals are presented and compared with the experimentally determined temperature dependence of the specific heat and entropy changes.     

Solventless ketalization of glycerol to solketal with acetone over the ionic liquid[P(C4H9)3C14H29][TsO]

The ketalization of glycerol with acetone was conducted over an ionic liquid [P(C_4H_9)_3C_(14)H_(29)][Ts O](TTPT) in a batch reactor. A scheme to obtain the purified product using TTPT as a homogeneous catalyst is proposed and a maximum solketal yield of 86% is achieved at acetone/glycerol molar ratio of 6/1, reaction time of 0.5 h, reaction temperature of 303 K, catalyst amount of 5 wt% of glycerol. TTPT was recycled and reused for ten times without obvious losses in terms of quantity and activity. Furthermore, effects of various experimental parameters(stirring speed, catalyst loadings, temperature and reactant composition) on the reaction kinetics are investigated. In terms of kinetics modeling, Kγis fitted by reactant composition at the temperature range 298 K–323 K, which was a concise strategy that showed good precision in the kinetics fitting. The activation energy for this ketalization reaction was evaluated to be 28.2 k J·mol~(-1). In addition, the kinetics of the reaction at a temperature exceeding the boiling point of acetone were also studied. We believe that all the results are important for further development of a technology for the continuous synthesis of solketal.     

Structural and Optical Properties of Barium Strontium Titanate (Ba0.5Sr0.5TiO3) Thin Films

Ferroelectric Barium Strontium Titanate (Ba_0.5Sr_0.5TiO₃) or BST thin films on quartz substrates have been prepared by using a modified sol gel processing technique. The starting materials are Barium 2-ethylhexanoate Ba[CH₃(CH₂)₃CH(C₂H₅)CO₂]_2, Strontium 2-ethylhexanoate Sr[CH₃(CH₂)₃CH(C₂H₅)CO₂]₂ and Titanium(IV) isopropoxide [TiOCH(CH₃)₂]₄. The precursors except [TiOCH(CH₃)₂]₄ were synthesized in the laboratory. Transparent and crack-free films were fabricated on quartz substrates by spin coating. The as-fired films were found to be amorphous, which crystallized to cubic phase after annealing at 550°C in air for 1 hr. In this paper we report the structural and optical properties of BST films prepared by the modified sol-gel process.

Communicated by Prof. E. C. Subbarao     

Ag-Zn_3(VO_4)_2光催化剂催化降解甲基橙溶液

采用水热法结合高温热处理制备Ag-Zn_3(VO_4)_2光催化剂,研究催化剂在可见光下降解甲基橙溶液的性能,并考察催化剂用量、甲基橙溶液初始浓度、pH值、盐效应和H_2O_2用量对光催化性能的影响,评价Ag-Zn_3(VO_4)_2光催化剂的重复使用性能。结果表明,在催化剂用量2.0 g·L~(-1)、甲基橙溶液初始浓度20 mg·L~(-1)和溶液pH=6.2条件下光照反应5 h,甲基橙溶液脱色率可达99.18%,Na_2SO_4对光催化降解甲基橙起抑制作用,且随着溶液中盐浓度增加,抑制作用更明显。H_2O_2在一定浓度范围可促进光催化降解甲基橙,100 mL甲基橙溶液中30%H_2O_2加入量为1.0 mL时,甲基橙溶液脱色率可提高21.68个百分点。催化剂重复使用5次后,光照5 h的甲基橙溶液脱色率仍可达到75.99%。