CN110193371B - S 6+ /S 4+ Sulfur-doped TiO with controllable ratio, shape and crystal form 2 Preparation method of visible light photocatalyst - Google Patents

S 6+ /S 4+ Sulfur-doped TiO with controllable ratio, shape and crystal form 2 Preparation method of visible light photocatalyst Download PDF

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CN110193371B
CN110193371B CN201910469690.8A CN201910469690A CN110193371B CN 110193371 B CN110193371 B CN 110193371B CN 201910469690 A CN201910469690 A CN 201910469690A CN 110193371 B CN110193371 B CN 110193371B
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sulfur
tio
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CN110193371A (en
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王家强
姜亮
陈永娟
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Yunnan University YNU
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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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/053—Sulfates
    • B01J35/39—
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The present invention provides a method for producing S 6+ /S 4+ Sulfur-doped TiO with controllable ratio, shape and crystal form 2 A method of preparing a visible light photocatalyst, the method comprising: firstly, dissolving a sulfur source into deionized water, and marking as a solution A; then uniformly mixing acetone, hydrochloric acid, acetylacetone and titanium tetraisopropoxide, marking as a solution B, dropwise adding the solution A into the solution B, transferring the formed suspension into a high-temperature high-pressure reaction kettle, and reacting at the heating temperature of 100-300 ℃ for 10 min-10 h; then cooling to room temperature, washing the obtained solid product with acetone and deionized water in sequence, and drying to obtain the sulfur-doped TiO 2 A visible light photocatalyst. The sulfur-doped TiO prepared by the method of the invention 2 S of visible light catalyst 6+ /S 4+ The ratio, the shape and the crystal form are controllable, the method is simple to operate, the product preparation cost is low, the sulfur source is cheap and easy to obtain, the toxicity is low, and the harm to the environment or human body is avoided.

Description

S 6+ /S 4+ Sulfur-doped TiO with controllable ratio, shape and crystal form 2 Preparation method of visible light photocatalyst
Technical Field
The invention belongs to the technical field of photocatalytic coatings, and relates to S 6+ /S 4+ Sulfur-doped TiO with controllable ratio, shape and crystal form 2 A preparation method of a photocatalyst material, in particular to a method for preparing S by a hydrothermal method 6+ /S 4+ Sulfur-doped TiO (titanium dioxide) with controllable ratio, morphology and crystal form 2 A visible light catalyst.
Background
The photocatalysis has the unique properties of deep reaction at room temperature, direct utilization of solar energy as a light source to drive the reaction and the like, and becomes an ideal environmental pollution treatment technology and a clean energy production technology.
In recent years, environmental pollution has become more serious, and researches on catalytic degradation of organic matters by using semiconductor powder as a photocatalyst have become hot. TiO 2 2 High activity, good chemical stability and no harm to human body, is an ideal environment-friendly photocatalyst and is more and more widely applied at present. Wherein, tiO 2 Has good application prospect in the aspects of sewage treatment and the like, but because the compound can not absorb visible light basically in a visible light area (more than 450 nm), the utilization rate of the compound is only 3 to 5 percent for sunlight, and the compound is used for realizing TiO 2 The visible light catalysis technology can be applied under natural conditions, and people modify the visible light catalysis technology by means of doping and the like to improve the visibility of the visible light catalysis technologyActivity in the light region.
Preparation of sulfur-doped TiO in the prior art 2 Thiourea and TiS are usually used 2 And CS 2 The sulfur source is used, but the use of the sulfur source has the defect of high cost, and most importantly, the sulfur source has high toxicity and can cause harm to the environment or human bodies. Thiourea is decomposed by heating, toxic gases such as oxides of nitrogen and sulfur are emitted, and meanwhile, the thiourea is harmful to the environment, toxic to aquatic organisms and possibly has long-term adverse effects on the water environment; meanwhile, the medicine can be inhaled through skin after being contacted for a long time, so that the functions of thyroid and hematopoietic organs are inhibited, central nerve paralysis, reduction of respiratory and cardiac functions and other symptoms are caused, and the health of a human body is harmed. The preparation method in the prior art can only realize S singly 6+ 、S 4+ Or S 6+ /S 4+ Doping to prepare visible light catalyst, S can not be realized 6+ /S 4+ The doping proportion and the regulation and control of solid crystalline phase and morphology, and further the visible light catalytic activity is regulated.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a standby S 6+ /S 4+ Sulfur-doped TiO (titanium dioxide) with controllable ratio, morphology and crystal form 2 Preparation method of visible light photocatalyst and sulfur-doped TiO prepared by same 2 S of catalytic material 6+ /S 4+ The ratio, the shape and the crystal form are controllable, the method is simple to operate, the product preparation cost is low, the sulfur source is cheap and easy to obtain, the toxicity is low, and the harm to the environment or human body is avoided.
The technical scheme for realizing the purpose is as follows:
s 6+ /S 4+ Sulfur-doped TiO (titanium dioxide) with controllable ratio, morphology and crystal form 2 The preparation method of the visible light photocatalyst comprises the following steps:
s1: weighing a sulfur source according to the required amount of the reaction, and dissolving the sulfur source into deionized water to obtain a solution A;
s2: uniformly stirring and mixing acetone, hydrochloric acid, acetylacetone and Titanium Tetraisopropoxide (TTIP), and marking as a solution B, wherein the volume ratio of the acetone, the hydrochloric acid, the acetylacetone and the TTIP is 300-400: 86-100: 9-12: 90-110; the mass concentration of the hydrochloric acid is preferably 36-38%.
S3: under the condition of stirring, dropwise adding the solution A into the solution B, transferring the formed suspension into a high-temperature high-pressure reaction kettle with a polytetrafluoroethylene lining, and reacting at the heating temperature of 100-300 ℃ for 10 min-10 h, preferably 2-5 h;
s4: then naturally cooling to room temperature, centrifugally washing the obtained solid product with acetone and deionized water in sequence, and drying at the temperature of over 90 ℃ overnight to obtain the sulfur-doped TiO 2 A photocatalyst.
Further, in the step S1, the amount of the sulfur source is 0.1 to 15mmol, preferably 1 to 10mmol, in terms of elemental sulfur.
In the step S1, the dosage of the deionized water is 2-30 ml, preferably 5-20 ml.
The sulfur source is metal sulfate or concentrated sulfuric acid, preferably transition metal sulfate; the metal sulfate is selected from FeSO 4 、Na 2 SO 4 、ZnSO 4 、MnSO 4 、 Fe 2 (SO 4 ) 3 Preferably FeSO 4 、ZnSO 4 、MnSO 4 、Fe 2 (SO 4 ) 3 。
SO in the Sulfur Source of the invention 4 2- Both as an S source and as a phase selector.
In the step S1 of this application, the solution a is provided with a sulfur source and water, and the solution a is added dropwise to the solution B, and the water serves to hydrolyze TTIP (titanium source, titanium tetraisopropoxide). In the step S2, no chemical reaction occurs in the solution B, but TTIP (titanium source, titanium tetraisopropoxide) is dissolved, in which acetone is used as a solvent, and hydrochloric acid and acetylacetone are used as hydrolysis inhibitors. And (4) dropwise adding the solution A in the step (S3) into the solution B to generate a suspension formed by hydrolysis of TTIP (titanium source, titanium tetraisopropoxide). In the step S4, the acetone is used for removing residual organic matters in the prepared material, and the water is used for mainly removing residual hydrochloric acid (hydrochloric acid).
The sulfate ions in the sulfur source of the present invention react with TiO via electrostatic interaction 6 2- Octahedral hydroxyl groupsAnd the anatase and the other crystal phases are mutually interacted, so that the generation of the anatase crystal phase is promoted, and the anatase crystal phase is inhibited from being converted into the other crystal phases, and the crystal form of the prepared catalyst is controllable. Meanwhile, sulfate ions have specific adsorption on different crystal faces in the crystal growth process, and the specific adsorption can change the growth direction of the material from a conventional crystal face to a crystal face with specific adsorption, so that the morphology of the catalyst is controlled.
When metal sulfate is used as the sulfur source, the metal ion in the metal sulfate promotes S 4+ Generated and doped, and metal ions are not doped into TiO 2 Crystal lattice, S can be regulated and controlled by different metal ions 6+ /S 4+ The doping ratio of (a).
Thus, the sulfur-doped TiO prepared by the process of the present invention 2 S of catalytic material 6+ /S 4+ The ratio, the morphology and the crystal form are controllable, the method is simple to operate, the product preparation cost is low, the equipment requirement is low, the sulfur source is cheap and easy to obtain, the toxicity is low, and the method cannot cause harm to the environment or human bodies.
Drawings
Fig. 1 is an X-ray diffraction (XRD pattern) of the prepared sample.
FIG. 2 is at SO 4 2- Transmission Electron Microscope (TEM) images in the presence of conditions. Wherein (a) is FeSO 4 -TiO 2 (ii) a (b) Shown as Na 2 SO 4 -TiO 2 (ii) a (c) As shown by ZnSO 4 -TiO 2 (ii) a (d) The figure is MnSO 4 -TiO 2 (ii) a (e) It is shown as Fe 2 (SO 4 ) 3 -TiO 2 (ii) a (f) Drawing H 2 SO 4 -TiO 2 。
FIG. 3 is a transmission electron micrograph [ TEM image (a) ] and HTEM image (b) of the blank control material (PT).
FIG. 4 is a S2p XPS high resolution scan spectrum. Wherein (a) is FeSO 4 -TiO 2 (ii) a (b) It is shown as Fe 2 (SO4) 3 -TiO 2 (ii) a (c) Is shown as ZnSO 4 -TiO 2 (ii) a (d) Shown as MnSO 4 -TiO 2 (ii) a (e) Drawing H 2 SO 4 -TiO 2 。
Detailed Description
The present invention will be further described with reference to the following examples.
According to the transition metal salt sulfate added in the preparation process, the materials are respectively named as FeSO 4 -TiO 2 ，Fe 2 (SO 4 ) 3 -TiO 2 ，ZnSO 4 -TiO 2 And MnSO 4 -TiO 2 。
According to the added different sulfur source metal sodium salts, the material is named Na 2 SO 4 -TiO 2 ，Na 2 SO 3 -TiO 2 And Na 2 S-TiO 2 。
With sulfuric acid, feCl 3 ·6H 2 O and FeCl 2 ·4H 2 The materials prepared by O are respectively marked as H 2 SO 4 -TiO 2 ，FeCl 3 -TiO 2 And FeCl 2 -TiO 2 。
The blank material was noted PT.
Example 1: with FeSO 4 -TiO 2 The preparation method of (1) is as follows:
(1) 2.035g of FeSO 4 ·7H 2 Dissolving O (7.3mmol of Fe and 7.3mmol of S) in 5mL of deionized water, and marking as a solution A;
(2) Stirring and uniformly mixing 20mL of acetone, 3mL of hydrochloric acid, 0.54mL of acetylacetone and 6.5mL of TTIP, and marking as a solution B;
(3) Dropwise adding the solution A into the solution B under the condition of vigorous stirring, transferring the formed suspension into a high-temperature high-pressure reaction kettle with a 100mL polytetrafluoroethylene lining, and reacting for 4 hours at 200 ℃;
(4) After naturally cooling to room temperature, the obtained solid product is centrifugally washed by acetone and deionized water respectively, and then dried at 90 ℃ overnight.
Comparative example 1: feCl 3 -TiO 2 And FeCl 2 -TiO 2 The preparation method comprises the following steps:
according to the same Fe addition (7.3 mmol), feSO in step (1) is added 4 ·7H 2 Replacement of O by FeCl of corresponding mass 3 ·6H 2 O and FeCl 2 ·4H 2 And O, the other steps are the same.
Comparative example 2: the preparation method of the blank control group PT comprises the following steps:
the preparation of the salt solution A in step S1 was omitted and 5mL of deionized water was added dropwise directly to the solution B in step S2 with vigorous stirring, as in example 1, which was followed.
Example 2: with Fe 2 (SO 4 ) 3 -TiO 2 The preparation method of (1) is as follows:
(1) 0.667g of Fe 2 (SO 4 ) 3 (S is 5.0 mmol) is dissolved in 6mL of deionized water and is marked as solution A;
(2) Stirring and uniformly mixing 40mL of acetone, 10mL of hydrochloric acid, 0.3mL of acetylacetone and 2mL of TTIP, and marking as a solution B;
(3) Dropwise adding the solution A into the solution B under the condition of vigorous stirring, transferring the formed suspension into a high-temperature high-pressure reaction kettle with a 100mL polytetrafluoroethylene lining, and reacting for 6 hours at 150 ℃;
(4) After naturally cooling to room temperature, the obtained solid product is centrifugally washed by acetone and deionized water respectively, and then dried at 95 ℃ overnight.
EXAMPLE 3 ZnSO 4 -TiO 2 The preparation method of (3) is as follows:
(1) 2.875g of ZnSO 4 ·7H 2 Dissolving O (S is 10 mmol) in 8mL of deionized water, and marking as a solution A;
(2) Stirring and uniformly mixing 100mL of acetone, 25mL of hydrochloric acid, 1mL of acetylacetone and 25mL of TTIP, and marking as a solution B;
(3) Dropwise adding the solution A into the solution B under the condition of vigorous stirring, transferring the formed suspension into a high-temperature high-pressure reaction kettle with a 100mL polytetrafluoroethylene lining, and reacting for 6 hours at 150 ℃;
(4) After naturally cooling to room temperature, the obtained solid product is centrifugally washed by acetone and deionized water respectively, and then dried at 90 ℃ overnight.
Example 4 as MnSO 4 -TiO 2 The preparation method of (1) is as follows:
(1) 0.034g of MnSO 4 ·H 2 Dissolving O (S is 0.2 mmol) in 3mL of deionized water, and marking as a solution A;
(2) Stirring and uniformly mixing 30mL of acetone, 1mL of hydrochloric acid, 1mL of acetylacetone and 10mL of TTIP, and marking as a solution B;
(3) Dropwise adding the solution A into the solution B under the condition of vigorous stirring, transferring the formed suspension into a high-temperature high-pressure reaction kettle with a 100mL polytetrafluoroethylene lining, and reacting for 4 hours at 260 ℃;
(4) After naturally cooling to room temperature, the obtained solid product is centrifugally washed by acetone and deionized water respectively, and then dried at 110 ℃ overnight.
Example 5 with Na 2 SO 4 -TiO 2 The preparation method of (1) is as follows:
(1) 1.704g of Na 2 SO 4 (S is 12 mmol) is dissolved in 6mL deionized water and is marked as solution A;
(2) Stirring and uniformly mixing 90mL of acetone, 25mL of hydrochloric acid, 2.8mL of acetylacetone and 12mL of TTIP, and marking as a solution B;
(3) Dropwise adding the solution A into the solution B under the condition of vigorous stirring, transferring the formed suspension into a high-temperature high-pressure reaction kettle with a 100mL polytetrafluoroethylene lining, and reacting for 8 hours at 120 ℃;
(4) After naturally cooling to room temperature, the obtained solid product is centrifugally washed by acetone and deionized water respectively, and then dried at 100 ℃ overnight.
Example 6 as H 2 SO 4 -TiO 2 The preparation method of (1) is as follows:
(1) 0.392g of sulfuric acid (S4 mmol) was dissolved in 5mL of deionized water and designated as solution A;
(2) Stirring and uniformly mixing 60mL of acetone, 15mL of hydrochloric acid, 1.5mL of acetylacetone and 15mL of TTIP, and marking as a solution B;
(3) Dropwise adding the solution A into the solution B under the condition of vigorous stirring, transferring the formed suspension into a high-temperature high-pressure reaction kettle with a 100mL polytetrafluoroethylene lining, and reacting for 7 hours at 130 ℃;
(4) After naturally cooling to room temperature, the obtained solid product is centrifugally washed by acetone and deionized water respectively, and then dried at 130 ℃ overnight.
As can be seen from FIG. 1, the prepared sample was analyzed by XRD and found to have a high SO content 4 2- Under the existing preparation conditions, the prepared materials are all anatase single crystal forms. In the absence of SO 4 2- Under the preparation condition of (3), the prepared material is anatase, brookite and rutile three-phase mixed crystal type TiO 2 。
As can be seen from FIG. 2, in SO 4 2- In the TEM image under the existing condition, the materials are all spherical, ellipsoidal and blocky, and the shapes are similar.
As can be seen from FIG. 3, there is no SO present 4 2- In the presence of PT in flower or rod form, respectively, from elongated, prismatic rutile TiO 2 Stacked to anatase, brookite TiO 2 The nanoparticles are attached to the surface thereof with lattice spacings of 0.325,0.290 and 0.352nm corresponding to the rutile (110), brookite (121) and anatase (101) interplanar spacings, respectively.
As can be seen from fig. 4, from the analysis results, it can be seen that: (1) SO (SO) 4 2- Not only plays a role in controlling crystalline phase and morphology in the preparation process, but also can be used as an S source to prepare S 6+ /S 4+ Doped TiO 2 (ii) a (2) Preparation of material from transition metal sulfate, metal ion can promote S 4+ Generation and doping of (2) and with modulation of S 6+ /S 4+ Effect of the ratio, with SO only being present 4 2- Root (dense H) 2 SO 4 Preparation) of the material is only S 6+ And (4) doping. With FeSO 4 -TiO 2 For example, the four fitting peaks in FIG. 4 (a) correspond to different doping patterns of sulfur atoms, i.e., S 6+ Doping and S 4+ And (4) doping. S 6+ 2p of 3/2 And 2p 1/2 Peaks were at 168.6 and 169.7eV 4+ 2p of 3/2 And 2p 1/2 Peaks were at 166.5 and 167.7eV, respectively. According to the study, S 6+ And S 4+ Doped form is SO 4 2- And SO 3 2- Coordinated to Ti through a bidentate bond, a Ti-O-S bond is formed.
From the analysis results, it can be seen that: (1) SO 4 2- Not only plays a role in controlling crystalline phase and morphology in the preparation process, but also can be used as an S source to prepare S 6+ /S 4+ Doped TiO 2 ；
(2) Preparation of material from transition metal sulfate, metal ion can promote S 4+ With modulated S 6+ /S 4+ Effect of the ratio, with only SO present 4 2- Root (dense H) 2 SO 4 Preparation) of the material is only S 6+ And (4) doping.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions.

Claims (1)

1. S 6+ /S 4+ Sulfur-doped TiO with controllable ratio, shape and crystal form 2 The preparation method of the visible light photocatalyst comprises the following preparation steps:
(1) 0.667g of Fe 2 (SO 4 ) 3 Dissolving in 6mL of deionized water, and marking as a solution A;
(2) Stirring and uniformly mixing 40mL of acetone, 10mL of hydrochloric acid, 0.3mL of acetylacetone and 2mL of titanium tetraisopropoxide, and marking as a solution B;
(3) Dropwise adding the solution A into the solution B under the condition of vigorous stirring, transferring the formed suspension into a high-temperature high-pressure reaction kettle with a 100mL polytetrafluoroethylene lining, and reacting for 6 hours at 150 ℃;
(4) After naturally cooling to room temperature, the obtained solid product is centrifugally washed by acetone and deionized water respectively, and then dried at 95 ℃ overnight.
CN201910469690.8A 2019-05-31 2019-05-31 S 6+ /S 4+ Sulfur-doped TiO with controllable ratio, shape and crystal form 2 Preparation method of visible light photocatalyst Active CN110193371B (en)

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CN102380403A (en) * 2011-09-28 2012-03-21 华东理工大学 Method for preparing visible photo-catalyst of titanium dioxide doped with sulphur
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