CN115779943A - KSCN (KSCN) -based modified carbon nitride, preparation method thereof and photocatalytic H production method 2 O 2 In (1) - Google Patents
KSCN (KSCN) -based modified carbon nitride, preparation method thereof and photocatalytic H production method 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 44
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 title claims abstract description 30
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- 239000007787 solid Substances 0.000 claims abstract description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 24
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- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a modified carbon nitride based on KSCN (KSCN), a preparation method thereof and a method for producing H by photocatalysis 2 O 2 The use of (1). The preparation method of the KSCN modified carbon nitride comprises the following steps: (1) Placing dicyandiamide or melamine and potassium thiocyanate in a hydrothermal reactor, adding water, uniformly stirring at room temperature, carrying out hydrothermal reaction, cooling after the hydrothermal reaction is finished, and drying to obtain a white solid; (2) Calcining the white solid obtained in the step (1), cooling to room temperature to obtain yellow solid, and cleaning the yellow solidAnd drying to obtain the KSCN based modified carbon nitride. The KSCN modified carbon nitride provided by the invention has excellent oxygen adsorption capacity, and can adsorb oxygen from air to participate in photocatalytic H production 2 O 2 And (4) reacting.
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 KSCN and the preparation method thereofPreparation method and photocatalytic H production 2 O 2 The use of (1).
Background art:
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. The photocatalytic hydrogen peroxide production is a very potential technology and has the advantages of energy conservation, environmental protection and the like. In the technology, hydrogen peroxide is obtained by oxygen reduction, and relates to processes of oxygen adsorption, activation and the like. Among the numerous photocatalysts, graphite-phase carbon nitride (carbon nitride) is a catalyst with high selectivity and good activity. Carbon nitride is an organic polymer semiconductor, and the molecular structure and the energy band structure of the carbon nitride are easy to regulate and control, so the carbon nitride is widely applied to photocatalytic reactions.
Photocatalytic production of H from carbon nitride 2 O 2 There are also some reports in the art [ Dang, x.m.; yang, r.y.; wang, z.; wu, s.y.; zhao, h.m. journal of Materials Chemistry a,2020,8,22720-22727; teng, z.y.; zhang, q.t.; yang, h.b.; kato, k.; yang, w.j.; lu, y.r.; liu, s.x.; wang, c.y.; yamakata, a.; su, c.l.; liu, b.; ohno, t.nature catalysis,2021,4,374-384; wu, s.; yu, h.t.; chen, s.; quan, x. Acs Catalysis,2020,10,14380-14389.]. Among these reports, modified carbon nitride is often prepared by elemental doping or molecular doping. Moreover, the oxygen activation on the surface of the carbon nitride is mainly promoted; meanwhile, oxygen gas needs to be continuously introduced into the reaction to improve the yield. It is well known that the adsorption of oxygen is a prerequisite for the reaction. How to improve the adsorption capacity of oxygen and directly adsorb oxygen in the air to participate in reaction is to expand the photocatalytic H production 2 O 2 Especially the key technology of mass production.
The invention content is as follows:
the invention solves the problems in the prior art, and provides modified carbon nitride based on KSCN, a preparation method thereof and a method for producing H by photocatalysis 2 O 2 The KSCN modified carbon nitride has excellent oxygen adsorption capacity and can adsorb oxygen from airGas-participated photocatalytic H production 2 O 2 And (4) reacting.
The invention aims to provide a preparation method of modified carbon nitride based on KSCN, which comprises the following steps:
(1) Placing dicyandiamide or melamine and potassium thiocyanate in a hydrothermal reactor, adding water, uniformly stirring at room temperature, carrying out hydrothermal reaction, cooling after the hydrothermal reaction is finished, and drying to obtain a white solid;
(2) And (2) calcining the white solid obtained in the step (1), cooling to room temperature to obtain yellow solid, and cleaning and drying the yellow solid to obtain KSCN modified carbon nitride, which is recorded as HCNSK.
Preferably, the mass ratio of dicyandiamide or melamine to potassium thiocyanate 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: the yellow solid is ground into powder and is respectively filtered and cleaned by distilled water and ethanol to obtain the KSCN-based modified carbon nitride.
The invention also protects the KSCN modified carbon nitride prepared by the preparation method.
The invention also protects the production of H in photocatalysis based on KSCN modified carbon nitride 2 O 2 The application comprises the following steps:
s1, putting the KSCN modified carbon nitride into a reaction container, adding an ethanol water solution, and stirring to uniformly disperse the KSCN modified carbon nitride 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 performing LED white light illumination to obtain H 2 O 2 。
Preferably, the mass-to-volume ratio of the KSCN modified carbon nitride to the ethanol aqueous solution in the step S1 is 0.0002-0.001 g/mL and the volume fraction of the ethanol aqueous solution is 10% -15%.
Preferably, the illumination time in step S2 is 50-70min.
Preferably, the flow rate of the oxygen in the step S2 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 invention not only obtains K + Modified carbon nitride co-doped with cyano group and producing H by photocatalysis 2 O 2 The activity is improved by 42 times compared with that of unmodified carbon nitride.
2. The modified carbon nitride provided by the invention has excellent oxygen adsorption capacity, and particularly, H is H under the excitation of LED white light and on the premise that oxygen or air is not introduced into an opening 2 O 2 The yield was 2102.11. Mu. Mol/(g × h), and the oxygen chemisorption of HCNSK-0.4 was 22.55. Mu. Mol/g, which is 4.6 times that of unmodified carbon nitride.
Description of the drawings:
FIG. 1 is a Fourier Infrared Spectroscopy (FT-IR) of KSCN modified carbon nitride based on example 1 versus unmodified carbon nitride based on comparative example 1.
FIG. 2 is a graph of the high resolution X-ray photoelectron spectrum C1s obtained in example 1 based on KSCN modified carbon nitride and unmodified carbon nitride of comparative example 1.
FIG. 3 is a schematic diagram of the structure of KSCN modified carbon nitride-based carbon nitride obtained in example 1 and unmodified carbon nitride obtained in comparative example 1.
FIG. 4 is a plot of the KSCN modified carbon nitride of example 1 versus the unmodified carbon nitride of comparative example 1 for H under white light excitation of an LED, as obtained in example 4 2 O 2 The yield of (2).
FIG. 5 is a graph of H in various atmospheres under white light excitation of LED for the KSCN modified carbon nitride-based LED obtained in example 1 from examples 5-7 2 O 2 The yield of (2).
FIG. 6 shows the results of example 1 in example 8Oxygen chemical temperature programmed desorption (O) based on KSCN modified carbon nitride and unmodified carbon nitride of comparative example 1 2 -TPD) curve.
FIG. 7 shows the dissolved oxygen concentrations of the reaction solutions of example 9 based on KSCN modified carbon nitride in different systems.
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 terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. 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 or air was 1.3mL/min, and the power of the LED white light was 30.69mW/cm 2 。
Example 1
The preparation method of the KSCN modified carbon nitride comprises the following steps:
(1) Weighing 5g of dicyanodiamide and 0.4g of potassium thiocyanate (KSCN), placing the dicyanodiamide and the potassium thiocyanate in a lining of a hydrothermal kettle made of Teflon, adding 30mL 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) Placing the white solid obtained in the step (3) in a muffle furnace for calcination treatment, calcining 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 KSCN modified carbon nitride, which is recorded as HCNSK-0.4.
Comparative example 1
Preparation of unmodified carbon nitride:
(1) Weighing 5g of dicyandiamide, placing the dicyandiamide in a muffle furnace for calcination treatment, calcining at 550 ℃ for 4h at the heating 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, namely BCN.
As shown in FIG. 1, the structure of KSCN modified carbon nitride obtained in example 1 successfully introduced cyano groups. As shown in FIGS. 2 and 3, K was successfully introduced into the structure of the modified carbon nitride + 。
Example 2
The preparation method of the KSCN-based modified carbon nitride comprises the following steps:
(1) Weighing 5g of melamine and 0.3g of potassium thiocyanate (KSCN), placing the melamine and the potassium thiocyanate in a liner of a hydrothermal kettle made of Teflon, adding 30mL 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 (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 KSCN modified carbon nitride, which is recorded as HCNSK-0.3.
Example 3
The preparation method of the KSCN modified carbon nitride comprises the following steps:
(1) Weighing 5g of dicyanodiamide and 0.6g of potassium thiocyanate (KSCN), placing the dicyanodiamide and the potassium thiocyanate in a lining of a hydrothermal kettle made of Teflon, adding 30mL 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 rate 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 filtering and washing the powder for 3 times by using distilled water and ethanol, and finally drying the powder to obtain KSCN modified carbon nitride which is recorded as HCNSK-0.6.
Example 4
The application of the KSCN modified carbon nitride specifically comprises the following steps:
s1, 0.01g of HCNSK-0.4 obtained in example 1 is put into a reaction bottle, 50mL of ethanol water solution (volume fraction is 10%) is added, and ultrasonic treatment is carried out for 20min to thoroughly disperse the mixture.
S2, placing the reaction bottle in the step S1 into a multi-channel reactor (Pofely PCX-50C), introducing cooling circulating water at 10 ℃, stirring, and irradiating for 1 hour by using LED white light.
S3, after illumination, 3mL of the reaction solution was taken every 15min, centrifuged (10000rpm, 5min), and 1mL of the supernatant was taken.
And S4, 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 S3, 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. 4, the performance of the modified carbon nitride HCNSK-0.4 is obviously better than that of the unmodified carbon nitride.
Example 5
The application of the KSCN modified carbon nitride specifically comprises the following steps:
s1, 0.01g of HCNSK-0.4 obtained in example 1 is put into a reaction bottle, 50mL of ethanol water solution (volume fraction is 10%) is added, and ultrasonic treatment is carried out for 20min to thoroughly disperse the mixture.
S2, placing the reaction bottle in the step S1 into a multi-channel reactor (Pofilly PCX-50C), introducing cooling circulating water at 10 ℃, stirring, continuously introducing air, and irradiating the LED for 1 hour in white light.
S3, after illumination, 3mL of the reaction solution was taken every 15min, centrifuged (10000rpm, 5min), and 1mL of the supernatant was taken.
And S4, 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 S3, 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 6
The application of the KSCN modified carbon nitride specifically comprises the following steps:
s1, 0.01g of HCNSK-0.4 obtained in example 1 is put into a reaction bottle, 50mL of ethanol water solution (volume fraction is 10%) is added, and ultrasonic treatment is carried out for 20min to thoroughly disperse the mixture.
S2, placing the reaction bottle in the step S1 into a multi-channel reactor (Pofely PCX-50C), introducing cooling circulating water at 10 ℃, stirring, continuously introducing oxygen, and illuminating for 1h by LED white light.
S3, after illumination, 3mL of the reaction solution was taken every 15min, centrifuged (10000rpm, 5min), and 1mL of the supernatant was taken.
And S4, 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 S3, 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 7
The application of the KSCN modified carbon nitride specifically comprises the following steps:
s1, 0.01g of HCNSK-0.4 obtained in example 1 is taken out of a reaction bottle, 50mL of pure water is added, and ultrasonic treatment is carried out for 20min to thoroughly disperse the mixture.
S2, placing the reaction bottle in the step S1 into a multi-channel reactor (Pofely PCX-50C), introducing cooling circulating water at 10 ℃, stirring, continuously introducing oxygen, and illuminating the LED for 1 hour in white light.
S3, after illumination, 3mL of the reaction solution was taken every 15min, centrifuged (10000rpm, 5min), and 1mL of the supernatant was taken.
S4, adding 1.25mL of distilled water into 1mL of supernatant in the step S30.8mL of phosphate buffer, 50. Mu.L of peroxidase and 50. Mu.L of N, N-diethyl-p-phenylenediamine were shaken up to develop color, and a liquid UV-visible spectrophotometer was measured. Calculation of H from the absorbance 2 O 2 The concentration of (2).
As shown in FIG. 5, modified carbon nitride HCNSK-0.4 has excellent activity under different systems of examples 5-7.
Example 8
The application of the KSCN modified carbon nitride specifically comprises the following steps:
s1, 0.05g of HCNSK-0.4 obtained in example 1 is placed in a reaction tube and purged for 2 hours at 300 ℃ under an inert atmosphere.
S2, continuously introducing 2000ppm of O when the temperature of the step S1 is reduced to 50 DEG C 2 And adsorbing for 2h to saturation.
And S3, after the adsorption saturation in the step S2, 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.
As shown in FIG. 6, the oxygen adsorption capacity of the modified carbon nitride HCNSK-0.4 is obviously better than that of the unmodified carbon nitride.
Example 9
The application of the KSCN modified carbon nitride specifically comprises the following steps:
s1, 0.05g of HCNSK-0.4 obtained in example 1 is placed in a reaction bottle, 50mL of ethanol water solution is added, and ultrasonic treatment is carried out for 20min to thoroughly disperse the mixture.
S2, placing the reaction bottle in the step S1 into a multi-channel reactor (Pofely PCX-50C), introducing cooling circulating water at 10 ℃, stirring, turning on a lamp for illumination, and simultaneously measuring the concentration of dissolved oxygen in the reaction liquid.
S3, the reaction process is divided into three conditions, namely a closed system, an open system and an air ventilation condition, and the result is shown in figure 7.
As shown in FIG. 7, the modified carbon nitride HCNSK-0.4 can rapidly consume the dissolved oxygen in the reaction liquid for producing H in an open system 2 O 2 At the same time, the oxygen required for the reaction can be rapidly replenished from the air.
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, for those skilled in the art, it is possible to 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 into the protection scope of the claims of the present invention.
Claims (9)
1. A preparation method of modified carbon nitride based on KSCN is characterized by comprising the following steps:
(1) Placing dicyanodiamine or melamine and potassium thiocyanate in a hydrothermal reactor, adding water, uniformly stirring at room temperature, carrying out hydrothermal reaction, cooling after the hydrothermal reaction is finished, and drying to obtain a white solid;
(2) And (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 KSCN-based modified carbon nitride.
2. The preparation method according to claim 1, wherein the mass ratio of dicyanodiamine or melamine to potassium thiocyanate in step (1) is 1.
3. 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.
4. 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.
5. 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: the yellow solid is ground into powder and is respectively filtered and cleaned by distilled water and ethanol to obtain the KSCN-based modified carbon nitride.
6. KSCN modified carbon nitride-based carbon nitride prepared by the preparation method of claim 1.
7. The KSCN modified carbon nitride-based photocatalytic H production method of claim 6 2 O 2 The method is characterized by comprising the following steps:
s1, adding the KSCN modified carbon nitride into a reaction container according to claim 6, adding an ethanol water solution, and stirring to uniformly disperse the KSCN modified carbon nitride 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 with LED white light to obtain H 2 O 2 。
8. The use according to claim 7, wherein the mass to volume ratio of the KSCN-based modified carbon nitride to the aqueous ethanol solution in step S1 is 0.0002 to 0.001 g/mL, and the volume fraction of the aqueous ethanol solution is 10% to 15%.
9. The use according to claim 7, wherein the illumination time of step S2 is 50-70min.
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