锌催化电还原脱氯合成2,3,5,6-四氯吡啶:反应机理和工艺优化

采用循环伏安法和恒电位电解法,探讨了含有ZnCl₂的乙睛水混合溶液中五氯吡啶(PCP)在不锈钢阴极表面电还原脱氯生成2,3,5,6-四氯吡啶(2,3,5,6-TCP)的反应机理;采用恒电流电解法对该电还原脱氯过程的各种工艺条件进行了优化。结果表明:该体系中PCP电还原脱氯生成2,3,5,6-TCP主要遵循以Zn/Zn²⁺为氧化还原媒介的间接电还原机理;优化工艺条件下(阴极液含0.025mol·L^-1HCl+15%(体积分数)水+0.2mol·L^-1苯磺酸钠+0.16mol·L^-1ZnCl₂的乙腈溶液;电流密度为1.25A·dm^-2),0.08mol·L^-1PCP能高选择性地脱氯生成2,3,5,6-TCP,2,3,5,6-TCP的收率和电解电流效率分别可达88.7%和59.1%。     

间接电氧化媒质Ce4+/Ce3+的循环与再利用

设计了一种适用于间接电氧化合成反应,中试规模的填充式隔膜电解槽.该电解槽以铜板为阴极,PbO2/Ti石墨颗粒填充电极为阳极,电解液[0.16mol/L Ce2(SO4)3,1.5 mol/L H2SO4]采用外循环的方式控制其温度为30～50℃,在50A/m2的电流密度下电解,获得大于80%的电流效率.讨论了电极材料、电流密度、电解液温度、Ce3+浓度和循环次数等对电流效率的影响.其中Ce3+浓度是限制电流密度和影响电流效率的主要因素;电解液在间接电氧化对甲氧基甲苯反应中连续循环使用20次,仍然保持高于85%的电流效率;PbO2/Ti石墨颗粒填充电极使用寿命超过6个月.     

Ce~(4+)/Ce~(3+)做氧化媒质间接电合成邻氯苯甲醛

用硫酸做介质、Ce4 + Ce3+ 做氧化媒质间接电合成邻氯苯甲醛。通过正交实验和单因素实验确定出最佳工艺条件为 :反应温度 348K ,表面活性剂浓度 1 .4× 1 0 - 3～ 2 .2× 1 0 - 3mol L ,硫酸浓度 7.5mol L。在优化的实验条件下邻氯苯甲醛的产率达 93.1 % ;在相应的电解实验中 ,电流效率为 89.46% ,电解收率为 50 .1 5%。     

“槽内式”间接电氧化法制备2-甲基-1,4-萘醌

以Ti/PbO2为阳极、Pb为阴极、硫酸为支持电解质,采用Cr6+/Cr3+为氧化媒质,四丁基溴化铵为相转移剂,在阳离子交换膜为隔膜的“板框式”电解槽中,进行“槽内式”间接电氧化2-甲基萘(2-MN)合成2-甲基-1,4-萘醌(2-MNQ)的研究。考察了2-MN间接电氧化制备2-MNQ的工艺条件对2-MNQ选择性和电流效率的影响规律。实验结果表明:在2-MN和Cr2O72-浓度分别为0.02 mol/L和0.03 mol/L,硫酸质量分数20%,温度50℃,电流密度110 A/m2,通电量为理论通电量0.2倍的工艺条件下进行电解,2-MNQ的平均选择性为71.9%,平均表观电流效率为69.7%。     

硫酸铬电解氧化反应的研究

为了制备间接电氧化合成菲醌的氧化剂Cr2O72-,对硫酸铬电解氧化反应进行了实验研究,考察了电流密度、电解时间、反应温度及硫酸含量对电解效率的影响。通过实验得出:在隔膜电解槽中,采用Pb作阴极,Pb-PbO2作阳极,Cr3 电氧化的最佳条件是反应时间4 h,电解液中硫酸浓度30%,电流密度67 mA/cm2,所得Cr2O72-收率为95%左右。     

Co~(3+)的电氧化合成及其在对甲砜基苯甲酸制备中的应用

以七水硫酸钴、浓硫酸、硫酸铵为原料,电氧化合成Co3+,用Co3+氧化对甲砜基甲苯合成对甲砜基苯甲酸。考察了电极材料、电解温度、电流密度、硫酸浓度以及电解液循环套用对电极反应和硫酸浓度、Co3+与对甲砜基甲苯物质的量比对氧化反应的影响。结果表明,在选用阳极二氧化铅、阴极铅为电极板,陶瓷膜作为阳离子交换膜,电解液浓度为c(Co2+)=0.5 mol/L、c (硫酸)=4.0 mol/L、c (硫酸铵)=0.15 mol/L,电极间距(d)为2 cm、电流密度(J)为350 A/m2、电解温度(T)为10℃时,电解液Co2+转化率可达80%,电解氧化电流效率达67.5%。在进行对甲砜基甲苯的氧化时,控制电解液浓度为c(Co3+)=0.4 mol/L、c(硫酸)=4.0 mol/L、c(硫酸铵)=0.15 mol/L,n(Co3+)∶n(对甲砜基甲苯)=6∶1,使得反应温度为30℃,反应时间为30 min,对甲砜基苯甲酸的收率可达97.8%,精制后纯度在98.5%以上。     

酸碱催化剂浓度对柔性硅气凝胶性能和结构的影响

以甲基三甲氧基硅烷(MTMS)和正硅酸乙酯(TEOS)作为混合硅源,甲醇为溶剂,十六烷基三甲基溴化铵(CTAB)为表面活性剂,通过酸碱两步催化溶胶凝胶法制备醇凝胶,经超临界干燥可以制备高弹性疏水块状硅气凝胶。分别采用0.1 mol·L^-1 和0.01 mol·L^-1 的草酸作为酸催化剂,5 mol·L^-1 和10 mol·L^-1 的氨水作为碱催化剂,研究不同酸碱催化剂浓度对其网络结构的影响。发现高浓度酸和高浓度碱以及低浓度酸和低浓度碱作为催化剂合成的硅气凝胶的网络结构更加均匀,孔径分布更窄。其中,在草酸浓度为0.01 mol·L^-1、氨水浓度为5mol·L^-1 时,所得硅气凝胶密度为0.135 g·cm^-3、比表面积为807 m²·g^-1、孔隙率约为93%,凝胶最大可压缩至其起始长度的60%,压缩回弹率为100%。     

2-氯-5-三氯甲基吡啶电化学氢化脱氯合成2-氯-5-甲基吡啶

2-氯-5-三氯甲基吡啶（TCMP）选择性氢化脱氯制备2-氯-5-氯甲基吡啶（CCMP）或2-氯-5-甲基吡啶（CMP）在农药“吡虫啉”合成中具有重要应用价值。首先在弱酸性的甲醇/乙酸/水混合溶剂中研究了TCMP电化学脱氯合成CCMP或CMP的可行性;其次,研究了阴极材料和电解液组成对TCMP选择性脱氯反应的影响;最后,采用膜厚度极距的板框式电解槽分别研究了阴、阳极支持电解质对电解槽压和电流密度与底物浓度对脱氯反应效率的影响。实验结果表明,在弱酸性的甲醇/乙酸/水混合溶剂中,TCMP能在银网阴极上高选择性的氢化脱氯成CMP;CMP收率从高到低的阴极依次为：银> 铜> 锌> 铅> 钛> 石墨> 镍。阴阳极支持电解质从四丁基高氯酸铵分别换成乙酸锂和硫酸,电解槽压大幅度下降。降低电流密度和提高底物浓度有利于TCMP电化学氢化脱氯效率。在优化条件下（阴极液：含10%乙酸+5%水+0.2 mol·L^-1乙酸锂的甲醇溶液;阴极：银网;电流密度：333 A·m^-2;温度：30℃）,0.2 mol·L^-1 TCMP 能高效地转化为CMP（收率：91%）,电流效率可达54%,电解槽压大约为3.0 V。     

液相还原法制备纳米镍粉

采用液相还原法在搅拌反应器内进行了纳米镍粉的制备研究。系统考察了反应物浓度、反应物配比（N₂H₄：NiSO₄）、引发剂浓度、氢氧化钠浓度、反应温度、搅拌速度等操作条件对镍粉物性的影响规律,获得了较优操作条件：NiSO₄为0.8 mol·L^-1,反应物配比为6：1,NaBH₄浓度为0.01 mol·L^-1,NaOH浓度为1 mol·L^-1,反应温度80℃,搅拌速度为2400 r·min^-1,在较优条件下制备出常温下稳定性良好、平均粒径107 nm的面心立方结构的纳米镍粉。     

硫代杯[4]冠-4在硝酸体系中对Sr2+的萃取

乏燃料后处理的高放废液分离过程中,发展新型分离材料实现对锶的高效萃取至关重要。合成了1,2交替构象的硫代杯[4]冠-4(TCACE),利用FT-IR、¹H NMR和MS对目标产物进行了表征。研究不同稀释剂对萃取的影响,优化得出CH₂Cl₂为稀释剂,在硝酸浓度为3 mol·L^-1,有机相中硫代杯[4]冠-4浓度为1×10^-3 mol·L^-1,水相中Sr²⁺浓度为5×10^-4 mol·L^-1,萃取温度为25℃,萃取80 min条件下,平均传质系数为1.36×10^{-5 m}·s^-1,Sr²⁺的分配比为0.69。分析了不同条件对硫代杯[4]冠-4对Sr²⁺的萃取影响,研究了萃取计量方程式,实验结果表明萃合物为{Sr(NO₃)₂}·{TCACE}。研究了TCACE对其他金属离子Mo⁶⁺、Ni²⁺、Ag⁺、Sn⁴⁺等的萃取效果,表明对Sr²⁺具有较好的选择性。     

Oxidation of Ce3+ by HO2 Radical and Ce3+-HO2 Complex Formation

The reaction of Ce⁴⁺ with H₂O₂ in H₂SO₄ is studied as a function of pH, Ce³⁺, SO₄⁼ and the ionic strength. The reaction mechanism proposed assumes the existence of a Ce³⁺ -HO₂ complex. Direct evidence for the reaction, Ce³⁺ + HO₂ + H⁺ → Ce⁴⁺ + H₂O₂ is presented.     

基于废旧锂离子电池正极材料LiMn2O4制备MnO2及其电化学性能

以废旧锂离子电池LiMn₂O₄正极材料为原料,通过控制酸浸条件分别制备出λ-MnO₂纳米粒子和β-MnO₂纳米棒,研究作为一次电池电极材料和超级电容器电极材料的相关电化学性能。利用X射线粉末衍射（XRD）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）和恒电流充放电、循环伏安等测试手段对样品成分、形貌和电化学性能进行分析表征。实验表明：在常温常压下,采用0.5 mol·L^-1的H₂SO₄酸浸3 h可制备出λ-MnO₂纳米颗粒;而于相似文献   

Reaction kinetics and reaction techniques for mediated oxidation of methylarenes to aromatic ketones

The Mn³⁺-mediated anodic oxidation of toluene and some substituted toluenes (p-chloro-,p-xylene-,p-nitro-) in 60 wt % H₂SO₄ has been investigated with respect to reaction kinetics and process techniques. The mediators Co³⁺ in 3.5 N HNO₃ and Ce⁴⁺ in 60 wt % H₂SO₄ are compared with Mn³⁺ in 60 wt % H₂SO₄ for unsubstituted toluene. The mediated oxidation of the toluenes proceeds in three well-distinguished steps: benzyl alcohol, benzaldehyde, benzoic acid. The last step, which destroys the desired product, the aldehyde, is crucial. Therefore, for continuous resaturation of the electrolyte with toluene and for extraction of benzaldehyde, the benzaldehyde content in the emulgated organic phase has to be kept below a critical value. For toluene,p-chlorotoluene and xylene Mn³⁺-mediated oxidation only becomes attractive with process temperatures above 60°C. The conversion ofp-nitrotoluene top-nitrobenzaldehyde can only be carried out by Co³⁺. The reactivities of the oxidants declines in the order: Co³⁺>Mn³⁺>Ce⁴⁺. Current efficiencies for the recuperation of all oxidants approaches 100%.     

Indirect electrolytic oxidation of some aromatic derivatives

High current efficiencies and material yields were attained in the indirect electrochemical oxidation of toluene and chlorotoluene to the corresponding aldehyde. The oxidant used was Ce⁴⁺ in HClO₄, which was regenerated at platinized titanium anodes. A cost estimate showed that the electrochemical route could be economically attractive.     

Electrochemical behaviour of Mn3+/Mn2+, Co3+/Co2+ and Ce4+/Ce4+ redox mediators in methanesulfonic acid

The redox behaviour of Mn³⁺/Mn²⁺, Co³⁺/Co²⁺ and Ce⁴⁺/Ce³⁺ mediators commonly used in indirect oxidation of organic compounds were evaluated in methane sulfonic acid on a glassy carbon working electrode employing cyclic voltammetry. Manganic methanesulfonate exhibits higher instability in dilute methanesulfonic acid. The solid MnO₂ formed during disproportionation on the glassy carbon electrode further affects the reproducibility. Cobaltic methanesulfonate formation occurs only at oxygen evolution region rendering the overall oxidation process less efficient. Ceric methane sulfonate formation is highly efficient over a wide acid concentration range. Ceric methanesulfonate can also be employed over a wide temperature range to oxidize different aromatic compounds.     

Effect of cations in solution on the oxidation of methanol on the surface of platinum electrode

The effect of metal cations in solution on the oxidation of methanol on the electrode surface of platinum is a neglected aspect to direct methanol fuel cell (DMFC). In this paper, a smooth platinum electrode absorbing metal cations as the working electrode was applied to investigate the methanol oxidation with the cyclic voltammetry (CV) in 1.0 mol L⁻¹ H₂SO₄. From the analysis of experiment, it is found that the cations, Li⁺, Ce⁴⁺, Mn²⁺, Ni²⁺, Cu²⁺, have some negative effect on the catalytic oxidation of methanol on the surface of platinum. The degree of the effect from different cations was analyzed.     

Electrochemical behavior of amorphous carbon films: kinetic and impedance-spectroscopy studies

Impedance spectra and potentiodynamic curves of oxidation and reduction reactions in the quinone/hydroquinone and Ce^3+/4+ systems were measured in a 0.5M H₂SO₄ solution on amorphous carbon thin-film electrodes grown by magnetron sputtering or ion source techniques. The electrode equivalent circuit contains a constant phase element. Only narrow-bandgap (“graphitelike”) amorphous carbon is electrochemically active; however, the wider bandgap (“diamondlike”) material also acquires the activity on “doping” it with platinum (ca 10%) in the course of film growth. The admixture of platinum does not effect film conductivity; its action probably is of catalytic character. In its electrochemical activity, the platinum-containing amorphous diamondlike carbon films resemble boron-doped polycrystalline diamond.     

Catalytic effects of the silver ion on the indirect electrochemical oxidation of toluene to benzaldehyde using Ce3+/Ce4+ as mediator

The catalytic effects of the silver ion on toluene oxidation by Ce⁴⁺ as well as the anodic generation of Ce⁴⁺ were investigated. The rates of toluene oxidation were first order with respect to both Ag⁺ and Ce⁴⁺. Argentic oxides formed on the surface of the platinum anode when Ag⁺ was present in the anolyte, which increased the activity of the electrode. About 3×10^–3M of Ag⁺ was needed to obtain maximum current efficiency.     

Coupling between electrolysis and liquid-liquid extraction in an undivided electrochemical reactor: applied to the oxidation of Ce3+ to Ce4+ in an emulsion Part I. Experimental

The effect ofin situ simultaneous extraction of tetravalent cerium by an organic phase (di-2 ethylhexylphosphoric acid in kerosene) on the performance of an undivided batch electrochemical reactor using the Ce³⁺/Ce⁴⁺ system was investigated. The influence of the most important parameters (initial concentration of Ce³⁺, composition and volume percentage of the organic phase) were studied experimentally under potentiostatic control of the anode potential. A conversion factor of Ce³⁺ and extraction factor larger than 90% are obtained for the best operating conditions, but the presence of the organic phase and the necessity of avoiding oxygen gas evolution considerably reduce the operating anodic current densities. The transient cell behaviour and the final equilibrium state conditions are found to be in very good qualitative agreement with the conclusions of a preliminary study of the electrochemical kinetics of the Ce³⁺/Ce⁴⁺ system and extraction mechanisms of Ce⁴⁺ by the organic phase.This paper is dedicated to Professor Dr Fritz Beck on the occasion of his 60th birthday.     

Activity of oxygen reduction reaction on small amount of amorphous CeOx promoted Pt cathode for fuel cell application

Pt on ceria (CeO_x) particles supported on carbon black (CB) were synthesized using the combined process of hot precipitation and impregnation methods. During 30 cycles of cyclic voltammetry pre-treatment in the potential ranging from −0.2 to 1.3 V (V vs. Ag/AgCl), it was observed that a small amount of CeO_x, which consisted of the interface region between Pt and CeO_x, remained on Pt particles. Other free CeO_x particles were dissolved into H₂SO₄ aqueous solution. To develop the Pt-CeO_x/CB catalyst, the surface chemical states, the net chemical composition, morphology and electrochemical behavior in H₂SO₄ aqueous solution were characterized. Our microanalysis and electrochemical analysis indicate that the active CeO₂ with high specific surface area provides the continuous amorphous cerium oxide (Ce³⁺, Ce⁴⁺) layer with pores on the surface of Pt particles. It is concluded that the amorphous cerium oxide layer on Pt inhibits the oxidation of Pt surface and contributes to enhancement of the activity on Pt cathode. The single cell performance was also improved using the Pt-CeO_x/CB cathode. Based on all data, it is expected that the design based on characterization of the interface between Pt and small amount of amorphous cerium oxide layer could help in preparation of more active Pt catalyst.