CN115090298A - Preparation method of copper-doped tin disulfide composite photocatalytic material - Google Patents
Preparation method of copper-doped tin disulfide composite photocatalytic material Download PDFInfo
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- CN115090298A CN115090298A CN202210748810.XA CN202210748810A CN115090298A CN 115090298 A CN115090298 A CN 115090298A CN 202210748810 A CN202210748810 A CN 202210748810A CN 115090298 A CN115090298 A CN 115090298A
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- ALRFTTOJSPMYSY-UHFFFAOYSA-N tin disulfide Chemical compound S=[Sn]=S ALRFTTOJSPMYSY-UHFFFAOYSA-N 0.000 title claims abstract description 32
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Images
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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
-
- 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
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
Abstract
The invention discloses a preparation method of a copper-doped tin disulfide composite photocatalytic material, which is prepared by adding SnCl 4 ·5H 2 Dissolving O and L-cysteine in deionized water, and dripping CuCl 2 An aqueous solution; transferring the mixture into a polytetrafluoroethylene lining of an autoclave, and preserving the heat of the mixture for 8-16 hours at 130-160 ℃; fully washing the obtained precipitate with water and ethanol, drying and grinding the precipitate into powder to obtain the copper-doped tin disulfide composite photocatalytic material; the invention adopts a simple and convenient in-situ hydrothermal method, and adds copper in situ in the hydrothermal process of synthesizing the tin disulfideA source. Copper ions are doped in situ to form nucleation centers in the growth process, and the number of nucleation centers is increased, so that the growth of tin disulfide is inhibited, and a thin tin disulfide nanosheet is obtained; meanwhile, the specific surface area of the photocatalyst can be increased, so that the adsorption effect of the sample on carbon dioxide is improved.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a preparation method of a photocatalytic material.
Background
Today we are not only facing the energy crisis, but also suffering from a series of global climate problems due to the excessive dependence on fossil energy: global warming, frequent extreme weather conditions, etc. These climatic problems have been linked to the fact that the carbon element, which is stored in the form of fossil fuels, is excessively converted by combustion to energy, being emitted in large quantities in the form of carbon dioxide, with the result that the carbon dioxide content of the atmosphere continues to increase. Therefore, how to capture, store and utilize carbon dioxide and how to reduce the carbon content in the earth atmosphere become the focus of global research.
In order to solve the problem, photocatalytic carbon dioxide provides a new idea for us. By "photocatalytic" is meant that carbon dioxide is first reduced to hydrocarbons such as methane, ethane, and the like. Hydrocarbons are also the stable, efficient, clean energy source that we often utilize. Therefore, the global energy crisis can be solved, carbon circulation is realized, and excessive carbon dioxide in the atmosphere is really applied to industrial life.
Under the condition of proper photocatalyst and illumination, the CO is reduced by photocatalysis 2 And H 2 The O oxidation can be carried out in the same photocatalytic reaction system. And depending on the reaction path, CO 2 The products of the reduction may be CO, HCHO, HCOOH, CH 3 OH、CH 4 And the like. The efficiency and performance of photocatalysis are determined by three key factors: light absorption, charge separation and migration, surface catalysis reactions. Therefore, in order to obtain high photocatalytic performance and conversion efficiency, a wide light absorption range, efficient charge separation and transport, rapidity and efficiencyEffective surface reaction is indispensable. Metal sulfides, which generally have a narrow band gap and a strong reducing power and thus satisfy two of the above three key conditions including a wide light absorption range and a rapid and efficient surface reaction, are promising solar CO 2 A reduced candidate material. In addition, since graphene was discovered, two-dimensional (2D) materials have attracted much attention due to their characteristics of high specific surface area and low charge recombination. Among them, two-dimensional layered transition metal sulfides have been widely paid attention and studied in the field of photocatalysis. Among the numerous metal sulfides, tin disulfide (SnS) 2 ) The device has a narrow band gap and an energy band structure for driving visible light photocatalytic reaction. Meanwhile, the paint is a golden paint (called as color gold) and has the characteristics of no toxicity, low price, chemical stability in acid or neutral solution and the like. Based on the above factors, SnS 2 Is considered to be a promising visible light responsive photocatalyst. However, since the band gap is small, the charge recombination is very fast, and thus the overall photocatalytic efficiency is still low.
Disclosure of Invention
To overcome the problems of the prior art, the invention aims to synthesize two-dimensional SnS 2 The nanosheet is subjected to Cu doping, and the impurity level is introduced, so that good visible light response photocatalytic reduction CO is obtained 2 And (4) performance.
In order to achieve the purpose, the technical scheme is as follows:
a preparation method of a copper-doped tin disulfide composite photocatalytic material comprises the following steps:
SnCl 4 ·5H 2 Dissolving O and L-cysteine in deionized water, and dripping CuCl 2 An aqueous solution; transferring the mixture into a polytetrafluoroethylene lining of an autoclave, and preserving the heat of the mixture for 8-16 hours at 130-160 ℃; and fully washing the obtained precipitate with water and ethanol, drying and grinding into powder to obtain the copper-doped tin disulfide composite photocatalytic material.
According to the scheme, the SnCl 4 ·5H 2 The molar ratio of O to L-cysteine is 1: 2-6; moles of Cu and SnThe ratio of (0.1-3) to 100.
According to the scheme, CuCl 2 The concentration of the aqueous solution is 2-10 mM;
according to the scheme, the SnCl 4 ·5H 2 The concentration of O dissolved in deionized water is 5-20 mM.
The invention has the beneficial effects that:
the semiconductor photocatalytic material provided by the invention has the forbidden band width of only 2.1eV, and can effectively absorb visible light in the photocatalytic reaction process. Meanwhile, the paint is a golden paint (called as color gold) and has the characteristics of no toxicity, low price, chemical stability in acid or neutral solution and the like.
The tin disulfide material prepared in the invention is of a hierarchical structure with self-assembled nano sheets, and has the advantages of a two-dimensional material and a hierarchical structure material.
The doping method adopted by the invention is a simple and convenient in-situ hydrothermal method, and a copper source is added in situ in the hydrothermal process of synthesizing the tin disulfide. Copper ions are doped in situ to form nucleation centers in the growth process, and the nucleation number is increased, so that the growth of tin disulfide is inhibited, and the thin tin disulfide nanosheet is obtained. Meanwhile, the specific surface area of the photocatalyst can be increased, so that the adsorption effect of the sample on carbon dioxide is improved.
Drawings
FIG. 1: field Emission Scanning Electron Microscope (FESEM) images of tin disulfide (a, c) and copper doped tin disulfide photocatalytic materials (b, d).
FIG. 2: x-ray diffraction patterns (XRD) of the samples prepared in examples 1-4 and comparative example 1.
FIG. 3: carbon dioxide sorption of the samples prepared in example 1 and comparative example 1 are shown.
FIG. 4: comparative figures comparing the performance of carbon dioxide reduction conversion to methanol for the samples prepared in examples 1-4 and comparative example 1.
Detailed Description
The following examples further illustrate the technical solutions of the present invention, but should not be construed as limiting the scope of the present invention.
The specific embodiment provides a preparation method of a copper-doped tin disulfide composite photocatalytic material, which comprises the following steps:
SnCl 4 ·5H 2 Dissolving O and L-cysteine in deionized water, and dripping CuCl 2 An aqueous solution; transferring the mixture into a polytetrafluoroethylene lining of an autoclave, and keeping the temperature of the mixture within the temperature range of 130-160 ℃ for 8-16 hours; and fully washing the obtained precipitate with water and ethanol, drying and grinding into powder to obtain the copper-doped tin disulfide composite photocatalytic material.
In particular, SnCl 4 ·5H 2 The molar ratio of the O to the L-cysteine is 1: 2-6; the molar ratio of Cu to Sn is (0.1-3) to 100.
Specifically, CuCl 2 The concentration of the aqueous solution is 2-10 mM; SnCl 4 ·5H 2 The concentration of O dissolved in deionized water is 5-20 mM.
Comparative example 1
Adding 1mmol of SnCl 4 ·5H 2 Stirring the O and 5mmol of L-cysteine for 1 hour under the action of a magnetic stirrer until the solution is uniformly dispersed, transferring the uniformly mixed solution into a 100 ml of a polytetrafluoroethylene-lined hydrothermal kettle, and then preserving the heat at 140 ℃ for 12 hours. The obtained precipitate was centrifuged thoroughly with water and ethanol, washed, dried under vacuum for 10 hours and ground in an agate mortar to prepare a powdery solid, and a sample of tin disulfide was obtained, and this sample was designated as S for convenience.
The FESEM image of the tin disulfide sample synthesized in this comparative example is shown in FIG. 1(a.c), showing SnS 2 A hierarchical structure formed by self-assembly of the nano-sheets is presented, and the transverse dimension of the nano-sheets can reach hundreds of nanometers. And is composed of SnS 2 The overall size of the hierarchical structure formed by self-assembly of the nanosheets can be up to several microns. The XRD pattern of FIG. 2 shows pure SnS 2 The sample is of a 2T type tripartite phase structure.
The catalyst prepared in the embodiment is subjected to photocatalytic carbon dioxide reduction activity test, and a photocatalytic carbon dioxide reduction laboratory of a sample is arranged in a self-made pyrex glass reactor with a container of 200mL at normal temperature and normal pressureThe process is carried out. In detail, a 50mg powder sample was uniformly dispersed in 10mL of deionized water by sonication, preheated to 80 ℃, and then incubated for 2 hours to evaporate the deionized water and deposit the sample on the bottom of the reactor to form a smooth film. Two openings of the reactor were sealed with silicone plugs. Before illumination, nitrogen is firstly introduced into the reactor to drive off oxygen in the system, so as to produce an oxygen-free environment. Carbon dioxide and water were provided by reaction of sodium bicarbonate (84mg, added before sealing the reactor) and aqueous sulfuric acid (0.3mL, 2M, injected into the reactor after nitrogen gas was introduced). A xenon lamp with a power of 300W is used as a light source, and the vertical distance between the lamp and the reactor is 20 c And m is selected. An ultraviolet cut-off filter (not less than 420nm) is used for filtering ultraviolet light, and the transmitted visible light is used as a light source for exciting the photocatalytic reaction. After the reaction was completed, 1mL of gas was extracted from the reactor and injected into a GC-2014C gas chromatograph (Himadzu corporation, Japan, using nitrogen as a carrier gas and a hydrogen flame ionization detector) to detect the content of the hydrocarbon. The reduction product in this experiment was calibrated by a mixed gas of standard gases, and the kind of the product was determined by the retention time.
SnS 2 Recombination of photogenerated carriers, CO, in a sample 2 Conversion to CH 3 The OH yield was only 0.48umol h -1 g -1 The results are shown in FIG. 4.
Example 1
1mmol of SnCl 4 ·5H 2 Stirring O and 5mmol L-cysteine for 1 hour under the action of a magnetic stirrer until the solution is uniformly dispersed, and then preparing CuCl with the concentration of 5mmol/L 2 ·2H 2 100 ml of aqueous O solution, then 1ml of the above CuCl was measured 2 ·2H 2 And the aqueous solution of O is stirred for 30 minutes to ensure that Cu ions are uniformly dispersed in the solution. The solution prepared above was transferred to a 100 ml teflon lined hydrothermal kettle and then incubated at 140 ℃ for 12 hours. The obtained precipitate was thoroughly centrifuged with water and ethanol, washed, and after vacuum drying for 10 hours, ground into a powdery solid by means of an agate mortar to obtain a copper-doped tin disulfide sample, which was designated as SC0.5 for simplicity.
FESEM of the SC0.5 sample synthesized in this example as shown in fig. 1(b.d), after introduction of the Cu source, a significant reduction in nanosheet size occurred, while self-assembly of the nanosheets was also inhibited to some extent. In addition, careful observation and comparison revealed that the nanosheet ratio SnS in the SC0.5 sample was 2 The nanoplatelets of the sample are thinner. The XRD pattern in figure 2 shows that the characteristic peak (101) of tin disulfide is broadened and moves towards a large angle, and the introduction of Cu is shown to enable SnS 2 The (101) plane growth is greatly suppressed, so that the d-pitch is reduced. The XRD and FESEM results show that the introduction of Cu inhibits SnS to a certain extent 2 The growth of (2). And the reduction of the thickness of the nano-sheet can reduce the diffusion distance of the photon-generated carriers, thereby being beneficial to the transmission of the photon-generated carriers.
The photocatalytic performance test and carbon dioxide adsorption of the composite photocatalyst prepared in the embodiment are carried out by the same method as the comparative example 1, and the results show that the CO of the SC0.5 composite material 2 The adsorption capacity is slightly higher than S, and with increasing relative pressure (P/PO), CO 2 The difference in adsorption capacity becomes significant, CH 3 The OH yield reaches a maximum (0.99umol h) -1 g -1 ) About pure SnS 2 The sample performance was 2 times as high, and the results are shown in FIGS. 3 and 4. The mass fraction of Cu ions in the S sample is 0, and the specific surface area S BET Is 541m 2 g -1 (ii) a The mass fraction of Cu ions actually present in the SC0.5 sample was 0.15 wt%, and the specific surface area S BET Is 53m 2 g -1 Compared with comparative example 1, the method is greatly improved.
Example 2
1mmol of SnCl 4 ·5H 2 Stirring O and 5mmol L-cysteine for L hours under the action of a magnetic stirrer until the solution is uniformly dispersed, and then preparing CuCl with the concentration of 5mmol/L 2 ·2H 2 100 ml of aqueous O solution, then 0.2 ml of the above CuCl was measured 2 ·2H 2 And the aqueous solution of O is stirred for 30 minutes to ensure that Cu ions are uniformly dispersed in the solution. The solution prepared above was transferred to a 100 ml teflon lined hydrothermal kettle and then incubated at 140 ℃ for 12 hours. Subjecting the obtainedThe precipitate was thoroughly centrifuged with water and ethanol, washed, dried under vacuum for 10 hours and ground in an agate mortar to give a powdery solid, and this sample was designated SC0.1 for simplicity.
The XRD pattern of the SC0.1 sample synthesized in the example shows that the characteristic peak (101) of tin disulfide is broadened and moves towards a large angle, which shows that the introduction of Cu leads to SnS 2 The (101) plane growth is greatly suppressed, so that the d-pitch is reduced. The photocatalytic performance test of the composite photocatalyst prepared in this example was carried out in the same manner as in comparative example 1, CH 3 OH yield was improved relative to comparative example 1.
Example 3
Adding 1mmol of SnCl 4 ·5H 2 Stirring O and 5mmol L-cysteine for 1 hour under the action of a magnetic stirrer until the solution is uniformly dispersed, and then preparing CuCl with the concentration of 5mmol/L 2 ·2H 2 100 ml of aqueous O solution, 2 ml of the above CuCl were then measured 2 ·2H 2 And the aqueous solution of O is stirred for 30 minutes to ensure that Cu ions are uniformly dispersed in the solution. The solution prepared above was transferred to a 100 ml teflon lined hydrothermal kettle and then incubated at 140 ℃ for 12 hours. The resulting precipitate was thoroughly centrifuged with water and ethanol, washed, dried under vacuum for 10 hours and ground in an agate mortar to give a powdery solid, a sample of tin disulfide, which was designated SC1 for convenience.
The XRD pattern of the SC1 sample synthesized in this example showed broadening of the characteristic peak (101) of tin disulfide and a shift toward large angles relative to comparative example 1, indicating that introduction of Cu caused SnS 2 The (101) plane growth is greatly suppressed, so that the d-pitch is reduced. The photocatalytic performance test of the composite photocatalyst prepared in this example was carried out in the same manner as in comparative example 1, CH 3 OH yield was greatly improved relative to comparative example 1, but relative to SC0.5 CH 3 The OH yield is reduced.
Example 4
Adding 1mmol of SnCl 4 ·5H 2 O and 5mmol of L-cysteine under magnetic stirringStirring for 1 hour under the action of a device until the solution is uniformly dispersed, and then preparing CuCl with the concentration of 5mmol/L 2 ·2H 2 100 ml of aqueous O solution, then 3ml of the above CuCl were measured 2 ·2H 2 And the aqueous solution of O is stirred for 30 minutes to ensure that Cu ions are uniformly dispersed in the solution. The solution prepared above was transferred to a 100 ml teflon lined hydrothermal kettle and then incubated at 140 ℃ for 12 hours. The resulting precipitate was thoroughly centrifuged with water and ethanol, washed, dried under vacuum for 10 hours and ground in an agate mortar to give a powdery solid, a sample of tin disulfide, which was designated SC3 for convenience.
The XRD pattern of the SC3 sample synthesized in this example showed broadening of the characteristic peak (101) of tin disulfide and shifting towards large angles relative to comparative example 1, indicating that the introduction of Cu caused SnS 2 The (101) plane growth is greatly suppressed, so that the d-pitch is reduced. The composite photocatalyst prepared in the embodiment was subjected to photocatalytic performance test by the same method as in comparative example 1, CH 3 The OH yield showed a decrease with respect to examples 2 and 3.
The X-ray diffraction patterns (XRD) of the samples prepared in examples 1 to 4 and comparative example 1 are shown in fig. 2.
A comparison of the carbon dioxide reduction to methanol performance of the samples prepared in examples 1-4 and comparative example 1 is shown in FIG. 4.
Claims (5)
1. A preparation method of a copper-doped tin disulfide composite photocatalytic material is characterized by comprising the following steps:
SnCl 4 ·5H 2 Dissolving O and L-cysteine in deionized water, and dripping CuCl 2 An aqueous solution; transferring the mixture into a polytetrafluoroethylene lining of an autoclave, and preserving the heat of the mixture for 8-16 hours at 130-160 ℃; and fully washing the obtained precipitate with water and ethanol, drying and grinding into powder to obtain the copper-doped tin disulfide composite photocatalytic material.
2. Preparation method of copper-doped tin disulfide composite photocatalytic material as claimed in claim 1Method characterized by SnCl 4 ·5H 2 The molar ratio of O to L-cysteine is 1 (2-6).
3. The preparation method of the copper-doped tin disulfide composite photocatalytic material as claimed in claim 1, wherein the molar ratio of Cu to Sn is (0.1-3): 100.
4. The method for preparing the copper-doped tin disulfide composite photocatalytic material as claimed in claim 1, wherein the CuCl is 2 The concentration of the aqueous solution is 2-10 mM.
5. The preparation method of the copper-doped tin disulfide composite photocatalytic material as claimed in claim 1, wherein SnCl is adopted as the material 4 ·5H 2 The concentration of O dissolved in deionized water is 5-20 mM.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108355678A (en) * | 2018-03-09 | 2018-08-03 | 南昌航空大学 | A kind of compound micron bouquet of artificial gold-bismuth tungstate and its preparation method and application |
| CN109133158A (en) * | 2017-06-16 | 2019-01-04 | 中国科学技术大学 | The SnS of selective oxidation2Preparation of sections method and products thereof and purposes |
| CN110194482A (en) * | 2019-06-21 | 2019-09-03 | 安阳师范学院 | Three-dimensional ultra-thin carbon dots/Copper-cladding Aluminum Bar stannic disulfide composite Nano piece preparation method |
| CN113753942A (en) * | 2021-08-25 | 2021-12-07 | 天津大学 | Transition metal doped stannic disulfide nanoflower and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109133158A (en) * | 2017-06-16 | 2019-01-04 | 中国科学技术大学 | The SnS of selective oxidation2Preparation of sections method and products thereof and purposes |
| CN108355678A (en) * | 2018-03-09 | 2018-08-03 | 南昌航空大学 | A kind of compound micron bouquet of artificial gold-bismuth tungstate and its preparation method and application |
| CN110194482A (en) * | 2019-06-21 | 2019-09-03 | 安阳师范学院 | Three-dimensional ultra-thin carbon dots/Copper-cladding Aluminum Bar stannic disulfide composite Nano piece preparation method |
| CN113753942A (en) * | 2021-08-25 | 2021-12-07 | 天津大学 | Transition metal doped stannic disulfide nanoflower and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116078402A (en) * | 2023-02-09 | 2023-05-09 | 辽宁大学 | Cerium doped tin disulfide photocatalyst and preparation method and application thereof |
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