CN109317166B - Preparation method and application of ternary composite photocatalyst - Google Patents
Preparation method and application of ternary composite photocatalyst Download PDFInfo
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- CN109317166B CN109317166B CN201811324347.6A CN201811324347A CN109317166B CN 109317166 B CN109317166 B CN 109317166B CN 201811324347 A CN201811324347 A CN 201811324347A CN 109317166 B CN109317166 B CN 109317166B
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000011206 ternary composite Substances 0.000 title claims abstract description 11
- 230000001699 photocatalysis Effects 0.000 claims abstract description 46
- 229910052751 metal Inorganic materials 0.000 claims abstract description 38
- 239000002184 metal Substances 0.000 claims abstract description 38
- 239000002131 composite material Substances 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000011068 loading method Methods 0.000 claims abstract description 14
- 238000000137 annealing Methods 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- 230000009467 reduction Effects 0.000 claims abstract description 5
- 239000012071 phase Substances 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 238000006731 degradation reaction Methods 0.000 claims description 19
- 230000015556 catabolic process Effects 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000002957 persistent organic pollutant Substances 0.000 claims description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000007791 liquid phase Substances 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 2
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 2
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 2
- 229910020437 K2PtCl6 Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 229910019891 RuCl3 Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(II) nitrate Inorganic materials [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 238000013032 photocatalytic reaction Methods 0.000 abstract description 12
- 239000000969 carrier Substances 0.000 abstract description 6
- 230000002195 synergetic effect Effects 0.000 abstract description 5
- 230000004913 activation Effects 0.000 abstract description 3
- 230000002708 enhancing effect Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 16
- 229960000907 methylthioninium chloride Drugs 0.000 description 16
- 238000007146 photocatalysis Methods 0.000 description 11
- 230000000593 degrading effect Effects 0.000 description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 239000000975 dye Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 5
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- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000001782 photodegradation Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 208000012868 Overgrowth Diseases 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
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- 231100000956 nontoxicity Toxicity 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical class O* 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- 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
- B01J27/043—Sulfides with iron group metals or platinum group metals
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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Abstract
The invention discloses a preparation method and application of a ternary composite photocatalyst, wherein the preparation method comprises the step of loading metal M and reduced graphene oxide RGO in CaIn by a low-temperature thermal reduction method2S4In cubic phase, then obtaining M-RGO-CaIn by low-temperature thermal annealing2S4A composite photocatalyst is provided. The synergistic loading of the metal M and the reduced graphene oxide RGO can not only improve the specific surface area of the composite photocatalyst and reduce the activation energy of the photocatalytic reaction, but also effectively promote the separation of photon-generated carriers, thereby obviously enhancing the cubic phase CaIn2S4The photocatalytic performance of (a). The preparation method provided by the invention has the advantages of simple process, mild reaction conditions and high yield. The preparation process related by the invention is simple, the reaction condition is mild, the yield is high, macroscopic preparation can be realized, the preparation method is environment-friendly, and the obtained M-RGO-CaIn2S4The composite photocatalyst shows good photocatalytic performance under visible light, and is a novel composite photocatalytic material system with potential application value.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to a preparation method and application of a three-way composite photocatalyst.
Background
Since the discovery of the photolysis of water by Fujishima and Honda on n-type semiconductor TiO2 single crystal electrodes in 1972, photocatalytic reactions have gained widespread attention in environmental governance and energy development. The solar energy with low density can be converted into chemical energy and electric energy with high density, and meanwhile, the solar energy with low density can be directly utilized to decompose water to produce hydrogen, degrade and mineralize various organic pollutants in water and air, and even reduce heavy metal ions. The technology has the advantages of reaction at room temperature, direct utilization of solar energy, no secondary pollution and the like, and has immeasurable significance for fundamentally solving the problems of environmental pollution and energy shortage.
Among the numerous semiconductor photocatalysts, TiO2 The photocatalyst is favored by people due to the advantages of good chemical stability, high photocatalytic activity, no toxicity, low cost and the like, and is the most widely used photocatalytic material at present. But TiO22 The band structure of the light-emitting diode determines that the photocatalysis technology has limitation in the popularization process. TiO22The band gap of the solar energy is wide (such as anatase structure 3.2 eV), the spectral response range is narrow, and only ultraviolet light of less than 5% of solar energy can be utilized, but visible light accounting for 43% of solar energy cannot be absorbed. Therefore, the need for TiO2 Modification studies were conducted to broaden its light absorption range, or to find a novel visible light photocatalyst.
Sulfides can be seen as the result of the substitution of oxygen atoms in the crystal lattice by sulfur atoms. The 3p orbital level of S is higher than the 2p orbital level of O, and sulfide has a relatively narrower forbidden bandwidth than corresponding oxide, so that more sunlight can be absorbed, and stronger photocatalytic activity is expected to be shown. In our earlier work, the first report of Ca-in-S CaIn with cubic phase structure2S4The photocatalyst (International Journal of Hydrogen Energy, 2013, 38 and 13153) not only can fully absorb visible light (1.68-1.84 eV), but also shows good photocatalytic activity and stability under visible light. However, CaIn for a single component2S4In other words, the photocatalytic activity under visible light is low because the photo-generated carriers generated under light have a high recombination probability. Therefore, the temperature of the molten metal is controlled,there is a need to improve cubic phase CaIn by further structural design2S4The photocatalytic performance of (a).
Disclosure of Invention
The invention aims at the cubic phase CaIn2S4The problem of low photocatalytic performance is to provide a cubic phase CaIn-based catalyst2S4The preparation method of the ternary composite photocatalyst and the application of the ternary composite photocatalyst in the field of photocatalysis. The ternary composite photocatalyst can fully exert the advantages of the interface structure between the components, and effectively realize the separation of photon-generated carriers, thereby efficiently enhancing the cubic phase CaIn2S4The photocatalysis performance of the method comprises hydrogen production by decomposing water, organic dye degradation in a liquid phase and volatile organic pollutant degradation in a gas phase.
The invention is realized by the following technical scheme:
a three-element composite photocatalyst is prepared by loading metal M and reduced graphene oxide RGO on cubic phase CaIn by low-temperature thermal reduction method2S4Then obtaining M-RGO-CaIn by low-temperature thermal annealing2S4The composite photocatalyst is applied to hydrogen production by decomposing water, organic dye degradation in a liquid phase and volatile organic pollutant degradation in a gas phase;
wherein the metal M is a metal of groups IB, IIB and VIII of the periodic Table of the elements.
The preparation method of the three-way composite photocatalyst comprises the following steps:
(1) firstly, preparing cubic phase CaIn by a hydrothermal method2S4Preparing graphene oxide by using a Hummers method, and adding a certain amount of CaIn2S4Mixing the powder, the GO powder and the metal M precursor with deionized water, and stirring to form uniform suspension;
(2) placing the suspension obtained in the step 1 in a water bath stirring heater, carrying out stirring reaction at a certain temperature, filtering, washing and drying to obtain a powder material;
(3) placing the powder material obtained in the step 2 into a tubular furnace, and annealing at low temperature under the condition of introducing inert gas to finally obtain M-RGO-CaIn2S4Ternary elementA composite photocatalytic material.
In the step 1, the metal M is an element in IB, IIB and VIII groups in the periodic table of elements.
Preferably, the metal M in step 1 is selected from any one of Au, Ag, Pt, Pd, Cu, and Rh.
The metal M precursor in the step 1 comprises chloride, nitrate and other water-soluble salts.
Preferably, the metal M precursor in step 1 is selected from HAuCl4、H2PtCl6、K2PtCl6、CuCl2、RuCl3、Fe(NO3)3、Ni(NO3)2、AgNO3、Pd(NO3)2、Cu(CH3COO)2。
In the step 1, the loading amount of the metal M is 0.1-10wt%, and the loading amount of GO or RGO is 0.5-10 wt%.
In the step 2, the reaction temperature is 60-200 ℃, and the reaction time is 0.5-10 hours.
The annealing temperature in the step 3 is 100-400 ℃, and the annealing time is 0.5-6 hours.
Preferably, the inert gas in step 3 is nitrogen or argon.
The invention also provides the technical scheme that the metal M and the reduced graphene oxide RGO share the cubic phase CaIn2S4The application of the ternary composite photocatalyst in the field of photocatalysis comprises hydrogen production by water decomposition, organic dye liquid phase degradation and volatile organic pollutant gas phase degradation.
The principle of the invention is as follows:
the invention provides a cubic phase CaIn co-loaded by metal M and reduced graphene oxide RGO2S4The ternary composite photocatalyst M-RGO-CaIn2S4From metal M, reduced graphene oxide RGO and CaIn2S4Wherein RGO and CaIn2S4Mixed, metal M supported on RGO or CaIn2S4Surface, for M-RGO-CaIn2S4The composite photocatalytic material has obviously raised RGO loadThe specific surface area of the composite photocatalyst can enhance the adsorption of a photocatalytic target product and provide more photocatalytic reaction adsorption sites and active sites; the load of the metal M can reduce the activation energy of the photocatalytic reaction, particularly the activation energy of the photocatalytic reduction reaction, and improve the rate of the photocatalytic reaction; the synergistic loading of the metal M and the RGO can further promote photogenerated carriers to be from CaIn2S4The migration to metal M or RGO improves the service life of the photon-generated carrier and reduces the recombination probability of the photon-generated carrier. Therefore, the loading of the metals M and RGO can greatly enhance the cubic phase CaIn2S4The photocatalytic performance under visible light comprises the steps of preparing hydrogen by decomposing water, degrading organic dye in a liquid phase and degrading volatile organic pollutants in a gas phase, thereby effectively compensating single cubic phase CaIn2S4The photocatalyst has low photocatalytic performance.
The invention has the advantages that:
1. the preparation method provided by the invention is very simple, firstly, the graphene oxide GO and the metal precursor are reduced into the reduced graphene oxide RGO and metal M nano-particles by a thermal reduction method, then, the post-annealing is carried out at a lower temperature, no acidic, alkaline, toxic or corrosive chemical reagent is used in the reaction process, the operation is simple, the reaction condition is mild, the yield is high, the macroscopic preparation can be carried out, and the preparation method is environment-friendly.
2. According to the invention, the metal precursor is reduced into the metal nanoparticles by using a thermal reduction method at a lower temperature, so that overgrowth and agglomeration of the metal nanoparticles can be effectively prevented, and the low-size metal nanoparticles can provide a larger specific surface area and more surface reaction active sites, thereby being beneficial to enhancement of photocatalytic performance.
3. The method is characterized in that metal M and reduced graphene oxide RGO are cooperatively loaded to cubic phase CaIn2S4In the method, the recombination probability of photogenerated carriers can be effectively reduced, so that the cubic phase CaIn can be obviously enhanced2S4The photocatalysis performance of the composite material comprises hydrogen production by decomposing water, organic dye degradation by liquid phase and volatile organic pollutant degradation by gas phase, and the composite material has good photocatalysis performanceThe stability is a novel composite photocatalytic material system with potential application value.
Drawings
FIG. 1 shows CaIn prepared in example 12S4、Ag-CaIn2S4、RGO-CaIn2S4And Ag-RGO-CaIn2S4X-ray diffraction pattern of (a).
FIG. 2 shows CaIn prepared in example 12S4、RGO-CaIn2S4、Ag-CaIn2S4And Ag-RGO-CaIn2S4And (3) an activity result graph of photocatalytic degradation of methylene blue under visible light.
FIG. 3 shows Au-RGO-CaIn prepared in example 22S4Transmission electron micrograph (D).
FIG. 4 shows CaIn prepared in example 22S4、RGO-CaIn2S4、Au-CaIn2S4And Au-RGO-CaIn2S4The activity result of photocatalytic hydrogen production under visible light.
FIG. 5 shows CaIn prepared in example 32S4、RGO-CaIn2S4、Cu-CaIn2S4And Cu-RGO-CaIn2S4And (3) an activity result chart of photocatalytic degradation of toluene under visible light.
Detailed Description
The technical scheme of the invention is further explained by combining the specific examples as follows:
example 1
0.05 g of GO powder is weighed and added into a beaker containing 100 ml of deionized water, and the mixture is subjected to ultrasonic treatment for 1 hour to uniformly and stably disperse the GO powder in the deionized water.
To the above suspension was added 1 g of CaIn2S4Powder and 800 microliter silver nitrate AgNO3The aqueous solution (40 g/l concentration) was then placed in a 70 ℃ water bath stirrer and stirred for 6 hours. After the reaction is finished, filtering, washing and drying.
Placing the dried powder in a nitrogen tube furnace at 200 deg.CMiddle annealing for 2 hours to obtain Ag-RGO-CaIn2S4The composite photocatalyst contains 2 wt% of Ag and 5 wt% of RGO.
For Ag-RGO-CaIn2S4In combination with CaIn2S4、RGO-CaIn2S4And Ag-CaIn2S4For comparison, the structure is shown in FIG. 1. In FIG. 1, A is a cubic phase CaIn2S4The X-ray diffraction spectrum of (A) is RGO-CaIn2S4The X-ray diffraction spectrum of (1) is that C is Ag-CaIn2S4The X-ray diffraction spectrum of (A) is Ag-RGO-CaIn2S4X-ray diffraction pattern of (a). For spectrum A, cubic phase CaIn synthesized2S4In full agreement with standard card # 310272. For spectra B, C and D, loading of metallic Ag and/or reduced graphene oxide RGO did not alter the cubic phase CaIn2S4The structure of (3), while no diffraction peak of the metal Ag and/or the reduced graphene oxide RGO was observed.
The performance of the photocatalyst for degrading organic dye in liquid phase is evaluated by degrading methylene blue through photocatalysis. The light source is a 300-watt xenon lamp (PLS-SXE 300 type, Beijing Pochly Tech technology Limited, the actual output power is 47 watts, and the visible light output power is 19.6 watts), and the exciting light of the photocatalytic reaction is ensured to be visible light by externally connecting a half-transmitting mirror and a long-pass filter (the wavelength is more than or equal to 420 nanometers).
The specific photocatalytic experiment steps are as follows: (1) weighing 100 mg of photocatalyst powder, adding the photocatalyst powder into a photocatalytic reactor containing 100 ml of methylene blue aqueous solution (the initial concentration of the methylene blue is 20 mu mol/L), and stirring for 30 minutes under the condition of no illumination to ensure that the methylene blue is saturated and adsorbed on the surface of the catalyst; (2) starting a photocatalytic reaction, and opening reflux water on the outer side of the reactor to ensure that the temperature of the solution is room temperature in the photocatalytic reaction process; (3) samples were taken at regular intervals, and then the absorption intensity at 665 nm was measured with a spectrophotometer, and the concentration of methylene blue was calculated according to the Lambert beer law, as shown in FIG. 2, in which A represents no lightAdsorption of the catalyst to methylene blue under irradiation with the photocatalyst, B represents photodegradation of methylene blue without irradiation with the photocatalyst, and C represents a single component CaIn2S4Degradation of methylene blue, D represents Ag-CaIn2S4Degradation of methylene blue, E represents RGO-CaIn2S4Degradation of methylene blue, F represents Ag-RGO-CaIn2S4And (3) degrading methylene blue. As can be seen from the figure, the adsorption effect of the photocatalyst on methylene blue is very weak, and the concentration is only reduced by less than 5% in 90 minutes. In the absence of catalyst under illumination, there was a direct photodegradation effect of methylene blue, as shown by curve B, with a 32% drop in concentration after 90 minutes. Under the condition of illumination and catalyst, the degradation rate of methylene blue is obviously improved. For CaIn2S4、Ag-CaIn2S4、RGO-CaIn2S4And Ag-RGO-CaIn2S4For 90 minutes, the degradation rates were 63.8%, 75.8%, 84.5%, and 99%, respectively. The result shows that the loading of the promoter metal Ag or the reduced graphene oxide RGO can improve the cubic phase CaIn2S4The property of degrading methylene blue under visible light, and the synergistic load of the metal Ag and the reduced graphite oxide RGO can further limit the enhancement of cubic phase CaIn2S4The photocatalytic performance of (a).
Example 2
0.01 g of GO powder is weighed and added into a beaker containing 120 ml of deionized water, and the mixture is subjected to ultrasonic treatment for 45 minutes to uniformly and stably disperse the GO powder in the deionized water.
To the above suspension was added 1 g of CaIn2S4Powder and 216 microliter of HAuCl chloroauric acid4The aqueous solution (40 g/l concentration) was then placed in a 80 deg.C water bath stirrer and stirred for 5 hours. After the reaction is finished, filtering, washing and drying.
The above dried powder was annealed in an argon tube furnace at 150 ℃ for 3 hours to obtain Au-RGO-CaIn2S4The composite photocatalyst contains 0.5 wt% of Au and 1 wt% of RGO.
For the obtained Au-RGO-CaIn2S4The microstructure of the composite photocatalyst is analyzed by a transmission electron microscope, and the result is shown in fig. 3. Cubic phase CaIn2S4Is in a sheet structure, the reduced graphene oxide RGO is in a two-dimensional layered structure, and the cubic phase CaIn2S4And Reduced Graphene Oxide (RGO) are coated with each other; the metal Au is in a nano granular structure, has an average grain diameter of 4-5 nanometers, and is loaded in a cubic phase CaIn2S4Or reduced graphene oxide RGO surface. Metals Au, RGO and CaIn2S4The interface between the two can effectively promote photogenerated electrons to be absorbed from the CaIn2S4The conduction band is transferred to the surface of Au or RGO, thereby degrading the recombination probability of photon-generated carriers and enhancing the performance of the photocatalyst.
The performance of the photocatalyst was evaluated by photocatalytic decomposition of water to produce hydrogen. The light source is a 300-watt xenon lamp (PLS-SXE 300 type, Beijing Pochly Tech technology Limited, the actual output power is 47 watts, and the visible light output power is 19.6 watts), and the exciting light of the photocatalytic reaction is ensured to be visible light by externally connecting a half-transmitting mirror and a long-pass filter (the wavelength is more than or equal to 420 nanometers).
The specific photocatalytic experiment steps are as follows: (1) 10 mg of photocatalyst powder was weighed and added to a photocatalytic reactor containing 100 ml of deionized water, and 3.15 g of Na sodium sulfite was added2SO3And 6 g of sodium sulfide Na2S·9H2O, stirring uniformly; (2) sealing the photocatalytic reactor, introducing argon to exhaust residual air in the photocatalytic reactor, and then starting photocatalytic hydrogen production reaction; (3) samples were taken every one hour, and the hydrogen production was measured by gas chromatography (family dawn GC 1690C, molecular sieve packed column, argon gas as carrier gas) and the average hydrogen production rate was calculated for 8 hours, and the results are shown in fig. 4.
FIG. 4 shows CaIn2S4、Au-CaIn2S4、RGO-CaIn2S4And Au-RGO-CaIn2S4And the activity result chart of visible light photocatalytic hydrogen production. First, CaIn for cubic phase2S4In other words, production under visible lightThe hydrogen rate was 19.6. mu. mol/h. For Au-CaIn2S4、RGO-CaIn2S4And Au-RGO-CaIn2S4In terms of hydrogen production rates under visible light were 61.4, 39.4 and 461.2. mu. mol/h, respectively. The results show that the loading of Au or RGO as single cocatalyst can enhance the cubic phase CaIn2S4The performance of photocatalytic hydrogen production, and the synergistic load of double promoters Au and RGO can greatly improve the cubic phase CaIn2S4The performance of photocatalytic hydrogen production. For Au-RGO-CaIn2S4In other words, the hydrogen production rate is CaIn2S4、Au-CaIn2S4And RGO-CaIn2S423.5, 7.5 and 11.7 times.
Example 3
0.05 g of GO powder is weighed and added into a beaker containing 80 ml of deionized water, and the mixture is subjected to ultrasonic treatment for 30 minutes to uniformly and stably disperse the GO powder in the deionized water.
To the above suspension was added 0.5 g of CaIn2S4Powder and 1.84 ml of Cu (NO) nitrate3)2The aqueous solution (40 g/l concentration) was then placed in a 100 ℃ water bath stirrer and stirred for 4 hours. After the reaction is finished, filtering, washing and drying.
The above dried powder was annealed in a helium tube furnace at 250 ℃ for 1.5 hours to obtain Cu-RGO-CaIn2S4The composite photocatalyst contains 5 wt% of Cu and 10wt% of RGO.
The performance of the photocatalyst for degrading organic pollutants through photocatalysis is evaluated by degrading toluene through photocatalysis. The light source is a 300-watt xenon lamp (PLS-SXE 300 type, Beijing Pochly Tech technology Limited, the actual output power is 47 watts, and the visible light output power is 19.6 watts), and the exciting light of the photocatalytic reaction is ensured to be visible light by externally connecting a half-transmitting mirror and a long-pass filter (the wavelength is more than or equal to 420 nanometers).
The specific photocatalytic experiment steps are as follows: (1) 150 mg of photocatalyst powder was weighed and uniformly dispersed in a petri dish (diameter 5 cm) containing 3 g of absolute ethanol under the action of ultrasound) Then drying the mixture at 60 ℃; (2) the culture dish is placed in a photocatalytic reactor, and the reactor is sealed at normal temperature and normal pressure. Before the reaction, the reactor was purged with high purity air at a flow rate of 60 ml/min to remove CO from the reactor and gas lines2And toluene and the like. Sealing the collection window, and keeping the system pressure at normal pressure, wherein the oxygen content is 22%, and the relative humidity is 70%; (3) manually injecting a certain volume of toluene gas into the reactor, waiting for 30 minutes to uniformly mix the toluene gas and air in the reactor, and measuring the initial concentration of the toluene at the moment to be 400 ppmV by a gas chromatograph (GC 1690C, under the heading of the science, capillary column, nitrogen as carrier gas and FID detector) after the toluene gas and the air reach a stable concentration; (4) the photocatalytic reaction was started and the timer was started. After 5 hours, a certain volume of gas was collected from the reactor, and the content of toluene in the photocatalytic reaction was analyzed on-line by gas chromatography (GC 1690C, family dawn, capillary column, nitrogen as carrier gas, FID detector, methane converter).
FIG. 5 shows CaIn2S4、Cu-CaIn2S4、RGO-CaIn2S4And Cu-RGO-CaIn2S4The activity result of the visible light photocatalytic degradation of toluene is shown in the figure. First, CaIn for cubic phase2S4In particular, the degradation rate of 400 ppmV of toluene in 5 hours was 19%. For Au-CaIn2S4、RGO-CaIn2S4And Au-RGO-CaIn2S4The degradation rate of visible light to toluene is 34%, 64% and 97%, respectively. Consistent with examples 1 and 2, loading of a single promoter, Cu or RGO, can enhance cubic phase CaIn2S4The performance of degrading toluene by photocatalysis is improved, and the synergistic loading of Cu and RGO serving as double promoters can greatly improve the cubic phase CaIn2S4The performance of photocatalytic degradation of toluene. Unlike example 2, examples 1 and 3 support the single cocatalyst RGO more favouring the cubic phase CaIn2S4Photocatalytic degradation of organic pollutants (including liquid-phase degradation of dyes and gas-phase degradation of volatile organic pollutants), while a single promoter metal M is more beneficialCubic phase CaIn2S4The performance of photocatalytic hydrogen production.
Claims (8)
1. The three-element composite photocatalyst is characterized in that metal M and reduced graphene oxide RGO are loaded on a cubic phase CaIn by a low-temperature thermal reduction method2S4Then obtaining M-RGO-CaIn by low-temperature thermal annealing2S4The composite photocatalyst is applied to hydrogen production by decomposing water, organic dye degradation in a liquid phase and volatile organic pollutant degradation in a gas phase; wherein the metal M is a metal of groups IB, IIB and VIII of the periodic Table of the elements;
the preparation method of the three-way composite photocatalyst comprises the following steps: (1) firstly, preparing cubic phase CaIn by a hydrothermal method2S4Preparing graphene oxide by using a Hummers method, and adding a certain amount of CaIn2S4Mixing the powder, the graphene oxide powder and the metal M precursor with deionized water, and stirring to form a uniform suspension; (2) placing the suspension obtained in the step (1) in a water bath stirring heater, carrying out stirring reaction at a certain temperature, filtering, washing and drying to obtain a powder material; (3) placing the powder material obtained in the step (2) in a tube furnace, and annealing at low temperature under the condition of introducing inert gas to finally obtain M-RGO-CaIn2S4A ternary composite photocatalytic material.
2. The method for preparing the three-element composite photocatalyst according to claim 1, wherein the metal M in the step (1) is selected from any one of Au, Ag, Pt, Pd, Cu and Rh.
3. The method for preparing the three-way composite photocatalyst as claimed in claim 1, wherein the metal M precursor in step (1) comprises chloride, nitrate and other water-soluble salts.
4. The method for preparing the three-way composite photocatalyst as claimed in claim 1, wherein the metal M precursor in step (1)Selected from HAuCl4、H2PtCl6、K2PtCl6、CuCl2、RuCl3、Fe(NO3)3、Ni(NO3)2、AgNO3、Pd(NO3)2、Cu(CH3COO)2。
5. The method for preparing the ternary composite photocatalyst as claimed in claim 1, wherein the loading amount of the metal M in the step (1) is 0.1-10wt%, and the loading amount of the graphene oxide is 0.5-10 wt%.
6. The method for preparing the ternary composite photocatalyst as claimed in claim 1, wherein the reaction temperature in the step (2) is 60-200 ℃ and the reaction time is 0.5-10 hours.
7. The method for preparing the three-way composite photocatalyst as claimed in claim 1, wherein the annealing temperature in the step (3) is 100-400 ℃, and the annealing time is 0.5-6 hours.
8. The method for preparing the three-way composite photocatalyst as claimed in claim 1, wherein the inert gas in step (3) is nitrogen or argon.
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