CN114768852A - Preparation method of potassium ion gradient doped carbon nitride material - Google Patents

Preparation method of potassium ion gradient doped carbon nitride material Download PDF

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CN114768852A
CN114768852A CN202210422019.XA CN202210422019A CN114768852A CN 114768852 A CN114768852 A CN 114768852A CN 202210422019 A CN202210422019 A CN 202210422019A CN 114768852 A CN114768852 A CN 114768852A
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potassium
carbon nitride
pcn
potassium ion
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CN114768852B (en
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严嘉玮
韦之栋
上官文峰
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Shanghai Jiaotong University
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Abstract

The invention relates to a preparation method of a potassium ion gradient doped carbon nitride material. The invention discloses a preparation method and application of a two-dimensional material for realizing gradient doping by using ion diffusion, and discloses a method for realizing gradient doping on the two-dimensional material by introducing an ion storage material as a doping source and performing ion diffusion action and application of the method. The doping source used in the invention is defect pyrochlore type potassium tantalate: tantalum oxide is uniformly dispersed in 6-12mol/L potassium hydroxide solution, and is calcined and synthesized at the temperature of 400-800 ℃ after hydrothermal alkalization at the temperature of 120-180 ℃. The two-dimensional substrate material used is a polymer carbon nitride laminated material: grinding and mixing potassium tantalate and urea, and calcining and synthesizing at the temperature of 400-600 ℃ under a closed condition. The catalyst prepared by the invention realizes gradient doping distribution of potassium ions constructed in situ on graphite-phase carbon nitride, enhances the migration of photon-generated carriers and further improves the photo-and photo-electro-catalytic properties.

Description

Preparation method of potassium ion gradient doped carbon nitride material
Technical Field
The invention belongs to the technical field of catalysis, particularly relates to a preparation method of a potassium ion gradient doped carbon nitride material, and particularly relates to a preparation method and application of a potassium ion radiation gradient doped polymer carbon nitride material guided by ion diffusion behavior.
Background
The increasing global energy consumption has caused extensive and intensive attention to the problems of resource sustainable utilization and environmental protection. The hydrogen energy with the characteristics of energy storage and zero carbon is considered to be an eco-friendly renewable clean energy with great potential and is an ideal substitute for the traditional fossil fuel. The traditional hydrogen production methods such as a water gas method, a methane steam thermal reforming method and a water electrolysis method relying on traditional electric power all have the problems of energy consumption and pollution. Therefore, the light/photoelectrocatalysis technology directly utilizing solar energy is more and more concerned and researched especially in the field of hydrogen production by water decomposition, and the solar water-saving hydrogen production device has wide application prospect.
In 1972, Japanese scientists Fujishima and Honda discovered that biased titanium dioxide electrodes decomposed water under ultraviolet light to produce hydrogen gas (Nature,1972,238(5358):37-38), whereby the Fujishima-Honda effect opened up the sequential screen for hydrogen production by artificial photocatalytic decomposition of water. In the systematic study of semiconductor photocatalytic powder systems, the problem of separation of photogenerated electron-hole pairs is considered to be a major obstacle limiting the access to efficient solar energy conversion to hydrogen. In a classical semiconductor material, the concentration level of carriers in the semiconductor can be effectively adjusted by doping different atoms, so that the purposes of adjusting a proper energy band structure and band gap width and improving the separation capability of the carriers are achieved. For titanium dioxide photocatalytic materials, the valence band composition is adjusted by nitrogen doping and the visible light response capability is given (Nano letters,2003,3(8): 1049-. For strontium titanate photocatalytic Materials, lanthanum and rhodium doping introduces electron reconstruction to greatly improve carrier lifetime (Nature Materials,2021,20(4):511-3+The defect density increases The oxygen vacancy content to suppress The intrinsic carrier recombination problem (The Journal of Physical Chemistry C,2009,113(45): 19386-. For visible light responding bismuth vanadate photocatalytic materials, tungsten and molybdenum doping introduces shallow impurity energy levels so as to promote the transfer efficiency of carriers (ChemSusChem,2012,5(10): 1926-. Compared with the traditional uniform doping, the gradient concentration doping can continuously regulate and control the bending of an energy band, and is beneficial to the directional migration of current carriers so as to inhibit the current carriersThe recombination of the molecules has become a hot research point in the modification of semiconductors in recent years. Xiao et al report that magnesium ion gradient doping realizes high-performance photoelectrocatalytic water oxidation efficiency by band design and defect regulation of a tantalum nitride photo-anode (Nature Catalysis,2020,3(11): 932-. Huang et al reported that a directional built-in electric field is constructed by phosphorus gradient doped cadmium sulfide nanorods to realize efficient separation of photogenerated carriers from bulk phase to surface (Nano letters,2017,17(6): 3803-.
The literature search of the prior art finds that Chinese invention patent with application publication number CN 110240133A, namely 'potassium ion doped graphite phase carbon nitride nanosheet photocatalyst and a preparation method thereof', discloses a uniform potassium ion doped graphite phase carbon nitride nanosheet photocatalyst and an equipment method thereof, and widens the spectral response range so as to enhance the photocatalytic activity. However, the ball milling method and the air oxidation etching method cannot control the doping distribution of potassium ions, and the modified carbon nitride skeleton structure has a stability problem.
The document retrieval of the prior art finds that the Chinese patent with the application publication number of CN 112626470A, namely 'a preparation method of a CN thin film with self-doping carbon and gradient distribution of concentration', discloses a preparation method of a CN thin film with gradient concentration of carbon content, and is used for designing and utilizing electronic elements. But the ion sputtering coating process and the bombardment of N by argon gas2As N+The ion source has the defects of complicated preparation process, expensive equipment and unsuitability for large-scale popularization and application.
The document retrieval of the prior art finds that the Chinese patent with the application publication number of CN 109835892A, namely 'a preparation method of boron-doped semiconductor graphite', discloses that boron atoms are released by a boron source at high temperature to form substitutional doped graphene. However, the synthesis temperature (2000-.
Disclosure of Invention
The invention aims to provide a preparation method of a potassium ion gradient doped carbon nitride material aiming at the problems in the prior art, and particularly relates to a preparation method for realizing a gradient doped two-dimensional material by using ion diffusion and application thereof.
The invention provides a two-dimensional material gradient doping method with low cost and simple process, which is characterized in that a particle source (defective pyrochlore potassium tantalate) with ion storage and release capacity is used as a potassium ion doping source, a classical Polymer Carbon Nitride (PCN) two-dimensional material is used as a substrate, and a potassium ion doping modified PCN (marked as (K) PCN & KTO) is obtained in an ion diffusion mode and presents radial potassium ion concentration gradient distribution.
The purpose of the invention can be realized by the following scheme:
in a first aspect, the invention provides a preparation method of a potassium ion gradient doped carbon nitride material, which specifically comprises the following steps:
s1, mixing the tantalum oxide powder with a potassium hydroxide solution to obtain a white suspension, heating for reaction, and centrifuging to obtain a white solid;
s2, calcining and crystallizing the white solid to obtain pyrochlore potassium tantalate (KTO) as a potassium ion sourcepyr) A solid powder;
s3, adding potassium ion source potassium tantalate (KTO)pyr) And mixing the solid powder with the carbon nitride precursor, sealing and heating to obtain the potassium ion gradient doped carbon nitride material.
As an embodiment of the present invention, the concentration of potassium hydroxide in step S1 is 6mol/L to 12 mol/L. The dosage ratio of the potassium hydroxide solution to the tantalum oxide is 100 mL: 5-8 g.
As an embodiment of the present invention, the mixing in step S1 is mixing by ultrasonic dispersion treatment. After dispersion, the mixture was further stirred to obtain a uniformly dispersed white suspension.
As an embodiment of the invention, the temperature of the heating reaction in the step S1 is 120-180 ℃, and the heating time is 6-12 h. The heating reaction is carried out in a hydrothermal kettle. The product of the centrifugation of the suspension was washed and dried to give a white solid. Too high or too low of the reaction temperature can affect the crystal form of a hydrothermal product, too low can form tantalum oxide impurities, and too high can form perovskite potassium tantalate.
As an embodiment of the invention, the temperature of the calcination crystallization in the step S2 is 400-800 ℃, and the time of the calcination crystallization is 6-12 h. The calcination is carried out under an air atmosphere. The crystallization temperature is too low, the crystallinity is poor, and the crystal structure is unstable; too high a crystallization temperature tends to cause transformation of the crystal form into the perovskite form.
As one embodiment of the present invention, the mixing in step S3 is mill mixing. The sealing is performed by using tin foil paper, and the calcination is performed in a ceramic crucible.
As one embodiment of the present invention, the mass of the potassium tantalate solid powder as the potassium ion source used in step S3 is 0.5% to 10% of the mass of the carbon nitride precursor. The gradient doping is formed by utilizing the slow release of potassium tantalate ions.
As an embodiment of the present invention, the carbon nitride precursor includes one of urea and melamine.
As an embodiment of the present invention, the heating temperature in the step S3 is 500 ℃ to 600 ℃, and the heating time is 3h to 6 h. The heating rate is 1-3 deg.C/min. When the temperature is too high, carbon nitride cannot be obtained, and when the temperature is too low, the crystallinity is poor. Too fast or too slow a temperature increase rate may affect the crystallinity and initial activity of the carbon nitride.
As an embodiment of the invention, the heating product is fully ground in the step S3, and is washed by water, dried and ground to obtain the potassium ion gradient doped carbon nitride material. The obtained carbon nitride material is PCN doped with potassium ions in a gradient manner and containing a particle doping source.
In a second aspect, the invention also provides an application of the potassium ion gradient doped carbon nitride material in the field of hydrogen production by photocatalytic water decomposition.
The invention introduces pyrochlore type K2Ta2O6(abbreviated as KTO)pyr) As a potassium ion doping source, potassium ion concentration gradient distribution is constructed in situ on the carbon nitride laminated material through potassium ion diffusion behavior.
Compared with the prior art, the invention has the following promotion effects:
(1) compared with the processes such as ion evaporation sputtering and the like, the two-dimensional gradient doping method has the advantages of economy, simplicity, low price and easy obtainment of used raw materials, and certain universality for doping modification of two-dimensional materials.
(2) Compared with the traditional modified PCN uniformly doped with potassium ions and the blank unmodified PCN, the modified PCN doped with potassium ions in a gradient manner is obviously improved in the aspect of photo/photoelectrocatalysis performance, and the problem of serious carrier recombination of the original PCN material is solved, so that the hydrogen production efficiency by decomposing water is improved.
Drawings
The main advantages and other features of the invention are demonstrated by reading the detailed description of a non-limiting embodiment with reference to the following figures:
FIG. 1 shows KTO in example 1pyrThe morphology of octahedral particles, a and b are KTO in example 1pyrSEM topography of octahedral particles; c is KTO from example 1pyrTEM topography of octahedral particles;
FIG. 2 is the morphology diagrams of (K) PCN & KTO in example 1, and a and b are SEM morphology diagrams of (K) PCN & KTO in example 1; c is the TEM topography of (K) PCN & KTO of example 1;
FIG. 3 is KTO of comparative example 1perMorphology of cubic particles, a is KTO in comparative example 1perSEM topography of cubic particles; b. c is KTO in comparative example 1perTEM topography of cubic particles;
FIG. 4 shows (K) PCN in comparative example 1&KTOperA TEM topography of (a);
FIG. 5 is a TEM morphology of (K) PCN & KOH in comparative example 2;
FIG. 6 is a morphology view of a blank PCN in comparative example 3, a is an SEM morphology view of a blank PCN in comparative example 3; b is the TEM topography of the blank PCN in comparative example 3.
FIG. 7 is a bright field map, an EDS map, relative contents of elements, and a K/N atomic ratio distribution map of (K) PCN & KTO of example 1, and a is a bright field map of (K) PCN & KTO of example 1; b. c and d are EDS (element distribution) graphs (corresponding to K, Ta and N elements respectively) of PCN & KTO in example 1, and the scale bars are all 200 nm; e. f is a distribution graph of the relative contents of the elements and the K/N atomic ratio of (K) PCN & KTO along the Line #1 and the Line #2 in example 1.
FIG. 8 shows (K) PCN of comparative example 1&KTOperA is a distribution diagram of (K) PCN in comparative example 1, a is a bright field diagram, an EDS diagram, a relative element content and a K/N atomic ratio&KTOperBright field map of (a); b. c, d are (K) PCN in comparative example 1&KTOperEDS (element distribution) chart (corresponding to K, Ta and N elements respectively) of (1), wherein the scale bar is 200 nm; e. f is (K) PCN in comparative example 1&KTOperThe distribution of the relative contents of elements and the K/N atomic ratios along the Line #1 and the Line # 2.
FIG. 9 is a bright field diagram, an EDS diagram, relative contents of elements, and a K/N atomic ratio distribution diagram of (K) PCN & KOH of comparative example 2, and a is a bright field diagram of (K) PCN & KOH of comparative example 2; b. c and d are EDS diagrams (corresponding to K, C, N elements respectively) of element distribution of (K) PCN & KOH in comparative example 2, and the scale bars are both 200 nm; e. f is a distribution graph of the relative contents of the elements (K) PCN & KOH and the K/N atomic ratio along the Line #1 and the Line #2 in the comparative example 2.
Detailed Description
The present invention is described in detail below with reference to the accompanying drawings and specific embodiments, and the following examples are implemented under the guidance of the technical solution of the present invention, and provide detailed implementation methods and specific operation procedures, which will help those skilled in the art to further understand the technical solution of the present invention. It should be noted that the protection scope of the present invention is not limited to the following embodiments, and several modifications and improvements made on the premise of the idea of the present invention belong to the protection scope of the present invention.
Example 1
1. Dissolving 48g of potassium hydroxide solid in 100mL of pure water, fully stirring to obtain a potassium hydroxide solution, adding 5g of tantalum (V) oxide, performing ultrasonic treatment for 10min, and stirring to obtain a uniformly dispersed white suspension.
2. The solution is transferred to a 100mL polytetrafluoroethylene lining and then placed in a hydrothermal kettle to be heated in an oven at 160 ℃ for 8 h.
3. Separating the white solid powder after the hydrothermal alkalization reaction from the supernatant alkali liquor, centrifugally washing the white solid powder for 5 times until the pH value of the centrifugate is 7, and then placing the centrifugally treated solid in a vacuum oven at 80 ℃ for overnight drying.
4. The dried white powder was thoroughly ground and calcined in an air atmosphere at 600 ℃ for 10 h.
5. And (3) putting 0.5g of calcined white powder and 20g of urea into an agate mortar for full mixing, transferring the mixture into a ceramic crucible, sealing the mixture by using 4 layers of tinfoil paper, putting the mixture into a muffle furnace, heating the mixture to 550 ℃ at the speed of 2.5 ℃/min, and calcining the mixture for 2 hours at the temperature to obtain a yellow honeycomb-shaped solid.
6. And fully grinding the yellow solid, filtering and washing the ground yellow solid by using deionized water, and then placing the washed yellow solid in a vacuum oven at 80 ℃ for overnight drying to obtain the PCN doped with potassium ions in a gradient manner, wherein the mark is (K) PCN & KTO (600) -2.5-2 h.
7. Weighing 50mg (K) PCN&Ultrasonically dispersing a KTO (600) -2.5-2H sample in 80mL of pure water, adding 20mL of methanol serving as a sacrificial agent, and adding 37mL of chloroplatinic acid (H)2PtCl6) The aqueous solution (1.48mgPt/mL) is placed in a Pyrex glass photocatalytic reactor, a 300W xenon lamp is used as a light source, the Pt promoter is firstly irradiated for 2h in-situ light deposition loading under a visible light wave band (more than or equal to 420nm), and then hydrogen production activity test is carried out every hour. The hydrogen generated by the photocatalytic reaction is quantitatively sampled and analyzed by a gas chromatograph with a thermal conductivity detector, and the average hydrogen production rate is 20.4 mu mol/h.
As shown in figure 1, KTO prepared by hydrothermal alkalizationpyrHas an octahedral structure typical of pyrochlore crystal forms.
KTO as shown in FIG. 2pyrGood composite contact is formed between the particles and the layered PCN.
As shown in FIG. 7, with KTOpyr(K) PCN with particles doped as a source of potassium ions&The KTO samples exhibited efficient potassium doping. Elemental distribution display of high resolution TEM as KTOpyrThe particle is taken as a source, the K/N atomic ratio shows a radial gradient descending trend along the Line #1, and the non-gradient distribution along the Line #2 shows that KTO is distributedpyrIon diffusion doping does not occur without effective contact of the particles with the PCN substrate.
Example 2
1.48 g of potassium hydroxide solid is dissolved in 100mL of pure water and fully stirred to obtain a potassium hydroxide solution, 5g of tantalum (V) oxide is added, and then ultrasonic treatment is carried out for 10min and stirring is carried out to obtain a uniform white suspension.
2. The solution is transferred to a 100mL polytetrafluoroethylene lining and then placed in a hydrothermal kettle to be heated in an oven at 160 ℃ for 8 hours.
3. Separating the white solid powder after the hydrothermal alkalization reaction from the supernatant alkali liquor, centrifugally washing the white solid powder for 5 times until the pH value of the centrifugate is 7, and then placing the centrifugally treated solid in a vacuum oven at 80 ℃ for overnight drying.
4. The dried white powder was thoroughly ground and calcined in an air atmosphere at 600 ℃ for 10 h.
5. And (3) putting 0.5g of calcined white powder and 20g of urea into an agate mortar for full mixing, transferring the mixture into a ceramic crucible, sealing the mixture by using 4 layers of tinfoil paper, putting the mixture into a muffle furnace, heating the mixture to 550 ℃ at the speed of 2.5 ℃/min, and calcining the mixture for 4 hours at the temperature to obtain a yellow honeycomb-shaped solid.
6. And (3) fully grinding the yellow solid, filtering and washing the ground yellow solid by using deionized water, and then placing the washed yellow solid in a vacuum oven at 80 ℃ for overnight drying to obtain the PCN doped with potassium ions in a gradient manner, wherein the PCN is marked as (K) PCN & KTO (600) -2.5-4 h.
7. Weighing 50mg (K) PCN&Ultrasonically dispersing a KTO (600) -2.5-4H sample in 80mL of pure water, adding 20mL of methanol serving as a sacrificial agent, and adding 37mL of chloroplatinic acid (H)2PtCl6) The aqueous solution (1.48mgPt/mL) is placed in a Pyrex glass photocatalytic reactor, a 300W xenon lamp is used as a light source, the Pt promoter is firstly irradiated for 2h in-situ light deposition loading under a visible light wave band (more than or equal to 420nm), and then hydrogen production activity test is carried out every hour. The hydrogen produced by the photocatalytic reaction is quantitatively sampled and analyzed by a gas chromatograph with a thermal conductivity detector, and the average hydrogen production rate is 24.6 mu mol/h.
Example 3
1.48 g of potassium hydroxide solid is dissolved in 100mL of pure water and fully stirred to obtain a potassium hydroxide solution, 5g of tantalum (V) oxide is added, and then ultrasonic treatment is carried out for 10min and stirring is carried out to obtain a uniform white suspension.
2. The solution is transferred to a 100mL polytetrafluoroethylene lining and then placed in a hydrothermal kettle to be heated in an oven at 160 ℃ for 8 hours.
3. Separating the white solid powder after the hydrothermal alkalization reaction from the supernatant alkali liquor, centrifugally washing the white solid powder for 5 times until the pH value of the centrifugate is 7, and then placing the centrifugally treated solid in a vacuum oven at 80 ℃ for overnight drying.
4. The dried white powder was thoroughly ground and calcined in an air atmosphere at 600 ℃ for 10 h.
5. And (3) putting 0.5g of calcined white powder and 20g of urea into an agate mortar for full mixing, transferring the mixture into a ceramic crucible, sealing the mixture by using 4 layers of tinfoil paper, putting the mixture into a muffle furnace, heating the mixture to 550 ℃ at the speed of 2.5 ℃/min, and calcining the mixture for 6 hours at the temperature to obtain a yellow honeycomb-shaped solid.
6. And fully grinding the yellow solid, filtering and washing the ground yellow solid by using deionized water, and then placing the washed yellow solid in a vacuum oven at 80 ℃ for overnight drying to obtain the PCN (K) with gradient doping of potassium ions, wherein the mark is (K) PCN & KTO (600) -2.5-8 h.
7. Weighing 50mg (K) PCN&Ultrasonically dispersing a KTO (600) -2.5-8H sample in 80mL of pure water, adding 20mL of methanol serving as a sacrificial agent, and adding 37mL of chloroplatinic acid (H)2PtCl6) The aqueous solution (1.48mgPt/mL) is placed in a Pyrex glass photocatalytic reactor, a 300W xenon lamp is used as a light source, the Pt promoter is loaded by irradiating for 2h of in-situ light deposition under a visible light wave band (not less than 420nm), and then the hydrogen production activity test is carried out every hour. The hydrogen generated by the photocatalytic reaction is quantitatively sampled and analyzed by a gas chromatograph with a thermal conductivity detector, and the average hydrogen production rate is 20.3 mu mol/h.
Example 4
1.48 g of potassium hydroxide solid is dissolved in 100mL of pure water and fully stirred to obtain a potassium hydroxide solution, 5g of tantalum (V) oxide is added, and then ultrasonic treatment is carried out for 10min and stirring is carried out to obtain a uniform white suspension.
2. The solution is transferred to a 100mL polytetrafluoroethylene lining and then placed in a hydrothermal kettle to be heated in an oven at 160 ℃ for 8 hours.
3. Separating the white solid powder after the hydrothermal alkalization reaction from the supernatant alkali liquor, centrifugally washing the white solid powder for 5 times until the pH value of the centrifugate is 7, and then placing the centrifugally treated solid in a vacuum oven at 80 ℃ for overnight drying.
4. 0.5g of white powder and 20g of urea are placed in an agate mortar and are fully mixed, then the mixture is transferred into a ceramic crucible and is sealed by 4 layers of tinfoil paper, the mixture is placed in a muffle furnace, the temperature is raised to 550 ℃ at the speed of 1.5 ℃/min, and the mixture is calcined for 4 hours at the temperature to obtain yellow honeycomb-shaped solid.
5. And (3) fully grinding the yellow solid, filtering and washing the yellow solid by using deionized water, and then placing the yellow solid in a vacuum oven at 80 ℃ for overnight drying to obtain the PCN (K) which is doped with potassium ions in a gradient manner and is marked as (K) PCN & KTO-2.5-4 h.
6. Weighing 50mg (K) PCN&The KTO-2.5% sample was ultrasonically dispersed in 80mL of pure water, 20mL of methanol was added as a sacrificial agent, and 37mL of chloroplatinic acid (H) was added2PtCl6) The aqueous solution (1.48mgPt/mL) is placed in a Pyrex glass photocatalytic reactor, a 300W xenon lamp is used as a light source, the Pt promoter is loaded by irradiating for 2h of in-situ light deposition under a visible light wave band (not less than 420nm), and then the hydrogen production activity test is carried out every hour. The hydrogen generated by the photocatalytic reaction is quantitatively sampled and analyzed by a gas chromatograph with a thermal conductivity detector, and the average hydrogen production rate is 13.3 mu mol/h.
Example 5
1.48 g of potassium hydroxide solid is dissolved in 100mL of pure water and fully stirred to obtain a potassium hydroxide solution, 5g of tantalum (V) oxide is added, and then ultrasonic treatment is carried out for 10min and stirring is carried out to obtain a uniform white suspension.
2. The solution is transferred to a 100mL polytetrafluoroethylene lining and then placed in a hydrothermal kettle to be heated in an oven at 160 ℃ for 8 h.
3. Separating the white solid powder after the hydrothermal alkalization reaction from the supernatant alkali liquor, centrifugally washing the white solid powder for 5 times until the pH value of the centrifugate is 7, and then placing the centrifugally treated solid in a vacuum oven at 80 ℃ for overnight drying.
4. The dried white powder was thoroughly ground and calcined in an air atmosphere at 800 ℃ for 10 h.
5. And (3) putting 0.5g of calcined white powder and 20g of urea into an agate mortar for full mixing, transferring the mixture into a ceramic crucible, sealing the mixture by using 4 layers of tinfoil paper, putting the mixture into a muffle furnace, heating the mixture to 550 ℃ at the speed of 2.5 ℃/min, and calcining the mixture for 4 hours at the temperature to obtain a yellow honeycomb-shaped solid.
6. And fully grinding the yellow solid, filtering and washing the ground yellow solid by using deionized water, and then placing the washed yellow solid in a vacuum oven at 80 ℃ for overnight drying to obtain the PCN (K) PCN & KTO (800) -2.5-4 h doped with potassium ions in a gradient manner.
7. Weighing 50mg (K) PCN&Ultrasonically dispersing a KTO (800) -2.5-4H sample in 80mL of pure water, adding 20mL of methanol serving as a sacrificial agent, and adding 37mL of chloroplatinic acid (H)2PtCl6) The aqueous solution (1.48mgPt/mL) is placed in a Pyrex glass photocatalytic reactor, a 300W xenon lamp is used as a light source, the Pt promoter is loaded by irradiating for 2h of in-situ light deposition under a visible light wave band (not less than 420nm), and then the hydrogen production activity test is carried out every hour. The hydrogen generated by the photocatalytic reaction is quantitatively sampled and analyzed by a gas chromatograph with a thermal conductivity detector, and the average hydrogen production rate is 14.8 mu mol/h.
Example 6
1.48 g of potassium hydroxide solid is dissolved in 100mL of pure water and fully stirred to obtain a potassium hydroxide solution, 5g of tantalum (V) oxide is added, and then ultrasonic treatment is carried out for 10min and stirring is carried out to obtain a uniform white suspension.
2. The solution is transferred to a 100mL polytetrafluoroethylene lining and then placed in a hydrothermal kettle to be heated in an oven at 160 ℃ for 8 hours.
3. Separating the white solid powder after the hydrothermal alkalization reaction from the supernatant alkali liquor, centrifugally washing the white solid powder for 5 times until the pH value of the centrifugate is 7, and then placing the centrifugally treated solid in a vacuum oven at 80 ℃ for overnight drying.
4. The dried white powder was thoroughly ground and calcined in an air atmosphere at 600 ℃ for 10 h.
5. Placing 2.0g of calcined white powder and 20g of urea in an agate mortar for fully mixing, transferring the mixture into a ceramic crucible, sealing the ceramic crucible by using 4 layers of tinfoil paper, placing the ceramic crucible in a muffle furnace, raising the temperature to 550 ℃ at the speed of 1.5 ℃/min, and calcining the mixture for 4 hours at the temperature to obtain a yellow honeycomb-shaped solid.
6. And fully grinding the yellow solid, filtering and washing the ground yellow solid by using deionized water, and then placing the washed yellow solid in a vacuum oven at 80 ℃ for overnight drying to obtain the PCN (K) PCN & KTO (600) -10-4 h doped with potassium ions in a gradient manner.
7. Weighing 50mg (K) PCN&Ultrasonically dispersing a KTO (600) -10-4H sample in 80mL of pure water, adding 20mL of methanol serving as a sacrificial agent, and adding 37mL of chloroplatinic acid (H)2PtCl6) The aqueous solution (1.48mgPt/mL) is placed in a Pyrex glass photocatalytic reactor, a 300W xenon lamp is used as a light source, the Pt promoter is loaded by irradiating for 2h of in-situ light deposition under a visible light wave band (not less than 420nm), and then the hydrogen production activity test is carried out every hour. The hydrogen produced by the photocatalytic reaction is quantitatively sampled and analyzed by a gas chromatograph with a thermal conductivity detector, and the average hydrogen production rate is 22.8 mu mol/h.
Example 7
1.48 g of potassium hydroxide solid is dissolved in 100mL of pure water and fully stirred to obtain a potassium hydroxide solution, 5g of tantalum (V) oxide is added, and then ultrasonic treatment is carried out for 10min and stirring is carried out to obtain a uniform white suspension.
2. The solution is transferred to a 100mL polytetrafluoroethylene lining and then placed in a hydrothermal kettle to be heated in an oven at 160 ℃ for 8 hours.
3. Separating the white solid powder after the hydrothermal alkalization reaction from the supernatant alkali liquor, centrifugally washing the white solid powder for 5 times until the pH value of the centrifugate is 7, and then placing the centrifugally treated solid in a vacuum oven at 80 ℃ for overnight drying.
4. The dried white powder was thoroughly ground and calcined in an air atmosphere at a temperature of 700 ℃ for 10 h.
5. And (3) putting 0.5g of calcined white powder and 20g of urea into an agate mortar for full mixing, transferring the mixture into a ceramic crucible, sealing the mixture by using 4 layers of tinfoil paper, putting the mixture into a muffle furnace, heating the mixture to 550 ℃ at the speed of 2.5 ℃/min, and calcining the mixture for 4 hours at the temperature to obtain a yellow honeycomb-shaped solid.
6. And fully grinding the yellow solid, filtering and washing the ground yellow solid by using deionized water, and then placing the washed yellow solid in a vacuum oven at 80 ℃ for overnight drying to obtain the PCN (K) with gradient doping of potassium ions, wherein the mark is (K) PCN & KTO (700) -2.5-4 h.
7. Weighing 50mg (K) PCN&Ultrasonically dispersing a KTO (700) -2.5-4H sample in 80mL of pure water, adding 20mL of methanol serving as a sacrificial agent, and adding 37mL of chloroplatinic acid (H)2PtCl6) The aqueous solution (1.48mgPt/mL) is placed in a Pyrex glass photocatalytic reactor, a 300W xenon lamp is used as a light source, the Pt promoter is firstly irradiated for 2h in-situ light deposition loading under a visible light wave band (more than or equal to 420nm), and then hydrogen production activity test is carried out every hour. The hydrogen generated by the photocatalytic reaction is quantitatively sampled and analyzed by a gas chromatograph with a thermal conductivity detector, and the average hydrogen production rate is 20.4 mu mol/h.
Example 8
1. Dissolving 48g of potassium hydroxide solid in 100mL of pure water, fully stirring to obtain a potassium hydroxide solution, adding 5g of tantalum (V) oxide, performing ultrasonic treatment for 10min, and stirring to obtain a uniformly dispersed white suspension.
2. The solution is transferred to a 100mL polytetrafluoroethylene lining and then placed in a hydrothermal kettle to be heated in an oven at 160 ℃ for 8 h.
3. Separating the white solid powder after the hydrothermal alkalization reaction from the supernatant alkali liquor, centrifugally washing the white solid powder for 5 times until the pH value of the centrifugate is 7, and then placing the centrifugally treated solid in a vacuum oven at 80 ℃ for overnight drying.
4. The dried white powder was thoroughly ground and calcined in an air atmosphere at 600 ℃ for 10 h.
5. And (3) putting 0.5g of calcined white powder and 20g of urea into an agate mortar, fully mixing, transferring into a ceramic crucible, sealing by using 4 layers of tinfoil paper, putting into a muffle furnace, heating to 550 ℃ at the speed of 4 ℃/min, and calcining for 2 hours at the temperature to obtain a yellow honeycomb solid.
6. And (3) fully grinding the yellow solid, filtering and washing the ground yellow solid by using deionized water, and then placing the washed yellow solid in a vacuum oven at 80 ℃ for overnight drying to obtain the PCN doped with potassium ions in a gradient manner, wherein the PCN is marked as (K) PCN & KTO (600) -2.5-2 h.
7. Weighing 50mg (K) PCN&Ultrasonically dispersing a KTO (600) -2.5-2H sample in 80mL of pure water, adding 20mL of methanol serving as a sacrificial agent, and adding 37mL of chloroplatinic acid (H)2PtCl6) The aqueous solution (1.48mgPt/mL) is placed in a Pyrex materialIn the glass photocatalytic reactor, a 300W xenon lamp is used as a light source, a Pt-loaded cocatalyst is irradiated for 2h in-situ light deposition under a visible light wave band (not less than 420nm), and then hydrogen production activity test is carried out every hour. The hydrogen generated by the photocatalytic reaction is quantitatively sampled and analyzed by a gas chromatograph with a thermal conductivity detector, and the average hydrogen production rate is 12.8 mu mol/h.
Comparative example 1
The comparative example relates to the effect of different potassium ion sources on the gradient doping effect, and the preparation method of the comparative example is only different from that of example 1 in that KTaO of perovskite type is replaced3(abbreviated as KTOper) The particles were doped with PCN and the sample was reported as (K) PCN&KTOper. The main synthesis steps are as follows:
1. 96g of potassium hydroxide solid is dissolved in 100mL of pure water and fully stirred to obtain a potassium hydroxide solution, 5g of tantalum (V) oxide is added, and then ultrasonic treatment is carried out for 10min and stirring is carried out to obtain a uniform white suspension.
2. The solution was transferred to a 100mL Teflon liner and heated in a 200 ℃ oven for 8h in a hydrothermal kettle. The alkalization hydrothermal time, reaction temperature and pH affect the product crystal form. Increasing the hydrothermal time and increasing the hydrothermal temperature increases the concentration of KOH and results in a perovskite-type product. In this comparative example, the hydrothermal temperature was 200 deg.C
3. Separating the white solid powder after the hydrothermal alkalization reaction from the supernatant alkali liquor, centrifugally washing the white solid powder for 5 times until the pH value of the centrifugate is 7, and then placing the centrifugally treated solid in a vacuum oven at 80 ℃ for overnight drying.
4. The dried white powder was thoroughly ground and calcined in an air atmosphere at 600 ℃ for 10 h.
5. And (3) putting 0.5g of calcined white powder and 20g of urea into an agate mortar for full mixing, transferring the mixture into a ceramic crucible, sealing the mixture by using 4 layers of tinfoil paper, putting the mixture into a muffle furnace, heating the mixture to 550 ℃ at the speed of 2.5 ℃/min, and calcining the mixture for 4 hours at the temperature to obtain a yellow honeycomb-shaped solid.
6. Grinding the yellow solid sufficiently, filtering and washing the ground yellow solid by deionized water, and then placing the ground yellow solid in a vacuum oven at 80 ℃ for overnight drying to obtain potassium ionsGradient doped PCN, denoted (K) PCN&KTOper-2.5％-4h。
7. Weighing 50mg (K) PCN&KTOperUltrasonically dispersing a sample in 80mL of pure water for 2.5-4H, adding 20mL of methanol serving as a sacrificial agent, and adding 37mL of chloroplatinic acid (H)2PtCl6) The aqueous solution (1.48mgPt/mL) is placed in a Pyrex glass photocatalytic reactor, a 300W xenon lamp is used as a light source, the Pt promoter is loaded by irradiating for 2h of in-situ light deposition under a visible light wave band (not less than 420nm), and then the hydrogen production activity test is carried out every hour. The hydrogen produced by the photocatalytic reaction is quantitatively sampled and analyzed by a gas chromatograph with a thermal conductivity detector, and the average hydrogen production rate is 3.6 mu mol/h.
As shown in fig. 3, KTO was prepared by hydrothermal alkalizationperThe cubic structure of typical perovskite crystal form is presented.
KTO as shown in FIG. 4perGood composite contact is formed between the particles and the layered PCN.
As shown in FIG. 8, with KTOper(K) PCN with particles doped as a source of potassium ions&KTOperThe sample did not exhibit effective potassium doping. Elemental distribution display of high resolution TEM as KTOperThe particles are taken as a source, no obvious K element is distributed, the K/N atomic ratio is close to zero along Line #1 and Line #2, and the conditions that the diffusion doping of the potassium ions does not occur and the KTO is generated are shownperThe particles are not suitable as a diffusion source for potassium ions.
By KTOper(K) PCN with particles doped as a source of potassium ions&KTOperThe hydrogen production activity of the sample is 3.6 mu mol/h, which is lower than that of KTOpyrThe PCN sample doped with particles as a potassium ion source was close in activity to the unmodified blank PCN.
Comparative example 2
The comparative example relates to the effect of different potassium ion sources on the gradient doping effect, and the preparation method is different from the example 1 only in that PCN doping is performed by replacing conventional KOH particles, and the sample is marked as (K) PCN & KOH.
1. Potassium hydroxide granules (potassium content equivalent to example 1) and 20g of urea were taken, placed in an agate mortar and thoroughly mixed, transferred into a ceramic crucible, sealed with 4 layers of tinfoil, placed in a muffle furnace, heated to 550 ℃ at a rate of 2.5 ℃/min, and calcined at the temperature for 4h to obtain a yellow honeycomb solid.
2. And fully grinding the yellow solid, filtering and washing the ground yellow solid by using deionized water, and then placing the washed yellow solid in a vacuum oven at 80 ℃ for overnight drying to obtain the PCN doped with potassium ions, wherein the mark is (K) PCN & KOH.
3. Weighing 50mg (K) PCN&The KOH sample was ultrasonically dispersed in 80mL of pure water, 20mL of methanol was added as a sacrificial agent, and 37mL of chloroplatinic acid (H) was added2PtCl6) The aqueous solution (1.48mgPt/mL) is placed in a Pyrex glass photocatalytic reactor, a 300W xenon lamp is used as a light source, the Pt promoter is firstly irradiated for 2h in-situ light deposition loading under a visible light wave band (more than or equal to 420nm), and then hydrogen production activity test is carried out every hour. The hydrogen produced by the photocatalytic reaction is quantitatively sampled and analyzed by a gas chromatograph with a thermal conductivity detector, and the average hydrogen production rate is 8.6 mu mol/h.
As shown in fig. 5, the modified PCN doped with KOH as a potassium source still retained a stable layered structure.
As shown in fig. 9, the (K) PCN & KOH samples doped with KOH as a potassium ion source exhibited uniform potassium doping. The element distribution of the high-resolution TEM shows that KOH particles are used as a source, K elements are uniformly distributed, and the K/N atomic ratio is kept between 3% and 5% along Line #1 and Line #2, which indicates that the doping of potassium ions occurs and the gradient diffusion distribution is not formed.
(K) PCN doped with KOH as a source of potassium ions&The hydrogen production activity of the KOH sample is 8.6 mu mol/h which is lower than that of KTOpyr(K) PCN with particles doped as a source of potassium ions&KTO sample, which shows that gradient doping modification of potassium ions is superior to uniform doping modification.
Comparative example 3
The comparative example relates to the influence of different potassium ion sources on the gradient doping effect, and the preparation method of the carbon nitride material is different from that of the carbon nitride material in example 1 only in that no potassium tantalate particles are added to prepare a blank non-modified carbon nitride material, and the sample is marked as PCN.
1. 20g of urea is placed in an agate mortar and is fully mixed, then the mixture is transferred into a ceramic crucible and is sealed by 4 layers of tin foil paper, the mixture is placed in a muffle furnace, the temperature is raised to 550 ℃ at the speed of 2.5 ℃/min, and the mixture is calcined for 4 hours at the temperature to obtain yellow honeycomb solid.
2. And fully grinding the yellow solid, filtering and washing the ground yellow solid by using deionized water, and then placing the washed yellow solid in a vacuum oven at 80 ℃ for overnight drying to obtain blank non-modified PCN.
3. A50 mg sample of PCN was weighed, ultrasonically dispersed in 80mL of pure water, 20mL of methanol was added as a sacrificial agent, and 37mL of chloroplatinic acid (H) was added2PtCl6) The aqueous solution (1.48mgPt/mL) is placed in a Pyrex glass photocatalytic reactor, a 300W xenon lamp is used as a light source, the Pt promoter is firstly irradiated for 2h in-situ light deposition loading under a visible light wave band (more than or equal to 420nm), and then hydrogen production activity test is carried out every hour. The hydrogen generated by the photocatalytic reaction is quantitatively sampled and analyzed by a gas chromatograph with a thermal conductivity detector, and the average hydrogen production rate is 3.1 mu mol/h.
As shown in fig. 6, the PCN material synthesized by the calcination polymerization method exhibits a layered stack.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.

Claims (10)

1. The preparation method of the potassium ion gradient doped carbon nitride material is characterized by comprising the following steps of:
s1, mixing tantalum oxide powder with a potassium hydroxide solution to obtain a white suspension, heating for reaction, and centrifuging to obtain a white solid;
s2, calcining and crystallizing the white solid to obtain pyrochlore type potassium tantalate solid powder serving as a potassium ion source;
s3, mixing the potassium ion source potassium tantalate solid powder with the carbon nitride precursor, sealing and heating to obtain the potassium ion gradient doped carbon nitride material.
2. The method according to claim 1, wherein the concentration of the potassium hydroxide solution in step S1 is 6mol/L to 12 mol/L.
3. The method according to claim 1, wherein the ratio of the amount of the potassium hydroxide solution to the amount of the tantalum oxide is 100 mL: 5-8 g.
4. The method according to claim 1, wherein the heating reaction in step S1 is carried out at a temperature of 120 ℃ to 180 ℃ for a time of 6h to 12 h.
5. The preparation method of claim 1, wherein the temperature of the calcination crystallization in the step S2 is 400-800 ℃, and the time of the calcination crystallization is 6-12 h.
6. The method according to claim 1, wherein the solid powder of potassium tantalate as the potassium ion source used in step S3 is 0.5 to 10% by mass based on the mass of the carbon nitride precursor.
7. The method of claim 1, wherein the carbon nitride precursor comprises one of urea and melamine.
8. The method according to claim 1, wherein the heating in step S3 is performed at a temperature of 500 ℃ to 600 ℃ for a time of 3h to 6 h.
9. The method of claim 1, wherein the heated product is fully ground in step S3, washed with water, dried, and ground to obtain the potassium ion gradient doped carbon nitride material.
10. Application of the potassium ion gradient doped carbon nitride material as defined in claim 1 in the field of hydrogen production through photocatalytic water decomposition.
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