利用金刚石膜电合成过氧碳酸钠
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摘要
电化学是研究电能和化学能相互转化关系的科学,这种转化是在电子导体(如金属、半导体)和离子导体(如电解质溶液、熔盐)的界面上发生的,因此现代电化学又被定义为研究电子导体和离子导体界面现象的一门科学。这是一门重要的边缘科学,因为带电的表面在自然界和生产实践中都是广泛存在的。电合成是指用电化学方法去合成化学物质,这也许是电化学科学应用于实践的一个最重要的分支,它为人类提供一系列用其他方法难于制得的材料,如钠、钾、铁、钙、铝,及许多强氧化性或还原性的物质、有机化合物等,它为解决目前化学工业给地球环境带来的污染问题,展示出一条有效而又切实可行的道路。
过氧化物和超氧化物都具有强氧化性。过氧化物在工业生产和人们生活中起着显著的作用。现有的电合成过氧碳酸钠技术是碱性条件下,在铂电极上电解碳酸钠溶液,可以电合成得到过氧碳酸钠。过氧碳酸钠的应用很容易受到添加物的影响,并且铂电极也很容易被所添加的催化剂腐蚀,因此最好不添加催化剂。然而电合成过氧碳酸钠时若不添加催化剂,其效率会大幅度的降低。
近年来,用金刚石膜作阳极进行电化学氧化在处理含有机物的工业污水有很广的应用前景。对比其他的电极材料,金刚石膜电极有更好的化学和电化学稳定性,并且有更高的电流效率。另外,它具有宽电化学势窗,低残留电流,极好的电化学稳定性以及表面不易被污染等,这是在电化学中很重要的优势。金刚石膜的电化学氧化电势很高,能大量的产生羟基自由基,羟基自由基氧化性很高,可以在金刚石膜的表面实现直接氧化。最近,有关于电合成过氧碳酸钠的报道。与传统的合成方式相比电合成有了很大的改进。
本论文具体论述了电极的选择的问题以及利用金刚石膜电极电合成过氧化物的优势。在电化学氧化中,电极材料的电极电势不同,电流效率不同,只有阳极的电极电势高于反应物的反应电势时,反应物才会被氧化,因此选择合适的电极材料是一个关键。研究金刚石膜电极的电化学特性,及其作为电极的优势。通过了解电合成的原理,掌握过氧化物电合成的特点,研究电合成过氧化物的关键。对比现有的过氧化物的电合成方法与用金刚石膜电极进行电合成,研究用金刚石膜电极用于电合成过氧化物的可行性。
Electrochemistry is a science of study the translation of electricity and chemistry. The translation is occurred on the surface of metal conductor and hydronium ion. It is a edge science which is very important,because it is useful very abroad both in the natrue and in the production. Electrochemical synthesis is to synthesize chymic substance by electrochemical method.,which is an important way to attain some material that is very hard to get,such as natrium, kalium,calcium aluminum some strong oxidation substance and deoxidizer. And it can get over the pollution problem all of the world.
Peroxide has strong oxidate character,which is very important both in the industry and the daily life. The electrochemical synthesis of sodium peroxycarbonate using Pt anode need to add fluorid and sulfid in alkalescent circumstance. Sodium peroxycarbonate is easy affected by the accretion. And the Pt anode is easy eroded by the added activators. Efficiency will be reduced if the progress without the activators.
In the recent years, the BDD anodes used in the electrochmical polluted water treatment has great application foreground. The BDD anodes have better chemical and electrochemical stability than any other anodes, and have higher efficiency. And It possesses many unique electrochemical properties, including a wide potential window , very low background current, and extreme chemical stability to deactivation. The BDD anode possesses high oxidation potential, so it can produce plenty of hydroxyl radical that is physically adsorbed at the electrode surface.
The discourse discusses the choice of the anodes and the predominance of the BDD anode. During the progress of the electrochemical oxidation, the anodes should possess higher electrode potential than the reaction potential of the reactant, and only in this way, the reactant will be oxidated. So the key point is to choose a appropriate anode. It studies the characteristic of the electrochemical oxidation of BDD anode, and the properties of the electrochemical synthesis. Contrasting the popular method of synthesis and the electrochemical synthesis using the BDD anode, to study the feasibility of using the BDD anode.
过氧化物和超氧化物都具有强氧化性。过氧化物在工业生产和人们生活中起着显著的作用。现有的电合成过氧碳酸钠技术是碱性条件下,在铂电极上电解碳酸钠溶液,可以电合成得到过氧碳酸钠。过氧碳酸钠的应用很容易受到添加物的影响,并且铂电极也很容易被所添加的催化剂腐蚀,因此最好不添加催化剂。然而电合成过氧碳酸钠时若不添加催化剂,其效率会大幅度的降低。
近年来,用金刚石膜作阳极进行电化学氧化在处理含有机物的工业污水有很广的应用前景。对比其他的电极材料,金刚石膜电极有更好的化学和电化学稳定性,并且有更高的电流效率。另外,它具有宽电化学势窗,低残留电流,极好的电化学稳定性以及表面不易被污染等,这是在电化学中很重要的优势。金刚石膜的电化学氧化电势很高,能大量的产生羟基自由基,羟基自由基氧化性很高,可以在金刚石膜的表面实现直接氧化。最近,有关于电合成过氧碳酸钠的报道。与传统的合成方式相比电合成有了很大的改进。
本论文具体论述了电极的选择的问题以及利用金刚石膜电极电合成过氧化物的优势。在电化学氧化中,电极材料的电极电势不同,电流效率不同,只有阳极的电极电势高于反应物的反应电势时,反应物才会被氧化,因此选择合适的电极材料是一个关键。研究金刚石膜电极的电化学特性,及其作为电极的优势。通过了解电合成的原理,掌握过氧化物电合成的特点,研究电合成过氧化物的关键。对比现有的过氧化物的电合成方法与用金刚石膜电极进行电合成,研究用金刚石膜电极用于电合成过氧化物的可行性。
Electrochemistry is a science of study the translation of electricity and chemistry. The translation is occurred on the surface of metal conductor and hydronium ion. It is a edge science which is very important,because it is useful very abroad both in the natrue and in the production. Electrochemical synthesis is to synthesize chymic substance by electrochemical method.,which is an important way to attain some material that is very hard to get,such as natrium, kalium,calcium aluminum some strong oxidation substance and deoxidizer. And it can get over the pollution problem all of the world.
Peroxide has strong oxidate character,which is very important both in the industry and the daily life. The electrochemical synthesis of sodium peroxycarbonate using Pt anode need to add fluorid and sulfid in alkalescent circumstance. Sodium peroxycarbonate is easy affected by the accretion. And the Pt anode is easy eroded by the added activators. Efficiency will be reduced if the progress without the activators.
In the recent years, the BDD anodes used in the electrochmical polluted water treatment has great application foreground. The BDD anodes have better chemical and electrochemical stability than any other anodes, and have higher efficiency. And It possesses many unique electrochemical properties, including a wide potential window , very low background current, and extreme chemical stability to deactivation. The BDD anode possesses high oxidation potential, so it can produce plenty of hydroxyl radical that is physically adsorbed at the electrode surface.
The discourse discusses the choice of the anodes and the predominance of the BDD anode. During the progress of the electrochemical oxidation, the anodes should possess higher electrode potential than the reaction potential of the reactant, and only in this way, the reactant will be oxidated. So the key point is to choose a appropriate anode. It studies the characteristic of the electrochemical oxidation of BDD anode, and the properties of the electrochemical synthesis. Contrasting the popular method of synthesis and the electrochemical synthesis using the BDD anode, to study the feasibility of using the BDD anode.
引文
[1]J.D.Genders,D.Pletcher,E.Spiegel,and N.L.Weinberg,U.S.Pat.5,246,551 1993.
[2]P.A.Michand,E.Mahé,W.Haenni,A.Perret,and Ch.Comninellis,Electrochem.Solid-State Lett.,3,77 2000
[3]金世雄,冯海霞,王岚.过碳酸离子阳极的形成.天津:南开大学化学系,1994
[4]Coe S E Sussmann R S.Optical thermal and mechanical properties of CVD diamond.Diamond and related materials,2000,9(9-10):1726-1729
[5]戴达煌,周克崧.金刚石薄膜沉积制备工艺与应用冶金工业出版社2001,6:4-6
[6]A.Fujishima,T.N.Rao,E.Popa,B.V.Sarada,I.Yagy,and D.A.Tryk,J.Electroanal.Chem.,473,179 1999
[7]冯玉杰,李晓岩.电化学技术在环境工程中的应用.北京:化学工业出版社,2002
[8]S H Kim,Y S Park,S K Jung,et aL Effect of the Substrate State on the Formation of Diamond Film in a Low Temperature Microwave-plasma-enhanced Chemical Vapor Deposition System.J Vac Sci Tech,1991,A13(3):1619-1623
[9]C H wu,M A Tamor,T J Potter,et al.A Comparative Study of Gas Chemistry in Methane/Hydrogen and Acetylene/Hydrogen Gas Mixtures during Hot-filament Vapor Deposition of Diamond.Mater Res Soc Proc,1990,162:133-138
[10]C H Wu,M A Tamor,TJ Potter,et al.A Study of Gas Chemistry during Hot-filament Vapor-deposition of Diamond Films using Methane Hydrogen and Acetylene Hydrogen Gas-mixtures.J Appl Phys,1990,68(9):4825-4829
[11]K E Spear.Diamond-ceramic Coating of the Future.J Am Ceram Soc,1989,72(2):171-191
[12]T R Anthony.Metastable Synthesis of Diamond.Vacuum,1990,41(4-6):1356-1359M Frenklach and H Wang.Delailed Surface and Gas-phase Chemical-kinetics of Diamond Deposition.Phys Rev,1991,B43(2):1520-1545
[13]J Esteve M C Polo and G Sanchez.Diamond and Diamond-like Carbon Films.Vacuum,1999,52:133-139
[14]黄建良,汪建华.微波法大功率稳定快速沉积金刚石膜.武汉:武汉工程大学学报,2007
[15]王季陶,张卫,刘志杰.金刚石低压气相生长热力学耦合模型.北京:科学出版社.1998:22
[16]Kapoor A et al.Proce.,3rd Internat,Syymp.on Diamond Mater.,1993:429-434
[17]只金芳,田如海.金刚石膜电化学.北京:中国科学院理化技术研究所.2005参考文献
[18]何贤 张志明 沈荷生 李戈扬 钨和钽丝碳化后的结构变化及其对金刚石成膜质量的影响上海交通大学学报Vol.29 No5 1995
[19]C H wu,M A Tamor.T J Potter,et al.A Comparative Study of Gas Chemistry in Methane/Hydrogen and Acetylene/Hydrogen Gas Mixtures during Hot-filament Vapor Deposition of Diamond. Mater Res Soc Proc, 1990,162: 133-138
[20] M Frenklach and H Wang .Delailed Surface and Gas-phase Chemical-kinetics of Diamond Deposition. Phys Rev,1991,B43 (2) : 1520-1545
[21] H C Shih, C P Sung, Y S Tang, et al. Microstructure and Characterization of Diamond Film Grown on Various Substrates. Surf Coat Tech, 1992, 52(2):105-114
[22] Huang B R , Chia C T, Chang M C, et all Biaseffects on large area polycrystalline diamond films synthesized by the bias enhanced grown technique [ J ] 1 Diamond and Related Materials ,2003 , 12 : 26 - 321
[23] Davies, G., Chemistry and Physics of Carbon, Vol. 13. (P. L., Walker, Jr., and P. A., Thrower,eds.)Marcel Dekker Inc, NY, (1997)
[24] Fbeck, HXrohn, W_Kaiser, M.Ftyda, CY.Klages, L.Schifer, Boron doped diamond/titanium composite electrodes for electrochemical gas generation from aqueous electrolytes, Electrochemical Acts 1998,44:523-532
[25] Shokoofeh Alehashern, Fred Chambers, CyclicVoltanrmetric Studies of Charge Transfer Reactions at Highly Baron-Doped Polycrystalline Diamond Thin-Film Electrodes, Analytical Chemistry 1995,67:2812-2821
[26] Greg M. Swain, The Electrochemical Activity of Boron-Doped Polycrystalline Diamond Thin Film Electrodes, Anal.Chem.1993, 65 :345-351
[27] A. Perret, W. Haenni, C.Comninellis, et al., Electrochemical behavior ofsynthetic Diamond thin film electrodes, Diamond and Related Materials 1999,8:820-823
[28] A. Perreta, W. Haennia, N. Skinnera, X-M. Tanga, D. Gandini b, C. Comninellis b,B. Correa b and G. Foti b Electrochemical Behavior of Synthetic Diamond Thin Film Electrodes Diamond and Related Materials 8 (1999) 820-823
[29] A.Perreta, W. Haennia, N. Skinnera, X-M. Tanga, D. Gandini b, C. Comninellis b,B. Correa b and G. Foti b Electrochemical Behavior of Synthetic Diamond Thin Film Electrodes Diamond and Related Materials 8 (1999) 820-823
[30] M Frenklach and H Wang .Detailed Surface and Gas-phase Chemical-kinetics of Diamond Deposition. Phys Rev,1991,B43 (2) : 1520-1545
[31] D Hung, M Frenklach and M Maroncelli. Energetics of Acetylene-addition Mechanism of Diamond Growth. J Phys Chem, 1988, 92(22): 6379-6381
[32] Wang Yaqiong(王雅琼), Tong Hongyang(童宏扬), xu Wenlin(许文林). Rare Metal [33] Materials and Engineering(稀有金属材料与工程)[J], 2004, 33(9): 976
[34] T.Srivinyunon, R.Phillips, C.Cutshaw, A.J.Joseph, and Y. Tzeng, in New Diamond Science and Technology, (1991 MRS Int. Conf. Proc), pp. 581-586
[35] J.Iniesta,P.A.Michaud,M.Panizza,et al. Electrochemical oxidation of 32methylpyridine
[36]At a boron-doped diamondelectrode:Application to electroorganic synthesis and wastewater treatment[J].Electrochemistry Communications,2001,3(7):346-351
[37]I.Troster,M.Fryda,D.herrmann.Electrochemical advanced oxidation process for water treatment using Di-aChem electrodes[J].Diamond and Related Materials,2002,11(3):640-645
[38]赵国华,李明利,祁源等.苯酚在金刚石膜电极上的电化学氧化降解过程[J].中国环境科学,2005,25(3):370-374
[2]P.A.Michand,E.Mahé,W.Haenni,A.Perret,and Ch.Comninellis,Electrochem.Solid-State Lett.,3,77 2000
[3]金世雄,冯海霞,王岚.过碳酸离子阳极的形成.天津:南开大学化学系,1994
[4]Coe S E Sussmann R S.Optical thermal and mechanical properties of CVD diamond.Diamond and related materials,2000,9(9-10):1726-1729
[5]戴达煌,周克崧.金刚石薄膜沉积制备工艺与应用冶金工业出版社2001,6:4-6
[6]A.Fujishima,T.N.Rao,E.Popa,B.V.Sarada,I.Yagy,and D.A.Tryk,J.Electroanal.Chem.,473,179 1999
[7]冯玉杰,李晓岩.电化学技术在环境工程中的应用.北京:化学工业出版社,2002
[8]S H Kim,Y S Park,S K Jung,et aL Effect of the Substrate State on the Formation of Diamond Film in a Low Temperature Microwave-plasma-enhanced Chemical Vapor Deposition System.J Vac Sci Tech,1991,A13(3):1619-1623
[9]C H wu,M A Tamor,T J Potter,et al.A Comparative Study of Gas Chemistry in Methane/Hydrogen and Acetylene/Hydrogen Gas Mixtures during Hot-filament Vapor Deposition of Diamond.Mater Res Soc Proc,1990,162:133-138
[10]C H Wu,M A Tamor,TJ Potter,et al.A Study of Gas Chemistry during Hot-filament Vapor-deposition of Diamond Films using Methane Hydrogen and Acetylene Hydrogen Gas-mixtures.J Appl Phys,1990,68(9):4825-4829
[11]K E Spear.Diamond-ceramic Coating of the Future.J Am Ceram Soc,1989,72(2):171-191
[12]T R Anthony.Metastable Synthesis of Diamond.Vacuum,1990,41(4-6):1356-1359M Frenklach and H Wang.Delailed Surface and Gas-phase Chemical-kinetics of Diamond Deposition.Phys Rev,1991,B43(2):1520-1545
[13]J Esteve M C Polo and G Sanchez.Diamond and Diamond-like Carbon Films.Vacuum,1999,52:133-139
[14]黄建良,汪建华.微波法大功率稳定快速沉积金刚石膜.武汉:武汉工程大学学报,2007
[15]王季陶,张卫,刘志杰.金刚石低压气相生长热力学耦合模型.北京:科学出版社.1998:22
[16]Kapoor A et al.Proce.,3rd Internat,Syymp.on Diamond Mater.,1993:429-434
[17]只金芳,田如海.金刚石膜电化学.北京:中国科学院理化技术研究所.2005参考文献
[18]何贤 张志明 沈荷生 李戈扬 钨和钽丝碳化后的结构变化及其对金刚石成膜质量的影响上海交通大学学报Vol.29 No5 1995
[19]C H wu,M A Tamor.T J Potter,et al.A Comparative Study of Gas Chemistry in Methane/Hydrogen and Acetylene/Hydrogen Gas Mixtures during Hot-filament Vapor Deposition of Diamond. Mater Res Soc Proc, 1990,162: 133-138
[20] M Frenklach and H Wang .Delailed Surface and Gas-phase Chemical-kinetics of Diamond Deposition. Phys Rev,1991,B43 (2) : 1520-1545
[21] H C Shih, C P Sung, Y S Tang, et al. Microstructure and Characterization of Diamond Film Grown on Various Substrates. Surf Coat Tech, 1992, 52(2):105-114
[22] Huang B R , Chia C T, Chang M C, et all Biaseffects on large area polycrystalline diamond films synthesized by the bias enhanced grown technique [ J ] 1 Diamond and Related Materials ,2003 , 12 : 26 - 321
[23] Davies, G., Chemistry and Physics of Carbon, Vol. 13. (P. L., Walker, Jr., and P. A., Thrower,eds.)Marcel Dekker Inc, NY, (1997)
[24] Fbeck, HXrohn, W_Kaiser, M.Ftyda, CY.Klages, L.Schifer, Boron doped diamond/titanium composite electrodes for electrochemical gas generation from aqueous electrolytes, Electrochemical Acts 1998,44:523-532
[25] Shokoofeh Alehashern, Fred Chambers, CyclicVoltanrmetric Studies of Charge Transfer Reactions at Highly Baron-Doped Polycrystalline Diamond Thin-Film Electrodes, Analytical Chemistry 1995,67:2812-2821
[26] Greg M. Swain, The Electrochemical Activity of Boron-Doped Polycrystalline Diamond Thin Film Electrodes, Anal.Chem.1993, 65 :345-351
[27] A. Perret, W. Haenni, C.Comninellis, et al., Electrochemical behavior ofsynthetic Diamond thin film electrodes, Diamond and Related Materials 1999,8:820-823
[28] A. Perreta, W. Haennia, N. Skinnera, X-M. Tanga, D. Gandini b, C. Comninellis b,B. Correa b and G. Foti b Electrochemical Behavior of Synthetic Diamond Thin Film Electrodes Diamond and Related Materials 8 (1999) 820-823
[29] A.Perreta, W. Haennia, N. Skinnera, X-M. Tanga, D. Gandini b, C. Comninellis b,B. Correa b and G. Foti b Electrochemical Behavior of Synthetic Diamond Thin Film Electrodes Diamond and Related Materials 8 (1999) 820-823
[30] M Frenklach and H Wang .Detailed Surface and Gas-phase Chemical-kinetics of Diamond Deposition. Phys Rev,1991,B43 (2) : 1520-1545
[31] D Hung, M Frenklach and M Maroncelli. Energetics of Acetylene-addition Mechanism of Diamond Growth. J Phys Chem, 1988, 92(22): 6379-6381
[32] Wang Yaqiong(王雅琼), Tong Hongyang(童宏扬), xu Wenlin(许文林). Rare Metal [33] Materials and Engineering(稀有金属材料与工程)[J], 2004, 33(9): 976
[34] T.Srivinyunon, R.Phillips, C.Cutshaw, A.J.Joseph, and Y. Tzeng, in New Diamond Science and Technology, (1991 MRS Int. Conf. Proc), pp. 581-586
[35] J.Iniesta,P.A.Michaud,M.Panizza,et al. Electrochemical oxidation of 32methylpyridine
[36]At a boron-doped diamondelectrode:Application to electroorganic synthesis and wastewater treatment[J].Electrochemistry Communications,2001,3(7):346-351
[37]I.Troster,M.Fryda,D.herrmann.Electrochemical advanced oxidation process for water treatment using Di-aChem electrodes[J].Diamond and Related Materials,2002,11(3):640-645
[38]赵国华,李明利,祁源等.苯酚在金刚石膜电极上的电化学氧化降解过程[J].中国环境科学,2005,25(3):370-374