CN110918102A - Preparation method of graphene oxide modified metal sulfide composite photocatalyst - Google Patents
Preparation method of graphene oxide modified metal sulfide composite photocatalyst Download PDFInfo
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- CN110918102A CN110918102A CN201911258790.2A CN201911258790A CN110918102A CN 110918102 A CN110918102 A CN 110918102A CN 201911258790 A CN201911258790 A CN 201911258790A CN 110918102 A CN110918102 A CN 110918102A
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- pyrite
- graphene oxide
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- metal sulfide
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- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 20
- 229910052976 metal sulfide Inorganic materials 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 229910052683 pyrite Inorganic materials 0.000 claims abstract description 27
- 239000011028 pyrite Substances 0.000 claims abstract description 27
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 6
- 239000012498 ultrapure water Substances 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 4
- 238000007605 air drying Methods 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000003517 fume Substances 0.000 claims abstract description 3
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims 1
- 238000007873 sieving Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 abstract description 18
- 230000015556 catabolic process Effects 0.000 abstract description 14
- 238000006731 degradation reaction Methods 0.000 abstract description 14
- 239000003054 catalyst Substances 0.000 abstract description 13
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 6
- 239000002351 wastewater Substances 0.000 abstract description 4
- 229940043267 rhodamine b Drugs 0.000 description 17
- 239000004065 semiconductor Substances 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000002296 pyrolytic carbon Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 231100000683 possible toxicity Toxicity 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
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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
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
-
- 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
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a preparation method of a metal sulfide composite photocatalyst modified by graphene oxide, belonging to the technical field of photocatalysts. After the pyrite is ball-milled for 5min, the pyrite is sieved by a 100-mesh sieve, washed for six times by ultrapure water (volume is 1:5), and put into a freeze dryer for drying for 48 h. Preparing graphene into 12mg/mL by using ultrapure water, performing ultrasonic treatment for 30min, adding 0.2g of pyrite into 1mL, grinding for 5min by using a mortar, and putting the obtained product into a fume hood for air drying to obtain the composite photocatalyst. The photocatalyst can be applied to photocatalytic degradation of rhodamine in dye wastewater. The photocatalytic activity of the catalyst is better than that of a pure pyrite catalyst under the condition of simulating sunlight at room temperature, and the degradation rate can be improved by 64 percent.
Description
Technical Field
The invention relates to a preparation method of a metal sulfide composite photocatalyst modified by graphene oxide, belonging to the technical field of photocatalysts.
Background
The printing and dyeing wastewater has the characteristics of large water quantity, high chromaticity, poor water quality and low biodegradability, also has the potential toxicity of carcinogenesis, teratogenesis and mutagenesis, belongs to the industrial wastewater difficult to degrade, and the phenomena of low removal efficiency, high cost, incomplete degradation and the like generally exist in the traditional water treatment technologies such as adsorption, membrane separation, photocatalysis, biological methods and the like, so that the wastewater is difficult to effectively degrade. Rhodamine B is a typical representative of such contaminants,
in recent years, the catalytic degradation of organic matters under ultraviolet light irradiation has been greatly progressed, but the proportion of ultraviolet light in the solar spectrum is less than 4%, and the visible light accounts for 43%. In order to make photocatalysis really become a high-efficiency and low-consumption treatment technology, the key point is to fully utilize visible light, and the photocatalysis process with semiconductor is an effective way for utilizing solar energy. Therefore, there is a great need for the development of low-consumption and environmentally friendly organic degradation techniques using semiconductor photocatalysts that respond to visible light. The photocatalysis technology shows great advantages in the aspect of pollutant degradation due to the characteristics of low cost, simple operation, high degradation efficiency and the like, and mainly utilizes the semiconductor catalytic material to absorb light to generate electron-hole pairs to induce oxidation and reduction reactions so as to degrade organic pollutants. Pyrite is the most widely distributed iron sulfide semiconductor in nature, and electrons on a valence band are easy to be excited by external energy to transit to a conduction band, so that good semiconductor performance and optical property are shown. However, at present, researchers at home and abroad mainly focus on the research on the adsorption and exchange of the pyrite and the mineralogical properties, and have little attention and research on the photocatalytic performance of the pyrite.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a graphene oxide modified metal sulfide composite photocatalyst, which is characterized in that graphene is better dispersed into an aqueous solution through water bath ultrasound, and the graphene oxide is favorably promoted to be combined into pyrite through grinding, so that the structure of the graphene oxide is changed, and not only physical mixing is realized. The obtained photocatalyst has good photocatalytic performance, the photocatalytic degradation rate of rhodamine B under the condition of simulating sunlight at room temperature is obviously improved, and the photocatalyst has good application prospect.
A preparation method of a graphene oxide modified metal sulfide composite photocatalyst comprises the following specific steps:
after the pyrite is ball-milled for 5min, the pyrite is sieved by a 100-mesh sieve, washed for six times by ultrapure water (volume is 1:5), and put into a freeze dryer for drying for 48 h.
Preparing graphene oxide into 12mg/mL by using ultrapure water, carrying out ultrasonic treatment in a water bath for 30min at the water bath temperature of 40-45 ℃, adding 0.2g of pyrite into 1mL, grinding for 5min by using a mortar, and putting the ground product into a fume hood for air drying to obtain the composite photocatalyst.
Ultrasonic treatment is carried out for 30min, and the temperature of the water bath is stabilized at 40-45 ℃.
The composite catalyst is applied to photocatalytic degradation of rhodamine B.
The application method of the composite catalyst in photocatalytic degradation of rhodamine B comprises the following specific steps:
adding the composite catalyst into a solution containing rhodamine B, uniformly mixing, and adsorbing to an equilibrium state to obtain a system A;
and (3) carrying out photocatalytic degradation reaction in the system A at room temperature under the illumination condition, measuring the absorbance of the rhodamine B by using an ultraviolet-visible spectrophotometry and calculating the conversion rate of the rhodamine B.
The concentration of rhodamine B in the rhodamine B containing solution is 10 mg/L.
The invention has the beneficial effects that:
the composite photocatalyst has high activity, is used for photocatalytic degradation of rhodamine B dye wastewater, and has better performance than pure FeS under the condition of simulating sunlight at room temperature2The photocatalytic activity and degradation rate of the catalyst can be improved by 67%.
The composite photocatalyst realizes a chemical combination mode of pyrite and graphene oxide through water bath ultrasound and grinding, rather than simple physical mixing.
The method has the advantages of simple process, no need of high temperature and high pressure, water bath temperature of 40-45 ℃, simple operation, easy process control, low price and easy use of pyrite with large dosage in the composite catalyst, and no danger.
Drawings
FIG. 1 is an FTIR chart of the composite photocatalyst of example 1
FIG. 2 is a Raman spectrum of the composite photocatalyst of example 1
FIG. 3 is a diagram illustrating degradation of the composite photocatalyst of example 1 to rhodamine B
From the FTIR chart of fig. 1, it is understood that the composite catalyst (GO-pyrolite) has more carbon-carbon double bonds (C ═ C) at 1628nm than the Pyrite (pyrolite) does, and that the carbon-oxygen single bond 1088nm in the Graphene Oxide (GO) is changed to 1051nm in the composite catalyst, and the formation of new bonds is considered, which indicates that the Pyrite and the graphene oxide are chemically bonded, not simply physically mixed.
From the raman spectrum of fig. 2, it is understood that the composite catalyst (GO-Pyrite) has a characteristic peak of Pyrite (Pyrite) and also has a characteristic peak of Graphene Oxide (GO), and the peak of the composite catalyst (GO-Pyrite) is shifted to the right, indicating that Pyrite and graphene oxide are chemically bonded.
According to a degradation diagram of the composite catalyst in the diagram 3 for rhodamine B, under the illumination condition, the degradation of rhodamine B in 90min reaches 90%, under the dark condition, the degradation of rhodamine B in 90min reaches 78%, the degradation of pure pyrite for rhodamine B is only 23% within 90min, and the degradation of pure pyrite for rhodamine B is only 10% under the dark condition. The prepared composite catalyst can improve the degradation rate of rhodamine B in a short time.
Claims (2)
1. A preparation method of a graphene oxide modified metal sulfide composite photocatalyst comprises the following specific steps:
(1) ball-milling pyrite for 5min by using a ball mill, sieving the pyrite by using a 100-mesh sieve, washing the pyrite by using ultrapure water with the volume of 1:5 for 6 times, and drying the pyrite in a freeze dryer for 48 hours;
(2) preparing graphene oxide into 12mg/mL by using ultrapure water, carrying out ultrasonic treatment in a water bath for 30min at the water bath temperature of 40-45 ℃, adding 0.2g of pyrite into 1mL, grinding for 5min by using a mortar, and putting the ground product into a fume hood for air drying to obtain the composite photocatalyst.
2. The method for preparing the graphene oxide modified metal sulfide composite photocatalyst according to claim 1, wherein the ultrasonic water bath temperature is 40-45 ℃ and the ultrasonic time is 30min, and then the graphene oxide modified metal sulfide composite photocatalyst is ground for 5 min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112961975A (en) * | 2021-01-21 | 2021-06-15 | 桂林理工大学 | Preparation method for inhibiting photo-corrosion by modifying pyrite through DTC-TETA |
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| CN106698526A (en) * | 2017-01-04 | 2017-05-24 | 江苏大学 | Method for preparing g-C3N4/FeS2 nano composite material |
| CN110075896A (en) * | 2019-04-09 | 2019-08-02 | 重庆大学 | FeS2/g-C3N4The preparation method and applications of heterojunction material |
| CN110152687A (en) * | 2019-04-22 | 2019-08-23 | 昆明理工大学 | A method of composite photo-catalyst is prepared using Natural pyrite |
-
2019
- 2019-12-10 CN CN201911258790.2A patent/CN110918102A/en active Pending
Patent Citations (6)
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|---|---|---|---|---|
| CN103326002A (en) * | 2013-06-26 | 2013-09-25 | 冯林杰 | Preparation method of graphene and ferrous disulfide composite positive electrode material |
| CN104402053A (en) * | 2014-11-04 | 2015-03-11 | 中国科学院大学 | Preparation method for graphene-like two-dimension nanosheet |
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| CN106698526A (en) * | 2017-01-04 | 2017-05-24 | 江苏大学 | Method for preparing g-C3N4/FeS2 nano composite material |
| CN110075896A (en) * | 2019-04-09 | 2019-08-02 | 重庆大学 | FeS2/g-C3N4The preparation method and applications of heterojunction material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112961975A (en) * | 2021-01-21 | 2021-06-15 | 桂林理工大学 | Preparation method for inhibiting photo-corrosion by modifying pyrite through DTC-TETA |
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Application publication date: 20200327 |