CN115364838A - TiO2 2 /CuS/TiO 2 Composite photo-thermal catalytic material and preparation method thereof - Google Patents
TiO2 2 /CuS/TiO 2 Composite photo-thermal catalytic material and preparation method thereof Download PDFInfo
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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
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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
- B01J27/04—Sulfides
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- B01J35/39—
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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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 TiO compound 2 /CuS/TiO 2 The invention discloses a composite photo-thermal catalytic material and a preparation method thereof 2 A thin layer. The composite photothermal catalytic material prepared by the invention has high specific surface area and good stability, the reticular photothermal catalyst is easy to be applied to a flow reactor, and the secondary recycling is easy to realize after pollutants are degradedThe catalyst has strong absorption in visible light and near infrared light regions, has high photo-thermal catalytic efficiency, and realizes high-efficiency degradation under the conditions of visible light and infrared light.
Description
Technical Field
The invention belongs to the technical field of photo-thermal catalytic materials, and particularly relates to TiO 2 /CuS/TiO 2 A composite photo-thermal catalytic material and a preparation method thereof.
Background
Has very important significance for the global energy crisis and the environmental pollution problem and the development of high-efficiency and clean renewable energy. Solar energy is a potential energy source which meets the global energy demand and promotes the world sustainable development as the most extensive renewable energy source. Since the advent of semiconductor photocatalytic technology, the conversion of solar energy into chemical energy has become a research hotspot. However, the traditional photocatalytic technology has low spectral utilization rate, and the practical application of the traditional photocatalytic technology is greatly limited. The photothermal catalysis refers to that the catalyst with the photothermal effect absorbs ultraviolet light, visible light and infrared light in sunlight by utilizing the characteristics of the catalyst, converts the ultraviolet light, the visible light and the infrared light into chemical energy and heat energy, and further raises the temperature of the catalyst, so that the photothermal effect synergistically induces the catalytic reaction. Compared with traditional photocatalysis, photothermal catalysis tends to have higher catalytic efficiency.
CuS is a narrow band gap semiconductor (2.0 eV), is a nontoxic, cheap and stable photocatalyst, is an ideal semiconductor material for environmental pollution treatment, and is a photo-thermal material capable of being excited under 660nm visible light and near infrared light to generate heat. The narrow band gap semiconductor CuS is mixed with TiO 2 The coupling can effectively reduce the recombination of photo-generated electron-hole pairs, the service life of photo-generated carriers is prolonged, meanwhile, the activation of molecular oxygen in the oxidation-reduction reaction process can be promoted by the heat energy generated by the excitation of CuS, and the catalytic reaction efficiency is promoted by the cooperation of photo-heat and photo-heat.
At present, most TiO compounds 2 the/CuS composite material is in a powder shape, is difficult to separate and recover from a treated solution after pollutants are degraded, and is easy to generate secondary pollution. Synthesis of TiO by Royal et al by hydrothermal method 2 CuS powder photothermal catalytic material (Solid State Sciences, 2019). In situ synthesis of CuS/TiO by LiguoGao, jingwenDu et al using cysteine as a sulfur source and a chelating agent 2 Powder photocatalyst (Ceramics International, 2017). ZHenWu, xingqiiangliu et al prepared TiO by precipitation 2 CuS powder photocatalystThe oxidizing agent has a better removing rate to hexavalent cadmium (Science of The Total environmental, 2021).
In recent years, the stationary phase catalyst has attracted wide attention, and CuS/TiO is immobilized by regenerated cellulose of corn stalk 2 Method for preparing fixed-phase CuS/TiO by using composite aerogel 2 Composite aerogel photocatalytic material (publication number: CN 111215143B). Shufanjia, xinyuLi et al adopts continuous ion layer adsorption reaction method to decorate CuS nanocluster on TiO2 nano array grown on conductive substrate to prepare stationary phase TiO 2 CuS photoanode (Applied Surface Science, 2019). BangJi, guingxuYan et al synthesized TiO of different shapes on the surface of titanium net by hydrothermal method 2 Nanomembranes (Ceramics International, 2020). JunweiHou, yeYang et al prepared TiO on a titanium mesh substrate by anodic oxidation 2 Nanotube array, and then CdS/TiO synthesized by hydrothermal method 2 Composite stationary phase photocatalyst (Ceramics International, 2020). However, the photocatalyst of the stationary phase has a problem of falling off widely in the catalytic process, and on the other hand, cuS is easily oxidized and subjected to photo-corrosion in the photo-thermal catalytic reaction process, so that the catalytic performance and stability of the material are affected.
Disclosure of Invention
The invention aims to provide TiO 2 /CuS/TiO 2 Composite photo-thermal catalyst and preparation method thereof are also provided.
In order to achieve the purpose, the invention adopts the following technical scheme:
TiO (titanium dioxide) 2 /CuS/TiO 2 The preparation method of the composite photo-thermal catalytic material comprises the following steps:
s1, polishing a titanium mesh in a mixed solution for 3-5S, cleaning, placing the titanium mesh in a high-pressure kettle with a NaOH solution, standing for 6-8h, carrying out hydrothermal reaction at 150-200 ℃ for 8-12h, cleaning, soaking in an HCl solution for 10-14h, cleaning, drying, calcining, keeping the temperature of a calcining furnace at the speed of 3-6 ℃/min to 400-600 ℃ during calcining for 1-2h, closing the calcining furnace, cooling along with the calcining furnace to obtain the titanium dioxide-doped titanium dioxide growing TiO 2 The titanium mesh of (2);
the concentration of the NaOH solution is 8-12 mol/L;
the concentration of the HCl solution is 0.1-0.2mol/L;
the mixed solution consists of 50-60vt% of hydrofluoric acid, 60-70vt% of nitric acid and deionized water, wherein the volume ratio of the 50-60vt% of hydrofluoric acid to the 60-70vt% of nitric acid to the deionized water is 1 to (3-5) to (6-8);
s2, adopting a continuous ion layer adsorption and reaction method (SILAR) to obtain the TiO in the step S1 2 CuS particles are attached to the surfaces of the nanowires; will grow TiO 2 The titanium mesh is placed in 1-5mmol/L Cu (NO) 3 ) 2 ·3H 2 In O for 1-5min, cleaning, and adding 1-5mmol/L Na 2 S·9H 2 Washing and cleaning with deionized water for 1-5min in O, performing SILAR cycle for 1-6 times, vacuum drying at 55-65 deg.C for 5-7 hr to obtain TiO 2 a/CuS composite;
s3, growing TiO on the surface of TiO2/CuS by ALD technology 2 The method comprises the steps of keeping the temperature of a titanium source bottle at 70-80 ℃ in an ALD system, setting the temperature of a reaction cavity at 150-200 ℃, enabling one ALD cycle to comprise four steps of introducing 0.2s titanium source, 30s N2 purging, introducing 0.02s oxygen source and 30s N2 purging, and obtaining TiO after 20-100 ALD cycles 2 /CuS/TiO 2 A composite photo-thermal catalytic material.
Preferably, the titanium mesh in S1 is sequentially subjected to ultrasonic treatment in acetone, absolute ethyl alcohol and deionized water for 8-12min before being placed into the mixed solution;
further, in order to achieve a better cleaning effect, the titanium mesh in the S1 is subjected to ultrasonic treatment for 10min in acetone, absolute ethyl alcohol and deionized water in sequence before being placed into the mixed solution. The titanium mesh can be selected according to actual requirements.
Preferably, the concentration of NaOH in S1 is 10mol/L, the mixed solution is polished for 5S, and the mixed solution is kept stand in an autoclave for 6h, wherein the calcining temperature is 500 ℃; carrying out hydrothermal reaction for 10h at 180 ℃; soaking in HCl solution for 12h, increasing the temperature of a calcining furnace to 500 ℃ at the speed of 5 ℃/min during calcining, and then preserving the heat for 1h; the concentration of the HCl solution is 0.1mol/L.
Preferably, in order to achieve a better etching effect on the oxide layer of the titanium surface, the mixed solution consists of 55vt% hydrofluoric acid, 65vt% nitric acid and deionized water, wherein the volume ratio of 55vt% hydrofluoric acid, 65vt% nitric acid and deionized water is 1:4: 7.
Preferably, S2 will have TiO grown therein 2 The titanium mesh is placed in 1mmol/L Cu (NO) 3 ) 2 ·3H 2 In O for 1min, washing, and placing in 1mmol/L Na 2 S·9H 2 Washing with deionized water for 1min, performing SILAR cycle for 1-6 times, and vacuum drying at 60 deg.C for 6 hr to obtain TiO 2 a/CuS composite material.
Preferably, the SILAR cycle in S2 is 1.
Preferably, the titanium source in S3 is titanium tetrachloride, 4, 2-methylaminotitanium or titanium tetraisopropoxide, and the oxygen source is H 2 O。
Preferably, in S3, the temperature of the reaction chamber is 180 ℃, and the temperature of the titanium source bottle is kept at 75 ℃.
Preferably, the number of ALD cycles is 40.
TiO2 2 /CuS/TiO 2 The composite photo-thermal catalytic material is prepared according to the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
(1) The composite photo-thermal catalyst TiO prepared by the invention 2 /CuS/TiO 2 The content of the medium CuS is low, the cost is low, secondary pollution cannot be caused in the catalysis process, the recovery is convenient, and the realization of industrial production is facilitated;
(2) Growing TiO with high specific surface area on the surface of a titanium mesh by a hydrothermal method 2 The nano-wire has a high specific surface junction, provides a large number of adsorption sites and active sites for the reaction process, and effectively enhances the adsorption and activation of dye molecules; the catalytic material is easy to recover, reduces pollution and improves repeatable practicability.
(3) CuS particles are attached to the surface of the nanowire by an ion layer impregnation and adsorption method, and TiO is irradiated by visible light and near infrared light 2 The photo-thermal performance coupling generated by the local plasma resonance of the photo-catalysis and the CuS shows that the efficient photo-thermal synergetic catalysis is reducedThe characteristics of the dye;
(4) Deposition of TiO by atomic layer 2 After the thin layer is formed, cuS photo-corrosion and shedding in the catalytic process are avoided, the stability of the material in the catalytic reaction process is effectively improved, and the material still has good catalytic efficiency after 20 times of cyclic tests.
Drawings
FIG. 1 shows TiO of the present invention 2 /CuS/TiO 2 SEM images of the material;
FIG. 2 shows TiO of the present invention 2 /CuS/TiO 2 Composite photo-thermal catalyst and TiO 2 And TiO 2 /CuS
A graph of degradation of the dye under visible and near infrared light illumination;
FIG. 3 is a diagram of TiO of the present invention 2 A circulation activity diagram of the/CuS composite photo-thermal catalyst;
FIG. 4 shows TiO of the present invention 2 /CuS/TiO 2 Cyclic activity profile of composite photothermal catalyst.
Detailed Description
The present invention is described in further detail with reference to the following examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and all the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
Example 1
TiO (titanium dioxide) 2 /CuS/TiO 2 The preparation method of the composite photo-thermal catalytic material comprises the following steps:
s1, carrying out ultrasonic treatment on a titanium mesh with the size of 2cm multiplied by 0.1cm in acetone, absolute ethyl alcohol and deionized water for 10min in sequence, then putting the titanium mesh into a mixed solution for polishing for 5S, washing, then putting the titanium mesh into a high-pressure kettle with NaOH solution for standing for 6h, then carrying out hydrothermal reaction for 10h at 180 ℃, washing, then soaking in HCl solution for 12h, washing again, drying and calcining, raising the temperature of a calcining furnace to 500 ℃ at the speed of 5 ℃/min during calcining, then preserving the temperature for 1h, then closing the calcining furnace and cooling along with the furnace to obtain the titanium dioxide catalyst growing with TiO 2 The titanium mesh of (2);
the concentration of the NaOH solution is 10mol/L;
the concentration of the HCl solution is 0.1mol/L;
the mixed solution consists of 55vt% hydrofluoric acid, 65vt% nitric acid and deionized water, wherein the volume ratio of the 55vt% hydrofluoric acid to the 65vt% nitric acid to the deionized water is 1:4: 7;
s2, adopting a continuous ion layer adsorption and reaction method (SILAR) to obtain the TiO obtained in the step S1 2 CuS particles are attached to the surfaces of the nanowires; will grow TiO 2 The titanium mesh is placed in 1mmol/L Cu (NO) 3 ) 2 ·3H 2 In O for 1min, washing, and placing in 1mmol/L Na 2 S·9H 2 Washing with deionized water for 1min, performing SILAR cycle for 1 time, and vacuum drying at 60 deg.C for 6 hr to obtain TiO 2 a/CuS composite;
s3, preparing TiO by ALD technology 2 Growth of TiO on the surface of CuS 2 The method comprises the steps of maintaining the temperature of a titanium source bottle at 75 ℃ in an ALD system, setting the temperature of a reaction cavity at 180 ℃, enabling one ALD cycle to comprise four steps of introducing 0.2s of titanium source, purging 30s N2, introducing 0.02s of oxygen source and purging 30s N2, and obtaining TiO after 40 times of ALD cycles 2 /CuS/TiO 2 The composite photo-thermal catalytic material comprises titanium tetrachloride serving as a titanium source and H serving as an oxygen source 2 O。
The catalytic material of example 1 was photographed using a scanning electron microscope, and the scanning electron microscope image is shown in fig. 1; in the figure, a is an SEM picture under 200 mu m, and it can be clearly observed that the surface of the titanium mesh is uniformly coated with a layer of white deposit, which indicates that TiO is successfully grown on the surface of the titanium mesh 2 A layer; b is an SEM image at 2 μm; c is SEM image at 500 nm; as shown in the graphs b and c, the grown TiO2 layer presents the shape of a nanowire structure and consists of a plurality of staggered nanowires with the diameter of 20-100nm, and CuS nanoparticles are uniformly adsorbed on the TiO 2 The surface of the nanowire.
Example 2
TiO2 2 /CuS/TiO 2 The preparation method of the composite photo-thermal catalytic material comprises the following steps:
s1, carrying out ultrasonic treatment on a titanium mesh with the size of 2cm multiplied by 0.1cm in acetone, absolute ethyl alcohol and deionized water for 8min in sequence, and then putting the titanium mesh into a mixed solution for polishing3s, placing the titanium mesh into a high-pressure autoclave with NaOH solution for standing for 8h after cleaning, then carrying out hydrothermal reaction for 8h at 150 ℃, soaking the titanium mesh into HCl solution for 10h after cleaning, drying and calcining again, raising the temperature of the calcining furnace to 400 ℃ at the speed of 3 ℃/min during calcining, then keeping the temperature for 2h, then closing the calcining furnace and cooling the calcining furnace along with the furnace to obtain the titanium dioxide with grown TiO 2 The titanium mesh of (2);
the concentration of the NaOH solution is 8mol/L;
the concentration of the HCl solution is 0.2mol/L;
the mixed solution consists of 50vt% hydrofluoric acid, 60vt% nitric acid and deionized water, wherein the volume ratio of the 50vt% hydrofluoric acid to the 60vt% nitric acid to the deionized water is 1: 3: 8;
s2, adopting a continuous ion layer adsorption and reaction method (SILAR) to obtain the TiO in the step S1 2 CuS particles are attached to the surfaces of the nanowires; will grow TiO 2 The titanium mesh is placed in 5mmol/L Cu (NO) 3 ) 2 ·3H 2 In O for 1min, washing, and placing in 5mmol/L Na 2 S·9H 2 Washing with deionized water for 1min in O, performing SILAR cycle for 6 times, vacuum drying at 55-deg.C for 5 hr to obtain TiO 2 a/CuS composite;
s3, preparing TiO by ALD technology 2 Growth of TiO on the surface of CuS 2 Film, the temperature of the titanium source bottle is kept at 70 ℃ in the ALD system, the temperature of the reaction chamber is set at 150 ℃, and one ALD cycle comprises the introduction of 0.2s titanium source and 30s N 2 Purging, introducing 0.02s oxygen source and 30s N 2 Purging four steps to obtain TiO after 100 ALD cycles 2 /CuS/TiO 2 The composite photo-thermal catalytic material comprises 4, 2-methylamino titanium as a titanium source and H as an oxygen source 2 O。
Example 3
TiO (titanium dioxide) 2 /CuS/TiO 2 The preparation method of the composite photo-thermal catalytic material comprises the following steps:
s1, carrying out ultrasonic treatment on a titanium mesh with the size of 2cm multiplied by 0.1cm in acetone, absolute ethyl alcohol and deionized water for 12min in sequence, then putting the titanium mesh into a mixed solution for polishing for 4S, washing, then putting the titanium mesh into a high-pressure kettle with NaOH solution for standing for 7h, and then carrying out ultrasonic treatment on the titanium meshCarrying out hydrothermal reaction at 160 ℃ for 11h, soaking in HCl solution for 13h after cleaning, drying and calcining again, raising the temperature of a calcining furnace to 600 ℃ at the speed of 6 ℃/min during calcining, keeping the temperature for 1.5h, then closing the calcining furnace and cooling along with the furnace to obtain the TiO growth product 2 The titanium mesh of (2);
the concentration of the NaOH solution is 12mol/L;
the concentration of the HCl solution is 0.1mol/L;
the mixed solution consists of 60vt% hydrofluoric acid, 70vt% nitric acid and deionized water, wherein the volume ratio of the 60vt% hydrofluoric acid to the 70vt% nitric acid to the deionized water is 1: 3: 6;
s2, adopting a continuous ion layer adsorption and reaction method (SILAR) to obtain the TiO in the step S1 2 CuS particles are attached to the surfaces of the nanowires; will grow TiO 2 The titanium mesh is placed in 4mmol/L Cu (NO) 3 ) 2 ·3H 2 In O for 3min, washing, and placing in 2mmol/L Na 2 S·9H 2 Washing with deionized water for 3min, performing SILAR cycle for 5 times, and vacuum drying at 65 deg.C for 7 hr to obtain TiO 2 a/CuS composite;
s3, growing TiO on the surface of TiO2/CuS by ALD technology 2 The method comprises the steps of keeping the temperature of a titanium source bottle at 80 ℃ in an ALD system, setting the temperature of a reaction cavity at 200 ℃, enabling one ALD cycle to comprise four steps of introducing 0.2s of a titanium source, 30s N2 purging, introducing 0.02s of an oxygen source and 30s N2 purging, and obtaining TiO after 20 ALD cycles 2 /CuS/TiO 2 The composite photo-thermal catalytic material comprises titanium tetraisopropoxide as a titanium source and H as an oxygen source 2 O。
Example 4
TiO2 2 /CuS/TiO 2 The preparation method of the composite photo-thermal catalytic material comprises the following steps:
s1, carrying out ultrasonic treatment on a titanium mesh with the size of 2cm multiplied by 0.1cm in acetone, absolute ethyl alcohol and deionized water for 9min in sequence, then putting the titanium mesh into a mixed solution for polishing for 3S, washing, then putting the titanium mesh into a high-pressure kettle with NaOH solution for standing for 6h, then carrying out hydrothermal reaction for 9h at 180 ℃, washing, then soaking in HCl solution for 14h, washing again, drying and then calcining, wherein a calcining furnace is used for calciningRaising the temperature to 450 ℃ at the speed of 4 ℃/min, preserving the heat for 1.8h, then closing the calcining furnace, and cooling along with the furnace to obtain the TiO grown 2 The titanium mesh of (2);
the concentration of the NaOH solution is 11mol/L;
the concentration of the HCl solution is 0.2mol/L;
the mixed solution consists of 58vt percent hydrofluoric acid, 68vt percent nitric acid and deionized water, wherein the volume ratio of the 58vt percent hydrofluoric acid to the 68vt percent nitric acid to the deionized water is 1: 5: 8;
s2, adopting a continuous ion layer adsorption and reaction method (SILAR) to obtain the TiO in the step S1 2 CuS particles are attached to the surfaces of the nanowires; will grow TiO 2 The titanium mesh is placed in 3mmol/L Cu (NO) 3 ) 2 ·3H 2 Adding into O for 5min, cleaning, and adding into 3mmol/L Na 2 S·9H 2 Washing with deionized water for 2min, performing SILAR cycle for 4 times, and vacuum drying at 58 deg.C for 6 hr to obtain TiO 2 a/CuS composite;
s3, growing TiO on the surface of TiO2/CuS by ALD technology 2 The method comprises the steps of maintaining the temperature of a titanium source bottle at 78 ℃ in an ALD system, setting the temperature of a reaction cavity at 170 ℃, enabling one ALD cycle to comprise four steps of introducing 0.2s of titanium source, purging 30s N2, introducing 0.02s of oxygen source and purging 30s N2, and obtaining TiO after 80 times of ALD cycles 2 /CuS/TiO 2 The composite photo-thermal catalytic material comprises 4, 2-methylamino titanium as a titanium source and H as an oxygen source 2 O。
Example 5
TiO2 2 /CuS/TiO 2 The preparation method of the composite photo-thermal catalytic material comprises the following steps:
s1, sequentially carrying out ultrasonic treatment on a titanium mesh with the size of 2cm multiplied by 0.1cm in acetone, absolute ethyl alcohol and deionized water for 11min, then putting the titanium mesh into a mixed solution for polishing for 5S, washing, then putting the titanium mesh into a high-pressure kettle with NaOH solution for standing for 7h, then carrying out hydrothermal reaction for 10h at 190 ℃, washing, soaking in HCl solution for 12h, washing, drying and calcining again, keeping the temperature for 1h after the temperature of a calcining furnace is increased to 550 ℃ at the speed of 5 ℃/min during calcining, then closing the calcining furnace and cooling along with the furnace to obtain the titanium dioxide (TiO) growing 2 The titanium mesh of (2);
the concentration of the NaOH solution is 10mol/L;
the concentration of the HCl solution is 0.2mol/L;
the mixed solution consists of 53vt% hydrofluoric acid, 63vt% nitric acid and deionized water, wherein the volume ratio of the 53vt% hydrofluoric acid to the 63vt% nitric acid to the deionized water is 1:4: 8;
s2, adopting a continuous ion layer adsorption and reaction method (SILAR) to obtain the TiO obtained in the step S1 2 CuS particles are attached to the surfaces of the nanowires; will grow TiO 2 The titanium mesh is placed in 2mmol/L Cu (NO) 3 ) 2 ·3H 2 In O for 4min, washing and putting in 4mmol/L Na 2 S·9H 2 Washing with deionized water for 4min, performing SILAR cycle for 3 times, and vacuum drying at 63 deg.C for 5.5 hr to obtain TiO 2 a/CuS composite;
s3, growing TiO on the surface of the TiO2/CuS through an ALD technology 2 Film, the temperature of the titanium source bottle is kept at 73 ℃ in the ALD system, the temperature of the reaction chamber is set at 160 ℃, and one ALD cycle comprises the introduction of 0.2s titanium source and 30s N 2 Purging, introducing 0.02s oxygen source and 30s N 2 Purging four steps, and obtaining TiO after 30 ALD cycles 2 /CuS/TiO 2 The composite photo-thermal catalytic material comprises titanium tetrachloride as a titanium source and H as an oxygen source 2 O。
Example 6
TiO (titanium dioxide) 2 /CuS/TiO 2 The preparation method of the composite photo-thermal catalytic material comprises the following steps:
s1, carrying out ultrasonic treatment on a titanium mesh with the size of 2cm multiplied by 0.1cm in acetone, absolute ethyl alcohol and deionized water for 8min in sequence, then putting the titanium mesh into a mixed solution for polishing for 4S, washing, then putting the titanium mesh into a high-pressure kettle with NaOH solution for standing for 6h, then carrying out hydrothermal reaction for 12h at 200 ℃, washing, soaking in HCl solution for 11h, washing again, drying and calcining, raising the temperature of a calcining furnace to 580 ℃ at the speed of 3 ℃/min during calcining, then preserving the temperature for 1.3h, then closing the calcining furnace and cooling to obtain the titanium dioxide growing with TiO 2 The titanium mesh of (2);
the concentration of the NaOH solution is 9mol/L;
the concentration of the HCl solution is 0.1mol/L;
the mixed solution consists of 50vt percent of hydrofluoric acid, 67vt percent of nitric acid and deionized water, wherein the volume ratio of the 50vt percent of hydrofluoric acid to the 67vt percent of nitric acid to the deionized water is 1: 5: 6;
s2, adopting a continuous ion layer adsorption and reaction method (SILAR) to obtain the TiO obtained in the step S1 2 CuS particles are attached to the surfaces of the nanowires; will grow TiO 2 The titanium mesh is placed in 1mmol/L Cu (NO) 3 ) 2 ·3H 2 In O for 2min, washing, and placing in 1mmol/L Na 2 S·9H 2 Washing with deionized water for 5min in O again to obtain SILAR cycle, performing SILAR cycle for 2 times, and vacuum drying at 61 deg.C for 6.5 hr to obtain TiO 2 a/CuS composite;
s3, growing TiO on the surface of the TiO2/CuS through an ALD technology 2 The method comprises the steps of keeping the temperature of a titanium source bottle at 71 ℃ in an ALD system, setting the temperature of a reaction cavity at 190 ℃, enabling one ALD cycle to comprise four steps of introducing 0.2s of titanium source, purging 30s N2, introducing 0.02s of oxygen source and purging 30s N2, and obtaining TiO after 50 times of ALD cycles 2 /CuS/TiO 2 The composite photo-thermal catalytic material comprises titanium tetraisopropoxide as a titanium source and H as an oxygen source 2 O。
Comparative example 1
Carrying out ultrasonic treatment on a titanium mesh with the size of 2cm multiplied by 0.1cm in acetone, absolute ethyl alcohol and deionized water for 10min in sequence. And (3) putting the cleaned titanium mesh into a mixed solution of 55% hydrofluoric acid, 65% nitric acid and deionized water in a volume ratio of 1. Transferring 30ml 12mol/L NaOH solution into a polytetrafluoroethylene-lined high-pressure kettle, putting a polished titanium mesh, reacting for 12 hours at 200 ℃ in a blast drying oven, washing a reaction product with two sides of deionized water after the reaction is finished, soaking a reactant in HCl with the concentration of 0.1mol/L for 12 hours, washing the reactant with two sides of deionized water, drying, putting the dried reactant into a tubular furnace for calcining, setting the calcining temperature to be 600 ℃, setting a temperature rise program, raising the temperature to 600 ℃ at the speed of 5 ℃/min, preserving the temperature for 60 minutes, cooling the heated reactant along with the furnace, and putting the titanium mesh on the surface after the reaction into a polytetrafluoroethylene-lined high-pressure kettleA layer of TiO grows on the surface 2 A nanowire.
Comparative example 2
Step S1: carrying out ultrasonic treatment on a titanium mesh with the size of 2cm multiplied by 0.1cm in acetone, absolute ethyl alcohol and deionized water for 10min in sequence. And (3) putting the cleaned titanium mesh into a mixed solution of 55% hydrofluoric acid, 65% nitric acid and deionized water in a volume ratio of 1. Transferring 30ml of a 10mol/L NaOH solution into a high-pressure autoclave with a polytetrafluoroethylene lining, putting a polished titanium net, reacting at 180 ℃ for 10 hours in an air-blowing drying box, washing two sides of a reaction product by using deionized water after the reaction is finished, soaking a reactant in HCl with the concentration of 0.1mol/L for 12 hours, washing two sides of the reaction product by using the deionized water, drying, putting the reaction product into a tubular furnace for calcination, setting a temperature-raising program at the calcination temperature of 500 ℃, raising the temperature to 500 ℃ at the speed of 5 ℃/min, preserving the temperature for 60min, cooling along with the furnace, and growing a layer of TiO on the surface of the reacted titanium net 2 A nanowire.
Step S2: tiO obtained in step S1 by continuous ion-layer adsorption and reaction (SILAR) 2 And CuS particles are attached to the surfaces of the nanowires. Growing step S1 with TiO 2 Placing the titanium net of the nanowire in 1mmol/L Cu (NO) 3 ) 2 ·3H 2 In O for 1min, then washing with deionized water on both sides, and then placing in 1mmol/L Na 2 S·9H 2 O for 1min, washing with deionized water on both sides, performing SILAR cycle for 1 time, vacuum drying at 60 deg.C for 6 hr to obtain TiO 2 A CuS composite material.
To verify the photothermal catalytic performance of the three products of comparative example 1, comparative example 1 and comparative example 2, an experiment was employed in which the dyes were degraded under irradiation with a xenon lamp equipped with a 420nm cut-off filter, in which the three products were vertically fixed in three 100ml quartz tubes each containing 50mL of 10mg/L rhodamine B. In order to establish the adsorption-desorption balance of the dye and the catalyst, the rhodamine B solution is stirred for 30 minutes under dark conditions before degradation. In the process of photocatalytic reaction, 2ml of rhodamine B solution is taken every 30min, and the rhodamine B is analyzed by adopting an ultraviolet-visible spectrometry methodConcentration of the solution of rhodamine B, the absorbance at 554nm was recorded and the photocatalytic efficiency was calculated using C/C0 x 100% (C is the final concentration of rhodamine B and C0 is the initial concentration of rhodamine B). The efficiency of the three products in degrading fuel under visible light and near infrared light is shown in FIG. 2, and TiO in comparative example 1 2 The catalyst shows certain catalytic activity under the irradiation of visible light, and the degradation rate reaches 33.5 percent. TiO in comparative example 1 2 CuS sample, catalytic Performance ratio TiO 2 The improvement is obvious. The result shows that the proper introduction of CuS can obviously improve TiO 2 The photocatalytic performance of (a). TiO in example 1 2 /CuS/TiO 2 The composite photo-thermal catalytic material has the best photocatalysis efficiency and effect.
To verify the catalytic cycling activity of the products in example 1 and comparative example 2, the following experiment was used: rhodamine B was degraded under xenon lamp irradiation with a 420nm cut-off filter. In the experiment, two prepared products are respectively vertically fixed in two 100ml quartz tubes filled with 50mL 10mg/L rhodamine B. In order to establish the adsorption-desorption balance of the dye and the catalyst, the rhodamine B solution is stirred for 30 minutes under dark conditions before degradation. Setting the photodegradation process to be 120min, taking 2ml of rhodamine B solution after the photodegradation process is finished, analyzing the concentration of the rhodamine B solution by adopting an ultraviolet-visible spectroscopy, recording the absorbance at 554nm, and calculating the photocatalytic efficiency by using C/C0 x 100% (C is the final concentration of RhB, and C0 is the initial concentration of rhodamine B), which is a degradation cycle experiment;
after each degradation cycle experiment, the products in the example 1 and the comparative example 2 are washed by deionized water on two sides, then the degradation cycle experiment is carried out again after drying at 60 ℃, and finally, the degradation cycle experiment frequency is recorded when the degradation efficiency of the products in the example 1 and the comparative example 2 is lower than 80%. The degradation cycle number is shown in fig. 3 and 4, and the degradation efficiency of the product in comparative example 2 in fig. 3 after 4-cycle degradation experiments is lower than 80%; FIG. 4 is a graph of the product degradation cycle experiment of example 1, which is applicable to TiO of the present application after at least 20 cycles of degradation experiments 2 /CuS/TiO 2 The catalytic degradation efficiency of the composite photo-thermal catalytic material is still higher than 90%, the performance is not obviously changed, the effect is excellent, and the degradation efficiency is highHigh catalytic stability.
Claims (10)
1. TiO (titanium dioxide) 2 /CuS/TiO 2 The preparation method of the composite photothermal catalytic material is characterized by comprising the following steps of:
s1, putting a titanium net into the mixed solution for polishing for 3-5S, putting the cleaned titanium net into a high-pressure kettle with NaOH solution for standing for 6-8h, carrying out hydrothermal reaction for 8-12h at 150-200 ℃, soaking in HCl solution for 10-14h after cleaning, drying again, calcining, keeping the temperature of the calcining furnace at 400-600 ℃ at the speed of 3-6 ℃/min for 1-2h after calcining, closing the calcining furnace, and cooling along with the furnace to obtain the titanium dioxide (TiO) growing crystal 2 The titanium mesh of (2);
the concentration of the NaOH solution is 8-12 mol/L;
the concentration of the HCl solution is 0.1-0.2mol/L;
the mixed solution consists of 50-60vt% of hydrofluoric acid, 60-70vt% of nitric acid and deionized water, wherein the volume ratio of the 50-60vt% of hydrofluoric acid to the 60-70vt% of nitric acid to the deionized water is 1 to (3-5) to (6-8);
s2, growing TiO 2 The titanium net is placed in 1-5mmol/L Cu (NO) 3 ) 2 ·3H 2 Adding O for 1-5min, cleaning, and adding 1-5mmol/L Na 2 S·9H 2 Washing with deionized water for 1-5min in O for 1-6 times, vacuum drying at 55-65 deg.C for 5-7 hr to obtain TiO 2 a/CuS composite;
s3, preparing TiO by ALD technology 2 Growth of TiO on the surface of CuS 2 Film, in ALD system, the titanium source bottle temperature is maintained at 70-80 deg.C, the reaction chamber temperature is set at 150-200 deg.C, and one ALD cycle includes introducing 0.2s titanium source and 30s N 2 Purging, introducing 0.02s oxygen source and 30sN 2 Purging four steps, and obtaining TiO after 20-100 ALD cycles 2 /CuS/TiO 2 A composite photo-thermal catalytic material.
2. The TiO of claim 1 2 /CuS/TiO 2 The preparation method of the composite photo-thermal catalytic material is characterized in that,and (S1) carrying out ultrasonic treatment on the titanium mesh in acetone, absolute ethyl alcohol and deionized water for 8-12min in sequence before the titanium mesh is placed into the mixed solution.
3. A TiO according to claim 1 2 /CuS/TiO 2 The preparation method of the composite photo-thermal catalytic material is characterized in that the concentration of NaOH in S1 is 10mol/L, the mixed solution is polished for 5S, the mixed solution is kept stand in a high-pressure kettle for 6h, and the calcining temperature is 500 ℃; carrying out hydrothermal reaction for 10h at 180 ℃; soaking in HCl solution for 12h, increasing the temperature of a calcining furnace to 500 ℃ at the speed of 5 ℃/min during calcining, and then preserving the heat for 1h; the concentration of the HCl solution is 0.1mol/L.
4. A TiO according to claim 1 2 /CuS/TiO 2 The preparation method of the composite photothermal catalytic material is characterized in that the mixed solution consists of 55vt percent of hydrofluoric acid, 65vt percent of nitric acid and deionized water, wherein the volume ratio of the 55vt percent of hydrofluoric acid to the 65vt percent of nitric acid to the deionized water is 1:4: 7.
5. A TiO according to claim 1 2 /CuS/TiO 2 The preparation method of the composite photo-thermal catalytic material is characterized in that TiO is grown in S2 2 The titanium mesh is placed in 1mmol/L Cu (NO) 3 ) 2 ·3H 2 Adding into O for 1min, cleaning, and adding into 1mmol/L Na 2 S·9H 2 Washing with deionized water for 1min, performing SILAR cycle for 1-6 times, and vacuum drying at 60 deg.C for 6 hr to obtain TiO 2 a/CuS composite material.
6. A TiO according to claim 1 2 /CuS/TiO 2 The preparation method of the composite photothermal catalytic material is characterized in that in S3, the temperature of the reaction cavity is 180 ℃, and the temperature of the titanium source bottle is kept at 75 ℃.
7. A TiO according to claim 1 2 /CuS/TiO 2 The preparation method of the composite photo-thermal catalytic material is characterized in that,SILAR cycling in S2 was 1.
8. A TiO according to claim 1 2 /CuS/TiO 2 The preparation method of the composite photo-thermal catalytic material is characterized in that a titanium source in S3 is titanium tetrachloride, 4, 2-methylamino titanium or titanium tetraisopropoxide, and an oxygen source is H 2 O。
9. A TiO according to claim 1 2 /CuS/TiO 2 The preparation method of the composite photothermal catalytic material is characterized in that the ALD cycle time is 40 times.
10. TiO2 2 /CuS/TiO 2 Composite photothermal catalytic material, characterized in that TiO according to any one of claims 1 to 9 2 /CuS/TiO 2 The composite photo-thermal catalytic material is prepared by the preparation method.
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