1,5-二硝基蒽醌电化学还原制备──1,5-二氨基-4,8-二羟基蒽醌的研究(英文)

采用循环伏安法、稳态极化曲线法和恒电位电解法相结合的实验手段，研究了１，５－二硝基蒽醌（１，５－ＤＮＡ）在硫酸溶液中、汞齐化铜电极上阴极还原制备１，５－二氨基－４，８－二羟基蒽醌（１，５－ＤＡ－４，８－ＤＨＡ）的电化学反应性能．结果表明：在１２．７５ｍｏｌ／ＬＨ２ＳＯ４和１４０℃温度下，１，５－ＤＮＡ在汞齐化铜阴极表面上具有反应物强吸附和不可逆随后化学反应的特征．电解最后的产物经红外光谱测定为１，５－二氨基－４，８－二羟基蒽醌，平均电流效率为７８％，产率为７２％．１，５－ＤＮＡ直接电化学还原的行为与电极材料、酸浓度、添加剂、反应物浓度等有关．作者联系地址：浙江工业大学化学工程学

Electrocatalytic Performances of Carbon Nanotube Air Electrode for Oxygen Reduction

　以不同质量比的铂、纳米碳管、活性碳为催化层制备空气电极并测定其稳态极化曲线和交流阻抗.研究发现,纳米碳管经硝酸处理后其氧还原反应性能得到提高,特别是将表面氧化后再沉积Pt,对氧的电还原反应影响更显著.以质量比4∶1的活性碳/纳米碳管载Pt制备的空气电极,在过电位ηc为500～600mV下,氧还原电流可达600～700mA·cm-2.EIS测试表明,纳米碳管载Pt后的欧姆极化阻抗和电化学阻抗均非常小.The air electrodes with different mass ratio of Pt/active carbon or carbon nanotube as catalyst layer material have been prepared. The electrocatalytic performances for oxygen reduction were evaluated by means of polarization curve and electrochemical impedance spectroscopy (EIS). The results disclosed that carbon nanotubes dealt with nitric acid in the catalyst layer had been improved obviously on the electrocatalytic activity. After the surface of carbon nanotube was oxygenated and aggraded with platinum, the catalyst had obviously effects on the electrocatalytic activity. The air electrode with the mass ratio of active carbon to Pt/carbon nanotube in 4∶1 showed better electrocatalytic activity, e.g., the output current density reached 600～700 mA cm~(-2) when the overpotential was 500～600 mV. The EIS showed that the addition of Pt/carbon nanotube in the catalyst decreased greatly ohmic and kinetic impedance and thereby produced greater enhancement in performances.作者联系地址：浙江工业大学应用化学系纳米科学与技术工程研究中心,浙江工业大学应用化学系纳米科学与技术工程研究中心 浙江杭州310032 ,浙江杭州310032Author's Address: Department of Applied Chemistry, Zhejiang University of Technology, Hangzhou 310014, Chin

Electrochemical Properties of the Modified Carbon Nanotubes

应用红外吸收光谱、扫描电子显微镜分别对纳米碳管和硝化后的纳米碳管进行表征,将其制备成粉末微电极,并在碱性溶液中测试它对对硝基苯酚的电还原性能.实验表明:经硝化处理后,碳管表面修饰了羰基,其电还原性能明显提高.依据实验结果探讨了硝化后纳米碳管于对硝基苯酚电还原过程中的反应机理.Powder micro-electrodes were prepared from raw carbon nanotubes and carbon nanotubes modified by carboxyl.The electro-reduction properties of both the raw and open-ended carbon nanotubes in p-Nitrophenol solution were investigated.The FTIR spectrum result indicated that the functional groups are successfully fixed on the surface of the carbon nanotubes after nitric acid treatment.The cyclic voltammetry results show that the electrochemical activity of carboxyl-modified carbon nanotubes was improved.The mechanism of electro-(reduction) for the carbon nanotubes after acid treatment was discussed.作者联系地址：绿色化学合成技术国家重点实验室培育基地浙江工业大学纳米科学与技术工程研究中心,绿色化学合成技术国家重点实验室培育基地浙江工业大学纳米科学与技术工程研究中心,绿色化学合成技术国家重点实验室培育基地浙江工业大学纳米科学与技术工程研究中心,绿色化学合成技术国家重点实验室培育基地浙江工业大学纳米科学与技术工程研究中心 浙江杭州310032,浙江杭州310032,浙江杭州310032,浙江杭州310032Author's Address: *,TANG Jun-yan,LI Guo-hua,LOU Ying-wei State Key Laboratory Breeding Base of Green Chem Synth Tech,Zhejiang University of Technology,Hangzhou,Zhejiang 310032,Research Center of Nano ST,Zhejiang University of Technology,Hangzhou 310032,Zhejiang,Chin

Electrochemical Reduction of Nitrobenzene on the WC Electrode in Acidic Solution

　以聚四氟乙烯为粘接剂制成碳化钨(WC)电极.采用循环伏安法、线性扫描法和恒电位阶跃法研究了硝基苯在酸性溶液中WC电极上的电化学行为.实验表明:WC电极对硝基苯的还原具有较好的活性,电极过程受扩散和电化学步骤混合控制;表观活化能为23.7kJ·mol 1,其中,电化学步骤的活化能10.91kJ·mol 1.The tungsten carbide (WC) electrode was constructed by using polyterafluoroethylene as binder. The electrochemical behavior of nitrobenzene on the WC electrode in acidic solution was investigated by cyclic voltammetry, linear scan method and chronoamperometry. Experimental results showed that WC electrode had good activity for the electrochemical reduction of nitrobenzene, and the electrode process was controlled by diffusion and electrochemical stepssimultaneously. The apparent active energy of the electrode process is 23.7kJ mol~(-1), while the active energy of the electrochemicalstep is 10.91kJ mol~(-1).作者联系地址：浙江工业大学应用化学系,浙江工业大学应用化学系,浙江工业大学应用化学系,浙江工业大学应用化学系 浙江杭州310032 ,浙江杭州310032 ,浙江杭州310032 ,浙江杭州310032Author's Address: *,CHU You-qun,ZHU Ying-hong,XU Zhi-hua Department of Applied Chemistry, Zhejiang University of Technology, Hangzhou 310032,Chin

Electrosynthesis of p-aminobenzenearsenic Acid

研究优化电解还原对硝基苯胂酸(p-A)合成对氨基苯胂酸(p-ASA)的工艺条件.实验表明:硫酸浓度、添加剂量、反应温度、投料量等工艺参数对合成产率有显著影响.初步得出比较适宜的电解合成条件为:硫酸浓度10%(bymass,下同)、添加剂量1%(bymass)NaCl、反应温度80℃、投料量71.4g/L、电流密度10A·dm-2.在上述工艺条件下,电解合成产率可达65.8%.The electrochemical reduction of p-nitrophenyl arsonit acid to p-aminobenzenearsenic acid was studied using controlled-current electrolysis.The results showed that the yield of p-aminobenzenearsenic acid was determinated by the following factors:the concentrations of sulphuric acid,the amount of additive,temperature and the concentrations of p-nitrophenyl arsenic acid.The optimum electrolytic conditions were obtained to be is 10% H2SO4,1% NaCl,80 ℃,25 g/350 mL p-nitrophenyl arsenic acid and 10 A·dm-2.The yield of arsanilic acid could be reached 64.7% under the optimum electrolytic conditions.作者联系地址：浙江工业大学绿色合成技术国家重点实验室培育基地;杭州利群环保纸业有限公司;Author's Address: 1.State Key Laboratory Breeding Base of Green Chemisitry Synthesis Technology,Zhejiang University of Technology,Hangzhou 310032,China;2.Hangzhou Liqun Environmental Paper Company,Hangzhou 310018,Chin

A Comparative Study of Ce3+/Ce4+ Redox Couple on Pt Electrode in Sulfuric Acid and Methanesulfonic Acid

采用循环伏安法和线性扫描法研究了硫酸和甲磺酸介质中Ce3+/Ce4+在Pt旋转圆盘电极（RDE）上的电化学性能，初步探索了Ce3+/Ce4+的络合行为，考察了Ce3+反应的交换电流密度、扩散系数以及反应速率常数，比较了两种酸介质中Ce3+在Pt电极氧化的活化能. 结果表明，硫酸介质中以Ce4+的络合为主，其平衡电位负移；甲磺酸介质中以Ce3+的络合为主，其平衡电位正移. 硫酸介质中Pt电极上Ce3+更容易氧化为Ce4+, 硫酸铈(III)的电氧化对温度更为敏感.The electrochemical oxidations of Ce3+ to Ce4+ on Pt rotating disk electrode (RDE) in both sulfuric acid and methanesulfonic acid (MSA) solutions were studied by using cyclic voltammetry and linear sweep voltammetry. The complexing behaviors of Ce3+/Ce4+ were preliminarily probed and the exchange current density, diffusion coefficient, as well as reaction rate constant were obtained from Butler-Volmer equation. The activation energies of Ce3+ oxidation on Pt electrode in two types of acidic media, obtained from Arrhenius equation, were also compared. The results indicate that Ce3+ can be oxidized to Ce4+ much easier in sulfuric acid than in MSA solutions. The equilibrium potential in sulfuric acid solutions moves negatively due to the predominant complexation of Ce4+, while that in MSA solutions positively because of the predominant complexation of Ce3+, The larger values of activation energy for the oxidation of Ce3+ to Ce4+ on Pt electrode in sulfuric acid solutions suggest that the oxidation of Ce3+ occurs more readily and the electro-oxidation of cerous sulfate is more susceptible to temperature.浙江省研究生教育创新基地基金项目（No. 1001）资助作者联系地址：浙江工业大学 绿色化学合成技术国家重点实验室培育基地，浙江 杭州 310014Author's Address: State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, Zhejiang University of Technology, Hangzhou 310014, China通讯作者E-mail：[email protected]

Electrochemical Reductive Behaviors of 3,4,5,6-tetrachloro-2-trichloromethylpyridine at Ag Electrode

应用循环伏安法研究了在乙腈和水的混合溶液中3,4,5,6-四氯-2-三氯甲基吡啶于银电极上的电化学行为及其脱氯反应.实验表明:3,4,5,6-四氯-2-三氯甲基吡啶在银电极上的电化学还原是扩散控制的不可逆过程,并有伴随后续化学反应的特征;温度对反应有促进作用.求得3,4,5,6-四氯-2-三氯甲基吡啶在乙腈和水的混合溶液(体积比5∶1)中的扩散系数D=3.0×10-5cm2/s.The electrochemical reductive behavior of 3,4,5,6-tetrachloro-2-trichloropyridine(heptachloropyridine) on silver electrode in the mixture of acetonitrile and water solutions containing TBAP was investigated by cyclic voltammetry.The influences of scan rate,concentration and temperature on the electrochemical behavior were discussed.It was shown that the reduction of heptachloropyridine on the silver electrode was a diffusion-controlled irreversible process.The diffusion coefficient of heptachloropyridine in the acetonitrile solution was 3.0×10-5 cm2/s.The mechanism of the dechloration of 3,4,5,6-tetrachloro-2-trichloropyridine was also discussed.作者联系地址：浙江工业大学绿色化学合成技术国家重点实验室培育基地;Author's Address: State Key Laboratory Breeding Base of Green Chemistry Synthesis Technology,Zhejiang University of Technology,Hangzhou 310032,Chin

The Activity of Alloy CuNi Electrode in Electroreduction of Aromatic NitroCompounds

本文采用共沉积法制备了以铜为基体的不同Ｃｕ／Ｎｉ比的Ｃｕ－Ｎｉ合金镀层，并用稳态极化法研究了这些镀层在使用硝基苯（ＮＢ）和１，５－二硝基蒽醌（１．５－ＤＮＡ）制备对氨基苯酚（ＰＡＰ）及１，５－二氨基－４，８－二羟基蒽醌（１，５－ＤＡ－４，８－ＤＨＡ）等电化学还原过程中的阴极活性．研究表明，在ＰＡＰ和１，５－ＤＡ－４，８－ＤＨＡ电合成体系中，不同Ｃｕ／Ｎｉ比的合金阴极具有不同的交换电流密度（ｉｏ）和表观活化能（ＥＡ），其中以０．０５ｍｏｌ／ＬＣｕＳＯ４·５Ｈ２Ｏ＋０．６ｍｏｌ／ＬＮｉＳＯ４·６Ｈ２Ｏ＋０．２５ｍｏｌ／ＬＮａ３Ｃｉｔ·２Ｈ２Ｏ组成的镀液，并在控制电流密度为０．６Ａ·ｄｍ－２、ｐＨ值为６、体系温度为５０℃等工艺条件下镀制的Ｃｕ－Ｎｉ合金试片（ＣＮ－３０），具有最大的ｉｏ和最小的ＥＡ值，与常规所用的Ｃｕ、Ｃｕ／Ｈｇ、蒙乃尔合金等阴极相比，ＣＮ－３０试片的电极性能最佳CuNi alloy on the basis of copper at different ratio Cu/Ni are prepared by codepostion. The cathode activtiy of film are studied by steadystate polarization for electroreduction nitrobenzene (NB) and 1,5dinitroanthraquinone (1,5DNA) to paminophenol and 1,5diamino4,8dihydroanthraquinone respectly. The results show that the alloy cathodes at different ratio Cu/Ni have different exchange current density (io) and apparent activition energy (EA). The alloy (CN30) has maximal io and minimal EA by codeposition at the following conditions: electrolyte: 0.05 mol/L CuSO4·5H2O+0.6 mol/L NiSO4·6H2O+0.25 mol/L Na3Cit·2H2O; current density: 0.6 A/dm2 , pH=6, temperature at 50 ℃. Compared with the common cathodes such as Cu, Cu/Hg, Monel alloy, CN30 alloy is more suitable in these system.作者联系地址：浙江工业大学化学工程学院应用化学系Author's Address: Chem. Engin. Coll., Zhejiang Univ. of Tech., Hangzhou 31001

A Comparative Study in Pretreatments of Acid Chemical Wastewater by Electrochemical Oxidation and Ozonation

保持一定酸度条件下对比了电化学氧化和臭氧氧化预处理酸性化工废水的效能（废水原pH 0.85）. 结果表明，在废水中添加2 g·L-1 NaCl电化学氧化预处理效果较佳，30 mA·cm-2条件下电解20 min后水样的CODCr（化学需氧量）去除率达43.4%，BOD5/CODCr（生化需氧量与化学需氧量的比值）值从原来的0.034上升至0.14，可生化性明显提高. 单独臭氧化仅在pH 7.0才能取得一定的预处理效能. Ti(Ⅳ)/O3/H2O2高级氧化体系在pH 2.85条件下亦有较好的预处理效果，16 min后水样CODCr去除率达22.9%，BOD5/CODCr值则提高至0.072.Under the condition of keeping certain acidity, the pretreatment efficiency of an acid chemical wastewater (pH 0.85) by electrochemical oxidation was compared with that by ozonation. The results showed that the electrochemical oxidation pretreatment could obtain a better result than the ozonation at pH 0.85. After the addition of 2 g·L-1 NaCl and with the electrochemical oxidation pretreatment at 30 mA·cm-2, the removal rate of chemical oxygen demand (CODCr) reached 43.4%, and the value of biochemical oxygen demand/chemical oxygen demand (BOD5/CODCr) also increased from 0.034 to 0.14 in 20 minutes, indicating significantly improvement in the biodegradability of the wastewater. However, the ozonation alone had a low pretreatment efficiency at pH 0.85, and could only become as effective as those done by the electrochemical oxidation pretreatment at pH 7.0. A ozone-based advanced oxidation technology, Ti(Ⅳ)/O3/H2O2, was also relatively effective at pH 2.85. The value of 22.9% for the removal rate of CODCr could be obtained and the value of BOD5/CODCr went up from 0.034 to 0.072 in 16 min.国家自然科学基金项目（No. 20406019，No. 21176225）资助作者联系地址：浙江工业大学化学工程与材料学院，绿色化学合成技术国家重点实验室培育基地，浙江 杭州 310032Author's Address: College of Chemical Engineering and Materials Science, State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, Zhejiang University of Technology, Hangzhou 310032,China通讯作者E-mail：[email protected]

Preparation and Electrocatalytic Activity of the Pt/WC/TiO2 Composites

以TiO2为载体制备了Pt/WC/TiO2三元复合催化剂，并由XRD、SEM和TEM等表征催化剂样品的形貌和结构特征.用循环伏安法测定了三元复合催化剂在酸性条件下对甲醇氧化的电催化性能，并将其与二元复合催化剂Pt/TiO2和Pt/WC的电催化性能进行比较.结果表明：三元复合催化剂具有更好的催化活性.进一步研究了二氧化钛晶相对Pt/WC/TiO2催化剂电催化活性的影响.TiO2 was used as the support for preparation of Pt/WC/TiO2 composite catalyst. The composites were characterized by XRD, SEM and TEM methods. The electrocatalytical activity of Pt/WC/TiO2 composite for oxidation of methanol was investigated by cyclic voltammetry. Pt/WC/TiO2 exhibited higher activity compared with that of Pt/TiO2 and Pt/WC composite catalysts. Based on this we discussed the effects of crystal phases of TiO2 on the electrocatalytical activity of Pt/WC/TiO2 composite catalyst.浙江省国际科技合作重大专项(No. 2008C14040)，国际科技合作计划（2010DFB63680），浙江省自然科学基金重点项目（No. Z4100790）及浙江省教育厅科研项目(No. Y200908436)作者联系地址：浙江工业大学化材学院，绿色化学合成技术国家重点实验室培育基地，浙江杭州，310032Author's Address: State Key Laboratory Breeding Base of Green Chemistry Synthesis Technology, College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310032通讯作者E-mail：[email protected]