CN113171791A - Composite catalyst capable of efficiently producing hydrogen peroxide and preparation method thereof - Google Patents
Composite catalyst capable of efficiently producing hydrogen peroxide and preparation method thereof Download PDFInfo
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- CN113171791A CN113171791A CN202110557653.XA CN202110557653A CN113171791A CN 113171791 A CN113171791 A CN 113171791A CN 202110557653 A CN202110557653 A CN 202110557653A CN 113171791 A CN113171791 A CN 113171791A
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 229920000642 polymer Polymers 0.000 claims abstract description 63
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000003756 stirring Methods 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 22
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 14
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 14
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000001301 oxygen Substances 0.000 abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 239000011941 photocatalyst Substances 0.000 description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 14
- 229910021135 KPF6 Inorganic materials 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 239000012153 distilled water Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- -1 Carbon nitride Chemical class 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 230000007281 self degradation Effects 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000013032 photocatalytic reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
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- 238000006731 degradation reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 239000003440 toxic substance Substances 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
- B01J27/24—Nitrogen compounds
-
- 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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/027—Preparation from water
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of photocatalysis, and particularly relates to a composite catalyst capable of efficiently producing hydrogen peroxide and a preparation method thereof. The preparation method of the catalyst comprises the following steps: (1) preparation of carbon nitride polymer: dissolving melamine and cyanuric acid in water, stirring to form a supramolecular complex, washing with water, and drying to obtain a carbon nitride polymer; (2) preparation of the composite catalyst: adding KPF to the carbon nitride polymer of step (1)6And water, mixing uniformly, and then drying and roasting in sequence to obtain the catalyst. The composite catalyst can photolyze water to produce hydrogen peroxide under the condition of not introducing oxygen, and has high catalytic efficiency.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to KPF capable of efficiently producing hydrogen peroxide under the condition of no oxygen introduction6Carbon nitride catalyst and its preparation method.
Background
In industry, H2O2Is an important oxidant which can be used as a clean energy carrier to replace H in fuel cells and even single-chamber cells2To generate electricity with an energy density higher than that of compressed H2Gas, a promising solar fuel. H2O2And can be widely used in the fields of water disinfection, pollutant degradation, bleaching and the like. And, H2O2Ratio H2Easier to store and transport, less risk of explosion, and therefore future H2O2Can be used as a supplementary energy source. Conventional H2O2The electrocatalytic preparation method has serious problems of energy consumption and production safety. And industrial production of H2O2The anthraquinone process consumes a lot of energy, and the cost and the process are complicated, and toxic substances are generated, so that other methods are needed to change the situation.
Photocatalytic production of H with water and oxygen2O2Is a safe, energy-saving, environment-friendly and promising method for realizing high selectivity and high yield of H2O2Production, increase by 2e-Oxygen Reduction Reaction (ORR) or 2e-Water oxidation is necessary. As a class of metal-free polymer photocatalysts, carbon nitride polymers have attracted extensive attention due to their advantages of low cost and tunable optical and electronic properties, but the original CN polymers have relatively weak photocatalytic performance. Mesoporous graphitic carbon nitride (g-C) reported to have high BET surface area3N4) Can be used for photocatalysis H2O2By generating in g-C3N4The nitrogen defect is introduced into the framework, and the photocatalytic activity of the photocatalyst can be obviously improved. But it requires the introduction of oxygen stripsProduction under parts H2O2And catalytic efficiency needs to be improved.
Therefore, further improvements to the prior art are needed.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides a composite catalyst capable of efficiently producing hydrogen peroxide, which can produce hydrogen peroxide without introducing oxygen and has high catalytic efficiency.
The invention also provides a preparation method of the catalyst for producing hydrogen peroxide, which is simple and convenient to popularize.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a composite catalyst capable of efficiently producing hydrogen peroxide and a preparation method thereof comprise the following steps:
(1) preparation of carbon nitride polymer: dissolving melamine and cyanuric acid in water, stirring to form supermolecular composite
Washing the composite with water, and drying to obtain the carbon nitride polymer;
(2) preparation of the composite catalyst: adding KPF to the carbon nitride polymer of step (1)6Mixing with water, mixing, and adding
Drying and roasting the mixture for the second time to obtain the composite catalyst (specifically KPF)6Carbon nitride polymer composite catalyst).
Preferably, the mass ratio of melamine to cyanuric acid in step (1) is (0.5-2): (0.5-2), more preferably 1: 1.
Preferably, in step (1), the melamine and the cyanuric acid are dissolved in water and stirred for 2 to 4 hours.
Preferably, the drying temperature in step (1) is 55 to 65 ℃, more preferably 60 ℃.
Preferably, KPF in step (2)6The mass ratio of the carbon nitride polymer to the carbon nitride polymer is (0.01-2): 10.
Preferably, the temperature at the time of drying in step (2) is 90 to 110 ℃, and more preferably 100 ℃.
Preferably, the roasting conditions of the step (2) are as follows: roasting at 500-600 deg.c for 3-5 hr.
The composite catalyst which is prepared by the method and can efficiently produce hydrogen peroxide.
The use of the above catalyst in the production of hydrogen peroxide.
This experiment can prepare hydrogen peroxide under the condition of not letting in oxygen, and in the experiment of producing hydrogen peroxide, solution and air contact during the stirring actually still have a small amount of oxygen to dissolve in water in order to promote the production of hydrogen peroxide, and a small amount of oxygen can produce hydrogen peroxide in this experiment with air, does not need to let in oxygen in addition.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention is realized by adopting the method in KPF6Thermally decomposing the melamine-cyanuric acid supramolecular complex in the presence of K+And PF6 -Is mixed with carbon nitride polymer to prepare a photocatalyst with high specific surface area2O2The composite material has reaction activity, so that the catalytic efficiency is high;
2. KPF prepared by the invention6The carbon nitride polymer composite catalyst can be used in the presence of oxygen2Under the condition of (1), the composite catalyst is used for efficiently preparing hydrogen peroxide by photolyzing water, thereby reducing the consumption of energy, has stable performance and low cost, saves energy, and can be used for preparing hydrogen peroxide without O communication2The hydrogen peroxide is produced by photocatalysis, and the method has good market application prospect.
Drawings
FIG. 1 is g-C prepared in comparative example 13N4And a scanning electron microscope image of the carbon nitride polymer prepared in example 1, wherein: the left picture is g-C3N4And the right figure is a carbon nitride polymer.
FIG. 2 is a graph showing the H production of the photocatalysts obtained in example 1 and comparative example 1 under the oxygen-free condition2O2A curve;
FIG. 3 shows the production of H by the photocatalyst obtained in example 1 under different conditions2O2A curve;
FIG. 4 shows the production of H by different electron donor pairs for the photocatalyst of example 12O2The impact of performance;
FIG. 5 shows a photocatalyst pair H prepared in example 1 and comparative example 12O2(ii) self-degradation conditions;
fig. 6 is an XRD pattern of the carbon nitride polymer and catalyst prepared in example 1.
Detailed Description
The present invention is further illustrated by the following examples, but is not intended to be limited thereto.
Example 1
The preparation method of the composite catalyst capable of efficiently producing hydrogen peroxide comprises the following steps:
(1) preparation of carbon nitride polymer: dissolving 5g of melamine and 5g of cyanuric acid in 40 ml of distilled water, stirring for 3 h to form a supramolecular complex, washing for 6 times with 25ml of distilled water, and drying in a vacuum oven at 60 ℃ to obtain a white sample, wherein about 8 g of carbon nitride polymer is obtained;
(2) preparation of the composite catalyst: 0.005g of KPF6Adding the mixture into 5g of the carbon nitride polymer prepared in the step (1), adding 10 ml of deionized water, continuously stirring and reacting for 1 h, drying at the temperature of 100 ℃, and finally burning in a tube furnace at the temperature of 550 ℃ for 4 h to obtain KPF with the mass ratio of 0.1 percent6A carbon nitride polymer composite catalyst (the mass ratio of 0.1% in this case means KPF)6The amount used was 0.1% by mass of the carbon nitride polymer, which is the same below).
Example 2
The preparation method of the composite catalyst capable of efficiently producing hydrogen peroxide comprises the following steps:
(1) preparation of carbon nitride polymer: dissolving 5g of melamine and 5g of cyanuric acid in 40 ml of distilled water, stirring for 2 h to form a supramolecular complex, washing with 25ml of distilled water for 6 times, and drying in a vacuum oven at 60 ℃ to obtain a white sample, wherein about 8 g of carbon nitride polymer is obtained;
(2) preparation of the composite catalyst: 0.05g of KPF6Adding the mixture into 5g of the carbon nitride polymer prepared in the step (1), adding 10 ml of deionized water, and continuously stirring the mixture to react the mixture 1h, drying at 100 ℃, and finally burning in a tube furnace at 550 ℃ for 4 h to obtain 1% KPF6A carbon nitride polymer composite catalyst.
Example 3
The preparation method of the composite catalyst capable of efficiently producing hydrogen peroxide comprises the following steps:
(1) preparation of carbon nitride polymer: dissolving 5g of melamine and 5g of cyanuric acid in 40 ml of distilled water, stirring for 2 h to form a supramolecular complex, washing with 25ml of distilled water for 6 times, and drying in a vacuum oven at 60 ℃ to obtain a white sample, wherein about 8 g of carbon nitride polymer is obtained;
(2) preparation of the composite catalyst: 0.25g of KPF6Adding the mixture into 5g of the carbon nitride polymer prepared in the step (1), adding 10 ml of deionized water, continuously stirring and reacting for 1 h, drying at 100 ℃, and finally burning in a tube furnace at 550 ℃ for 4 h to obtain 5 mass percent KPF6A carbon nitride polymer composite catalyst.
Example 4
The preparation method of the composite catalyst capable of efficiently producing hydrogen peroxide comprises the following steps:
(1) preparation of carbon nitride polymer: dissolving 5g of melamine and 5g of cyanuric acid in 40 ml of distilled water, stirring for 2 h to form a supramolecular complex, washing with 25ml of distilled water for 6 times, and drying in a vacuum oven at 60 ℃ to obtain a white sample, wherein about 8 g of carbon nitride polymer is obtained;
(2) 0.5g of KPF6Adding the mixture into 5g of the carbon nitride polymer prepared in the step (1), adding 10 ml of deionized water, continuously stirring and reacting for 1 h, drying at 100 ℃, and finally burning in a tube furnace at 550 ℃ for 4 h to obtain KPF with the mass ratio of 10%6A carbon nitride polymer composite catalyst.
The invention uses a small amount of KPF6Modifying the carbon nitride polymer to prepare KPF6Carbon nitride polymers, optionally with O2Photolysis of water to produce H under the conditions of (1)2O2。
Example 5
The preparation method of the composite catalyst capable of efficiently producing hydrogen peroxide comprises the following steps:
(1) preparation of carbon nitride polymer: dissolving 5g of melamine and 5g of cyanuric acid in 40 ml of distilled water, stirring for 4 h to form a supramolecular complex, washing with 25ml of distilled water for 6 times, and drying in a vacuum oven at 60 ℃ to obtain a white sample, wherein about 8 g of carbon nitride polymer is obtained;
(2) preparation of the composite catalyst: 0.1g of KPF6Adding the mixture into 5g of the carbon nitride polymer prepared in the step (1), adding 10 ml of deionized water, continuously stirring and reacting for 1 h, drying at 100 ℃, and finally burning in a 600 ℃ tubular furnace for 3 h to obtain 2 mass percent of KPF6A carbon nitride polymer composite catalyst.
Example 6
The preparation method of the composite catalyst capable of efficiently producing hydrogen peroxide comprises the following steps:
(1) preparation of carbon nitride polymer: dissolving 5g of melamine and 5g of cyanuric acid in 40 ml of distilled water, stirring for 3.5 h to form a supramolecular complex, washing for 6 times with 25ml of distilled water, and drying in a vacuum oven at 60 ℃ to obtain a white sample, wherein about 8 g of carbon nitride polymer is obtained;
(2) preparation of the composite catalyst: 1g of KPF6Adding the mixture into 5g of the carbon nitride polymer prepared in the step (1), adding 10 ml of deionized water, continuously stirring and reacting for 1 h, drying at 100 ℃, and finally burning in a tubular furnace at 500 ℃ for 5 h to obtain 20 mass percent of KPF6A carbon nitride polymer composite catalyst.
Comparative example 1
This comparative example uses g-C3N4The preparation method of the catalyst comprises the following steps: 2 g of melamine is roasted for 4 hours in a muffle furnace at 550 ℃ to obtain the melamine.
FIG. 1 shows g-C3N4And a scanning electron microscope image of the carbon nitride polymer, wherein: the left panel is g-C prepared in comparative example 13N4In the SEM image of (A) of (B),the right figure is an SEM image of the carbon nitride polymer prepared in example 1. As can be seen from FIG. 1, the carbon nitride polymer has a larger specific surface area, and therefore has better hydrogen peroxide generation performance, so that the catalytic efficiency is improved.
Photolytic water production of H2O2：
Simulating visible light by using a 3W LED lamp, carrying out dark reaction for 30 min before illumination to achieve adsorption balance, adding 99.5% of isopropanol in the reaction process, and analyzing and testing H by adopting a common titanium salt spectrophotometry2O2The concentration of (c).
And (3) carrying out an effect test:
1. investigation of catalytic Performance of the catalysts prepared in examples 1-4 and comparative example 1:
is not communicated with2Produce H2O2Experiment: A3W LED lamp is used as a light source, the stirring of a reaction bottle is magnetic suspension, and a cooling system is externally connected. The catalysts (g-C) prepared in comparative example 1 were each separately prepared3N4) 50 mg of KPF prepared in examples 1-46Carbon nitride Polymer composite catalyst 50 mg (catalyst KPF prepared in examples 1-4)6The mass ratio of the carbon nitride polymer to the carbon nitride polymer is as follows in sequence: 0.1 wt%, 1 wt%, 5 wt%, 10 wt%) was added to 45 mL of deionized water, and 5mL of isopropyl alcohol was added to obtain a suspension. In birth of H2O2Firstly, ultrasonically dispersing a quartz reaction bottle filled with five groups of suspension for 5 min, then placing the quartz reaction bottle into a photocatalytic reaction system, only opening a stirring device, and not introducing O2Stirring and adsorbing under dark condition, reaching adsorption equilibrium for 30 min, then turning on a light source, sampling after 10 min, wherein the volume of the sampled sample is about 2 mL, adding 1 mL of color developing agent, and testing absorbance at 410 nm after developing for 10 min.
Production of H by the photocatalysts obtained in examples 1 to 4 and comparative example 12O2The curves are shown in figure 2. As can be seen from FIG. 2, even when O is not turned on2Under the condition, the photocatalyst prepared by the invention produces H2O2The performance had little effect, whereas the catalytic performance of the catalyst prepared in comparative example 1 was significantly worse than that of example 1. Specifically, the product H is produced in 70 min2O2In the experimentComparative example 1 catalyst (g-C)3N4) Produce H2O2In an amount of 1.01 mmol/L, example 2 catalyst (1 wt%) and example 3 catalyst (5 wt%) produced H2O2In amounts of 2.24 mmol/L and 2.23 mmol/L, respectively, in examples 1-4, example 2 catalyst (KPF)6The dosage is 1 percent of the mass of the carbon nitride polymer) to produce H2O2The performance is the best.
2. Examination of the photocatalyst obtained in example 1 under different conditions for H production2O2The method has the effects that a 3 w LED lamp is used as a light source, four parts of the photocatalyst prepared in the example 2, which are respectively 50 mg, are respectively added into 50 ml of deionized water, then air is respectively blown into the four parts of the catalyst for 30 min, 30 mu L of 2 mol/L hydrochloric acid is dropwise added, and 30 min of O is introduced2Adding 5ml of isopropanol and introducing O for 30 min2 5ml of isopropanol are added and 8 drops of 2 mol/L hydrochloric acid are added dropwise. In birth of H2O2Firstly, ultrasonically dispersing a quartz reaction bottle filled with four parts of suspension for 5 min, stirring and adsorbing the suspension under dark conditions, keeping the adsorption balance for 30 min, then placing the quartz reaction bottle into a photocatalytic reaction system, only starting a stirring device, then turning on a light source, sampling after 10 min, and repeating the operation to test the absorbance. The test results are shown in FIG. 3.
As can be seen from FIG. 3, O is not turned on2Production of H under the conditions2O2Best performance, can produce H in 70 min2O2About 2.24 mmol/L.
3. Examination of the different electron donor pairs H yield of the photocatalyst of example 12O2Impact of Performance: five portions of the photocatalyst prepared in example 2, each 50 mg, were added to 45 mL of deionized water, and 5mL of isopropyl alcohol, ethanol, methanol, formic acid, and benzyl alcohol, respectively, were added. In birth of H2O2Firstly, ultrasonically dispersing a quartz reaction bottle filled with five parts of suspension for 5 min, then putting the quartz reaction bottle into a photocatalytic reaction system, only opening a stirring device, and introducing O2Stirring and adsorbing under dark condition, keeping dissolved oxygen balance for 30 min, turning on light source, sampling after 10 min, and repeating the above steps to test absorbance. Test knotThe result is shown in FIG. 4.
As can be seen from FIG. 4, at 70 min, isopropanol was added to produce H2O2The amount of the ethanol reaches 2.20 mmol/L, and the ethanol is added to produce H2O2The amount of the methanol reaches 2.34 mmol/L, and methanol is added to produce H2O2The amount of the sodium hydrogen carbonate reaches 2.18 mmol/L, and formic acid is added to produce H2O2The amount of the catalyst reaches 2.24 mmol/L, and benzyl alcohol is added to produce H2O2The amount of (b) was 3.61 mmol/L. H production of photocatalysts prepared by adding the first 4 electron donors2O2The performance is almost the same, but the yield is obviously higher when benzyl alcohol is added, because the electron delocalization on the aromatic ring in the aromatic alcohol is possible to change the H production2O2Of redox reaction pathway, or inhibition of H2O2Decomposition of (3).
4. Photocatalyst pairs H prepared in examples 1 to 4 and comparative example 12O2Investigation of self-degradation conditions of (1): 50 mg of the catalyst (g-C) prepared in comparative example 1 was added to each of the catalyst solutions3N4) KPF prepared in examples 1-46Adding carbon nitride polymer composite catalyst (the dosage of the five groups of catalysts is 50 mg) into 50 ml of 2 mmol/L H2O2And (3) dripping 30 mu L of 2 mol/L hydrochloric acid into the solution, only starting a stirring device, stirring and adsorbing under the dark condition, keeping the adsorption balance for 30 min, then turning on a light source, sampling after 10 min, and repeating the operation to test the absorbance. The test results are shown in FIG. 5.
The self-degradation was seen by the reaction of hydrochloric acid with the hydrogen peroxide produced, and as can be seen in fig. 5, the self-degradation with the catalyst of example 2 was always minimal, with H at 70 min2O2The concentration of (D) was still 1.91 mmol/L.
5. Carbon nitride Polymer prepared in example 1, KPF prepared in examples 1-46The XRD pattern of the/carbon nitride polymer composite catalyst is shown in figure 6. As can be seen, two diffraction peaks at 13.0 DEG and 27.4 DEG, which can be assigned to g-C, were observed in the XRD pattern of the carbon nitride polymer3N4The (100) and (002) planes of (1). The former peak indicates in-plane stacking and the latter peak indicates g-C3N4Interfacial stacking of sheets. Carbon nitride polymersTwo diffraction peaks at 13.0 DEG and 27.4 DEG were observed in the XRD pattern, corresponding to g-C reported in the literature3N4The (100) and (002) planes of (A) are completely identical, demonstrating that the prepared sample is a carbon nitride polymer. KPFs of examples 1-46Peak height as KPF observed in/carbon nitride Polymer composite catalysts6The increase in content gradually decreased, but the peak did not move at all at 27.4 °. This indicates KPF6The presence of (b) promotes the formation of a carbon nitride polymer network without altering the interlaminar stacking of the carbon nitride polymer matrix.
It should be noted that: the invention produces H by photolyzing water2O2The devices and systems used in the process may be conventional in the art.
Claims (8)
1. A preparation method of a composite catalyst capable of efficiently producing hydrogen peroxide is characterized by comprising the following steps:
(1) preparation of carbon nitride polymer: dissolving melamine and cyanuric acid in water, stirring to form composite, and mixing
Washing the compound with water, and drying to obtain the carbon nitride polymer;
(2) preparation of the composite catalyst: adding KPF to the carbon nitride polymer of step (1)6Mixing with water, mixing, and adding
And drying and roasting the mixture for the second time to obtain the composite catalyst.
2. The method for preparing a composite catalyst capable of efficiently producing hydrogen peroxide according to claim 1, wherein the mass ratio of melamine to cyanuric acid in the step (1) is (0.5-2) to (0.5-2).
3. The method for preparing a composite catalyst capable of efficiently producing hydrogen peroxide according to claim 1, wherein the stirring time in the step (1) is 2 to 4 hours.
4. The method for preparing a composite catalyst for efficient production of hydrogen peroxide according to claim 1, wherein the drying temperature in the step (1) is 55 to 65 ℃.
5. The method for preparing a composite catalyst for efficiently producing hydrogen peroxide according to claim 1, wherein KPF is used in the step (2)6The mass ratio of the carbon nitride polymer to the carbon nitride polymer is (0.01-2): 10.
6. The method for preparing a composite catalyst capable of efficiently producing hydrogen peroxide according to claim 1, wherein the drying temperature in the step (2) is 90 to 110 ℃.
7. The method for preparing a composite catalyst capable of efficiently producing hydrogen peroxide according to claim 1, wherein the calcination conditions in the step (2) are as follows: roasting at 500-600 deg.c for 3-5 hr.
8. The composite catalyst for efficiently producing hydrogen peroxide, which is prepared by the method of any one of claims 1 to 7.
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