Electrochemical Investigation of Effect of Br - on Redox Behavior of (TPP)Co

用微电极和薄层循环伏安（ＣＶ）技术研究了Ｂｒ－对四苯基钴卟啉（（ＴＰＰ）Ｃｏ）在１，２＿二氯乙烷（ＤＣＥ）中电化学行为的影响．发现在较高电位下，两个Ｂｒ－轴向配位的（ＴＰＰ）Ｃｏ（ＩＩ）（Ｂｒ－）２其一个Ｂｒ－发生脱落表现出（ＴＰＰ）Ｃｏ（ＩＩ）（Ｂｒ－）的行为特征，这被证明是Ｂｒ－的氧化所致．证明了（ＴＰＰ）Ｃｏ（ＩＩ）（Ｂｒ－）在约０．１２Ｖ（ＳＣＥ）处还原，而（ＴＰＰ）Ｃｏ（ＩＩ）（Ｂｒ－）２则在大约Ｃｏ（Ｉ）／Ｃｏ（Ｉ）还原过程出现的更负的电位处发生还原The effect of Br - anion on electrochemical behavior of (TPP)Co was investigated in 1,2 dichloroethane solution by microelectrode and thin layer cyclic voltammetry technique. It was found that the axially coordination of one Br - anion to (TPP)Co(Ⅲ)(Br -) 2 shifts the potential of porphyrin system to more positive value. The reduction peak of 0.12 V(vs.SCE) is attributed to the reduction of (TPP)Co(Ⅲ)(Br -). It is also postulated that the reduction of (TPP)Co(Ⅲ)(Br -) 2 occurred at a more negative potential where the reduction of the Co(Ⅱ)/Co(Ⅰ) process happened.作者联系地址：中国科学院金属腐蚀与防护研究所金属腐蚀与防护国家重点实验室,中国科学技术大学化学系Author's Address: State Key Lab. for Corrosion and Prot., Inst. of Corr. and Prot. of Metals, Chinese Acad.of Sci., Shenyang 110015 Lin Xiangqin Dept. of Chem., Univ. of Sci. and Tec. of China, Hefei 230026$$

Research Progress on Electrode Material in All-vanadium Redox Battery

全钒氧化还原液流电池是一种新型的蓄电池 ,较之传统蓄电池有许多的优点 ,本文介绍了钒电池中的两类电极材料 (金属类和复合类 )的发展情况An all_vanadium redox flow storage battery possesses many advantages over conventional storage batteries.The development statue of two types electrode materials(metal and compound type)is introduced in this article.作者联系地址：中国科学院金属研究所金属腐蚀与防护国家重点实验室,中国科学院金属研究所金属腐蚀与防护国家重点实验室,中国科学院金属研究所金属腐蚀与防护国家重点实验室 辽宁沈阳110016 ,辽宁沈阳110016 ,辽宁沈阳110016Author's Address: State Key Library for Corrosion and Protection,Institute of Metal Research, Chinese Academy of Sciences, shenyang 110016, Chin

Study on Preparing Technology and Corrosion Resistance of Ti/Zr Based Chromium-free Chemical Conversion Coating on Zinc Electroplating Layer

借助优化钛/锆基化学转化工艺,在碱性无氰镀锌层基体上获得了环保型的无铬转化膜,并与铬酸盐彩色钝化膜作对比.中性盐雾试验、动电位极化和电化学阻抗谱测试结果表明:钛/锆基化学转化膜出现白锈时间为96 h,达到铬酸盐彩色钝化膜标准,且呈现出较低的腐蚀电流和较高的极化电阻,但钝化特性不如铬酸盐彩色钝化膜明显.In this paper,we obtained environmental-friendly chromium-free chemical conversion coating on the non-cyanide alkaline zinc electroplating layer by employing the optimized Ti/Zr based conversion technique.At the same time,the performances of the Ti/Zr based conversion coating were compared with chromate colour passivation coating.The corrosion resistances of the conversion coatings were investigated by using neutral salt spray(NSS) test,potentiodynamic polarization and electrochemical impedance spectroscopy(EIS).The results showed that the white rust appeared after 96 hours when the NSS test was performed on the Ti/Zr based conversion coating,which was close to the corrosion resistance rating of chromate colour passivation coating.Compared with the chromate passivation coating,the Ti/Zr based conversion coating showed lower corrosion current and higher polarization resistance.However,the passivation characteristic of the former was less evident than the latter.作者联系地址：中国科学院金属研究所金属腐蚀与防护国家重点实验室;Author's Address: State Key Laboratory for Corrosion and Protection,Institute of Metal Research,Chinese Academy of Sciences,Shenyang 110016,Chin

Preparation and Characterization of the Silane-Phosphonic Acid Composite Passivation Coating for Electrogalvanized Steel

利用N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷(AAPTMS)、γ-(2,3-环氧丙氧基)丙基三甲氧基硅烷(GPTMS)和1-羟基亚乙基-1,1-二膦酸(HEDP),在电镀锌钢基体上制备了一种新型硅烷-有机膦酸复合钝化膜.X射线光电子能谱、傅立叶变换红外光谱以及中性盐雾试验、动电位极化曲线和电化学阻抗谱测试表明:该复合钝化膜主体结构由Si—O—Si、Si—O—P等组成;120 h中性盐雾试验后白锈面积小于5%,达到铬酸盐彩色钝化膜水平;且其腐蚀反应呈现更为明显的阳极扩散控制特征,属于物理阻挡机制.A new silane-phosphonic acid composite passivation coating process has been developed for the protection of electrogalvanized steel based on N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane(AAPTMS),γ-(2,3-epoxypropoxy)propyltrimethoxy-silane(GPTMS) and 1-hydroxy ethylidene-1,1-diphosphonic acid(HEDP).The results of X-ray photoelectron spectroscopy(XPS),Fourier transform infrared spectroscopy(FTIR),potentiodynamic polarization scan,electrochemical impedance spectroscopy(EIS) and neutral salt spray(NSS) tests indicated that the major structure of the prepared silane-phosphonic acid composite passivation coating consisted mainly of Si—O—Si and Si—O—P bonds.The area of white rust was not more than 5% of the total panal after 120 h NSS test,which could be compared favourably with the chromate colour passivation coating.However,the corrosion reaction on the anode of the silane-phosphonic acid composite passivation coating had more distinct diffusion control characteristics and belonged to the physical blocking mechanism.作者联系地址：中国科学院金属研究所金属腐蚀与防护国家重点实验室;Author's Address: State Key Laboratory for Corrosion and Protection,Institute of Metal Research,Chinese Academy of Sciences,Shenyang 110016,Chin

Effects of KSCN on Kinetic Characters of the Positive Couple and Performance for Vanadium Redox Flow Battery

应用循环伏安、交流阻抗(EIS)等方法,研究了硫氰酸钾(KSCN)添加剂对石墨电极上(正极)钒电池电对(VO2+/VO2+)动力学特征及电池性能的影响.结果表明:1)KSCN的添加提高了VO2+/VO2+电对氧化峰的峰电流,但对还原峰的影响很小;2)添加KSCN,增加了充放电电量,提高了钒电池中活性物质的利用效率;3)VO2+/VO2+电对的速率常数K0,随着KSCN浓度的增加而逐渐增大.In order to improve the reaction activity of VO2+/VO2+ and the battery performance of Vanadium redox flow battery,different concentration of potassium sulfocyanates KSCN were added into 0.1mol/L VOSO4/ H2SO4 solution,and the kinetic characters of electrochemical reaction of VO2+/VO2+ was studied by CV and EIS.The results showed that the addition of KSCN could improve the oxidative peak current value of positive couple VO2+/VO2+ reaction,but had little influence in the reductive peak.The addition of KSCN decreased the impedance at 1.0 V.And the value of standard rate constant k0 was also improved with the concentration of KSCN increased.The total coulomb during the charge and discharge processes increased after the addition of KSCN,which means that the usage efficiency of active species in the VRB solution was improved.作者联系地址：中国科学院金属研究所金属腐蚀与防护国家重点实验室;东北大学理学院;Author's Address: 1.State Key Laboratory for Corrosion and Protection,Institute of Metal Research,Shenyang 110016,China;2.College of Science,Northeast University,Shenyang 110004,Chin

Cyclic Voltammetric Investigation of the Axial Coordination Effects of Pyridine on the Redox Behaviours of (TPP)Co

本文考察了吡啶（Ｐｙ）对（ＴＰＰ）Ｃｏ在１，２－二氧乙烷中的电化学氧化还原行为的影响，观察到当存在一定量Ｐｙ时，Ｃｏ（Ⅲ）／Ｃｏ（Ⅱ）还原过程出现两个还原峰，分别在０．２５和－０．４０Ｖ（ｖｓ．ＳＣＥ）两处．由于吡啶在电极表面的吸附，在远小于形成二轴向Ｐｙ配合物的加入量时，Ｃｏ（Ⅲ）／Ｃｏ（Ⅱ）还原过程表现出了二个吡啶轴向配合物的伏安行为．证明在０．２５Ｖ与－０．４０Ｖ两个还原峰分别对应于一个和两个Ｐｙ分子配位的Ｃｏ（Ⅲ）／Ｃｏ（Ⅱ）还原峰．本工作还观察到了Ｃｏ（Ⅱ）／Ｃｏ（Ⅰ）还原受吡啶影响的伏安图变化过程，证实在－１．２Ｖ（ＳＣＥ）的还原峰是（ＴＰＰ）Ｃｏ（Ｐｙ）的直接电极还原．给出了Ｐｙ存在下（ＴＰＰ）Ｃｏ金属中心电化学氧化还原电位发生负移的机理．The electrochemistry of (TPP)Co in presence of pyridine was investigated in dichloroethane solution by cyclic voltammetry. Upon the addition of pyridine to the solution, two reduction peaks of Co(Ⅲ)/Co(Ⅱ) at 0.25 and -0.40 V (SCE) were observed. It was infered that the peaks were belong to the reductions of the complex compounds with one and two axial pyridine, (TPP)Co(Ⅲ)(Py) and (TPP)Co(Ⅲ)(Py)2. Even though the mole ratio of added pyridine was less than 1 the reduction of Co(Ⅲ)/Co(Ⅱ) still mainly occured at -0.40 V, which evidently resulted from pyridine adsorption on the electrodes. Besides, it was observed that the reduction peak of Co(Ⅱ)/Co(Ⅰ) was shifted to -1.20 V (SCE) with large amount of added pyridine. The new reduction peak could be attributed to the direct reduction of the axially coordination complex (TPP)Co(Ⅱ)(Py). The mechanisms of the effect of pyridine on the electrochemical redox behaviours of (TPP)Co were given.作者联系地址：中国科学院金属腐蚀与防护研究所金属腐蚀与防护国家重点实验室,中国科学技术大学化学系Author's Address: a State Kay Lab. for Corrosion and Protection, Inst. of Corrosion and Protection of Metals, Chinese Academy of Sciences, shenyang 110015b Dept. of chem., Univ. of

Dissolved Oxygen Seawater Battery with Electrochemical Capacitance

以氧化处理的碳纤维刷（Carbon fibre brush，CFB）作阴极材料，提出海水超级电容溶解氧电池（Seawater battery with electrochemical capacitance, SWB-EC）概念，并制造了3台联用实海测试样机. 分别由循环伏安和稳态恒流放电方法研究了氧化处理前后的CFB和镁合金牺牲阳极的放电性能. 结果表明：氧化处理的CFB具有准电容特性，在动态海水中其氧阴极还原反应（Oxygen reduction reaction, ORR）活性比未处理的CFB有大幅度提高；镁合金牺牲阳极的开路电位为-1.74 V，工作电位高，溶解较均匀. 用以上阴、阳极材料制成3台联用样机作连续实海放电测试，经运行2个月，相关实验数据分析表明：与商品化海水电池SWB1200初步相比，该海水超级电容溶解氧电池具有更高的体积比功率密度.A new concept of seawater battery with electrochemical capacitance (SWB-EC) has been proposed using carbon fibre brush (CFB) as the cathode material, and three testing prototypes have been made accordingly. The discharge performances of the CFB before- and after-oxidation and Mg alloy sacrifice anode were studied by cyclic voltammetry and constant current discharge tests under steady state conditions. Results show that the oxidized CFB exhibits the pseudo-capacitive characteristic and its activity of oxygen reduction reaction (ORR) in stirred seawater highly increases, comparing with the non-oxidized CFB. The open circuit potential of Mg alloy sacrifice anode is -1.74 V, having the advantages of high working potential and uniform dissolution. The consecutive marine discharge test is conducted for prototypes made of the oxidized CFB cathode and Mg alloy sacrifice anode. The preliminary data collected in two months reveals that comparing with the commercial seawater battery—SWB1200, the home-made SWB-EC achieves a higher volume specific power density.山东省博士基金(BS2011NJ019)和中央高校基本科研业务费专项资金(201022006)资助作者联系地址：1. 中国海洋大学化学化工学院，山东 青岛 266100；2. 中国科学院金属研究所，辽宁 沈阳 110016；3. 钢铁研究总院青岛海洋腐蚀研究所，山东 青岛 266071；4. 山东省科学院海洋仪器仪表研究所，山东 青岛 266001；5. 青岛旭日金一机械有限公司，山东 青岛 266109Author's Address: 1. College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao 266100, Shandong, China; 2. Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016; 3. Qingdao Marine Corrosion Institute, China Iron & Steel Research Institute Group, Qingdao 266071, Shandong, China; 4. Shandong Academy of Sciences Institue of Oceanographic Instrumentation, Qingdao 266001, Shandong, China; 5. Qingdao Xuri Jinyi Machinery Co., Ltd, Qingdao 266109, Shandong, China通讯作者E-mail：[email protected]

JUNO Sensitivity on Proton Decay p→νˉK+p\to \bar\nu K^+ Searches

The Jiangmen Underground Neutrino Observatory (JUNO) is a large liquid scintillator detector designed to explore many topics in fundamental physics. In this paper, the potential on searching for proton decay in $p\to \bar\nu K^+$ mode with JUNO is investigated.The kaon and its decay particles feature a clear three-fold coincidence signature that results in a high efficiency for identification. Moreover, the excellent energy resolution of JUNO permits to suppress the sizable background caused by other delayed signals. Based on these advantages, the detection efficiency for the proton decay via $p\to \bar\nu K^+$ is 36.9% with a background level of 0.2 events after 10 years of data taking. The estimated sensitivity based on 200 kton-years exposure is $9.6 \times 10^{33}$ years, competitive with the current best limits on the proton lifetime in this channel

JUNO sensitivity on proton decay p → ν K + searches*

The Jiangmen Underground Neutrino Observatory (JUNO) is a large liquid scintillator detector designed to explore many topics in fundamental physics. In this study, the potential of searching for proton decay in the $p\to \bar{\nu} K^+$ mode with JUNO is investigated. The kaon and its decay particles feature a clear three-fold coincidence signature that results in a high efficiency for identification. Moreover, the excellent energy resolution of JUNO permits suppression of the sizable background caused by other delayed signals. Based on these advantages, the detection efficiency for the proton decay via $p\to \bar{\nu} K^+$ is 36.9% ± 4.9% with a background level of $0.2\pm 0.05({\rm syst})\pm$$0.2({\rm stat})$ events after 10 years of data collection. The estimated sensitivity based on 200 kton-years of exposure is $9.6 \times 10^{33}$ years, which is competitive with the current best limits on the proton lifetime in this channel and complements the use of different detection technologies