CN110711574A - Method for preparing black titanium dioxide by low-temperature liquid-phase hydrothermal reduction method - Google Patents
Method for preparing black titanium dioxide by low-temperature liquid-phase hydrothermal reduction method Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 238000000034 method Methods 0.000 title claims abstract description 98
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- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims abstract description 40
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- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 36
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B01J35/39—
-
- B01J35/50—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a method for preparing black titanium dioxide by a low-temperature liquid-phase hydrothermal reduction method, belonging to the technical field of photocatalysis. The invention provides a method for preparing black titanium dioxide by a low-temperature liquid-phase hydrothermal reduction method for preparing black titanium with excellent performance under mild conditions, which comprises the following steps: mixing the normal titanate gel with a reducing agent, adding a NaOH solution into the normal titanate gel until the pH value of the system is 9-12, and carrying out hydrothermal reaction after uniformly stirring; and washing and drying the hydrothermal sample to obtain black titanium dioxide. According to the invention, tetrabutyl titanate is used as a raw material, glacial acetic acid is added to inhibit the hydrolysis of tetrabutyl titanate, orthotitanic acid gel is prepared, reducing agents such as hydrazine hydrate are added, and the pH value of the system is controlled to carry out hydrothermal reduction reaction, so that the black titanium dioxide with excellent performance is prepared.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to a method for preparing black titanium dioxide by a low-temperature liquid-phase hydrothermal reduction method.
Background
Titanium black, also known as titanium suboxide, or magneli phase titanium suboxide, is the first black titanium metal oxide in the world. The titanium black is modified by titanium dioxide, so that the titanium black has the characteristics of a functional material. Titanium black is non-toxic, has high thermal stability and good dispersibility in water and resin, can provide resistance values in different ranges, can be used as a black pigment instead of carbon black and iron black for coatings, paints, cosmetics, printing ink, plastic colorants and catalysts in food industry, and can also be used as an excellent conductive material and an antistatic material for preparing electrodes. The titanium black is generally TiO2Is prepared from the main raw materials through heating reduction in reducing medium (Ti and TIH)2Boron and its compound, reducing gas (H)2、NH3CO, methylamine, etc.). The titanium black may be cyan black, violet black, etc. depending on the degree of reduction. The titanium resource of China is very rich, the production of titanium dioxide has a considerable scale, but the preparation of titanium black is rarely reportedTherefore, the titanium black has wide prospect as a titanium white deep processing product.
At present, more process routes are available for preparing titanium black, but only a thermal reduction method is actually applied to production, and the basic ideas are as follows: (1) selection of TiO2The product is taken as raw material, and reducing gas such as: h2，N2And the like (or reducing substances such as C, Ti and the like are added), and the titanium black product is prepared by keeping the temperature for a period of time under the high-temperature condition. The method has high energy consumption, low productivity and high pollution; (2) the oxidation method takes substances of low-valence titanium as initial raw materials, increases the valence state through oxidation, and also comprises the process of preparing titanic acid and the like as precursors by taking titanium as a base material and obtaining titanium protoxide with different components through subsequent treatment. In this method, since the oxidation process is a process of increasing the mass of the substance, the Ti valence is increased, and the volume is usually expanded, which is not favorable for the formation of fine or even nano-structure material in many cases.
At present, the titanium black material in China mainly depends on foreign import. The titanium black has the application of two aspects of functionality and colorability, and the titanium black has a bright prospect in the aspects of bipolar batteries, LED black matrixes, photocatalysts and the like. At present, manufacturers in China master the production technology of the titanium black, and further improvement of the titanium black technology and reduction of the production cost of the titanium black are two main factors restricting the development of the titanium black. The unique electron transport property of the titanium black can effectively reduce the recombination of photo-generated electrons and holes, thereby improving the quantum efficiency in the photocatalysis process. Photocatalysis has become a strategic choice common in many countries as a clean energy production technology and an ideal environmental pollution treatment technology. The Panxi area has rich titanium resources, the reserves are in the front of China, the production of titanium dioxide has a considerable scale, but the preparation of titanium black is not reported, and the titanium black has a wide prospect as a deep processing product of titanium white. The development of the preparation and the performance mechanism research of the titanium black is beneficial to improving the way of comprehensive utilization of resources, changes the current situation that only low-level primary products are produced at present, produces functional materials with high added values, and has important theoretical significance and practical value.
CN102249300B discloses a preparation methodA process for black titanium dioxide comprising the steps of: 1. mixing butyl titanate and absolute ethyl alcohol in a volume ratio of 1: 2-10 to prepare a mixed system A; 2. distilled water and glacial acetic acid are mixed according to the volume ratio of 150-250: 1 preparing a mixed system B; 3. adding the mixed system A into the mixed system B under stirring, wherein the volume ratio of the mixed system A to the mixed system B is 1: 0.5-2, stirring for 2 hours at normal temperature, and standing overnight; 4. then stirring the mixture at the constant temperature of 80 ℃ until gel is generated, and then mixing the gel with the mixture according to the volume ratio of 1: adding glacial acetic acid into the mixture 300-350, fully stirring and washing, drying the gel, baking the gel for 30-100 min at 100-150 ℃, fully grinding the gel for 15-30 min, sieving the gel with a 200-mesh sieve, keeping the temperature of the gel for 1-3 h at 300-600 ℃ under the protection of inert gas, and cooling the gel to room temperature along with the furnace to obtain black titanium dioxide powder. The process adopts high-temperature calcination, which causes serious sintering of particles and reduction of product performance, and the product obtained by the process is black in appearance but mainly caused by carbonization of organic matters, wherein titanium dioxide is TiO2Exists in the form of (1) without generating new substances.
CN201310052983.9 discloses a preparation method of a visible light response black titanium dioxide photocatalyst, comprising the following steps: 1. adding a certain amount of lithium acetate dihydrate into 30mL of glacial acetic acid and amide solvent, stirring until the mixture is clear, transferring the mixture into a 50mL of polytetrafluoroethylene hydrothermal kettle, adding a titanium sheet as a titanium source, and adding 2mL of 1-methyl-3-imidazole tetrafluoroborate ionic liquid; 2. the hydrothermal kettle is reacted for 8 to 48 hours at the temperature of 150 ℃ and 220 ℃; washing with deionized water and ethanol for three times respectively, and vacuum drying at 80 deg.C for 12 hr to obtain black anatase type titanium dioxide photocatalyst. The process takes the titanium sheet as a reducing agent, and has the advantages of poor reduction effect, low reduction rate, high price of the titanium sheet and relatively high cost for large-scale production under the hydrothermal condition.
CN201610390623.3 discloses a preparation method of a nanometer black titanium dioxide photocatalyst, which comprises the following specific operations: a. adding 2-10g of trivalent titanium salt which is titanium trichloride or TiOCl and 0-1g of reducing agent which is sodium borohydride, ascorbic acid or hydrazine hydrate into 20-100mL of deionized water, and continuously stirring for 1-3 hours to obtain a purple transparent solution; b. step a isAdding 0.2-1.5mol/L sodium hydroxide solution into the solution until the pH value is 2-10, and continuously stirring for 2-3 hours to obtain a black titanium dioxide solution; c. transferring the solution in the step b to a 100mL hydrothermal kettle, and reacting at the temperature of 80-260 ℃ for 4-20 hours to obtain nano black titanium dioxide; d. and c, respectively cleaning the nano black titanium dioxide obtained in the step c with 50mL of deionized water and 50mL of ethanol until the pH value is 7, and drying to obtain the nano black titanium dioxide photocatalyst. The process takes titanium trichloride or TiOCl as a raw material, has relatively high cost, is easy to hydrolyze and oxidize, is not easy to control, has high acidity of solution, is difficult to hydrolyze, has low yield, and in the hydrolysis process, Ti is heated along with the rise of temperature3+The oxidation degree is higher, and the produced product is mainly metatitanic acid.
Disclosure of Invention
The technical problem to be solved by the invention is how to prepare black titanium dioxide with excellent performance under mild conditions.
The technical scheme adopted by the invention for solving the technical problem is to provide a method for preparing black titanium dioxide by a low-temperature liquid-phase hydrothermal reduction method, which comprises the following steps:
A. mixing the normal titanate gel with a reducing agent, adding a NaOH solution into the normal titanate gel until the pH value of the system is 9-12, and carrying out hydrothermal reaction after uniformly stirring; the reducing agent is sodium borohydride, potassium borohydride, ascorbic acid or hydrazine hydrate;
B. and washing and drying the hydrothermal sample to obtain black titanium dioxide.
Preferably, in the method for preparing black titanium dioxide by using the low-temperature liquid-phase hydrothermal reduction method, the reducing agent is hydrazine hydrate.
Further, in the method for preparing black titanium dioxide by using the low-temperature liquid-phase hydrothermal reduction method, the mass ratio of the normal titanate gel to the hydrazine hydrate is 1: 1 to 20.
In the method for preparing the black titanium dioxide by the low-temperature liquid-phase hydrothermal reduction method, the concentration of the NaOH solution is 4-7 mol/L.
In the method for preparing the black titanium dioxide by the low-temperature liquid-phase hydrothermal reduction method, the amount of the NaOH solution is adjusted to adjust the pH of the system to 9-12.
In the method for preparing the black titanium dioxide by the low-temperature liquid-phase hydrothermal reduction method, the temperature of the hydrothermal reaction is 100-250 ℃ and the time is 4-48 h.
In the method for preparing the black titanium dioxide by the low-temperature liquid-phase hydrothermal reduction method, the temperature of the hydrothermal reaction is 200-250 ℃.
In the method for preparing the black titanium dioxide by the low-temperature liquid-phase hydrothermal reduction method, ethanol and water are used for washing until the pH value is 6-7.
In the method for preparing black titanium dioxide by using the low-temperature liquid-phase hydrothermal reduction method, the normal titanate gel is prepared by the following steps: and uniformly mixing tetrabutyl titanate and ethanol, adding glacial acetic acid, dropwise adding water in the stirring process until the solution is gelatinous, and drying to obtain the n-titanic acid gel.
In the method for preparing black titanium dioxide by using the low-temperature liquid-phase hydrothermal reduction method, the volume ratio of tetrabutyl titanate to ethanol to glacial acetic acid is 1: 1.5-2: 0.25 to 0.3.
The invention has the beneficial effects that:
according to the invention, tetrabutyl titanate is used as a raw material, glacial acetic acid is added to inhibit hydrolysis of tetrabutyl titanate, orthotitanic acid gel with a macromolecular structure is prepared, then orthotitanic acid gel is used as a raw material, hydrazine hydrate and other reducing agents are added, and the pH of a system is controlled to carry out hydrothermal reduction reaction, so that agglomeration is not easy to occur in the reaction process, and the product is light and fine, thereby preparing black titanium dioxide with excellent performance, and from the test, the degradation rate of methyl orange under the ultraviolet irradiation condition can reach 99.9% to the maximum; the method has the advantages of low reaction temperature, low energy consumption, low pollution, energy conservation, environmental protection and high industrial utilization value.
Drawings
FIG. 1 is a flow chart of the process for preparing black titanium dioxide by the low-temperature liquid-phase hydrothermal reduction method of the invention.
FIG. 2 is a diagram showing the thermodynamic analysis of hydrazine hydrate for reducing orthotitanic acid.
FIG. 3 shows TiO under different process conditions2XRD pattern of (a).
FIG. 4 shows the results of the degradation test in test example 1 of the present invention.
FIG. 5 shows the effect of hydrazine hydrate addition on the degradation rate of hydrothermal products in test example 1 of the present invention.
FIG. 6 shows the effect of the amount of NaOH added on the degradation rate of hydrothermal products in test example 1 of the present invention.
FIG. 7 shows the effect of hydrothermal temperature on the degradation rate of hydrothermal products in test example 1 of the present invention.
Detailed Description
Specifically, the method for preparing the black titanium dioxide by the low-temperature liquid-phase hydrothermal reduction method comprises the following steps:
A. mixing the normal titanate gel with a reducing agent, adding a NaOH solution into the normal titanate gel until the pH value of the system is 9-12, and carrying out hydrothermal reaction after uniformly stirring; the reducing agent is sodium borohydride, potassium borohydride, ascorbic acid or hydrazine hydrate;
B. and washing and drying the hydrothermal sample to obtain black titanium dioxide.
In the method, the black titanium dioxide is prepared by adopting the orthotitanic acid gel, and the orthotitanic acid gel can be prepared by the following method: and uniformly mixing tetrabutyl titanate and ethanol, adding glacial acetic acid, dropwise adding water in the stirring process until the solution is gelatinous, and drying to obtain the n-titanic acid gel.
Orthotitanic acid chemical formula H4TiO4It is white amorphous solid, also called alpha-titanic acid. Orthotitanic acid is an amphoteric substance, is dissolved in hot concentrated alkali solution, is dissolved in strong-acidity inorganic acids such as dilute hydrochloric acid, dilute sulfuric acid, organic acids and the like at normal temperature, is insoluble in water and alcohol, but is easily converted into colloid in water. Orthotitanic acid can be converted to metatitanic acid by washing with hot water, heating or by vacuum drying. In general, orthotitanic acid can be precipitated from soluble titanium compounds at room temperature, but if the temperature is slightly higher, for example above 50 ℃, the product is partially or completely converted into metatitanic acid.
The invention takes tetrabutyl titanate as a main test reagent, and tetrabutyl titanate is very easy to hydrolyze in water to generate white precipitate, so that the inventor adds glacial acetic acid to inhibit hydrolysis, slowly drops deionized water at a constant speed in the stirring process to obtain uniform transparent gel, and then dries and dehydrates to obtain the orthotitanic acid gel. The reaction of glacial acetic acid to inhibit hydrolysis of tetrabutyl titanate is as follows:
Ti(OC4H9)4+n(CH3COOH)→(CH3COO)nTi(OC4H9)4-n+n(C4H9OH) … … formula 1.
Wherein CH3COO-acts as a ligand site in the reaction. The reaction first produces a large amount of (CH)3COO)nTi(OC4H9)4-nThe polymer further undergoes hydrolytic polycondensation reaction in water, so that the hydrolytic polycondensation reaction of tetrabutyl titanate and water is delayed.
The hydrolysis of tetrabutyl titanate presents the following equilibrium relationship:
[M-(OH2)]z+→[M-(OH)]z-1+H+→[M-(O)]z-2+2H+… … formula 2.
The addition of water has a great influence on the hydrolysis process of tetrabutyl titanate, and the hydrolysis and polycondensation reaction formula of tetrabutyl titanate is as follows:
Ti(OC4H9)4+4H2O→Ti(OH)4+4C4H9OH … … formula 3.
Due to the addition of glacial acetic acid, the complexation of the tetrabutyl titanate by the glacial acetic acid inhibits the progress of the polycondensation hydrolysis reaction to a certain extent, and the reaction rate is reduced. Under the conditions, water is used as a reactant, and the hydrolysis polycondensation reaction speed is accelerated along with the addition of more water, namely the concentration of the reactant is increased, so that the gel formation time is shortened; the amount of water added is also related to the viscosity of the gel, and as the amount of water added increases, the degree of crosslinking and the degree of polymerization of the hydrolyzed polycondensate increase, and the gel formation time is also shortened.
Through tests, when tetrabutyl titanate organic titanium is used as a raw material to prepare the n-titanic acid gel, the ratio of tetrabutyl titanate, ethanol and glacial acetic acid is controlled to be 1: 1.5-2: 0.25-0.3 (volume ratio), the drying temperature is 100-120 ℃, the time is 8-12 h, the obtained orthotitanate gel has the best effect, and the black titanium dioxide performance is favorably improved.
The method of the invention deeply studies the influence of hydrazine hydrate on the performance of the black titanium dioxide when the reducing agent is hydrazine hydrate. In the process of reducing orthotitanic acid by hydrazine hydrate, the reaction formula is as follows:
8Ti(OH)4+N2H4＝2Ti4O7+N2+18H2o … … formula 4.
As can be seen from FIG. 2, Ti7O13The △ G value is large and the reaction conditions are rather harsh, so that the titanium black product cannot contain Ti in the invention7O13Other titanium suboxide products, △ G is smaller and smaller with the increase of n value under the same reaction condition, and the difficulty degree of the orthotitanic acid reduction product is that Ti10O19＞Ti9O17＞Ti8O15＞Ti6O11＞Ti5O9＞Ti4O7。
Through tests, the mass ratio of the orthotitanic acid gel to the hydrazine hydrate solution is 1: 1-20 hours, preparing black titanium dioxide, wherein the dosage of hydrazine hydrate solution has influence on the reduction degree and the impurity content in the final product, and when the mass ratio of the normal titanic acid gel to the hydrazine hydrate solution is 1: when the time is 10, the degradation rate of the obtained black titanium dioxide can reach 99.9 percent. The hydrazine hydrate adopted by the invention is a commercial product, and the hydrazine content is about 55 percent.
As the optimal conditions of reducing agents such as hydrazine hydrate and the like are alkaline conditions, the pH value of the system is adjusted to 9-12 by adopting 4-7 mol/L NaOH solution. The increase of the pH is beneficial to the reaction of reduction, but the corrosion of equipment is aggravated by the over-high pH, and the composition content of the product is also greatly influenced. From the test results, it is best to control the pH at 11.
In the method, the hydrothermal reaction can be carried out in a drying oven, the temperature of the drying oven is set to be 100-250 ℃ (preferably 200-250 ℃), and then the uniformly stirred mixed solution is poured into a digestion tank and placed in the drying oven for hydrothermal treatment for 4-48 hours. The higher the temperature is, the content of anatase type crystal form titanium dioxide in the hydrothermal product is increased, but the oxidation degree is correspondingly increased; the influence of the hydrothermal time on the product is small, but the influence on the production period is large, the crystal form of the product is incomplete when the hydrothermal time is short, and the aggregation degree of the product is increased when the hydrolysis time is too long.
According to the method, a hydrothermal sample is washed by ethanol and deionized water until the pH value is 6-7, and then the sample is placed into a vacuum drying oven to be dried for 8-12 hours at the temperature of 110-120 ℃ to prepare the black titanium dioxide. In order to prevent secondary oxidation of the low-valence titanium oxide, vacuum drying is required, and ethanol is used as a detergent except for the last washing with deionized water.
The present invention is further illustrated by the following test examples and examples, but the scope of the present invention is not limited thereto.
Test example 1
TiO obtained under different process conditions2The XRD pattern of (a) is shown in fig. 3, and analyzed as follows:
1. a # is titanium/hydrazine hydrate ratio of 1: the titanium black product obtained by hydrothermal at 20 and 250 ℃ for 20h and vacuum drying at 110 ℃ for 10h has a plurality of dense peaks of a #, and XRD (X-ray diffraction) characterization results show that the main component of the product is Na0.23TiO2Containing a small amount of brookite TiO2、Ti8O15And Ti9O17It is shown that hydrazine hydrate reduces orthotitanic acid to produce effect. The particle size of a # was calculated to be 29.06 nm.
2. And b # is an amorphous product obtained by drying for 20 hours at 120 ℃ without reduction after gelation, and the particle size of b # is calculated to be 10.55 nm.
3. c # is TiO obtained by drying the gel at 120 ℃ for 20h without reduction and then calcining the gel at 500 ℃ for 1h2Product, c # is standard anatase TiO2And 2 θ ═ 25.55 °, 38 °, 48.3 °, 54.1 °, 55.25 °, and 62.95 °, corresponding to the diffraction crystal planes of (101), (004), (200), (105), (211), and (204), respectively, and the particle diameter of c # was calculated to be 19.5nm, and the particle diameters were uniform.
4. d # is dried at 120 ℃ for 20h after being gelled, and then calcined at 700 DEG CTiO obtained by 1h of calcination2The characterization result of XRD shows that d # is rutile TiO2However, two small peaks, probably peaks resulting from the anatase to rutile phase transition at a calcination temperature of 700 ℃, appeared at 25.5 ° and 26.6 °, calculated as a particle size of d # of 51.26 nm.
Therefore, the order of the grain sizes from large to small is d # > a # > c # > b #, and the reduction reaction is promoted by adding hydrazine hydrate; the hydrothermal process can promote the growth of crystal grains and increase the content of anatase crystal; the increase of the calcination temperature can cause the growth of crystal grains and the agglomeration of particles.
Test example 2
TABLE 1 hydrothermal orthogonal test and degradation test results
| Test group | Orthotitanic acid: hydrazine hydrate | Orthotitanic acid: NaOH | Hydrothermal temperature (. degree.C.) | Degradation Rate (%) | Degradation time (min) |
| 1 | 1：10 | 1：1 | 150 | 34.7 | 90 |
| 2 | 1：10 | 1：2.5 | 200 | 42.5 | 90 |
| 3 | 1：10 | 1：5 | 250 | 99.9 | 45 |
| 4 | 1：15 | 1：1 | 200 | 38.6 | 90 |
| 5 | 1：15 | 1：2.5 | 250 | 18.7 | 90 |
| 6 | 1：15 | 1：5 | 150 | 13.4 | 90 |
| 7 | 1：20 | 1：1 | 250 | 47.6 | 90 |
| 8 | 1：20 | 1：2.5 | 150 | 36.1 | 90 |
| 9 | 1：20 | 1：5 | 200 | 32.4 | 90 |
Note: in table 1, "orthotitanic acid: hydrazine hydrate "," orthotitanic acid: NaOH "are mass ratios.
Compared with the color of the degraded solution, the color of the degraded solution of the samples of the test groups 5 and 6 is not much different from that of the original solution, the color of the degraded solution of the samples of the test groups 1, 2, 4, 7, 8 and 9 is slightly lighter, and the degraded solution of the sample of the test group 3 is basically a white solution. According to the Lambert-beer law, the color of the solution is in a direct proportion to the concentration of methyl orange, and the lighter the color of the degraded solution is, the lower the concentration of methyl orange in the solution is. Therefore, it is considered that the test group 3 has the best degradation effect and the methyl orange is decomposed almost completely.
Fig. 4 is a graph showing the results of the test in which the titanium black photocatalyst prepared by the liquid phase reduction method of test example 1 degrades methyl orange under the irradiation of a mercury lamp. As can be seen by combining FIG. 4 and Table 1, the highest degradation rate is that of test group 3, and 99.9% can be achieved after 45min of illumination; the lowest degradation rate is the test group 2, and the illumination time is 13.4 percent for 90 min; from the comprehensive view of the degradation rate and the degradation time, the highest degradation efficiency is the test group 3, the degradation efficiencies of other 8 samples are the test group 7>2>4>8>1>9>5>6 from large to small, and the result is matched with the detection result of the solution color.
As can be seen from FIG. 5, the influence of the added amount of hydrazine hydrate on the degradation rate of the product by the liquid phase reduction method is large. The ratio of the added hydrazine hydrate to the orthotitanic acid is 1: the degradation rate of the hydrothermal method product prepared by the method 10 is obviously higher than that of the product prepared by other proportions, and the method is preliminarily considered as follows: along with the increase of the addition amount of hydrazine hydrate, crystal grains grow up, the specific surface area is reduced, and the photodegradation rate is in a descending trend; when the adding amount of hydrazine hydrate 1: after 1.5, titanium suboxide is generated on the surface, and the existence of oxygen holes improves the photodegradation rate.
As can be seen from FIG. 6, the addition of NaOH has a small influence on the degradation rate of the hydrothermal process product. And as the addition amount of NaOH increases, the degradation rate of the sample decreases firstly and then slowly increases. After the pH value of the solution is adjusted to be more than 11, the addition amount of NaOH has little influence on the reaction result.
As can be seen from FIG. 7, the degradation rates of the products obtained by hydrothermal reaction at different temperatures are greatly different, and the degradation rates almost linearly increase with the increase of the temperature. As the hydrothermal temperature increases, the reduction degree of orthotitanic acid is enhanced, resulting in better photocatalytic performance.
In conclusion, the mass ratio of hydrazine hydrate to orthotitanic acid is controlled to be 1: 10, the mass ratio of the orthotitanic acid to the NaOH is 1: 5 (pH at this time is about 11) and the hydrothermal temperature is 250 ℃ which is the optimum reaction condition, the black titanium dioxide obtained has the most excellent performance.
Example 1
Preparation of orthotitanic acid: pouring 120mL of ethanol into 60g of tetrabutyl titanate, uniformly mixing, adding 15mL of glacial acetic acid, uniformly mixing, placing the mixed solution on a magnetic stirrer, stirring, slowly dropwise adding deionized water in the stirring process, and dropwise adding until the solution is gelatinous; standing the gel solution for 30min, then placing in a drying oven, heating to 100 deg.C, drying for 12 hr to obtain granular orthotitanic acid, and grinding into powder.
Hydrazine hydrate reduction of orthotitanic acid: according to the mass ratio of 1: and 20, taking the orthotitanic acid gel and hydrazine hydrate, pouring orthotitanic acid powder into a hydrazine hydrate solution, preparing NaOH with the concentration of 7mol/L, titrating until the pH value of the mixed solution is 11, placing the mixed solution in a magnetic stirrer to stir for 10min, setting the temperature of a drying box to be 250 ℃, then pouring the uniformly stirred mixed solution into a digestion tank, and placing the digestion tank in the drying box to carry out hydrothermal treatment for 20 h.
Washing and drying: washing the hydrothermal sample with ethanol and deionized water until the pH value is 6-7, and then drying the sample in a vacuum drying oven at 110 ℃ for 10 hours to obtain black titanium dioxide.
And (3) photocatalytic degradation of methyl orange: under the irradiation condition of a mercury lamp, the titanium black photocatalyst prepared by a liquid phase reduction method by using a photochemical reaction instrument degrades methyl orange, and the degradation rate of the methyl orange reaches 99.8 percent after the titanium black photocatalyst is illuminated for 45 min.
Comparative example 1
Preparation of orthotitanic acid: dissolving metatitanic acid with sulfuric acid, precipitating orthotitanic acid with ammonia water, and washing with deionized water until no sulfate radical and other soluble impurities are contained in the orthotitanic acid.
Hydrazine hydrate reduction of orthotitanic acid: according to the mass ratio of 1: 10, taking the orthotitanic acid gel and hydrazine hydrate, pouring orthotitanic acid powder into a hydrazine hydrate solution, preparing NaOH with the concentration of 7mol/L, titrating until the pH value of the mixed solution is 10, placing the mixed solution in a magnetic stirrer to stir for 10min, setting the temperature of a drying box to be 250 ℃, then pouring the uniformly stirred mixed solution into a digestion tank, and placing the digestion tank in the drying box to carry out hydrothermal treatment for 16 h.
Washing and drying: washing the hydrothermal sample with ethanol and deionized water until the pH value is 6-7, and then drying the sample in a vacuum drying oven at 110 ℃ for 10 hours to obtain black titanium dioxide.
And (3) photocatalytic degradation of methyl orange: under the irradiation condition of a mercury lamp, the titanium black photocatalyst prepared by a liquid phase reduction method by using a photochemical reaction instrument degrades methyl orange, and the degradation rate of the methyl orange reaches 47.64 percent after illumination for 105 min.
As can be seen from the example 1 and the comparative example 1, the invention adopts tetrabutyl titanate as a raw material to prepare the orthotitanic acid gel with a macromolecular structure, and then the orthotitanic acid gel can be used to prepare the black titanium dioxide with the methyl orange degradation rate of 99.8 percent, so that the black titanium dioxide is greatly improved compared with the orthotitanic acid precipitate obtained by precipitating the metatitanic acid dissolved with ammonia water as the raw material.
Claims (10)
1. The method for preparing the black titanium dioxide by the low-temperature liquid-phase hydrothermal reduction method is characterized by comprising the following steps: the method comprises the following steps:
A. mixing the normal titanate gel with a reducing agent, adding a NaOH solution into the normal titanate gel until the pH value of the system is 9-12, and carrying out hydrothermal reaction after uniformly stirring; the reducing agent is sodium borohydride, potassium borohydride, ascorbic acid or hydrazine hydrate;
B. and washing and drying the hydrothermal sample to obtain black titanium dioxide.
2. The method for preparing black titanium dioxide by using a low-temperature liquid-phase hydrothermal reduction method according to claim 1, wherein the method comprises the following steps: the reducing agent is hydrazine hydrate.
3. The method for preparing black titanium dioxide by using a low-temperature liquid-phase hydrothermal reduction method according to claim 2, wherein: the mass ratio of the normal titanic acid gel to the hydrazine hydrate is 1: 1 to 20.
4. The method for preparing black titanium dioxide by using a low-temperature liquid-phase hydrothermal reduction method according to claim 1, wherein the method comprises the following steps: the concentration of the NaOH solution is 4-7 mol/L.
5. The method for preparing black titanium dioxide by using a low-temperature liquid-phase hydrothermal reduction method according to claim 1, wherein the method comprises the following steps: the dosage of the NaOH solution is based on the regulation of the pH value of the system to 9-12.
6. The method for preparing black titanium dioxide by using a low-temperature liquid-phase hydrothermal reduction method according to claim 1, wherein the method comprises the following steps: the temperature of the hydrothermal reaction is 100-250 ℃, and the time is 4-48 h.
7. The method for preparing black titanium dioxide by using a low-temperature liquid-phase hydrothermal reduction method according to claim 6, wherein the method comprises the following steps: the temperature of the hydrothermal reaction is 200-250 ℃.
8. The method for preparing black titanium dioxide by using a low-temperature liquid-phase hydrothermal reduction method according to claim 1, wherein the method comprises the following steps: the washing is performed by adopting ethanol and water until the pH value is 6-7.
9. The method for preparing black titanium dioxide by using a low-temperature liquid-phase hydrothermal reduction method according to any one of claims 1 to 8, wherein the method comprises the following steps: the normal titanate gel is prepared by the following method:
and uniformly mixing tetrabutyl titanate and ethanol, adding glacial acetic acid, dropwise adding water in the stirring process until the solution is gelatinous, and drying to obtain the n-titanic acid gel.
10. The method for preparing black titanium dioxide by using a low-temperature liquid-phase hydrothermal reduction method according to claim 9, wherein: the volume ratio of tetrabutyl titanate to ethanol to glacial acetic acid is 1: 1.5-2: 0.25 to 0.3.
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