CN102732902A - Preparation method of conductive metal oxide nanorod - Google Patents
Preparation method of conductive metal oxide nanorod Download PDFInfo
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- CN102732902A CN102732902A CN2011100939853A CN201110093985A CN102732902A CN 102732902 A CN102732902 A CN 102732902A CN 2011100939853 A CN2011100939853 A CN 2011100939853A CN 201110093985 A CN201110093985 A CN 201110093985A CN 102732902 A CN102732902 A CN 102732902A
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Abstract
The invention adopts an electrolytic method to prepare a conductive metal oxide nanorod. According to the method, a cation exchange membrane (6) is used to divide an electrolytic tank (3) into a cathode chamber and an anode chamber, through which positive ions can pass freely. An organic matter containing coordination groups and an oxide A and adulterant B containing salt solution which needs to be prepared are added into the anode chamber (4), wherein the concentration of A is between 0.05 mol/L and 2 mol/L; and the mol ratio of A to B is 1:0.01-1:0.20. An anti-agglomerant is added into the cathode chamber (10). Due to the existence of the cation exchange membrane (6), during the electrolytic process, metal ions in the anode chamber (4) pass through the cation exchange membrane (6), enter the cathode chamber (10) and bond with OH- which is slowly released from a negative electrode (7) to form a hydroxide precipitate. The precipitate is filtered, washed and dried and is calcined in an electric resistance furnace so as to obtain the doped conductive oxide nanorod.
Description
Technical field
The present invention relates to a kind of employing electrolytic process and prepare the conducting metal oxide nanometer rod.
Background technology
Monodimension nanometer material is because of its microcosmic property dimensionally, thereby shows special light, electricity, magnetic properties.These characteristics make it aspect Jie's sight field and the nano-device development important application prospects arranged.
At present, conductive powder body commonly used is that metal is that powder, carbon are powder and metal conductive oxide powder.Easy oxidation, corrosion-resistant such as the copper in the metal-powder, iron, aluminium are along with the prolongation of time can make the electric conductivity of system significantly descend; The price of gold and silver powder is high, be difficult to scale and use, and the metallic conduction powder density is big, is prone to sink to the bottom caking thereby dispersed bad in matrix; And the content of metallics will just can make the remarkable reduction of ratio resistance of system usually up to about 70% (wt), and so high content can influence mechanical property, the textile performance of superpolymer.
Though carbon series conductive powder electroconductibility and stability are better, more difficult homodisperse, high-temperature oxidation resistance are not strong, and it is and do not accepted especially to make look black.Advantages such as conducting metal oxide is high with its fusing point, resistance of oxidation is strong, moderate cost, lighter color, density are lower and being studied and the extensive concern of application personnel.
Conducting metal oxide can be used for conduction or anlistatig fiber, rubber, pottery, plastics, coating; Antistatic Paint is used conductive filler material; Replace platinum or rare metal to be used in glass melting furnace and chemical industry as electrode materials; Semi-conductor pole plate storage vessel, solar cell material, semi-conductor air-sensitive and humidity-sensitive element etc.; Liquid-crystal display (LCD), geseous discharge show, electroluminescent shows (ELD), flat teletube, fluorescence shows and electricity causes colour TV demonstration various display devices such as (ECD) with in the various fields such as three anti-(anti-electrostatic, anti-dazzle, radioprotective) transparent conducting coatings.In recent years, Along with people's is to ergonomic attention, and whether teletron or image display have the key that three anti-characteristics become business success.
It is that powder and carbon are the shortcoming of powder that the light-coloured transparent property of conducting metal oxide has just in time been filled up metal; Both can play decoration function; Have high light transmission effect again, and very little to the intensity effect of material own, make it in aerospace and electronic industry, be applied.
Also have a kind of antistatic material now: organic additive, added this organic additive in the polymkeric substance after, the time grown be prone to aging, intensity is relatively poor, thereby lose anti-static function easily, and very sensitive to environment for use humidity, should not be exposed to the external world.Opposite conducting metal oxide antistatic material acid, alkali and mechanical wear that but ability is certain do not receive the restriction of weather and environment for use, have clear superiority.
The conducting metal oxide nanometer rod has tangible nano effect: surface effects, volume effect and quantum effect, so it has many body phase materials and the not available unique physical chemical property of micro materials.The high conductivity of utilizing its nanometer to have makes conducting metal oxide body material have wide application field more.Because the yardstick of conducting metal oxide nanometer rod is little, can process stable coating or slurry, and can be spun in the fiber.Conducting metal oxide body nanometer rod also has functions such as good antireflective, radioprotective, ir absorption, can be applicable in the fields such as low-E glass for building, ir absorption lagging material.And nanometer rod can have better conduction or anti-electrostatic effect by the ratio nano powder owing to have " bridging effect ", can when very low addition, just reach favorable conductive or antistatic effect.
The general method for preparing nano-oxide can be divided into physics method and chemical process.Physics method (mechanical process) is to utilize special crushing technology that common powder is broken, but because the restriction of existing crushing technology and equipment is difficult to prepare real nano level; Chemical method mainly contains sol-gel method, microemulsion method, spray-drying process, plasma method, combustion method, the precipitator method, chemical vapor deposition (CVD) method, laser CVD method at present; Or the like; Though these methods all can be prepared nano level oxide compound; But also exist some weakness: the reaction times is long or output is lower, control condition is strict, etc.
It is extensive, simple to operate that the electrolytic process that the present invention adopts prepares conductive oxide nanometer rod raw material, and energy efficiency is high, generally just can carry out at normal temperatures and pressures, both can be used as separately, can combine with other treatment process again.Employing template (Shen Laifa is arranged at present; Gong Liangyu; Mr. Zhang's great waves. battery industry .2009,14 (6): 404-408), though controllability is strong on the pattern; But in subsequent disposal,, all inevitable influence can be arranged to the dispersiveness of product, electroconductibility, light transmission etc. because the introducing impurity of template is difficult to handle clean.The silica bound of employing sodium-chlor is also arranged as crystal formation inductor (Hu Yong, Chen Guojian, old snow plum; Deng. chemistry world .2004, method 8:395-399) is removed silicon-dioxide but in aftertreatment, need use the deleterious hydrofluoric acid of very corrosive; Cost is high, therefore also is restricted.(red legend is outstanding for Zhao Heyun, Yang Liufang to adopt redox method in addition; Deng. material Leader .2004,18 (4): 96), this method need be used POTASSIUM BOROHYDRIDE 97MIN; In reaction process, will emit a large amount of hydrogen possibly set off an explosion, and cost is high, and produces a large amount of organic liquid waste contaminate environment.
The present invention adopts electrolytic method to adopt cationic exchange membrane (6) to be divided into anolyte compartment (4) and cathode compartment (10) to electrolyzer (3) for barrier film.Metallic cation in the anolyte compartment in electrolytic process (4) obtains corresponding precipitation of hydroxide through cationic exchange membrane (6) in cathode compartment (10).Be prepared into the metal oxide nano rod through high-temperature calcination then, technology is simple, and is easy to implement the method, and wide application promise in clinical practice and economic benefit are arranged.
Summary of the invention
The objective of the invention is to: utilize electrolytic method to prepare the conducting metal oxide nanometer rod.
For achieving the above object, the technical scheme that the present invention adopts is: utilize cationic exchange membrane (6) to be divided into anolyte compartment (4) and cathode compartment (10) to electrolyzer (3).In anolyte compartment (4), add the organism that contains coordinating group; Solubility A salt is as the soluble salt solution of A source and hotchpotch B; Its A source concentration is between 0.05mol/L～2mol/L, and the mol ratio of A and B added the anti-agglomeration agent in cathode compartment (10) between 1: 0.01～1: 0.20.In electrolytic process, the different current density of control cathode (7), the metals ion of anolyte compartment (4) arrives cathode compartment (10) through cationic exchange membrane (6).Negative electrode (7) constantly consumes H in cathode compartment (10)
+Produce H
2, and the OH that slowly-releasing goes out
-Combine to form precipitation of hydroxide with metallic cation.Its oxyhydroxide is calcined the nanometer rod of mixing B oxide compound A that can obtain conducting electricity in resistance furnace.
Present method is employed in the salts solution that adds the MOX that needs preparation in the anolyte compartment (4), and in electrolytic process, metals ion arrives cathode compartment (10) through cationic exchange membrane (6) under effect of electric field.Electrolytic solution can discharge H2 or consume H+ in cathode compartment (10), and reaction equation is following in the salts solution of metal chloride:
In metal-nitrate solutions, reaction equation is following:
In sulfate liquor, reaction equation is following:
Go up the oxyhydroxide of precipitating metal salt simultaneously at negative electrode (7), its reaction equation is following:
Because negative electrode (7) can uniform slow release go out OH
-, and prevent that under the effect that the whisking appliance of negative electrode (8) are installed throw out from upward depositing at negative electrode (7).Anode (5) in anolyte compartment (4) has gas release such as chlorine or oxygen to come out simultaneously.
In the salts solution of metal chloride, reaction equation is following:
In nitrate soln, reaction equation is following:
In sulfate liquor, reaction equation is following:
Deposition in the anticathode chamber (10) is filtered, is washed, and drying can obtain the oxyhydroxide of metal.Its oxyhydroxide calcined in resistance furnace can obtain the conductive oxide nanometer rod.
Because the utilization of technique scheme, the present invention compared with prior art has advantage:
1. the purity of the oxide compound that a process for preparing is high, particularly to the salts solution of electrolytic chlorination thing, has effectively solved other compound method because Cl
-Absorption and be difficult to wash the technical problem of removing.
2. the formed electric field of electrolysis reactor in present method; The electrostatic double layer of suspended particles in the water is changed; Each state in particle one side of positive and negative electric charge appears; Make between particle to become attraction, coalescence, thereby make hotchpotch realize better mixing, also therefore obtain the special appearance of nanometer rod by original mutual repulsion.
3. the oxide compound that utilizes the electrolysis process preparation is than other method, and synthetic required reactant is simple, does not need other additive, and raw material sources are extensive.
4. utilize the energy efficiency of electrolytic process technology high, generally just can carry out at normal temperatures and pressures, both can be used as separately, can combine with other treatment process again.
Prepare the conductiving doping oxide nano-rod with electrolytic process, be applicable to that metal doping is like gallium, germanium, indium, tin, antimony, thallium, lead, bismuth, zinc, aluminium.
Description of drawings
Fig. 1 is electrolyzer figure of the present invention
(among the figure: 1 direct supply, 2 anolyte compartment's vapor pipes, 3 electrolyzers, 4 anolyte compartments, 5 anodes, 6 cationic exchange membranes, 7 negative electrodes, 8 are equipped with the whisking appliance of negative electrode, 9 water discharge valves, 10 cathode compartments, 11 cathode compartment vapor pipes, 12 agitator motor), 13,14 gas collectors;
Fig. 2 is an electrolysis process principle schematic of the present invention;
Fig. 3 is the TEM figure of preparation instance 1 synthetic ATO nanometer rod;
Fig. 4 is the TEM figure of preparation instance 2 synthetic ATO nanometer rod;
Fig. 5 is the TEM figure of preparation instance 3 synthetic ITO nanometer rod;
Fig. 6 is the TEM figure of preparation instance 4 synthetic ITO nanometer rod;
Fig. 7 is the TEM figure of preparation instance 6 synthetic AZO nanometer rod;
Fig. 8 is the TEM figure of preparation instance 7 synthetic ATO nano particles;
Fig. 9 is the TEM figure of preparation instance 8 synthetic ATO nano particles.
Embodiment
On behalf of this method, instance only to prepare following metal oxide nano rod here, in the concrete scope of application see claim 7: use the electrolytic process preparation to have adulterated conductive oxide nanometer rod suitable metal and be gallium, germanium, indium, tin, thallium, lead, bismuth, zinc, aluminium.
Preparation instance 1
1 utilizes cationic exchange membrane (6) to be divided into anolyte compartment (4) and cathode compartment (10) to electrolyzer (3).The tartrate that in anolyte compartment (4), adds 0.02mol/L～0.10mol/L successively, 2mol/L stannic chloride pentahydrate and 0.04mol/L butter of antimony, the mol ratio of tin and antimony is: 1: 0.01.In cathode compartment (10), add and contain 6%～10% polyoxyethylene glycol (PEG-6000) solution.The current density of negative electrode (7) is controlled at 0.10A/cm
2About.Sn in the anolyte compartment (4)
4+And Sb
3+Constantly arrive in the cathode compartment (10), obtain Sn (OH) under whisking appliance (8) violent stirring in cathode compartment (10) through cationic exchange membrane (6)
4And Sb (OH)
3Mix throw out.(4) electrolysis obtains chlorine in the anolyte compartment simultaneously, has hydrogen to discharge at cathode compartment (10).With the deposition that obtains filter, wash, drying, 800 ℃ of calcinings can obtain diameter about 20nm in resistance furnace then, length is seen Fig. 3 at the bar-shaped pewter ATO powder of 30～110nm.
2 utilize cationic exchange membrane (6) to be divided into anolyte compartment (4) and cathode compartment (10) to electrolyzer (3).The Hydrocerol A that in anolyte compartment (4), adds 0.02mol/L～0.10mol/L successively, 2mol/L stannic chloride pentahydrate and 0.04mol/L butter of antimony, the mol ratio of tin and antimony is: 1: 0.05.In cathode compartment (10), add and contain 6%～10% polyoxyethylene glycol (PEG-6000) solution.The current density of negative electrode (7) is controlled at 0.10A/cm
2About.Sn in the anolyte compartment (4)
4+And Sb
3+Constantly arrive in the cathode compartment (10), obtain Sn (OH) under whisking appliance (8) violent stirring in cathode compartment (10) through cationic exchange membrane (6)
4And Sb (OH)
3Mix throw out.(4) electrolysis obtains chlorine in the anolyte compartment simultaneously, has hydrogen to discharge at cathode compartment (10).With the deposition that obtains filter, wash, drying, 800 ℃ of calcinings can obtain diameter about 20nm in resistance furnace then, length is seen Fig. 4 at the bar-shaped pewter ATO powder of 30～150nm.
3 utilize cationic exchange membrane (6) to be divided into anolyte compartment (4) and cathode compartment (10) to electrolyzer (3).The coffic acid that in anolyte compartment (4), adds 0.04mol/L～0.10mol/L successively, 2mol/L stannic chloride pentahydrate and 0.04mol/L four water Indium-111 chlorides, the mol ratio of tin and indium is: 1: 0.01.In cathode compartment (10), add and contain 6%～10% polyoxyethylene glycol (PEG-6000) solution.The current density of negative electrode (7) is controlled at 0.20A/cm
2About.Sn in the anolyte compartment (4)
4+And In
3+Constantly arrive in the cathode compartment (10), obtain Sn (OH) under whisking appliance (8) violent stirring in cathode compartment (10) through cationic exchange membrane (6)
4And In (OH)
3Mix throw out.(4) electrolysis obtains chlorine in the anolyte compartment simultaneously, has hydrogen to discharge at cathode compartment (10).With the deposition that obtains filter, wash, drying, 700 ℃ of calcinings can obtain diameter about 20nm in resistance furnace then, length is seen Fig. 5 at the bar-shaped ito powder of 20～120nm.
Preparation instance 4
4 utilize cationic exchange membrane (6) to be divided into anolyte compartment (4) and cathode compartment (10) to electrolyzer (3).Coffic acid, stannic chloride pentahydrate and four water Indium-111 chlorides are dissolved in hydrochloric acid successively, are mixed with the coffic acid of 0.04mol/L～0.10mol/L, 2mol/L stannic chloride pentahydrate and 0.04mol/L four water Indium-111 chloride acid solutions earlier.In anolyte compartment (4), add acid solution, the mol ratio of tin and indium is: 1: 0.05.In cathode compartment (10), add and contain 6%～10% polyoxyethylene glycol (PEG-6000) solution.The current density of negative electrode (7) is controlled at 0.20A/cm
2About.Sn in the anolyte compartment (4)
4+And In
3+Constantly arrive in the cathode compartment (10), obtain Sn (OH) under whisking appliance (8) violent stirring in cathode compartment (10) through cationic exchange membrane (6)
4And In (OH)
3Mix throw out.(4) electrolysis obtains chlorine in the anolyte compartment simultaneously, has hydrogen to discharge at cathode compartment (10).With the deposition that obtains filter, wash, drying, 700 ℃ of calcinings can obtain diameter about 40～80nm in resistance furnace then, length is seen Fig. 6 at the bar-shaped ito powder of 150～500nm.
Preparation instance 5
5 utilize cationic exchange membrane (6) to be divided into anolyte compartment (4) and cathode compartment (10) to electrolyzer (3).The tartrate that in anolyte compartment (4), adds 0.02mol/L～0.10mol/L successively, 2mol/L tin tetrachloride and 0.04mol/L butter of antimony, the mol ratio of tin and antimony is: 1: 0.01.In cathode compartment (10), add and contain 6%～10% polyoxyethylene glycol (PEG-6000) solution.The current density of negative electrode (7) is controlled at 0-10A/cm
2About.Sn in the anolyte compartment (4)
4+And Sb
3+Constantly arrive in the cathode compartment (10), obtain Sn (OH) under whisking appliance (8) violent stirring in cathode compartment (10) through cationic exchange membrane (6)
4And Sb (OH)
3Mix throw out.(4) electrolysis obtains chlorine in the anolyte compartment simultaneously, has hydrogen to discharge at cathode compartment (10).With the deposition that obtains filter, wash, drying, 800 ℃ of calcinings can obtain diameter about 20nm in resistance furnace then, length is at the bar-shaped pewter ATO powder of 30～100nm, and is similar with Fig. 3.
6 utilize cationic exchange membrane (6) to be divided into anolyte compartment (4) and cathode compartment (10) to electrolyzer (3).The tartrate that in anolyte compartment (4), adds 0.02mol/L～0.10mol/L successively, 2mol/L zinc nitrate hexahydrate and 0.04mol/L nine water aluminum nitrates, the mol ratio of zinc and aluminium is: 1: 0.01.In cathode compartment (10), add and contain 6%～10% polyoxyethylene glycol (PEG-6000) solution.The current density of negative electrode (7) is controlled at 0.10A/cm
2About.Zn in the anolyte compartment (4)
2+And Al
3+Constantly arrive in the cathode compartment (10), obtain Zn (OH) under whisking appliance (8) violent stirring in cathode compartment (10) through cationic exchange membrane (6)
2And Al (OH)
3Mix throw out.(4) electrolysis obtains oxygen in the anolyte compartment simultaneously, has hydrogen to discharge at cathode compartment (10).With the deposition that obtains filter, wash, drying, 800 ℃ of calcinings can obtain diameter about 15nm in resistance furnace then, length is seen Fig. 7 at the bar-shaped AZO powder of 50～110nm.
7 add the coffic acid of 0.04mol/L～0.10mol/L successively in three-necked flask, 2mol/L stannic chloride pentahydrate and 0.04mol/L butter of antimony, and the mol ratio of tin and antimony is: 1: 0.01, and 6%～10% polyoxyethylene glycol (PEG-6000) solution stirs.Be that precipitation agent drips with 0.5mol/L～5mol/L sodium hydroxide solution then.With the deposition that obtains filter, wash, drying, 700 ℃ of calcinings fail to obtain nanometer rod in resistance furnace then, but the ATO particle about diameter 20nm is seen Fig. 8.
8 add the coffic acid of 0.04mol/L～0.10mol/L successively in three-necked flask, 2mol/L stannic chloride pentahydrate and 0.04mol/L butter of antimony, and the mol ratio of tin and antimony is: 1: 0.01, and 6%～10% polyoxyethylene glycol (PEG-6000) solution stirs.Be that precipitation agent drips with 0.1mol/L～1mo1/L ammoniacal liquor then.With the deposition that obtains filter, wash, drying, 700 ℃ of calcinings fail to obtain nanometer rod in resistance furnace then, but the ATO particle about diameter 15nm is seen Fig. 9.
Claims (7)
1. the preparation method of a conducting metal oxide nanometer rod; It is characterized in that: in electrolyzer (3), be divided into anolyte compartment (4) and the cathode compartment (10) that has only positively charged ion freely to pass through to electrolyzer (3) with cationic exchange membrane (6), negatively charged ion then can not pass through.In anolyte compartment (4), add the organism that contains coordinating group; Need the oxide compound A of preparation and the salts solution of hotchpotch B; Wherein A concentration is between 0.05mol/L～2mol/L, and the mol ratio of A and B added the anti-agglomeration agent in cathode compartment (10) between 1: 0.01～1: 0.20.Because the existence of cationic exchange membrane (6), the metals ion in anolyte compartment in electrolytic process (4) gets into cathode compartment (10) through cationic exchange membrane (6).The OH that negative electrode (7) discharges in the cathode compartment (10)
-Form precipitation of hydroxide with metals ion.Deposition in the anticathode chamber (10) is filtered, is washed, and drying can obtain the oxyhydroxide of metal.Its oxyhydroxide is calcined the oxide nano-rod that can obtain having conductiving doping in resistance furnace.
2. the preparation method of a kind of conducting metal oxide nanometer rod according to claim 1 is characterized in that: prepare the conductive oxide nanometer rod with electrolytic method, raw material is extensive, and is simple to operate, and wide application promise in clinical practice and economic benefit are arranged.
3. the preparation method of a kind of conducting metal oxide nanometer rod according to claim 1; It is characterized in that: in anolyte compartment (4), adding the organism that contains coordinating group is a kind of or mixture in Hydrocerol A, tartrate, amino acid, oxalic acid, Whitfield's ointment, coffic acid, YD 30 (EDTA) and the oxysuccinic acid etc., is used to prevent that metals ion from shifting to an earlier date hydrolysis.
4. the preparation method of a kind of conducting metal oxide nanometer rod according to claim 1 is characterized in that: in cathode compartment (10), adding the anti-agglomeration agent is sucrose ester, Soxylat A 25-7, T 46155 one polyoxypropylene multipolymer, polysorbate, glycerin fatty acid ester, polyoxyethylene glycol (PEG-1000,1500; 2000; 4000,6000,8000; 10000,20000) a kind of or mixture etc.
5. the preparation method of a kind of conducting metal oxide nanometer rod according to claim 1 is characterized in that: current density is controlled at 0.01～0.80A/cm
2
6. the preparation method of a kind of conducting metal oxide nanometer rod according to claim 1 is characterized in that: oxyhydroxide in resistance furnace the incinerating temperature according to different samples and difference.
7. the preparation method of a kind of conducting metal oxide nanometer rod according to claim 1 is characterized in that: the preparation of use electrolytic process has adulterated conductive oxide nanometer rod suitable metal and is: gallium, germanium, indium, tin, thallium, lead, bismuth, zinc, aluminium.
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| CN102916257A (en) * | 2012-10-23 | 2013-02-06 | 中国科学技术大学 | Low-cost coating with self-cleaning and infrared broadband hiding functions, preparation method and application of coating |
| CN103184466A (en) * | 2013-01-10 | 2013-07-03 | 昆明贵千新型材料技术研究有限公司 | Novel process for preparing high purity metal oxide |
| CN107236963A (en) * | 2017-05-10 | 2017-10-10 | 东北大学 | A kind of method that chlorination ferroelectricity conversion directly prepares iron hydroxide or iron oxide |
| CN114920559A (en) * | 2022-06-07 | 2022-08-19 | 西北工业大学 | High-entropy oxide powder material for thermal barrier coating and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102916257A (en) * | 2012-10-23 | 2013-02-06 | 中国科学技术大学 | Low-cost coating with self-cleaning and infrared broadband hiding functions, preparation method and application of coating |
| CN102916257B (en) * | 2012-10-23 | 2015-02-04 | 中国科学技术大学 | Low-cost coating with self-cleaning and infrared broadband hiding functions, preparation method and application of coating |
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| CN107236963A (en) * | 2017-05-10 | 2017-10-10 | 东北大学 | A kind of method that chlorination ferroelectricity conversion directly prepares iron hydroxide or iron oxide |
| CN114920559A (en) * | 2022-06-07 | 2022-08-19 | 西北工业大学 | High-entropy oxide powder material for thermal barrier coating and preparation method and application thereof |
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