CN117046499A - S, N-TiO 2 Photocatalyst, preparation method thereof and application of photocatalyst in removal of nitrate in water - Google Patents

S, N-TiO 2 Photocatalyst, preparation method thereof and application of photocatalyst in removal of nitrate in water Download PDF

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Publication number
CN117046499A
CN117046499A CN202310924533.8A CN202310924533A CN117046499A CN 117046499 A CN117046499 A CN 117046499A CN 202310924533 A CN202310924533 A CN 202310924533A CN 117046499 A CN117046499 A CN 117046499A
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tio
photocatalyst
nitrate
water
reaction
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刘琳
彭宏运
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SD Steel Rizhao Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/30Treatment of water, waste water, or sewage by irradiation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063Titanium; Oxides or hydroxides thereof
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24Nitrogen compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08Heat treatment
    • B01J37/10Heat treatment in the presence of water, e.g. steam
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/16Nitrogen compounds, e.g. ammonia
    • C02F2101/163Nitrates

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Hydrology & Water Resources (AREA)
  • Water Supply & Treatment (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Toxicology (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to the technical field of water treatment, in particular to S, N-TiO 2 A photocatalyst, a preparation method thereof and application in removing nitrate in water. The preparation method is that hydrazine hydrate, titanium butoxide and cysteine are used as raw materials, methanol is used as a solvent, and S, N-TiO is prepared through one-step hydrothermal reaction 2 The photocatalyst has a hydrothermal reaction temperature of 150-220 ℃ and a hydrothermal reaction time of 6-24h. The invention adopts N, S atoms to TiO 2 The modification can effectively introduce an intermediate state into the band gap, reduce the band gap, generate n-p co-doping and effectively improveHigh TiO 2 Light absorption properties, S, N-TiO prepared 2 The photocatalyst has strong stability, simple synthesis process and low cost, and has industrial application potential.

Description

S, N-TiO 2 Photocatalyst, preparation method thereof and application of photocatalyst in removal of nitrate in water
Technical Field
The invention relates to the technical field of water treatment, in particular to S, N-TiO 2 A photocatalyst, a preparation method thereof and application in removing nitrate in water.
Background
Nitrite and nitrate are toxic substances, and nitrite/nitrate easily enters the body along with drinking water after entering the drinking water to cause methemoglobin, so that great threat is generated to human health. The nitrate radical removing method in water comprises a physical method, a biological method, a chemical reduction method and the like, but all have the problems of treatment cost, process complexity, removing efficiency and the like.
The related practitioners have also proposed various solutions, wherein the semiconductor photocatalysis technology is one of the leading edge and the key point of the current research, and the principle is to utilize the semiconductor to convert light energy into chemical energy under the irradiation of light, promote the synthesis of compounds or decompose organic matters and inorganic matters, and make TiO 2 The advantages of good structural stability, safety, low cost and the like are widely studied. However, it also has disadvantages of poor light absorption capability, low charge separation efficiency, limited performance under visible light irradiation, and the like. Thus, tiO is effectively improved 2 The light absorption properties of (2) are the focus of research.
CN 114177906A discloses a high-efficiency stable photocatalytic denitrification material and a preparation method thereof. TiO synthesis by hydrothermal method 2 Ultra-thin nanosheets, palladium-indium alloy is loaded on TiO by chemical deposition method 2 The PIATN catalytic material is obtained on the ultrathin nanosheets. The method effectively reduces nitrate radical in water into nitrogen through photocatalysis reaction. CN 110227516A discloses a ZnIn 2 S 4 /BiPO 4 Heterojunction photocatalyst, preparation method and application thereof. Firstly, adding bismuth nitrate and trisodium phosphate into ethylene glycol, and preparing bismuth phosphate by a hydrothermal method; secondly, adding zinc acetate, indium nitrate and cysteine into deionized water, and preparing ZnIn by a hydrothermal method 2 S 4 The method comprises the steps of carrying out a first treatment on the surface of the Finally, znIn 2 S 4 Preparation of ZnIn by adding bismuth phosphate into methanol solution 2 S 4 /BiPO 4 And a heterojunction. However, both of the above materials have a disadvantage of having many synthesis steps, resulting in an increase in synthesis cost. And palladium, indium and bismuth belong to noble metals, so that the cost of the catalytic material is high, and industrial application cannot be realized.
Disclosure of Invention
For TiO 2 As a technical problem of poor light absorption performance when the photocatalytic material is used for water treatment, the invention providesSpecies S, N-TiO 2 Photocatalyst, preparation method thereof and application of photocatalyst in removal of nitrate radical in water, and N, S atoms are adopted for TiO 2 By modifying, intermediate state can be effectively introduced into band gap, band gap is reduced, n-p co-doping is generated, and TiO is effectively improved 2 Light absorption properties, S, N-TiO prepared 2 The photocatalyst has strong stability, simple synthesis process and low cost, and has industrial application potential.
In a first aspect, the present invention provides an S, N-TiO 2 The preparation method of the photocatalyst takes hydrazine hydrate, titanium butoxide and cysteine as raw materials and methanol as a solvent, and prepares S, N-TiO through one-step hydrothermal reaction 2 The photocatalyst has a hydrothermal reaction temperature of 150-220 ℃, preferably 180 ℃, and a hydrothermal reaction time of 6-24 hours, preferably 12 hours.
Further, the molar ratio of hydrazine hydrate to titanium butoxide to Ti to cysteine to S is 1:0.4-0.6:0.05-0.25, such as 1:0.5:0.1, 1:0.5:0.2, etc.
Further, the amount of methanol to be used is determined according to the lining specification of the reaction kettle, and 80mL of methanol is preferably used for a 100mL reaction kettle.
Further, the preparation method specifically comprises the following steps:
s1: adding hydrazine hydrate and titanium butoxide into methanol and stirring;
s2: adding cysteine into the methanol solution of S1, and carrying out ultrasonic-assisted dissolution and stirring;
s3: transferring the solution stirred by the step S2 into a reaction kettle, and keeping the temperature at 150-220 ℃ for 6-24 hours for hydrothermal reaction;
s4: washing the hydrothermal product with methanol and water, and drying to obtain yellowish product S, N-TiO 2 A photocatalyst.
In a second aspect, the present invention provides an S, N-TiO composition comprising 2 A photocatalyst.
In a third aspect, the present invention also provides the above S, N-TiO 2 Use of a photocatalyst to remove nitrate from water.
Further, S, N-TiO 2 PhotocatalysisAdding the agent into nitrate-containing water, controlling the pH value to be 1-3, performing photocatalysis reaction after dark adsorption for 1h, wherein the photocatalysis reaction time is 1-6h.
Further, both the dark adsorption and the photocatalytic reaction are carried out at normal temperature.
Further, the nitrate concentration in the water is 0.01-0.2g/L.
Furthermore, the nitrate radical removal rate in water reaches more than 90 percent.
The invention has the beneficial effects that:
the invention prepares N-TiO by taking titanium butoxide as a titanium source and hydrazine hydrate as a nitrogen source 2 The nitrogen doping has wide prospect in photocatalysis due to the equivalent atomic size, small ionization energy and stability, methanol is taken as a solvent to be beneficial to improving the photocatalytic activity of the photocatalyst, and cysteine is taken as a sulfur source to N-TiO 2 The modification is carried out to narrow the lattice band gap, the red shift occurs, the light response performance and the light catalytic activity of the photocatalyst under the condition of visible light are improved, and the reaction and the crystal growth are effectively controlled by adjusting the reaction temperature, the reaction time and other factors of the one-step hydrothermal reaction. S, N-TiO prepared 2 The photocatalyst is light yellow, and is more white than white N-TiO 2 Has better light absorption.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the description of the embodiments or the prior art will be briefly described below, and it will be obvious to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is an SEM photograph of the photocatalyst prepared in examples 1-3 and comparative example 1.
FIG. 2 is an XRD pattern of the photocatalyst prepared in examples 1-3.
FIG. 3 is an S, N-TiO of application example 1 2 -2 comparison of nitrate removal effect of photocatalyst at different pH values.
FIG. 4 is an S, N-TiO of application example 2 2 -2 comparison of the effect of the photocatalyst on nitrate removal at different nitrate contents.
FIG. 5 is S, N-TiO in application example 3 2 -2 comparison of nitrate removal effect of photocatalyst at different addition amounts.
FIG. 6 is a graph showing the comparison of nitrate removal effects of different photocatalysts in application example 4.
FIG. 7 is a graph showing the comparison of nitrate removal effects of different photocatalysts in application example 5.
In fig. 3 to 7, the point in time when the horizontal axis ends the dark reaction and starts the photocatalytic reaction is 0 point, and the portion with the horizontal axis coordinate <0 represents the dark reaction and the portion with the horizontal axis coordinate >0 corresponds to the photocatalytic reaction.
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
EXAMPLE 1S, N-TiO 2 Preparation of the photocatalyst-1
S1: accurately transferring 0.7679mL of hydrazine hydrate and 5.3991mL of titanium butoxide, adding the hydrazine hydrate and the 5.3991mL of titanium butoxide into 80mL of methanol, and stirring for 20min;
s2: accurately weighing 0.2863g of cysteine, adding the cysteine into the methanol solution of S1, performing ultrasonic-assisted dissolution, and stirring for 30min;
s3: transferring the solution after stirring the S2 into a sealed reaction kettle (polytetrafluoroethylene lining), and keeping the solution at 180 ℃ for 12 hours for hydrothermal reaction;
s4: after the reaction is completed, the hydrothermal product is washed by methanol and water and dried, and the obtained yellowish product is S, N-TiO 2 -1 a photocatalyst.
S, N-TiO pairs using scanning electron microscopy (S-4800) 2 1. The micro-morphology of the photocatalyst was observed and the results are shown in FIG. 1B.
EXAMPLE 2S, N-TiO 2 -2Preparation of photocatalyst
S1: accurately transferring 0.7679mL of hydrazine hydrate and 5.3991mL of titanium butoxide, adding the hydrazine hydrate and the 5.3991mL of titanium butoxide into 80mL of methanol, and stirring for 20min;
s2: accurately weighing 0.3817g of cysteine, adding the cysteine into the methanol solution of S1, performing ultrasonic-assisted dissolution, and stirring for 30min;
s3: transferring the solution after stirring the S2 into a sealed reaction kettle (polytetrafluoroethylene lining), and keeping the solution at 180 ℃ for 12 hours for hydrothermal reaction;
s4: after the reaction is completed, the hydrothermal product is washed by methanol and water and dried, and the obtained yellowish product is S, N-TiO 2 -2 a photocatalyst.
S, N-TiO pairs using scanning electron microscopy (S-4800) 2 2 the micro-morphology of the photocatalyst was observed and the results are shown in FIG. 1C.
EXAMPLE 3S, N-TiO 2 Preparation of the photocatalyst
S1: accurately transferring 0.7679mL of hydrazine hydrate and 5.3991mL of titanium butoxide, adding the hydrazine hydrate and the 5.3991mL of titanium butoxide into 80mL of methanol, and stirring for 20min;
s2: accurately weighing 0.4771g of cysteine, adding the cysteine into the methanol solution of S1, performing ultrasonic-assisted dissolution, and stirring for 30min;
s3: transferring the solution after stirring the S2 into a sealed reaction kettle (polytetrafluoroethylene lining), and keeping the solution at 180 ℃ for 12 hours for hydrothermal reaction;
s4: after the reaction is completed, the hydrothermal product is washed by methanol and water and dried, and the obtained yellowish product is S, N-TiO 2 -3 a photocatalyst.
S, N-TiO pairs using scanning electron microscopy (S-4800) 2 3 the micro-morphology of the photocatalyst was observed and the results are shown in FIG. 1D.
The products obtained in examples 1-3 were analyzed by means of an X-ray diffractometer (Ultima IV) and the results are shown in FIG. 2. XRD patterns indicate that S, N-TiO 2 -1、S,N-TiO 2 -2、S,N-TiO 2 -3 all diffraction peaks correspond to anatase TiO 2 (PDF # 21-1272), no impurity diffraction peak appears in the spectrum, indicating that the introduction of sulfur does not affect the crystallinity of titanium dioxide.
Comparative example 1N-TiO 2 Preparation of photocatalyst
Comparative example 1 was substantially identical to the preparation procedure of example 2, except that the step of adding cysteine was absent.
S1: accurately transferring 0.7679mL of hydrazine hydrate and 5.3991mL of titanium butoxide, adding the hydrazine hydrate and the 5.3991mL of titanium butoxide into 80mL of methanol, and stirring for 20min;
s2: transferring the solution stirred in the step S1 into a sealed reaction kettle (polytetrafluoroethylene lining), and keeping the solution at 180 ℃ for 12 hours for hydrothermal reaction;
s3: after the reaction is completed, the hydrothermal product is washed by using methanol and water and dried, and the obtained white product is N-TiO 2 A photocatalyst.
N-TiO using scanning electron microscope (S-4800) 2 The microscopic morphology of the photocatalyst was observed, and the result is shown in fig. 1A.
N-TiO in SEM photograph 2 (fig. 1A) is a microsphere, the microsphere is modified by adopting S, and as the proportion of S increases, the number of nanospheres increases (fig. 1B and 1C), so that the specific surface area of the microsphere is effectively increased, the reaction sites of the photocatalyst are increased, and the reduction efficiency of nitrate radical is improved. However, as the proportion of S continues to increase, the nanospheres agglomerate (fig. 1D), impeding the contact of photogenerated carriers, resulting in a decrease in catalytic performance.
Comparative example 2S, N-TiO 2 Preparation of the-4 photocatalyst
Comparative example 2 the preparation procedure was essentially the same as example 2, except that ethanol was used as solvent instead of methanol.
S1: accurately transferring 0.7679mL of hydrazine hydrate and 5.3991mL of titanium butoxide, adding the hydrazine hydrate and the 5.3991mL of titanium butoxide into 80mL of ethanol, and stirring for 20min;
s2: accurately weighing 0.3817g of cysteine, adding the cysteine into the ethanol solution of S1, performing ultrasonic-assisted dissolution, and stirring for 30min;
s3: transferring the solution after stirring the S2 into a sealed reaction kettle (polytetrafluoroethylene lining), and keeping the solution at 180 ℃ for 12 hours for hydrothermal reaction;
s4: after the reaction is completed, the hydrothermal product is washed by methanol and water and dried, and the obtained yellowish product is S, N-TiO 2 -4 a photocatalyst.
Comparative example 3S, N-TiO 2 Preparation of the photocatalyst
Comparative example 3 was substantially identical to the preparation procedure of example 2, except that acetone was used as a solvent instead of methanol.
S1: accurately transferring 0.7679mL of hydrazine hydrate and 5.3991mL of titanium butoxide, adding the hydrazine hydrate and the 5.3991mL of titanium butoxide into 80mL of acetone, and stirring for 20min;
s2: accurately weighing 0.3817g of cysteine, adding the cysteine into an acetone solution of S1, performing ultrasonic-assisted dissolution, and stirring for 30min;
s3: transferring the solution after stirring the S2 into a sealed reaction kettle (polytetrafluoroethylene lining), and keeping the solution at 180 ℃ for 12 hours for hydrothermal reaction;
s4: after the reaction is completed, the hydrothermal product is washed by methanol and water and dried, and the obtained yellowish product is S, N-TiO 2 -5 a photocatalyst.
Application example 1
S, N-TiO prepared using example 2 2 -2 removing nitrate radical in water by a photocatalyst, which comprises the following specific steps:
1) Four portions of 40mL aqueous solution containing 60mg/L nitrate were taken and the pH values of the solutions were adjusted to 1, 2, 3, and 4 with HCl, respectively.
2) 40mg of S, N-TiO are added to each of the four nitrate solutions of 1) 2 The photocatalyst is firstly subjected to dark adsorption for 1h at normal temperature, and then the photocatalytic reaction is carried out in a photocatalytic reaction box for 2h.
3) Centrifuging the solution after the reaction of 2) to separate the solid from the liquid.
4) The concentration of nitrate in the effluent after photocatalysis is detected by an alkaline potassium persulfate digestion ultraviolet spectrophotometry, and the result is shown in figure 3.
FIG. 3 shows that S, N-TiO at pH 2 2 The photocatalyst shows better photocatalytic property, and the nitrate concentration is reduced from the initial 60mg/L to less than 5mg/L.
Application example 2
S, N-TiO prepared using example 2 2 -2 removing nitrate radical in water by a photocatalyst, which comprises the following specific steps:
1) Four 40mL portions of aqueous solutions (40, 60, 80, 100 mg/L) of different nitrate contents were taken and the pH of the solution was adjusted to 2 using HCl.
2) 40mg of S, N-TiO are added to each of the four nitrate solutions of 1) 2 The photocatalyst is firstly subjected to dark adsorption for 1h at normal temperature, and then is subjected to photocatalytic reaction in a photocatalytic reaction box for 2h.
3) Centrifuging the solution after the reaction of 2) to separate the solid from the liquid.
4) The concentration of nitrate in the effluent after photocatalysis is detected by an alkaline potassium persulfate digestion ultraviolet spectrophotometry, and the result is shown in figure 4.
Application example 3
S, N-TiO prepared using example 2 2 -2 removing nitrate radical in water by a photocatalyst, which comprises the following specific steps:
1) Four portions of 40mL aqueous solution containing 60mg/L nitrate were taken and the pH of the solution was adjusted to 2 using HCl.
2) S, N-TiO of different masses are added to the four nitrate solutions of 1) respectively 2 The photocatalyst (20, 30, 40, 50 mg) is firstly subjected to dark adsorption for 1h at normal temperature, and then is subjected to photocatalytic reaction in a photocatalytic reaction box for 2h.
3) Centrifuging the solution after the reaction of 2) to separate the solid from the liquid.
4) The concentration of nitrate in the effluent after photocatalysis is detected by an alkaline potassium persulfate digestion ultraviolet spectrophotometry, and the result is shown in figure 5.
Application example 4
The photocatalysts prepared in examples 1-3 and comparative example 1 were used to remove nitrate in water, respectively, as follows:
1) Four portions of 40mL aqueous solution containing 60mg/L nitrate were taken and the pH of the solution was adjusted to 2 using HCl.
2) 40mg of photocatalyst is added into each of the four parts of nitrate radical solution in the step 1), dark adsorption is carried out for 1h at normal temperature, and then photocatalysis reaction is carried out for 2h in a photocatalysis reaction box.
3) Centrifuging the solution after the reaction of 2) to separate the solid from the liquid.
4) The concentration of nitrate in the effluent after photocatalysis is detected by an alkaline potassium persulfate digestion ultraviolet spectrophotometry, and the result is shown in figure 6.
Application example 5
The photocatalysts prepared in example 2 and comparative examples 2-3 were used to remove nitrate in water, respectively, and the specific steps are as follows:
1) Four portions of 40mL aqueous solution containing 60mg/L nitrate were taken and the pH of the solution was adjusted to 2 using HCl.
2) 40mg of photocatalyst is added into each of the four parts of nitrate radical solution in the step 1), dark adsorption is carried out for 1h at normal temperature, and then photocatalysis reaction is carried out for 2h in a photocatalysis reaction box.
3) Centrifuging the solution after the reaction of 2) to separate the solid from the liquid.
4) The concentration of nitrate in the effluent after photocatalysis is detected by an alkaline potassium persulfate digestion ultraviolet spectrophotometry, and the result is shown in figure 7.
Although the present invention has been described in detail by way of preferred embodiments with reference to the accompanying drawings, the present invention is not limited thereto. Various equivalent modifications and substitutions may be made in the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and it is intended that all such modifications and substitutions be within the scope of the present invention/be within the scope of the present invention as defined by the appended claims.

Claims (9)

1. S, N-TiO 2 The preparation method of the photocatalyst is characterized in that hydrazine hydrate, titanium butoxide and cysteine are used as raw materials, methanol is used as a solvent, and S, N-TiO is prepared through one-step hydrothermal reaction 2 The photocatalyst has a hydrothermal reaction temperature of 150-220 ℃ and a hydrothermal reaction time of 6-24h.
2. The method of claim 1, wherein hydrazine hydrate is calculated as N, titanium butoxide is calculated as Ti, cysteine is calculated as S, N: ti: s molar ratio = 1:0.4-0.6:0.05-0.25.
3. The preparation method according to claim 1, comprising the specific steps of:
s1: adding hydrazine hydrate and titanium butoxide into methanol and stirring;
s2: adding cysteine into the methanol solution of S1, and carrying out ultrasonic-assisted dissolution and stirring;
s3: transferring the solution stirred by the step S2 into a reaction kettle, and keeping the temperature at 150-220 ℃ for 6-24 hours for hydrothermal reaction;
s4: washing the hydrothermal product with methanol and water, and drying to obtain yellowish product S, N-TiO 2 A photocatalyst.
4. An S, N-TiO film prepared by the preparation method as claimed in any one of claims 1 to 3 2 A photocatalyst.
5. An S, N-TiO as defined in claim 4 2 Use of a photocatalyst to remove nitrate from water.
6. The method according to claim 5, wherein S, N-TiO 2 Adding the photocatalyst into nitrate-containing water, controlling the pH value to be 1-3, performing photocatalysis reaction after dark adsorption for 1h, wherein the photocatalysis reaction time is 1-6h.
7. The method according to claim 5, wherein the dark adsorption and the photocatalytic reaction are carried out at room temperature.
8. The use according to claim 5, wherein the nitrate concentration in water is 0.01-0.2g/L.
9. The use according to claim 8, wherein the nitrate removal rate in water is up to 90%.
CN202310924533.8A 2023-07-26 2023-07-26 S, N-TiO 2 Photocatalyst, preparation method thereof and application of photocatalyst in removal of nitrate in water Pending CN117046499A (en)

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