CN115779944A - Modified carbon nitride based on alkali metal ions, preparation method thereof and photocatalytic H production 2 O 2 In (1) - Google Patents
Modified carbon nitride based on alkali metal ions, preparation method thereof and photocatalytic H production 2 O 2 In (1) Download PDFInfo
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical class N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 45
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses an alkali metal ion-based modified carbon nitride, a preparation method thereof and a method for producing H by photocatalysis 2 O 2 The use of (1). A preparation method of modified carbon nitride based on alkali metal ions comprises the following steps: (1) Adding an alkali metal salt into dicyanodiamine or melamine, then adding water, uniformly stirring, carrying out hydrothermal reaction, cooling after the hydrothermal reaction is finished, and drying to obtain a white solid, wherein the alkali metal salt is a rubidium salt and/or a cesium salt; (2) Calcining the white solid obtained in the step (1),and after cooling to room temperature, obtaining a yellow solid, and cleaning and drying the yellow solid to obtain the alkali metal ion-based modified carbon nitride. The alkali metal ion modified carbon nitride provided by the invention can be used for producing H by photocatalysis 2 O 2 Good activity, especially for producing H by cesium ion modified carbon nitride photocatalysis 2 O 2 The activity is improved by 21 times compared with that of unmodified carbon nitride.
Description
The technical field is as follows:
the invention relates to a method for producing H by photocatalytic carbon nitride 2 O 2 The technical field, in particular to modified carbon nitride based on alkali metal ions, a preparation method thereof and H production by photocatalysis 2 O 2 The use of (1).
The background art comprises the following steps:
hydrogen peroxide is also called hydrogen peroxide (chemical formula H) 2 O 2 ) It is an important inorganic chemical product, and can be extensively used in the fields of paper pulp bleaching, organic synthesis, environmental remediation, disinfection, fuel cell and military affairs, etc. And, in H 2 O 2 In the application process, only water and active oxygen are generated, the environment is not polluted, and the product is called as a green product. Currently, H is established industrially 2 O 2 The mode of production of (A) is almost derived from the anthraquinone process. It is prepared by multi-stage hydrogenation and organic solvent oxidation processes, followed by extraction and distillation. In the reaction process, 2-alkylanthraquinone needs to be hydrogenated and reduced into hydroquinone under the action of Pd catalyst, and a large amount of H is needed 2 And a noble metal catalyst, which not only causes an increase in cost, but also easily causes problems such as environmental pollution in the production process. Still others are based on H 2 And O 2 Obtained by direct chemical combination on noble metal catalyst; however, H in the course of this reaction 2 And O 2 Explosions are prone to occur and so the proportion must be maintained outside the explosive limits. And the photocatalysis produces H 2 O 2 Is one without H 2 And can react at room temperature. Meanwhile, carbon nitride (carbon nitride) has been studied in a large amount as a photocatalyst with high selectivity in this reaction.
Carbon nitride as a product of H 2 O 2 The common modification method of the photocatalyst comprises preparation of a composite semiconductor, molecular doping, element doping, surface sensitization and the like. The element doping is more applied, and the main doping elements comprise Na, K, P and the like. Although these modification methods greatly improve the photocatalytic H production 2 O 2 However, no performance studies have been made in river, lake or tap water systems. As is well known, H 2 O 2 Is Fenton advanced oxidationThe main reactant of the technology, and the Fenton advanced oxidation technology is mainly applied to the fields of sewage treatment and the like. Therefore, the photocatalytic production of H by carbon nitride in practical water source environments (such as river water, lake water, tap water, etc.) was explored 2 O 2 The technology is very necessary.
The invention content is as follows:
the invention solves the problems in the prior art, and provides alkali metal ion-based modified carbon nitride, a preparation method thereof and photocatalytic H production 2 O 2 The invention provides application of alkali metal ion modified carbon nitride in producing H in river water, lake water and tap water system by photocatalysis 2 O 2 The activity was not significantly attenuated compared to distilled water.
The invention aims to provide a preparation method of modified carbon nitride based on alkali metal ions, which comprises the following steps:
(1) Adding an alkali metal salt into dicyanodiamine or melamine, then adding water, uniformly stirring, carrying out hydrothermal reaction, cooling after the hydrothermal reaction is finished, and drying to obtain a white solid, wherein the alkali metal salt is a rubidium salt and/or a cesium salt;
(2) Calcining the white solid obtained in the step (1), cooling to room temperature to obtain a yellow solid, and cleaning and drying the yellow solid to obtain the alkali metal ion-based modified carbon nitride.
Preferably, the rubidium salt is rubidium chloride or cesium chloride, and the cesium salt is cesium chloride or cesium nitrate.
Preferably, the mass ratio of dicyandiamide or melamine to alkali metal salt in the step (1) is 1.
Preferably, the reaction temperature of the hydrothermal reaction in the step (1) is 160-200 ℃, and the reaction time is 8-12h.
Preferably, the calcining temperature in the step (2) is 500-600 ℃, the calcining time is 2-4h, and the heating rate is 2-10 ℃/min.
Preferably, the specific steps of washing and drying the yellow solid in the step (2) to obtain the modified carbon nitride are as follows: grinding the yellow solid into powder, and respectively filtering and cleaning the powder by using distilled water and ethanol to obtain the alkali metal ion modified carbon nitride.
The invention also protects the alkali metal ion-based modified carbon nitride prepared by the preparation method.
The invention also protects the photocatalytic H production based on the alkali metal ion modified carbon nitride 2 O 2 The application comprises the following steps:
s1, putting the carbon nitride modified based on the alkali metal ions into a reaction container, adding an ethanol water solution, and stirring to uniformly disperse the carbon nitride modified based on the alkali metal ions in the ethanol water solution;
s2, placing the reaction container in the step S1 in a multi-channel reactor (Pofely PCX-50C), introducing cooling circulating water at 10 ℃, stirring, continuously introducing oxygen, and illuminating by using an LED white light or a xenon lamp to obtain H 2 O 2 。
The alkali metal ion-based modified carbon nitride provided by the invention is particularly applied to photocatalytic H production in river water, lake water or tap water systems 2 O 2 。
Preferably, the mass-to-volume ratio of the alkali metal ion-modified carbon nitride-based solution in step S1 to the ethanol aqueous solution is 0.0006 to 1g/mL, and the volume fraction of the ethanol aqueous solution is 10% to 15%.
Preferably, the illumination time in step S2 is 50-70min.
Preferably, the flow rate of the oxygen is 1.3mL/min, and the power of the LED white light is 30.69mW/cm 2 。
Compared with the prior art, the invention has the following advantages:
1. the alkali metal ion modified carbon nitride provided by the invention can be used for producing H by photocatalysis 2 O 2 Good activity, in particular to the photocatalytic production of H by cesium ion modified carbon nitride (CN-Cs) 2 O 2 The activity is improved by 21 times compared with that of unmodified carbon nitride.
2. Photocatalytic production of H from cesium ion modified carbon nitride (CN-Cs) in river, lake and tap water systems 2 O 2 Activity is not significantly attenuated compared to distilled water, cesiumIon-modified carbon nitride (CN-Cs) is continuously illuminated for 12H 2 O 2 The yield of (2) was more than 8mmol/g, and no decay occurred.
3. The oxygen chemisorption amount of the cesium ion modified carbon nitride (CN-Cs) was 112.47. Mu. Mol/g, which was 8.53 times that of the unmodified carbon nitride, and was also superior to the adsorption amounts of CN-K and CN-Rb (47.96 and 97.47. Mu. Mol/g, respectively).
Description of the drawings:
FIG. 1 is a Fourier infrared (FT-IR) spectrum of cesium ion modified carbon nitride of example 1 versus unmodified carbon nitride of comparative example 1.
FIG. 2 is a structural diagram of cesium ion-modified carbon nitride in example 1 and unmodified carbon nitride in comparative example 1.
Fig. 3 is a water contact angle picture of cesium ion-modified carbon nitride in example 1, unmodified carbon nitride in comparative example 1, lithium ion-modified carbon nitride in comparative example 2, sodium ion-modified carbon nitride in comparative example 3, potassium ion-modified carbon nitride in comparative example 4, and rubidium ion-modified carbon nitride in comparative example 5.
FIG. 4 is a graph showing the difference in dissolved oxygen (. DELTA.DO) in the solution before and after addition of the catalyst to cesium ion-modified carbon nitride in example 1, unmodified carbon nitride in comparative example 1, lithium ion-modified carbon nitride in comparative example 2, sodium ion-modified carbon nitride in comparative example 3, potassium ion-modified carbon nitride in comparative example 4, and rubidium ion-modified carbon nitride in comparative example 5.
FIG. 5 shows the H of cesium ion-modified carbon nitride and the unmodified carbon nitride of comparative example 1 under white light excitation of LED in example 4 2 O 2 The yield of (2).
FIG. 6 shows the visible light excitation of cesium ion-modified carbon nitride and the unmodified carbon nitride of comparative example 1 in example 5 2 O 2 The yield of (2).
FIG. 7 is H in different water source systems under the excitation of LED white light for cesium ion modified carbon nitride in examples 4 and 6-8 2 O 2 The yield of (2).
The specific implementation mode is as follows:
the following examples are further illustrative of the present invention and are not intended to be limiting thereof.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention. Unless otherwise specified, the experimental materials and reagents used herein are all conventional commercial products in the art.
In the following examples, the flow rate of oxygen was 1.3mL/min, and the power of LED white light was 30.69mW/cm 2 。
Example 1
The preparation method of the modified carbon nitride based on the alkali metal ions comprises the following steps:
(1) Weighing 5g of dicyanodiamine and 0.5g of cesium chloride, putting the dicyanodiamine and the cesium chloride into a lining of a hydrothermal kettle made of a teflon material, adding 50mL of distilled water, and stirring for 2 hours at room temperature on an electromagnetic stirrer;
(2) Putting the hydrothermal kettle in the step (1) into an oven at 180 ℃ for hydrothermal reaction for 10 hours;
(3) After the hydrothermal reaction in the step (2) is finished, drying the cooled reaction liquid in an oven at 80 ℃ for 10 hours to obtain a white solid;
(4) Calcining the white solid obtained in the step (3) in a muffle furnace at 550 ℃ for 4h at a heating rate of 4 ℃/min, and cooling to room temperature to obtain a yellow solid;
(5) And (5) grinding the yellow solid powder obtained in the step (4), respectively performing suction filtration and cleaning for 3 times by using distilled water and ethanol, and finally drying to obtain cesium ion modified carbon nitride, which is recorded as CN-Cs.
Comparative example 1
The preparation of the unmodified carbon nitride comprises the following steps:
(1) Weighing 5g of dicyanodiamide, placing the dicyanodiamide in a muffle furnace for calcination treatment, calcining for 4h at 550 ℃, heating at the rate of 2 ℃/min, and cooling to room temperature to obtain yellow solid;
(2) And (3) grinding the yellow solid powder obtained in the step (2) to obtain unmodified carbon nitride, which is recorded as CN.
As shown in FIGS. 1 and 2, the CN-Cs obtained in example 1 have a structure similar to that of CN obtained in comparative example 1, and the structure of CN-Cs has succeeded in introducing Cs + 。
Comparative example 2
Same as example 1, except that cesium chloride was replaced with lithium chloride.
Comparative example 3
Same as example 1, except that cesium chloride was replaced with sodium chloride.
Comparative example 4
The same as in example 1, except that cesium chloride was replaced with potassium chloride.
Comparative example 5
Same as example 1, except that cesium chloride was replaced with rubidium chloride.
As shown in FIG. 3, the CN-Cs has the smallest water contact angle and the best hydrophilicity, and as shown in FIG. 4, the CN-Cs has the highest dissolved oxygen difference and can autonomously adsorb a large amount of oxygen in the air.
Example 2
The preparation method of the carbon nitride based on cesium ion modification comprises the following steps:
(1) Weighing 5g of melamine and 0.3g of cesium chloride, placing the melamine and the cesium chloride into a lining of a hydrothermal kettle made of Teflon, adding 50mL of distilled water, and stirring for 2 hours at room temperature on an electromagnetic stirrer;
(2) Placing the hydrothermal kettle in the step (1) in an oven at 170 ℃ for hydrothermal reaction for 11h;
(3) After the hydrothermal reaction in the step (2) is finished, drying the cooled reaction liquid in an oven at 80 ℃ for 10 hours to obtain a white solid;
(4) Placing the white solid obtained in the step (3) in a muffle furnace for calcination treatment, calcining at 500 ℃ for 4.5h, heating at a rate of 2 ℃/min, and cooling to room temperature to obtain a yellow solid;
(5) And (5) grinding the yellow solid powder obtained in the step (4), respectively performing suction filtration and cleaning for 3 times by using distilled water and ethanol, and finally drying to obtain cesium ion modified carbon nitride, which is recorded as CN-Cs.
Example 3
The preparation method of the cesium ion modified carbon nitride comprises the following steps:
(1) Weighing 5g of dicyanodiamine and 0.7g of cesium chloride, putting the dicyanodiamine and the cesium chloride into a lining of a hydrothermal kettle made of a teflon material, adding 50mL of distilled water, and stirring for 2 hours at room temperature on an electromagnetic stirrer;
(2) Placing the hydrothermal kettle in the step (1) in an oven at 190 ℃ for hydrothermal reaction for 9 hours;
(3) After the hydrothermal reaction in the step (2) is finished, drying the cooled reaction liquid in an oven at 80 ℃ for 10 hours to obtain a white solid;
(4) Calcining the white solid obtained in the step (3) in a muffle furnace for 3.5h at 600 ℃, heating at a speed of 10 ℃/min, and cooling to room temperature to obtain a yellow solid;
(5) And (4) grinding the yellow solid powder obtained in the step (4), respectively carrying out suction filtration and cleaning for 3 times by using distilled water and ethanol, and finally drying to obtain cesium ion modified carbon nitride which is marked as CN-Cs.
Example 4
The application of the cesium ion modified carbon nitride specifically comprises the following steps:
(1) 0.03g of CN-Cs obtained in example 1 was taken in a reaction flask, and 50mL of an aqueous ethanol solution (volume fraction: 10%) was added thereto, followed by sonication for 20min to thoroughly disperse the CN-Cs.
(2) And (2) placing the reaction bottle in the step (1) into a multi-channel reactor (Pofely PCX-50C), introducing cooling circulating water at 10 ℃, stirring, and irradiating for 1h by using LED white light.
(3) After the light irradiation, 3mL of the reaction mixture was collected every 15min, centrifuged (10000rpm, 5min), and 1mL of the supernatant was collected.
(4) And (3) adding 1.25mL of distilled water, 0.8mL of phosphate buffer solution, 50 mu L of peroxidase and 50 mu L of N, N-diethyl-p-phenylenediamine to 1mL of supernatant obtained in the step (3), shaking uniformly for color development, and measuring a liquid ultraviolet-visible spectrophotometer. Calculation of H from the absorbance 2 O 2 The concentration of (c).
As shown in FIG. 5, it was demonstrated that CN-Cs has excellent activity.
Example 5
The application of the cesium ion modified carbon nitride specifically comprises the following steps:
(1) 0.05g of CN-Cs obtained in example 1 was taken in a reaction flask, and 200mL of an aqueous ethanol solution (volume fraction: 10%) was added thereto, followed by sonication for 20min to thoroughly disperse the CN-Cs.
(2) The reaction flask in step (1) was stirred and xenon-lamp illuminated for 12h (λ >420 nm).
(3) After the light irradiation, 3mL of the reaction mixture was collected every 1 hour, centrifuged (10000rpm, 5min), and 1mL of the supernatant was collected.
(4) Adding 1.25mL of distilled water, 0.8mL of phosphate buffer solution, 50 mu L of peroxidase and 50 mu L of N, N-diethyl p-phenylenediamine to 1mL of supernatant obtained in the step (3), shaking uniformly, developing color, and measuring a liquid ultraviolet-visible spectrophotometer. Calculation of H from absorbance 2 O 2 The concentration of (2).
As shown in FIG. 6, CN-Cs are shown to have excellent long-term stability.
Example 6
The application of the cesium ion modified carbon nitride specifically comprises the following steps:
(1) 0.03g of CN-Cs obtained in example 1 was taken in a reaction flask, and 50mL of an aqueous ethanol solution (volume fraction: 10%) was added thereto, followed by sonication for 20min to thoroughly disperse the CN-Cs. The ethanol water solution is prepared by river water.
(2) And (2) placing the reaction bottle in the step (1) into a multi-channel reactor (Pofilly PCX-50C), introducing cooling circulating water at 10 ℃, stirring, and irradiating by using LED white light for 1h.
(3) After the light irradiation, 3mL of the reaction mixture was collected every 15min, centrifuged (10000rpm, 5min), and 1mL of the supernatant was collected.
(4) And (3) adding 1.25mL of distilled water, 0.8mL of phosphate buffer solution, 50 mu L of peroxidase and 50 mu L of N, N-diethyl-p-phenylenediamine to 1mL of supernatant obtained in the step (3), shaking uniformly for color development, and measuring a liquid ultraviolet-visible spectrophotometer. Calculation of H from the absorbance 2 O 2 The concentration of (c).
Example 7
The application of the cesium ion modified carbon nitride specifically comprises the following steps:
(1) 0.03g of CN-Cs obtained in example 1 was put in a reaction flask, 50mL of pure water was added thereto, and the mixture was dispersed thoroughly by sonication for 20 min. The ethanol aqueous solution is prepared by lake water.
(2) And (2) placing the reaction bottle in the step (1) into a multi-channel reactor (Pofely PCX-50C), introducing cooling circulating water at 10 ℃, stirring, and irradiating for 1h by using LED white light.
(3) After the light irradiation, 3mL of the reaction mixture was collected every 15min, centrifuged (10000rpm, 5min), and 1mL of the supernatant was collected.
(4) And (3) adding 1.25mL of distilled water, 0.8mL of phosphate buffer solution, 50 mu L of peroxidase and 50 mu L of N, N-diethyl-p-phenylenediamine to 1mL of supernatant obtained in the step (3), shaking uniformly for color development, and measuring a liquid ultraviolet-visible spectrophotometer. Calculation of H from absorbance 2 O 2 The concentration of (2).
Example 8
The application of the cesium ion modified carbon nitride specifically comprises the following steps:
(1) 0.03g of CN-Cs obtained in example 1 was placed in a reaction tube, and 50mL of an aqueous ethanol solution (volume fraction: 10%) was added thereto, followed by sonication for 20min to thoroughly disperse the CN-Cs. The ethanol water solution is prepared by tap water.
(2) And (2) placing the reaction bottle in the step (1) into a multi-channel reactor (Pofely PCX-50C), introducing cooling circulating water at 10 ℃, stirring, and irradiating for 1h by using LED white light.
(3) After the light irradiation, 3mL of the reaction mixture was collected every 1 hour, centrifuged (10000rpm, 5min), and 1mL of the supernatant was collected.
(4) Adding 1.25mL of distilled water, 0.8mL of phosphate buffer solution, 50 mu L of peroxidase and 50 mu L of N, N-diethyl p-phenylenediamine to 1mL of supernatant obtained in the step (3), shaking uniformly, developing color, and measuring a liquid ultraviolet-visible spectrophotometer. Calculation of H from the absorbance 2 O 2 The concentration of (c).
As shown in FIG. 7, it is demonstrated that CN-Cs has excellent activity under different systems.
Example 9
The application of the cesium ion modified carbon nitride specifically comprises the following steps:
(1) 0.03g of CN-Cs obtained in example 1 was placed in a reaction tube and purged at 300 ℃ for 2 hours under an inert atmosphere.
(2) When the temperature in the step (1) is reduced to 50 ℃, continuously introducing 2000ppm of O 2 And adsorbing for 2h to saturation.
(3) And (3) after the adsorption in the step (2) is saturated, introducing 50mL/min Ar for purging for 1h, heating from 50 ℃ to 500 ℃ in 50mL/min Ar atmosphere at the heating rate of 10 ℃/min, and detecting the desorbed gas by TCD.
The above embodiments are only for the purpose of helping understanding the technical solution of the present invention and the core idea thereof, and it should be noted that those skilled in the art can make several improvements and modifications to the present invention without departing from the principle of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.
Claims (10)
1. A preparation method of modified carbon nitride based on alkali metal ions is characterized by comprising the following steps:
(1) Adding an alkali metal salt into dicyandiamide or melamine, then adding water, uniformly stirring, carrying out hydrothermal reaction, cooling after the hydrothermal reaction is finished, and drying to obtain a white solid, wherein the alkali metal salt is rubidium salt and/or cesium salt;
(2) Calcining the white solid obtained in the step (1), cooling to room temperature to obtain a yellow solid, and cleaning and drying the yellow solid to obtain the alkali metal ion-based modified carbon nitride.
2. The method according to claim 1, wherein said rubidium salt in step (1) is rubidium chloride or rubidium nitrate, and said cesium salt is cesium chloride or cesium nitrate.
3. The method according to claim 1 or 2, wherein the mass ratio of dicyanodiamine or melamine to alkali metal salt in step (1) is 1.
4. The preparation method according to claim 1 or 2, characterized in that the reaction temperature of the hydrothermal reaction in step (1) is 160-200 ℃ and the reaction time is 8-12h.
5. The preparation method of claim 1, wherein the calcination temperature in the step (2) is 500-600 ℃, the calcination time is 2-4h, and the temperature rise rate is 2-10 ℃/min.
6. The preparation method according to claim 1, wherein the step (2) of washing and drying the yellow solid to obtain the modified carbon nitride comprises the following specific steps: grinding the yellow solid into powder, and respectively performing suction filtration and cleaning by using distilled water and ethanol to obtain the alkali metal ion modified carbon nitride.
7. The alkali metal ion-modified carbon nitride-based material prepared by the preparation method of claim 1.
8. Photocatalytic H production based on alkali metal ion modified carbon nitride as claimed in claim 7 2 O 2 The application in (2), characterized by comprising the following steps:
s1, placing the carbon nitride modified based on the alkali metal ions in the reaction container according to claim 7, adding an ethanol water solution, and stirring to uniformly disperse the carbon nitride modified based on the alkali metal ions in the ethanol water solution;
s2, placing the reaction container in the step S1 in a multi-channel reactor, stirring, continuously introducing oxygen, and illuminating by LED white light to obtain H 2 O 2 。
9. The use according to claim 8, wherein the mass volume ratio of the alkali metal ion-modified carbon nitride to the ethanol aqueous solution in step S1 is 0.0006 to 1g/mL, and the volume fraction of the ethanol aqueous solution is 10 to 15 percent.
10. The use according to claim 8, wherein the illumination time of step S2 is 50-70min.
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