CN102373491B - A kind of with the method for pharmaceutics wastewater technology electrodeposited nanocrystalline material - Google Patents
A kind of with the method for pharmaceutics wastewater technology electrodeposited nanocrystalline material Download PDFInfo
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- CN102373491B CN102373491B CN201110344490.3A CN201110344490A CN102373491B CN 102373491 B CN102373491 B CN 102373491B CN 201110344490 A CN201110344490 A CN 201110344490A CN 102373491 B CN102373491 B CN 102373491B
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Abstract
The invention discloses a kind of with the method for pharmaceutics wastewater technology electrodeposited nanocrystalline material, belong to technical field of nanometer material preparation, present method is that the micro-electrolysis stuffing be made up of active anode and inert cathode is placed in pharmaceutics wastewater reactor, and the deposit fluid aqueous solution is fed micro-electrolysis reactor, outside under electric field-enhanced effect after pharmaceutics wastewater electrodeposit reaction, in deposit fluid, metal ion is reduced into metal simple-substance at filling surface, by controlling external electric field field intensity size to reach the object controlling micro-electrolysis reaction process, different external electric field field intensity size promotes light electrolysis, strengthening effect is different, the homogenizing of galvanic deposit particle is also different from nanometer degree, finally prepared specific dimensions, the nano material that composition etc. require, present method has nano material size tunable, energy consumption is low, reaction conditions is gentle, the advantage such as easy and simple to handle.
Description
Technical field
The present invention relates to a kind of method preparing nano material, particularly relate to a kind of with the method for pharmaceutics wastewater technology electrodeposited nanocrystalline material, belong to technical field of nanometer material preparation.
Background technology
Nano material is the type material science grown up the eighties in 20th century, compared with common material, make it have special magnetic, optics, mechanics, electricity, chemical catalysis performance because nano material has small-size effect, surface and interface effect, quantum size effect, macro quanta tunnel effect etc., thus become one of the most attractive hot topic research of 21 century Material Field.
Preparation method of nano material is varied, solid phase method, liquid phase method and vapor phase process is divided into from the angle of raw material, be divided into Physical and chemical method from the angle of reaction, common preparation method has vacuum-evaporation condensation method, ball milled, the precipitator method, sol-gel method, water reaction method, electrodip process, microemulsion method and template synthesis method.In numerous preparation methods, electrodip process is more and more subject to concern and the favor of people, has the following advantages this is because electrodip process prepares nano material:
be applicable to preparing nano metal, alloy and matrix material;
galvanic deposit crystallization chief motivation-----overpotential, can manual control, and whole deposition process easily realizes computer monitoring, and difficulty is less technically, technique is flexible;
normal temperature and pressure operates, and avoids the thermal stresses etc. that high temperature is introduced at material internal simultaneously.
Conventional electrodeposition technology has DC electrodeposition, pulse electrodeposition and jet-electrodeposited method, these electro-deposition techniques are controlling the nano material that all can obtain specific dimensions size under certain condition, but such electrodeposition process needs to consume electric energy, this must make material preparation cost higher, how to reduce energy consumption and then lower material preparation cost and will become a study hotspot, light electrolysis electrodeposit metals can reach because deposition process does not need to consume electric energy the object reducing material preparation cost, preparation for nano material opens a new route, the method adopts active anode particle and inert cathode granulometric composition micro-electrolysis stuffing, corrosion galvanic cell reaction is there is between micro-electrolysis stuffing in deposit fluid, active anode is dissolved, and metal ion galvanic deposit to be deposited is in inert cathode surface, the preparation of material is finally completed on inert cathode surface, but the impellent of light electrolysis electro-deposition techniques reaction derives from the electric current and voltage that corrosion galvanic cell produces, by the metallic particles particle diameter comparatively large (generally in micron level) that the restriction galvanic deposit of this electric current and voltage is obtained, do not reach the object of preparation nano material.
For the larger problem of material particle size prepared by above light electrolysis electro-deposition techniques, how to pass through to improve, improve this technology or exploitation United Technologies, under the prerequisite keeping light electrolysis electro-deposition techniques advantage, effectively solve above-mentioned drawback problem, thus the obtained nano material meeting certain particle size requirement becomes an important technical problem.
Summary of the invention
Instant invention overcomes deficiency and shortcoming that light electrolysis electro-deposition techniques prepares material, provide a kind of with the preparation method of pharmaceutics wastewater technology electrodeposited nanocrystalline material.
For realizing object of the present invention, the present invention is when metal particle material is prepared in traditional light electrolysis galvanic deposit, by introducing an External Electrical Field on micro-electrolysis stuffing, promote the carrying out of corrosion galvanic cell reaction between micro-electrolysis stuffing, galvanic interaction is made acutely to change the larger galvanic cell voltage of generation one, and metallic particles high dispersing, nanometer that this large voltage can impel galvanic deposit to obtain, finally obtain nano material at filling surface.
Of the present invention a kind of with the method for pharmaceutics wastewater technology electrodeposited nanocrystalline material, the concrete technical scheme adopted is: the micro-electrolysis stuffing that active anode and inert cathode form is placed in pharmaceutics wastewater reactor, the ratio of the 200-500ml deposit fluid aqueous solution is added in 100g micro-electrolysis stuffing, the deposit fluid aqueous solution is added in micro-electrolysis reactor, under the external electric field strengthening effect of some strength after 5 ~ 120min pharmaceutics wastewater electrodeposit reaction, in deposit fluid, metal ion is reduced into metal simple-substance at filling surface to be deposited, by controlling external electric field field intensity size to reach the object controlling micro-electrolysis reaction process, different external electric field field intensity size promotes light electrolysis, strengthening effect is different, the homogenizing of galvanic deposit particle is also different from nanometer degree, final obtained specific dimensions, the nano material that composition etc. require.
The deposit fluid aqueous solution described in the present invention comprises the metal ion of concentration 1 ~ 10000mg/L, the ionogen of concentration 1 ~ 100g/L, deposit fluid solution ph=1-9.
Ionogen of the present invention is Na
2sO
4, NaCl, K
2sO
4, a kind of in KCl etc.
Metal ion of the present invention is one or more arbitrary combination in cupric ion, nickel ion, silver ions, platinum ion, gold ion.
The external electric field of some strength of the present invention is a kind of electric field in DC electric field, alternating-electric field, pulsed electrical field or several electric field; External electric field is the electric field of strength of electric field >=0.1V/cm.
The binary micro-electrolysis stuffing system that micro-electrolysis stuffing of the present invention is iron, aluminium, copper, carbon arbitrary combination are formed, or the ternary that forms of iron, copper, aluminium, zinc, carbon arbitrary combination or the above micro-electrolysis stuffing system of ternary, or the micro-electrolysis stuffing system that iron, copper, aluminium, the alloy of zinc arbitrary combination and carbon are formed.
The micro-electrolysis stuffing system Anodic of binary micro-electrolysis stuffing system of the present invention or alloy and carbon and the mass ratio >=1:10 of negative electrode, alloy is commercial alloys material; By the order that each Ingredients Active is descending, the mass ratio in ternary or ternary above micro-electrolysis stuffing system between each composition all >=1:10.
The form of micro-electrolysis stuffing of the present invention is decentralized composite grain irregularity filler form, or mating type composite grain structured packing form.
The strengthening effect main manifestations of introducing to light electrolysis metal electrodeposition process of external electric field of the present invention is: the reaction of light electrolysis metal electrodeposition can impel galvanic interaction to produce a larger galvanic interaction voltage under the effect of extra electric field, improve the reacted current potential of metal electrodeposition, and then promote the formation of nucleus needed for metal electric crystallization, electrocrystallization process grows into multinuclear transient growth from monokaryon and grows continuously to multinuclear, and the nucleus that filling surface enriches is conducive to metallic particles high dispersing, the nanometer that electrocrystallization is formed; Meanwhile, galvanic interaction changes the chemical potential energy of metal ion in solution under the polarized action of extra electric field, required activation energy during reduction metal electrodeposition, and then reduces overpotential needed for electrocrystallization nucleation, and nucleation rate increases, and makes nucleus growth facilitation; And, extra electric field can promote the migration of micro-electrolysis stuffing surface electronic, make filling surface homogeneous current distribution, can also promote that metal ion in solution is to the migration of filling surface, compression double electric layer simultaneously, reduce electrostatic double layer current potential, improve mass-transfer efficiency, accelerate the carrying out of metal electrodeposition reaction, the introducing of external electric field enhances metal electrodeposition reaction process, is conducive to the preparation of metal nano material.
A kind of method with pharmaceutics wastewater technology electrodeposited nanocrystalline material of the present invention compared with prior art has the following advantages:
1, compared with the material prepared with traditional micro-electrolysis method, material particle size prepared by present method is little, homogenizing, nanometer degree are high, and material particle size is controlled.
2, compared with conventional electrodeposition method, present method energy consumption is low, and material preparation cost is low.
3, compared with other physico-chemical processes, present method has that technique is simple, easy and simple to handle, speed of response is fast, reaction conditions is gentleer---the features such as normal temperature and pressure.
Embodiment
Below by embodiment, the inventive method is described in further detail, but protection scope of the present invention is not limited to described content.
Embodiment 1: this is with the method for pharmaceutics wastewater technology electrodeposited nanocrystalline material, and concrete steps are as follows:
Preparation is containing Ag
+=1mg/L, NaCl=1g/L, the deposit fluid aqueous solution of pH=9, the ratio of 500ml deposit fluid solution is added in 100g micro-electrolysis stuffing, the deposit fluid aqueous solution is added in pharmaceutics wastewater reactor, iron carbon decentralized composite grain filler is filled in pharmaceutics wastewater reactor, iron carbon mass ratio is 1:10, be that the External Electrical Field of 0.1V/cm is on packing layer by parallel-plate electrode control inputs ac electric field strength, silver ions in deposit fluid solution is reduced into silver-colored simple substance at iron carbon surface and separates out, thus reach the object of preparation nano material, filler is taken out after pharmaceutics wastewater electrodeposit reaction 50min, carry out the separation of iron carbon granule, carbon granule after separation is successively through clear water, washes of absolute alcohol postlyophilization, last by scanning electron microscope (SEM, Hitachi S3400N) observe carbon surface deposited silver layer pattern, find that deposition of silver particle is uniformly distributed at carbon surface, Argent grain particle diameter is about 95nm.
Embodiment 2: this is with the method for pharmaceutics wastewater technology electrodeposited nanocrystalline material, and concrete steps are as follows:
Preparation is containing Cu
2+=100mg/L, KCl=20g/L, the deposit fluid aqueous solution of pH=1, the ratio of the 300ml deposit fluid aqueous solution is added in 100g micro-electrolysis stuffing, the deposit fluid aqueous solution is added in pharmaceutics wastewater reactor, aluminum bronze carbon mating type filler is filled in pharmaceutics wastewater reactor, aluminum bronze carbon mass ratio is 2:1:1, be that the External Electrical Field of 3V/cm is on packing layer by parallel-plate electrode control inputs impulse electric field strength, cupric ion in the deposit fluid aqueous solution is reduced into copper simple substance at aluminum bronze carbon surface and separates out, thus reach the object of preparation nano material, filler is taken out after pharmaceutics wastewater electrodeposit reaction 120min, carry out the separation of aluminum bronze carbon granule, carbon granule after separation is successively through clear water, washes of absolute alcohol postlyophilization, last by scanning electron microscope (SEM, Hitachi S3400N) observe carbon surface copper deposits pattern, find that copper deposited particles is uniformly distributed at carbon surface, copper grain diameter is about 30nm.
Embodiment 3: this is with the method for pharmaceutics wastewater technology electrodeposited nanocrystalline material, and concrete operations are as follows:
Preparation is containing Pt
2+=10000mg/L, K
2sO
4=100g/L, the deposit fluid aqueous solution of pH=4, the ratio of the 200ml deposit fluid aqueous solution is added in 100g micro-electrolysis stuffing, the deposit fluid aqueous solution is added in pharmaceutics wastewater reactor, filling aluminum copper alloy mating type filler in pharmaceutics wastewater reactor, aluminum bronze mass ratio is 2:1, be that the External Electrical Field of 6V/cm is on packing layer by parallel-plate electrode control inputs DC electric field intensity, platinum ion in deposit fluid solution is reduced into platinum simple substance and separates out on aluminum-copper alloy surface, thus reach the object of preparation nano material, filler is taken out after pharmaceutics wastewater electrodeposit reaction 5min, alloy packing is successively through clear water, washes of absolute alcohol postlyophilization, last by scanning electron microscope (SEM, Hitachi S3400N) observe alloy surface platinum settled layer pattern, find that platinum deposited particles is uniformly distributed at alloy surface, platinum grain particle diameter is about 50nm.
Embodiment 4: this is with the method for pharmaceutics wastewater technology electrodeposited nanocrystalline material, and concrete steps are as follows:
Preparation is containing Cu
2+=300mg/L, Ni
2+=100mg/L, Na
2sO
4=20g/L, the deposit fluid aqueous solution of pH=4, the ratio of the 300ml deposit fluid aqueous solution is added in 100g micro-electrolysis stuffing, the deposit fluid aqueous solution is added in pharmaceutics wastewater reactor, filling aluminum carbon decentralized granular filler in pharmaceutics wastewater reactor, Al_2O_3-C based amount is than being 6:1, be that the External Electrical Field of 5V/cm is on packing layer by parallel-plate electrode control inputs DC electric field intensity, Cu in deposit fluid solution, Ni ion is reduced into alloyed metal simple substance at aluminium carbon surface codeposition, thus reach the object of preparation copper-nickel alloy material, filler is taken out after pharmaceutics wastewater electrodeposit reaction 60min, carry out the separation of aluminium carbon granule, carbon granule after separation is successively through clear water, washes of absolute alcohol postlyophilization, last by scanning electron microscope (SEM, Hitachi S3400N, EDAX, E-550) observe carbon surface alloy deposition layer pattern, find that alloy deposition particle is uniformly distributed at carbon surface, alloying pellet particle diameter is the display of about 60nm, EDS results of elemental analyses, and in this alloy, copper nickel mass ratio is about 0.35.
Claims (2)
1. one kind with the method for pharmaceutics wastewater technology electrodeposited nanocrystalline material, it is characterized in that: the micro-electrolysis stuffing that active anode and inert cathode form is placed in pharmaceutics wastewater reactor, the ratio of 200 ~ 500ml deposit fluid aqueous solution is added in 100g micro-electrolysis stuffing, the deposit fluid aqueous solution is added in micro-electrolysis reactor, outside under electric field-enhanced effect after 5 ~ 120min pharmaceutics wastewater electrodeposit reaction, obtained metal nano material;
The described deposit fluid aqueous solution comprises the metal ion of concentration 1 ~ 10000mg/L, the ionogen of concentration 1 ~ 100g/L, deposit fluid aqueous solution pH=1 ~ 9;
The binary micro-electrolysis stuffing system that described micro-electrolysis stuffing is iron, aluminium, copper, carbon arbitrary combination are formed, or the ternary that forms of iron, copper, aluminium, zinc, carbon arbitrary combination or the above micro-electrolysis stuffing system of ternary, or the micro-electrolysis stuffing system that iron, copper, aluminium, the alloy of zinc arbitrary combination and carbon are formed;
Described ionogen is Na
2sO
4, NaCl, K
2sO
4, a kind of in KCl;
Described metal ion is one or more in cupric ion, nickel ion, silver ions, platinum ion, gold ion;
Described external electric field is one or more electric fields in DC electric field, alternating-electric field, pulsed electrical field, external electronic field >=0.1V/cm;
The micro-electrolysis stuffing system Anodic of described binary micro-electrolysis stuffing system or alloy and carbon and the mass ratio >=1:10 of negative electrode; By the order that each Ingredients Active is descending, the mass ratio in ternary or ternary above micro-electrolysis stuffing system between each composition all >=1:10.
2. according to claim 1 with pharmaceutics wastewater technology electrodeposited nanocrystalline MATERIALS METHODS, it is characterized in that: the form of micro-electrolysis stuffing is decentralized composite grain irregularity filler form, or mating type composite grain structured packing form.
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