CN104357874A - Method for preparing nickel molybdate by using cationic membrane electrolysis process - Google Patents
Method for preparing nickel molybdate by using cationic membrane electrolysis process Download PDFInfo
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Abstract
The invention provides a method for preparing nickel molybdate by using a cationic membrane electrolysis process. The method comprises the steps of utilizing a nickel sheet as an anode, a noble electrode as a cathode, an aqueous solution containing a depolarizer and sodium molybdate as an anode liquor, and an acid/alkali/salt solution as a cathode liquor; in a double-compartment electrolytic cell with a cationic membrane as a diaphragm, controlling the temperature from room temperature to 90 DEG C to electrolyze the aqueous solution containing the depolarizer and the sodium molybdate in a constant-current electrolysis or constant-voltage electrolysis manner till all Na<+> ions are transferred to a cathode compartment; simultaneously cleaning and filtering products from the anode by using deionized water to obtain a filter cake, drying the filter cake, and then increasing the temperature to 500-700 DEG C under air atmosphere at the speed of 2.5-10 DEG C/min to perform high-temperature roasting on the dried filter cake for 1-5 hours; naturally cooling down the temperature of the roasted product to the room temperature, and then obtaining the nickel molybdate with high purity and no impure phase. According to the method for preparing the nickel molybdate by using the cationic membrane electrolysis process, all the Na<+> ions are transferred to the cathode compartment under the action of the cationic membrane electrolysis, so that the Na<+> influence is eliminated and the reaction time is short.
Description
Technical field
The invention belongs to field of inorganic materials, particularly relate to nickel molybdate, specifically a kind of method utilizing cationic membrane electrolytic preparation nickel molybdate.
Technical background
Metal molybdate is (as CoMoO
4, NiMoO
4, MnMoO
4deng) be the important component part of inorganic materials family, it is cheap, environmental friendliness, aboundresources, show distinctive performance in a lot of fields, molybdate micro/nano material has superior optics, electricity, magnetic property, is widely used in the fields such as laser donor material, optical fiber, humidity sensor, luminescent material, magnetic material, catalytic material and anti-biotic material.Proven reserve height is at the forefront in the world for molybdenum resource of China, and by Mo resource advantage, the molybdenum base product innovation of research and development high added value has significant economic worth and social effect for the scientific and efficient of Mo resource and Appropriate application.
At NiMoO
4synthesis aspect, applies more method and mainly comprises: sol-gel method, spray pyrolysis, self-propagating combustion, solid state synthesis, molten-salt growth method, mechanochemical synthesis, supersonic method, masterplate method, hydrothermal method etc.But solid state synthesis method has evenly caused a lot of metal oxide impurities due to raw material mixing cloth; The shortcoming of sol-gel method, aqueous phase precipitation method, hydrothermal method, microwave method etc. has the existence of additive or reaction times longer (reach several hours even several days time).
Cationic membrane has certain selective penetrated property, can to make in anode by the cation permeable ionic membrane selected in cathode compartment, and perfluorinated sulfonic acid cationic exchange membrane can allow the Na in anolyte compartment
+ion permeable ionic membrane enters cathode compartment, thus cancellation Na
+the impact of ionic impurity.
Summary of the invention
Object of the present invention is in order to solve long reaction time in above-mentioned nickel molybdate preparation process, technical problems such as impurity is many in the product of final gained and a kind of method adopting cationic membrane electrolytic process to prepare nickel molybdate is provided, it is short that the method has the reaction times, the nickel molybdate inclusion-free of final gained.
Technical scheme of the present invention
Utilize cationic membrane electrolytic process to prepare a method for nickel molybdate, specifically comprise the steps:
(1), take nickel sheet as anode, take noble electrode as negative electrode, with the aqueous solution containing depolarizer and Sodium orthomolybdate for anolyte, with acid solution, alkaline solution or salts solution for catholyte, be in the two-compartment cell of barrier film at cationic membrane, adopt the mode of constant-current electrolysis or constant-potential electrolysis, control temperature scope is room temperature to 90 DEG C, preferably carry out the sodium molybdate aqueous solution that electrolysis contains depolarizer, until Na from room temperature to 50 DEG C
+ion all transfers to cathode compartment;
Described noble electrode is glass-carbon electrode, Graphite Electrodes, titanium net or platinum guaze etc.;
Described containing in the aqueous solution of depolarizer and Sodium orthomolybdate, the concentration of Sodium orthomolybdate is 0.005-2.5mol/L, and be preferably 0.01-0.5mol/L, be more preferably 0.1mol/L, the concentration of depolarizer is 0.01-0.1mol/L;
Described depolarizer is one or more mixture of soluble chloride, Citrate trianion, tartrate;
Wherein soluble chloride is ammonium chloride or sodium-chlor etc.;
Citrate trianion is Trisodium Citrate, ammonium citrate or ammonium hydrogen citrate etc.;
Tartrate is sodium tartrate, sodium hydrotartrate, ammonium tartrate or ammonium hydrogen tartrate etc.;
Aqueous hydrochloric acid or the concentration of described acid solution to be concentration be 0.001-1mol/L are the aqueous sulfuric acid of 0.001-1mol/L;
Described alkaline solution is the aqueous sodium hydroxide solution of concentration 0.001-1mol/L or concentration is the potassium hydroxide aqueous solution of 0.001-1mol/L;
Described salts solution is the sodium chloride aqueous solution of concentration 0.001-1mol/L or concentration is the aqueous sodium carbonate of 0.001-1mol/L;
Described cationic membrane is perfluorinated sulfonic acid cationic exchange membrane;
The electric current of described constant-current electrolysis is 0.08-0.8A, and be preferably 0.4-0.8A, be more preferably 0.6A, current density is 1-100mA/cm
2, be preferably 50-100mA/cm
2, be more preferably 75mA/cm
2;
The voltage of described constant-potential electrolysis is 10-300V, is preferably 20-150V, is more preferably 20V;
(2), electrolysis complete after, cleaning limit, product deionized water limit that anode obtains is filtered, so that by Na
+and depolarizer cleans up, and be 30-80 DEG C of dry 1-2h by the filter cake control temperature after filtering, dry complete, be warming up to 500-700 DEG C with the temperature rise rate of 2.5-10 DEG C/min under air atmosphere and carry out high-temperature roasting 1-5h, naturally cool to room temperature after roasting is complete, obtain pure nickel molybdate.
Beneficial effect of the present invention
A kind of method utilizing cationic membrane electrolytic process to prepare nickel molybdate of the present invention, because the cationic membrane adopted in preparation process has certain selective penetrated property, particularly Nafion series perfluorinated sulfonic acid cationic exchange membrane can allow the Na in anolyte compartment
+ion permeable ionic membrane enters cathode compartment, thus cancellation Na
+ionic impurity is on the impact of the finished product nickel molybdate purity, and therefore to have the nickel molybdate product purity of final gained high for preparation method of the present invention, without the feature of dephasign.
Further, a kind of method utilizing cationic membrane electrolytic process to prepare nickel molybdate of the present invention, its reaction times is short, as can be seen from specific embodiment, its electrolytic preparation time is only 0.5h, can obtain pure nickel molybdate, therefore subsequent disposal is simple, thus preparation cost reduces.
Further, a kind of method utilizing cationic membrane electrolytic process to prepare nickel molybdate of the present invention, catholyte scope used is wide, acid solution, alkali lye and saline solution are all passable, in addition, no matter electrolytic process is the mode of constant-current electrolysis or constant-potential electrolysis, can obtain pure nickel molybdate.
Further, a kind of method utilizing cationic membrane electrolytic process to prepare nickel molybdate of the present invention, owing to only needing one-step electrolysis to prepare nickel molybdate, therefore its preparation process technique is simple, easily operates, invests little, and resultant quantity is large, can directly apply to suitability for industrialized production.
Accompanying drawing explanation
The EDS figure of the nickel molybdate obtained in Fig. 1 a, embodiment 1;
The XRD figure of the nickel molybdate obtained in Fig. 1 b, embodiment 1;
The EDS figure of the nickel molybdate obtained in Fig. 2 a, embodiment 2;
The XRD figure of the nickel molybdate obtained in Fig. 2 b, embodiment 2;
The EDS figure of the nickel molybdate obtained in Fig. 3 a, embodiment 3;
The XRD figure of the nickel molybdate obtained in Fig. 3 b, embodiment 3;
The EDS figure of the nickel molybdate obtained in Fig. 4 a, embodiment 4;
The XRD figure of the nickel molybdate obtained in Fig. 4 b, embodiment 4.
Embodiment
Also by reference to the accompanying drawings the present invention is set forth further below by specific embodiment, but do not limit the present invention.
Perfluorinated sulfonic acid cationic exchange membrane used in various embodiments of the present invention is the Nafion perfluorinated sulfonic acid 212 type cationic exchange membrane that du pont company produces.
embodiment 1
Utilize cationic membrane electrolytic process to prepare a method for nickel molybdate, specifically comprise the steps:
(1), take nickel sheet as anode, take noble electrode as negative electrode, the aqueous solution of depolarizer and Sodium orthomolybdate is contained for anolyte with 95ml, with 90ml acid solution for catholyte, be in the two-compartment cell of barrier film at cationic membrane, adopt the mode of constant-potential electrolysis, control temperature scope is the aqueous solution 30min that room temperature to 50 DEG C constant-potential electrolysis contains depolarizer and Sodium orthomolybdate, i.e. Na
+ion all transfers to cathode compartment;
Described noble electrode is titanium net;
Described containing in the aqueous solution of depolarizer and Sodium orthomolybdate, the concentration of Sodium orthomolybdate is 0.1mol/L, and the concentration of depolarizer is 0.01mol/L, and described depolarizer is ammonium chloride;
The aqueous hydrochloric acid of described acid solution to be concentration be 0.1mol/L;
Described cationic membrane is Nafion perfluorinated sulfonic acid 212 type cationic exchange membrane;
The voltage of described constant-potential electrolysis is 20V;
(2), electrolysis complete after, cleaning limit, product deionized water limit that anode obtains is filtered, so that by Na
+and depolarizer cleans up, and be 60 DEG C of dry 2h by the filter cake control temperature after filtering, dry complete, be warming up to 600 DEG C with the temperature rise rate of 2.5 DEG C/min under air atmosphere and carry out high-temperature roasting 2h, naturally cool to room temperature after roasting is complete, obtain pure nickel molybdate crystal.
The nickel molybdate of 4010 type X-ray detection instrument to above-mentioned gained of German Brooker ALX company is adopted to measure, its EDS schemes as shown in Figure 1a, as can be seen from Fig. 1 a, obtain in product, only having Ni, Mo, O tri-kinds of elements, indicating the nickel molybdate that the present invention adopts cationic membrane electrolytic process to prepare the method gained of nickel molybdate is thus pure phase, inclusion-free.
Adopt the nickel molybdate of D8 Advance type x-ray diffractometer to above-mentioned gained of German Brooker AXS company to measure, as shown in Figure 1 b, as can be seen from Fig. 1 b, the product obtained is NiMoO to its XRD figure
4.
embodiment 2
Utilize cationic membrane electrolytic process to prepare a method for nickel molybdate, concrete steps are as follows:
(1), take nickel sheet as anode, take noble electrode as negative electrode, the aqueous solution of depolarizer and Sodium orthomolybdate is contained for anolyte with 95ml, with 90ml acid solution for catholyte, be in the two-compartment cell of barrier film at cationic membrane, adopt the mode of constant-current electrolysis, control temperature scope is the aqueous solution 30min that room temperature to 50 DEG C electrolysis contains depolarizer and Sodium orthomolybdate, i.e. Na
+ion all transfers to cathode compartment;
Described noble electrode is titanium net;
Described containing in the aqueous solution of depolarizer and Sodium orthomolybdate, the concentration of Sodium orthomolybdate is 0.1mol/L, and the concentration of depolarizer is 0.01mol/L, and described depolarizer is sodium-chlor;
The aqueous hydrochloric acid of described acid solution to be concentration be 0.1mol/L;
Described cationic membrane is Nafion perfluorinated sulfonic acid 212 type cationic exchange membrane;
The electric current of described constant-current electrolysis is 0.6A, and current density is 75mA/cm
2;
(2), electrolysis complete after, cleaning limit, product deionized water limit that anode obtains is filtered, so that by Na
+and depolarizer cleans up, and be 60 DEG C of dry 2h by the filter cake control temperature after filtering, dry complete, be warming up to 600 DEG C with the temperature rise rate of 2.5 DEG C/min under air atmosphere and carry out high-temperature roasting 2h, naturally cool to room temperature after roasting is complete, obtain pure nickel molybdate.
The nickel molybdate of 4010 type X-ray detection instrument to above-mentioned gained of German Brooker ALX company is adopted to measure, its EDS schemes as shown in Figure 2 a, as can be seen from Fig. 2 a, obtain in product, only having Ni, Mo, O tri-kinds of elements, indicating the nickel molybdate that the present invention adopts cationic membrane electrolytic process to prepare the method gained of nickel molybdate is thus pure phase, inclusion-free;
Adopt the nickel molybdate of D8 Advance type x-ray diffractometer to above-mentioned gained of German Brooker AXS company to measure, as shown in Figure 2 b, as can be seen from Fig. 2 b, the product obtained is NiMoO to its XRD figure
4.
embodiment 3
Utilize cationic membrane electrolytic process to prepare a method for nickel molybdate, specifically comprise the steps:
(1), take nickel sheet as anode, take noble electrode as negative electrode, the aqueous solution of depolarizer and Sodium orthomolybdate is contained for anolyte with 95ml, with 90ml alkaline solution for catholyte, be in the two-compartment cell of barrier film at cationic membrane, adopt the mode of constant-current electrolysis, control temperature scope is the aqueous solution 30min that room temperature to 50 DEG C is carried out electrolysis and contained depolarizer and Sodium orthomolybdate, i.e. Na
+ion all transfers to cathode compartment;
Described noble electrode is titanium net;
Described containing in the aqueous solution of depolarizer and Sodium orthomolybdate, the concentration range of Sodium orthomolybdate is at 0.1mol/L, and the concentration of depolarizer is 0.01mol/L, and described depolarizer is sodium-chlor;
The aqueous sodium hydroxide solution of described alkaline solution to be concentration be 0.1mol/L;
Described cationic membrane is Nafion perfluorinated sulfonic acid 212 type cationic exchange membrane;
The electric current of described constant-current electrolysis is 0.6A, and current density is 75mA/cm
2;
(2), electrolysis complete after, cleaning limit, product deionized water limit that anode obtains is filtered, so that by Na
+and depolarizer cleans up, and be 60 DEG C of dry 2h by the filter cake control temperature after filtering, dry complete, be warming up to 600 DEG C with the temperature rise rate of 2.5 DEG C/min under air atmosphere and carry out high-temperature roasting 2h, naturally cool to room temperature after roasting is complete, obtain pure nickel molybdate.
The nickel molybdate of 4010 type X-ray detection instrument to above-mentioned gained of German Brooker ALX company is adopted to measure, its EDS schemes as shown in Figure 3 a, as can be seen from Fig. 3 a, obtain in product, only having Ni, Mo, O tri-kinds of elements, indicating the nickel molybdate that the present invention adopts cationic membrane electrolytic process to prepare the method gained of nickel molybdate is thus pure phase, inclusion-free;
Adopt the nickel molybdate of D8 Advance type x-ray diffractometer to above-mentioned gained of German Brooker AXS company to measure, as shown in Figure 3 b, as can be seen from Fig. 3 b, the product obtained is NiMoO to its XRD figure
4.
embodiment 4
Utilize cationic membrane electrolytic process to prepare a method for nickel molybdate, specifically comprise the steps:
(1), take nickel sheet as anode, take noble electrode as negative electrode, the aqueous solution of the Sodium orthomolybdate of depolarizer is contained for anolyte with 95ml, with 90ml salts solution for catholyte, be in the two-compartment cell of barrier film at cationic membrane, adopt the mode of constant-current electrolysis, control temperature scope is the aqueous solution 30min that room temperature to 50 DEG C is carried out electrolysis and contained depolarizer and Sodium orthomolybdate, i.e. Na
+ion all transfers to cathode compartment;
Described noble electrode is titanium net;
Described containing in the aqueous solution of depolarizer and Sodium orthomolybdate, the concentration range of Sodium orthomolybdate is at 0.1mol/L, and the concentration of depolarizer is 0.01mol/L, and described depolarizer is ammonium chloride;
Described salts solution is the sodium-chlor of concentration 0.1mol/L;
Described cationic membrane is Nafion perfluorinated sulfonic acid 212 type cationic exchange membrane;
The electric current of described constant-current electrolysis is 0.6A, and current density is 75mA/cm
2;
(2), electrolysis complete after, cleaning limit, product deionized water limit that anode obtains is filtered, so that by Na
+and depolarizer cleans up, and be 60 DEG C of dry 2h by the filter cake control temperature after filtering, dry complete, be warming up to 600 DEG C with the temperature rise rate of 2.5 DEG C/min under air atmosphere and carry out high-temperature roasting 2h, naturally cool to room temperature after roasting is complete, obtain pure nickel molybdate.
The nickel molybdate of 4010 type X-ray detection instrument to above-mentioned gained of German Brooker ALX company is adopted to measure, its EDS schemes as shown in fig. 4 a, as can be seen from Fig. 4 a, obtain in product, only having Ni, Mo, O tri-kinds of elements, indicating the nickel molybdate that the present invention adopts cationic membrane electrolytic process to prepare the method gained of nickel molybdate is thus pure phase, inclusion-free;
Adopt the nickel molybdate of D8 Advance type x-ray diffractometer to above-mentioned gained of German Brooker AXS company to measure, as shown in Figure 4 b, as can be seen from Fig. 4 b, the product obtained is NiMoO to its XRD figure
4.
In sum, a kind of method utilizing cationic membrane electrolytic process to prepare nickel molybdate of the present invention, owing to adopting cationic exchange membrane electrolysis, no matter be therefore constant-potential electrolysis, or constant-current electrolysis; No matter catholyte is acid solution, alkali lye or saline solution, no matter depolarizer is ammonium chloride or sodium-chlor, all can obtain nickel molybdate, and the electrolytic preparation time is only 0.5h, the nickel molybdate of final gained is pure phase, without dephasign.
The above is only the citing of embodiments of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the technology of the present invention principle; can also make some improvement and modification, these improve and modification also should be considered as protection scope of the present invention.
Claims (7)
1. utilize cationic membrane electrolytic process to prepare a method for nickel molybdate, it is characterized in that specifically comprising the steps:
(1), take nickel sheet as anode, take noble electrode as negative electrode, with the aqueous solution containing depolarizer and Sodium orthomolybdate for anolyte, with acid solution, alkaline solution or salts solution for catholyte, be in the two-compartment cell of barrier film at cationic membrane, adopt the mode of constant-current electrolysis or constant-potential electrolysis, control temperature scope is the aqueous solution that room temperature to 90 DEG C is carried out electrolysis and contained depolarizer and Sodium orthomolybdate, until Na
+ion all transfers to cathode compartment;
Described noble electrode is glass-carbon electrode, Graphite Electrodes, titanium net or platinum guaze;
Described containing in the aqueous solution of depolarizer and Sodium orthomolybdate, the concentration of Sodium orthomolybdate is 0.005-2.5mol/L, and the concentration of depolarizer is 0.01-0.1mol/L;
Described depolarizer is one or more mixture of soluble chloride, Citrate trianion, tartrate;
Wherein soluble chloride is ammonium chloride or sodium-chlor;
Citrate trianion is Trisodium Citrate, ammonium citrate or ammonium hydrogen citrate;
Tartrate is sodium tartrate, sodium hydrotartrate, ammonium tartrate or ammonium hydrogen tartrate;
Aqueous hydrochloric acid or the concentration of described acid solution to be concentration be 0.001-1mol/L are the aqueous sulfuric acid of 0.001-1mol/L;
Described alkaline solution is the aqueous sodium hydroxide solution of concentration 0.001-1mol/L or concentration is the potassium hydroxide aqueous solution of 0.001-1mol/L;
Described salts solution is the sodium chloride aqueous solution of concentration 0.001-1mol/L or concentration is the aqueous sodium carbonate of 0.001-1mol/L;
Described cationic membrane is perfluorinated sulfonic acid cationic exchange membrane;
The electric current of described constant-current electrolysis is 0.08-0.8A, and current density is 1-100mA/cm
2;
The voltage of described constant-potential electrolysis is 10-300V;
(2), electrolysis complete after, cleaning limit, product deionized water limit that anode obtains is filtered, so that by Na
+and depolarizer cleans up, and be 30-80 DEG C of dry 1-2h by the filter cake control temperature after filtering, dry complete, be warming up to 500-700 DEG C with the temperature rise rate of 2.5-10 DEG C/min under air atmosphere and carry out high-temperature roasting 1-5h, naturally cool to room temperature after roasting is complete, obtain pure nickel molybdate.
2. a kind of method utilizing cationic membrane electrolytic process to prepare nickel molybdate as claimed in claim 1, is characterized in that described in step (1), noble electrode is titanium net;
Described containing in the aqueous solution of depolarizer and Sodium orthomolybdate, the concentration of Sodium orthomolybdate is for being 0.01-0.5mol/L, and described depolarizer is ammonium chloride or sodium-chlor;
The aqueous hydrochloric acid of described acid solution to be concentration be 0.001-1mol/L;
Described alkaline solution is the aqueous sodium hydroxide solution of concentration 0.001-1mol/L;
Described salts solution is the sodium chloride aqueous solution of concentration 0.001-1mol/L;
In constant-current electrolysis or constant-potential electrolysis process, control temperature scope is room temperature to 50 DEG C;
The electric current of described constant-current electrolysis is 0.4-0.8A, and current density is 50-100mA/cm
2;
The voltage of described constant-potential electrolysis is 20-150V.
3. a kind of method utilizing cationic membrane electrolytic process to prepare nickel molybdate as claimed in claim 2, is characterized in that the concentration of Sodium orthomolybdate is 0.1mol/L containing in the aqueous solution of depolarizer and Sodium orthomolybdate described in step (1);
The filter cake control temperature that step (2) filters rear gained is 60 DEG C of dry 2h, dry complete, is warming up to 600 DEG C carries out high-temperature roasting 2h under air atmosphere with the temperature rise rate of 2.5 DEG C/min.
4. a kind of method utilizing cationic membrane electrolytic process to prepare nickel molybdate as claimed in claim 3, it is characterized in that containing described in step (1) in the aqueous solution of depolarizer and Sodium orthomolybdate, the concentration of depolarizer is 0.01mol/L, and described depolarizer is ammonium chloride;
Take acid solution as catholyte, the aqueous hydrochloric acid of described acid solution to be concentration be 0.1mol/L;
Adopt the mode of constant-potential electrolysis to carry out electrolysis, the voltage of constant-potential electrolysis is 20V.
5. a kind of method utilizing cationic membrane electrolytic process to prepare nickel molybdate as claimed in claim 3, it is characterized in that containing described in step (1) in the aqueous solution of depolarizer and Sodium orthomolybdate, the concentration of depolarizer is 0.01mol/L, and described depolarizer is sodium-chlor;
Take acid solution as catholyte, the aqueous hydrochloric acid of described acid solution to be concentration be 0.1mol/L;
Adopt the mode of constant-current electrolysis to carry out electrolysis, the current density of constant-current electrolysis is 75mA/cm
2, electric current is 0.6A.
6. a kind of method utilizing cationic membrane electrolytic process to prepare nickel molybdate as claimed in claim 3, it is characterized in that containing described in step (1) in the aqueous solution of depolarizer and Sodium orthomolybdate, the concentration of depolarizer is 0.01mol/L, and described depolarizer is sodium-chlor;
Take alkaline solution as catholyte, the aqueous sodium hydroxide solution of described alkaline solution to be concentration be 0.1mol/L;
Adopt the mode of constant-current electrolysis to carry out electrolysis, the current density of constant-current electrolysis is 75mA/cm
2, electric current is 0.6A.
7. a kind of method utilizing cationic membrane electrolytic process to prepare nickel molybdate as claimed in claim 3, it is characterized in that containing described in step (1) in the aqueous solution of depolarizer and Sodium orthomolybdate, the concentration of depolarizer is 0.01mol/L, and described depolarizer is ammonium chloride;
Take salts solution as catholyte, described salts solution is the sodium-chlor of concentration 0.1mol/L;
Adopt the mode of constant-current electrolysis to carry out electrolysis, the current density of constant-current electrolysis is 75mA/cm
2, electric current is 0.6A.
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| CN105420810A (en) * | 2015-11-25 | 2016-03-23 | 上海应用技术学院 | Novel crystal form multi-metal molybdate micro-nano-particles and preparing method thereof |
| CN106350848A (en) * | 2016-09-19 | 2017-01-25 | 上海应用技术大学 | Method for preparing nanometer material by depositing molybdate on carbon fiber surface |
| CN106350848B (en) * | 2016-09-19 | 2018-08-03 | 上海应用技术大学 | A kind of preparation method of carbon fiber surface deposition molybdate nano material |
| CN106191903A (en) * | 2016-09-23 | 2016-12-07 | 上海应用技术大学 | A kind of preparation method of silver vanadate photocatalyst |
| CN106367773A (en) * | 2016-09-23 | 2017-02-01 | 上海应用技术大学 | Preparation method of vanadic acid copper |
| CN106367772A (en) * | 2016-09-23 | 2017-02-01 | 上海应用技术大学 | Preparation method of 3D flower-like spherical zinc vanadium oxide hydroxide hydrate photocatalyst |
| CN106367773B (en) * | 2016-09-23 | 2018-08-17 | 上海应用技术大学 | A kind of preparation method of copper vanadate |
| CN106367772B (en) * | 2016-09-23 | 2018-08-24 | 上海应用技术大学 | A kind of preparation method of 3D flower ball-shapeds pyrovanadic acid zinc photochemical catalyst |
| CN106191903B (en) * | 2016-09-23 | 2018-12-04 | 上海应用技术大学 | A kind of preparation method of silver vanadate photochemical catalyst |
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