CN113413905B - Vanadium tetrasulfide-nickel sulfide/graphite phase carbon nitride photocatalyst and preparation method thereof - Google Patents

Vanadium tetrasulfide-nickel sulfide/graphite phase carbon nitride photocatalyst and preparation method thereof Download PDF

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CN113413905B
CN113413905B CN202110871012.1A CN202110871012A CN113413905B CN 113413905 B CN113413905 B CN 113413905B CN 202110871012 A CN202110871012 A CN 202110871012A CN 113413905 B CN113413905 B CN 113413905B
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carbon nitride
phase carbon
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CN113413905A (en
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曹丽云
陈倩
肖婷
冯亮亮
牛梦凡
黄剑锋
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Shaanxi University of Science and Technology
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Abstract

The invention discloses a vanadium tetrasulfide-nickel sulfide/graphite phase carbon nitride photocatalyst and a preparation method thereof, belonging to the technical field of photocatalysis. The g-C is obtained by calcining cyanamide in one step, cooling the calcined sample and grinding3N4(ii) a Uniformly mixing a nickel source, vanadium chloride, urea, ammonium chloride and polyvinylpyrrolidone to obtain a mixed solution, carrying out hydrothermal reaction on the mixed solution, collecting precipitates, and drying to obtain NiV-LDH; grinding the NiV-LDH and g-C3N4Uniformly mixing, and carrying out composite reaction to obtain a starch precipitation body D; and mixing the powder D with ammonium thiocyanate in an inert atmosphere to carry out calcination treatment, thus obtaining the vanadium tetrasulfide-nickel sulfide/graphite phase carbon nitride photocatalyst. The vanadium tetrasulfide-nickel sulfide/graphite phase carbon nitride photocatalyst prepared by the preparation method can avoid the problems of blockage of active sites and agglomeration of double promoters in a limited way; and can effectively improve the problem of low conductivity of the metal sulfide.

Description

Vanadium tetrasulfide-nickel sulfide/graphite phase carbon nitride photocatalyst and preparation method thereof
Technical Field
The invention belongs to the technical field of photocatalysis, and relates to a vanadium tetrasulfide-nickel sulfide/graphite phase carbon nitride photocatalyst and a preparation method thereof.
Background
The two most important topics of the 21 st century are energy and environment. The consumption of fossil energy and the continuous deterioration of the environment constitute a great threat to the survival and development of the whole human being. As an environment-friendly and efficient clean energy, hydrogen occupies an important position in the current energy research field. The conversion of solar energy into clean hydrogen by means of photocatalytic technology is an effective way to meet the increasing energy demand worldwide and alleviate environmental problems, and also more conforms to the concept of sustainable development, so that the development of low-cost, environment-friendly and efficient catalysts is a target constantly explored by researchers.
g-C3N4As a non-noble metal catalyst, the catalyst has stable chemical properties, easy preparation and low cost, and draws wide attention in the field of photocatalysis. But due to pure phase g-C3N4The application of the composite material is limited by the lower specific surface area and the higher carrier recombination rate. [ Liukai, Su Yan, Han Yaxiang, etc.. mesoporous NiS2/S-g-C3N4Preparation and photocatalytic hydrogen production performance study thereof [ J]Functional materials, 2020,51(7):7007-7014.]. And the separation efficiency of hydrogen and light source carrier is low due to excessive surface release, pure g-C3N4The evolution activity towards hydrogen is very low.
Scientists are constantly exploring various modifications to increase g-C3N4Efficiency of photocatalytic hydrogen production, e.g. introduction of defect vacancies to increase g-C3N4The active site of (1) to increase the hydrogen production [ Li Xiao is, fir, Yi Wen Xuan, etc.. Cu2+Modified g-C3N4Photocatalytic Property of photocatalyst [ J]The journal of Physics 2020,36(3):38-47.]Or compounded with other semiconductor materials to reduce the forbidden band width, thereby expanding the absorption range of visible light and improving the hydrogen production rate [ Lu X, Jin Y, Zhang X, et al3N4/ultrathin MoS2nanosheet hybrid nanostructures with enhanced photocatalytic performance[J].Dalton Transactions,2016,45(39):15406-15414.]. But the introduction of defects is difficult to control, the realization conditions are complex, and the environmental protection concept of low consumption and high energy can not be achieved. Thus, sulfur is a typical element having semiconductor properties. Nickel sulfide is distinguished by its low band gap energy (about 0.9eV), low overpotential for the synthesis and release of hydrogen. However, efficient separation of photo-generated carriers is hindered due to the low conductivity of nickel sulfide and limited contact between the host catalyst and the cocatalyst.
Disclosure of Invention
In order to overcome the disadvantages of the prior art, the invention aims to provide vanadium tetrasulfide-nickel sulfide/graphite phase carbon nitride (VS)4-NiS/g-C3N4) A photocatalyst and a preparation method thereof. The problems of blockage of active sites and agglomeration of double promoters can be avoided to a limited extent; and can effectively improve the problem of low conductivity of the metal sulfide.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a preparation method of a vanadium tetrasulfide-nickel sulfide/graphite phase carbon nitride photocatalyst, which comprises the following steps:
a) in an inert atmosphere, performing one-step calcination treatment on cyanamide to obtain a calcined sample, naturally cooling the calcined sample along with a furnace, and grinding to obtain g-C3N4；
b) Mixing a nickel source, vanadium chloride, urea and ammonium chloride to obtain mixed powder B, uniformly dispersing the mixed powder B in water for ultrasonic treatment, continuously adding polyvinylpyrrolidone, uniformly stirring to obtain mixed liquid, carrying out hydrothermal reaction on the obtained mixed liquid, cooling to obtain reaction solution, washing the obtained reaction solution to obtain precipitate, and drying the obtained precipitate to obtain NiV-LDH;
c) grinding the NiV-LDH, and mixing with g-C3N4Uniformly mixing to obtain a mixed reaction system, carrying out composite reaction on the obtained mixed reaction system, centrifuging after the reaction is finished to obtain a precipitate, drying the obtained precipitate, and grinding to obtain powder D;
d) and in an inert atmosphere, calcining the mixture obtained by mixing the powder D with ammonium thiocyanate, cooling and grinding the calcined mixture to obtain the vanadium tetrasulfide-nickel sulfide/graphite phase carbon nitride photocatalyst.
Preferably, in step a), the process parameters of the one-step calcination treatment include: the calcination temperature is 450-600 ℃, the heat preservation time is 2-4h, and the temperature rise speed is 2-10 ℃/min.
Preferably, in step b), the nickel source is nickel chloride;
mixing nickel chloride, vanadium chloride, urea, ammonium chloride and polyvinylpyrrolidone according to a feed ratio of (0.5-5) mmol, (1-3) mmol, (1-5) mmol, (0.003-0.02) g;
preferably, in step b), the time of ultrasonic treatment is 60-150 min; stirring for 60-250 min;
in the step b), the temperature of the hydrothermal reaction is 100-.
Preferably, in step C), NiV-LDH is reacted with g-C3N4Mixing the components in a mass ratio of (0.1-3) to (1-10).
Preferably, in step c), the process parameters of the recombination reaction include: stirring for 15-36h after ultrasonic treatment for 80-240 min.
Preferably, in the step D), the powder D and the ammonium thiocyanate are mixed according to the mass ratio of (1-10) to (0.5-8).
Preferably, in step d), the calcination treatment comprises: raising the temperature to 650 ℃ at the temperature raising speed of 2-10 ℃/min, and then preserving the heat for 2-6 h.
Preferably, in step a), the grinding time of the calcined sample is 20-60 min;
in the step c), the grinding time of the NiV-LDH is 30-120 min;
in the step c), the grinding time of the dried precipitate is 30-120 min;
in the step d), the grinding time after the calcination treatment is 40-100 min.
The invention discloses a vanadium tetrasulfide-nickel sulfide/graphite phase carbon nitride photocatalyst prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses vanadium tetrasulfide-nickel sulfide/graphite phase carbon nitride (VS)4-NiS/g-C3N4) According to the preparation method of the photocatalyst, a double-metal hydroxide precursor is prepared through hydrothermal, and a double-promoter catalyst of a double-metal sulfide is obtained through one-step vulcanization, so that the problems of low conductivity and the like of the photocatalyst are effectively solved. Said preparation of VS4-NiS/g-C3N4In the process of the photocatalytic material, a hydrothermal method and a solid-phase sintering method are combined, a nickel source is vulcanized in one step to obtain the composite photocatalytic material, the preparation condition is easy to control, the production cost is low, and the industrial production is easy to realize. According to the invention, a bimetallic hydroxide precursor is prepared by hydrothermal method, and the precursor forms a nano spherical structure consisting of nano sheets, so that the problems of active site blockage and agglomeration of the double-promoter can be avoided to a limited extent. And the double-promoter catalyst of the bimetallic sulfide is obtained through one-step vulcanization, and the problems of low conductivity of the metal sulfide and the like can be effectively solved.
Furthermore, the particle size, the morphology and the like of the nanosphere can be effectively regulated and controlled by regulating the proportion of the five hydrothermal raw materials, namely nickel chloride (nickel chloride hexahydrate), vanadium chloride, urea, ammonium chloride and polyvinylpyrrolidone.
Further, by adjusting VS4-NiS and g-C3N4The composite proportion can effectively regulate and control the catalytic performance, VS4Too little NiS catalytic activity is lower, while VS4Too much NiS load will block the original g-C3N4The active sites, reduces the exposure of the active sites, thereby reducing catalytic activity.
The invention also discloses vanadium tetrasulfide-nickel sulfide/graphite phase carbon nitride (VS) prepared by the preparation method4-NiS/g-C3N4) Photocatalyst of making VS by the above preparation method4NiS forms a ball cactus-like structure that can be used to enhance VS4-NiS/g-C3N4The visible light absorption capacity of the composite photocatalyst can effectively promote the separation and transmission of photo-generated charges, thereby achieving the purpose of improving the hydrogen production efficiency. Wherein g-C3N4Is a typical nano-platelet structure, whereas VS4NiS is composed of nano-particlesThe ball cactus shaped nanosphere structure is formed by stacking the tablets; and VS4-NiS/g-C3N4VS in composite photocatalysts4-NiS nanospheres are uniformly dispersed in g-C3N4And (4) nano-chips.
Drawings
FIG. 1 shows VS prepared in example 14-NiS/g-C3N4X-ray diffraction analysis of the photocatalyst;
FIG. 2 shows g-C prepared in comparative example 13N4X-ray diffraction patterns of (a);
FIG. 3 is a pure phase VS prepared in comparative example 24-X-ray diffraction analysis of NiS;
FIG. 4 is VS prepared in comparative example 24-a scan of NiS at 5 μm;
FIG. 5 shows VS prepared in example 14-NiS/g-C3N4Scanning of the photocatalyst.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention discloses vanadium tetrasulfide-nickel sulfide/graphite phase carbon nitride (VS)4-NiS/g-C3N4) The preparation method of the photocatalyst comprises the following steps:
1)g-C3N4can be obtained by one-step calcination in a tube furnace. Firstly, placing 8-16g of cyanamide into a white porcelain boat, and under the protection of inert gas, calcining at the temperature of 450-600 ℃, keeping the temperature for 2-4h, and raising the temperature at the speed of 2-10 ℃/min;
2) naturally cooling the calcined sample along with the furnace, grinding in a mortar for 20-60min to obtain yellow powder A, i.e. g-C3N4；
3) Mixing nickel chloride (nickel chloride hexahydrate), vanadium chloride, urea and ammonium chloride to obtain mixed powder B, adding 30-100mL of ultrapure water, performing ultrasonic treatment for 60-150min, adding polyvinylpyrrolidone, stirring for 60-250min on a magnetic stirrer, and quickly pouring the mixed solution into a 50mL reaction kettle; wherein, the nickel chloride, the vanadium chloride, the urea, the ammonium chloride and the polyvinylpyrrolidone are mixed according to the feeding ratio of (0.5-5) mmol, (1-3) mmol, (1-5) mmol, 0.003-0.02 g.
4) Setting the working temperature of the drying oven to be 100-200 ℃, after the temperature in the drying oven is raised to the set temperature, putting the reaction kettle into the drying oven, preserving the temperature for 10-24 h to carry out hydrothermal reaction, and after the temperature in the drying oven is reduced to room temperature, taking out the reaction kettle and cooling. Pouring the cooled reaction solution out, centrifuging, washing with ultrapure water and absolute ethyl alcohol for more than three times respectively to obtain precipitates, and drying in a vacuum drying oven for 8-26h to obtain solid C, namely NiV-LDH;
5) grinding the solid C for 30-120min, mixing the solid C with the powder A according to the mass ratio of (0.1-3) to (1-10), placing the mixture into 30-60mL of ultrapure water, carrying out ultrasonic treatment for 80-240min, placing the mixture on a magnetic stirrer, stirring for 15-36h, carrying out composite reaction, centrifuging to obtain a precipitate, drying, and grinding for 30-120min to obtain powder D;
firstly, mixing powder D and ammonium thiocyanate according to the mass ratio of (1-10) to (0.5-8), then pumping the tubular furnace to a vacuum state, slowly introducing argon, repeatedly operating for three times until all air in the tubular furnace is exhausted, raising the temperature of the tubular furnace to 650 ℃ at the heating speed of 2-10 ℃/min, then preserving heat for 2-6h, taking out and grinding for 40-100min after the product is cooled, and obtaining VS4-NiS/g-C3N4A photocatalyst.
The present invention is described in further detail below with reference to specific examples:
example 1:
1) firstly, 10g of cyanamide is put into a white porcelain boat, the calcining temperature is 450 ℃, the heat preservation time is 4h, the heating rate is 2 ℃/min under the protection of inert gas, a yellow blocky substance A is obtained after the reaction is finished, then the yellow blocky substance A is taken out and put into a mortar and ground for 30min until no obvious granular sensation exists, and the g-C is collected for standby use, so that the g-C is obtained3N4；
2) Mixing nickel chloride, vanadium chloride, urea, ammonium chloride and polyvinylpyrrolidone according to a feeding ratio of 2mmol:1mmol:1mmol:2mmol:0.02 g: specifically, the amount of polyvinylpyrrolidone added therein was 0.003 g. Firstly, nickel chloride, vanadium chloride, urea and ammonium chloride are mixed to obtain mixed powder B, 80mL of ultrapure water is added, ultrasonic treatment is carried out for 100min, then 0.003mg of polyvinylpyrrolidone is added, the mixture is placed on a magnetic stirrer to be stirred for 80min, and then the mixed solution is quickly poured into a 50mL reaction kettle;
3) setting the working temperature of the oven to be 120 ℃, when the temperature in the oven rises to the set temperature, putting the reaction kettle into the oven, preserving the heat for 16 hours, and taking out the reaction kettle for cooling after the temperature in the oven is reduced to the room temperature;
4) pouring the cooled reaction solution out, centrifuging, washing with ultrapure water-removed water and absolute ethyl alcohol for more than three times respectively to obtain precipitates, and drying in a vacuum drying oven for 10 hours to obtain solid C, namely NiV-LDH;
5) grinding the solid C for 40min, mixing the solid C with the powder A in a mass ratio of 0.1:5, placing the mixture into 40mL of ultrapure water, carrying out ultrasonic treatment for 100min, placing the mixture on a magnetic stirrer, stirring for 16h, centrifuging to obtain a precipitate, drying, and grinding for 30min to obtain powder D;
6) firstly, mixing the powder D and ammonium thiocyanate according to the mass ratio of 5:2, then pumping the tubular furnace to a vacuum state, slowly introducing argon, and repeatedly operating for three times until all air in the tubular furnace is discharged;
7) then the temperature of the tube furnace is raised to 500 ℃ at the heating rate of 2 ℃/min, the temperature is preserved for 5h, and after the product is cooled, the product is taken out and ground for 40min, thus obtaining VS4-NiS/g-C3N4A photocatalyst;
8) VS obtained by adopting LabSolar 6A type equipment pair4-NiS/g-C3N4And (4) carrying out a photocatalytic effect test on the photocatalyst. The specific test process comprises weighing 60mg of VS4-NiS/g-C3N4The photocatalyst and 10mL of EDTA (ethylene diamine tetraacetic acid) were sequentially placed in a glass reaction vessel containing 90mL of ultrapure water, and irradiated with light for 4 hours.
Example 2:
1) firstly, 12g of cyanamide is put into a white porcelain boat, the calcining temperature is 500 ℃, the heat preservation time is 4 hours, the heating rate is 4 ℃/min under the protection of inert gas, a yellow blocky substance A is obtained after the reaction is finished, then the yellow blocky substance A is taken out and put into a mortar and ground for 40min until no obvious granular sensation exists, and the g-C is collected for standby use, so that the g-C is obtained3N4；
2) The preparation method comprises the following steps of mixing nickel chloride, vanadium chloride, urea, ammonium chloride and polyvinylpyrrolidone according to a feeding ratio of 2mmol:1mmol:2mmol:3mmol:0.01g, wherein the addition amount of the polyvinylpyrrolidone is 0.02 g. Firstly, nickel chloride, vanadium chloride, urea and ammonium chloride are mixed to obtain mixed powder B, 80mL of ultrapure water is added, ultrasonic treatment is carried out for 100min, then the mixed powder is placed on a magnetic stirrer to be stirred for 80min, and then the mixed solution is quickly poured into a 50mL reaction kettle;
3) setting the working temperature of the oven to 140 ℃, after the temperature in the oven is raised to the set temperature, putting the reaction kettle into the oven, preserving the temperature for 14 hours, and after the temperature in the oven is lowered to the room temperature, taking out the reaction kettle and cooling;
4) pouring the cooled reaction solution out, centrifuging, washing with ultrapure water-removed water and absolute ethyl alcohol for more than three times respectively to obtain precipitates, and drying in a vacuum drying oven for 14 hours to obtain solid C, namely NiV-LDH;
5) grinding the solid C for 60min, mixing the solid C with the powder A in a mass ratio of 0.5:5, placing the mixture into 50mL of ultrapure water, performing ultrasonic treatment for 120min, placing the mixture on a magnetic stirrer, stirring for 20h, performing centrifugation to obtain a precipitate, drying, and grinding for 40min to obtain powder D;
6) firstly, mixing the powder D and ammonium thiocyanate in a mass ratio of 1:1, then pumping the tubular furnace to a vacuum state, slowly introducing argon, and repeatedly operating for three times until all air in the tubular furnace is discharged;
7) then the temperature of the tube furnace is raised to 550 ℃ at the heating rate of 5 ℃/min, the temperature is preserved for 4h, and after the product is cooled, the product is taken out and ground for 50min, thus obtaining VS4-NiS/g-C3N4A photocatalyst;
8) VS obtained by adopting LabSolar 6A type equipment pair4-NiS/g-C3N4And (4) carrying out a photocatalytic effect test on the photocatalyst. The specific test procedure comprises weighing 50mg of VS4-NiS/g-C3N4The photocatalyst and 15mL of EDTA (ethylene diamine tetraacetic acid) were sequentially placed in a glass reaction vessel containing 85mL of ultrapure water, and irradiated with light for 5 hours.
Example 3:
1) firstly, placing 14g of cyanamide into a white porcelain boat, calcining at 550 ℃ under the protection of inert gas, keeping the temperature for 3h, raising the temperature at 5 ℃/min to obtain a yellow blocky substance A after the reaction is finished, taking out the yellow blocky substance A, placing the yellow blocky substance A into a mortar, grinding the yellow blocky substance A for 50min until no obvious granular sensation exists, and collecting the yellow blocky substance for later use to obtain g-C3N4；
2) The preparation method comprises the following steps of mixing nickel chloride, vanadium chloride, urea, ammonium chloride and polyvinylpyrrolidone according to a feeding ratio of 4mmol:3mmol:3mmol:4mmol:0.004g, wherein the addition amount of the polyvinylpyrrolidone is 0.01 g. Firstly, nickel chloride, vanadium chloride, urea and ammonium chloride are mixed to obtain mixed powder B, then 60mL of ultrapure water is added, ultrasonic treatment is carried out for 100min, then the mixed powder is placed on a magnetic stirrer to be stirred for 140min, and then the mixed liquid is rapidly poured into a 50mL reaction kettle;
3) setting the working temperature of the oven to 160 ℃, putting the reaction kettle into the oven when the temperature in the oven is raised to the set temperature, preserving the heat for 12 hours, and taking out the reaction kettle for cooling after the temperature in the oven is reduced to room temperature;
4) pouring the cooled reaction solution out, centrifuging, washing with ultrapure water-removed water and absolute ethyl alcohol for more than three times respectively to obtain precipitates, and drying in a vacuum drying oven for 18 hours to obtain solid C, namely NiV-LDH;
5) grinding the solid C for 50min, mixing the solid C with the powder A in a mass ratio of 1:8, placing the mixture into 50mL of ultrapure water, carrying out ultrasonic treatment for 150min, placing the mixture on a magnetic stirrer, stirring for 24h, centrifuging to obtain a precipitate, drying, and grinding for 50min to obtain powder D;
6) firstly, mixing the powder D and ammonium thiocyanate in a mass ratio of 3:1, then pumping the tubular furnace to a vacuum state, slowly introducing argon, and repeatedly operating for three times until all air in the tubular furnace is discharged;
7) then the temperature of the tube furnace is raised to 600 ℃ at the heating rate of 6 ℃/min, then the temperature is preserved for 3h, after the product is cooled, the product is taken out and ground for 60min, and VS is obtained4-NiS/g-C3N4A photocatalyst;
8) VS obtained by adopting LabSolar 6A type equipment pair4-NiS/g-C3N4And testing the photocatalytic effect of the photocatalyst. The specific test process comprises weighing 40mg of VS4-NiS/g-C3N4The photocatalyst and 15mL of EDTA (ethylene diamine tetraacetic acid) were sequentially placed in a glass reaction vessel containing 85mL of ultrapure water, and irradiated for 6 hours.
Example 4:
1) firstly, placing 16g of cyanamide into a white porcelain boat, calcining at 600 ℃ under the protection of inert gas, keeping the temperature for 2h at the heating rate of 10 ℃/min, obtaining a yellow blocky substance A after the reaction is finished, taking out the yellow blocky substance A, placing the yellow blocky substance A into a mortar, grinding the yellow blocky substance A for 50min until no obvious granular sensation exists, and collecting the yellow blocky substance for later use to obtain the g-C3N4；
2) The preparation method comprises the following steps of mixing nickel chloride, vanadium chloride, urea, ammonium chloride and polyvinylpyrrolidone according to a feeding ratio of 5mmol:2mmol:3mmol:5mmol:0.05g, wherein the addition amount of the polyvinylpyrrolidone is 0.005 g. Firstly, nickel chloride, vanadium chloride, urea and ammonium chloride are mixed to obtain mixed powder B, then 100mL of ultrapure water is added, ultrasonic treatment is carried out for 120min, then the mixed powder is placed on a magnetic stirrer to be stirred for 190min, and then the mixed liquid is quickly poured into a 50mL reaction kettle;
3) setting the working temperature of the oven to 200 ℃, putting the reaction kettle into the oven when the temperature in the oven is raised to the set temperature, preserving the temperature for 10 hours, and taking out the reaction kettle for cooling after the temperature in the oven is lowered to the room temperature;
4) pouring the cooled reaction solution out, centrifuging, washing with ultrapure water and absolute ethyl alcohol for more than three times respectively to obtain precipitates, and then putting the precipitates into a vacuum drying oven for drying for 26 hours to obtain solid C, namely NiV-LDH;
5) grinding the solid C for 30min, mixing the solid C with the powder A in a mass ratio of 3:1, placing the mixture in 60mL of ultrapure water, carrying out ultrasonic treatment for 180min, placing the mixture on a magnetic stirrer, stirring for 30h, centrifuging to obtain a precipitate, drying, and grinding for 60min to obtain powder D;
6) firstly, mixing the powder D and ammonium thiocyanate according to the mass ratio of 10:5.7, then pumping the tubular furnace to a vacuum state, slowly introducing argon, and repeatedly operating for three times until all air in the tubular furnace is discharged;
7) then the temperature of the tube furnace is raised to 500 ℃ at the heating rate of 8 ℃/min, the temperature is preserved for 5h, and after the product is cooled, the product is taken out and ground for 60min to obtain VS4-NiS/g-C3N4A photocatalyst;
8) VS obtained by adopting LabSolar 6A type equipment pair4-NiS/g-C3N4And testing the photocatalytic effect of the photocatalyst. The specific test process comprises weighing 60mg of VS4-NiS/g-C3N4The photocatalyst and 10mL of EDTA (ethylene diamine tetraacetic acid) were sequentially placed in a glass reaction vessel containing 90mL of ultrapure water, and irradiated with light for 4 hours.
Example 5:
1) first, 16g of cyanamide was put in whiteIn a porcelain boat, under the protection of inert gas, the calcining temperature is 600 ℃, the heat preservation time is 2h, the temperature rising speed is 8 ℃/min, a yellow blocky substance A is obtained after the reaction is finished, then the yellow blocky substance A is taken out and placed in a mortar and ground for 20min until no obvious granular sensation exists, and the yellow blocky substance A is collected for standby use, namely g-C3N4；
2) The preparation method comprises the following steps of mixing nickel chloride, vanadium chloride, urea, ammonium chloride and polyvinylpyrrolidone according to a feeding ratio of 0.5mmol:1.5mmol:0.1mmol:1mmol:0.015g, wherein the adding amount of the polyvinylpyrrolidone is 0.15 g. Firstly, nickel chloride, vanadium chloride, urea and ammonium chloride are mixed to obtain mixed powder B, 50mL of ultrapure water is added, ultrasonic treatment is carried out for 60min, then the mixed powder is placed on a magnetic stirrer to be stirred for 80min, and then the mixed solution is quickly poured into a 50mL reaction kettle;
3) setting the working temperature of the oven to 200 ℃, putting the reaction kettle into the oven when the temperature in the oven is raised to the set temperature, preserving the temperature for 10 hours, and taking out the reaction kettle for cooling after the temperature in the oven is lowered to the room temperature;
4) pouring the cooled reaction solution out, centrifuging, washing with ultrapure water-removed water and absolute ethyl alcohol for more than three times respectively to obtain precipitates, and drying in a vacuum drying oven for 8 hours to obtain solid C, namely NiV-LDH;
5) grinding the solid C for 120min, mixing the solid C with the powder A in a mass ratio of 2:2.5, placing the mixture into 30mL of ultrapure water, carrying out ultrasonic treatment for 80min, placing the mixture on a magnetic stirrer, stirring for 15h, centrifuging to obtain a precipitate, drying, and grinding for 90min to obtain powder D;
6) firstly, mixing the powder D and ammonium thiocyanate according to the mass ratio of 7:0.5, then pumping the tubular furnace to a vacuum state, slowly introducing argon, and repeatedly operating for three times until all air in the tubular furnace is discharged;
7) then the temperature of the tube furnace is raised to 650 ℃ at the heating rate of 10 ℃/min, the temperature is kept for 2h, after the product is cooled, the product is taken out and ground for 75min, and VS is obtained4-NiS/g-C3N4A photocatalyst;
8) VS obtained by adopting LabSolar 6A type equipment pair4-NiS/g-C3N4Photocatalyst for photocatalysisAnd (5) testing the chemical effect. The specific test process comprises weighing 60mg of VS4-NiS/g-C3N4The photocatalyst and 10mL of EDTA (ethylene diamine tetraacetic acid) were sequentially placed in a glass reaction vessel containing 90mL of ultrapure water, and irradiated with light for 4 hours.
Example 6:
1) firstly, placing 16g of cyanamide into a white porcelain boat, calcining at 600 ℃ under the protection of inert gas, keeping the temperature for 2h, heating at a speed of 10 ℃/min, obtaining a yellow blocky substance A after the reaction is finished, taking out, placing into a mortar, grinding for 60min until no obvious granular sensation exists, and collecting for later use to obtain g-C3N4；
2) The preparation method comprises the following steps of mixing nickel chloride, vanadium chloride, urea, ammonium chloride and polyvinylpyrrolidone according to a feeding ratio of 1mmol:2.5mmol:0.5mmol:3.8mmol:0.003g, wherein the addition amount of the polyvinylpyrrolidone is 0.02 g. Firstly, nickel chloride, vanadium chloride, urea and ammonium chloride are mixed to obtain mixed powder B, then 90mL of ultrapure water is added, ultrasonic treatment is carried out for 150min, then the mixed powder is placed on a magnetic stirrer to be stirred for 250min, and then the mixed liquid is quickly poured into a 50mL reaction kettle;
3) setting the working temperature of the oven to be 100 ℃, putting the reaction kettle into the oven when the temperature in the oven is raised to the set temperature, preserving the heat for 24 hours, taking out the reaction kettle after the temperature in the oven is lowered to the room temperature, and cooling;
4) pouring the cooled reaction solution out, centrifuging, washing with ultrapure water-removed water and absolute ethyl alcohol for more than three times respectively to obtain precipitates, and drying in a vacuum drying oven for 20 hours to obtain solid C, namely NiV-LDH;
5) grinding the solid C for 100min, mixing the solid C with the powder A according to the mass ratio of 1.7:10, placing the mixture into 40mL of ultrapure water, performing ultrasonic treatment for 240min, placing the mixture on a magnetic stirrer, stirring for 36h, performing centrifugation to obtain a precipitate, drying, and grinding for 120min to obtain powder D;
6) firstly, mixing the powder D and ammonium thiocyanate in a mass ratio of 2.5:8, then pumping the tubular furnace to a vacuum state, slowly introducing argon, and repeatedly operating for three times until all air in the tubular furnace is discharged;
7) then the temperature of the tube furnace is raised to 580 ℃ at the heating rate of 4 ℃/min, the temperature is kept for 6h, and after the product is cooled, the product is taken out and ground for 100min, thus obtaining VS4-NiS/g-C3N4A photocatalyst;
8) VS obtained by adopting LabSolar 6A type equipment pair4-NiS/g-C3N4And testing the photocatalytic effect of the photocatalyst. The specific test process comprises weighing 60mg of VS4-NiS/g-C3N4The photocatalyst and 10mL of EDTA (ethylene diamine tetraacetic acid) were sequentially placed in a glass reaction vessel containing 90mL of ultrapure water, and irradiated with light for 4 hours.
Example 7:
1) firstly, placing 8g of cyanamide into a white porcelain boat, calcining at 600 ℃ under the protection of inert gas, keeping the temperature for 2h, heating at the speed of 6 ℃/min, obtaining a yellow blocky substance A after the reaction is finished, taking out, placing into a mortar, grinding for 60min until no obvious granular sensation exists, and collecting for later use to obtain g-C3N4；
2) The preparation method comprises the following steps of mixing nickel chloride, vanadium chloride, urea, ammonium chloride and polyvinylpyrrolidone according to a feeding ratio of 1mmol:2.5mmol:0.5mmol:2.5mmol:0.003g, wherein the addition amount of the polyvinylpyrrolidone is 0.02 g. Firstly, nickel chloride, vanadium chloride, urea and ammonium chloride are mixed to obtain mixed powder B, then 30mL of ultrapure water is added, ultrasonic treatment is carried out for 150min, then the mixed powder is placed on a magnetic stirrer to be stirred for 150min, and then the mixed liquid is quickly poured into a 50mL reaction kettle;
3) setting the working temperature of the oven to be 100 ℃, when the temperature in the oven rises to the set temperature, putting the reaction kettle into the oven, preserving the temperature for 24 hours, and taking out the reaction kettle to cool after the temperature in the oven falls to the room temperature;
4) pouring the cooled reaction solution out, centrifuging, washing with ultrapure water and absolute ethyl alcohol for more than three times respectively to obtain precipitates, and then putting the precipitates into a vacuum drying oven for drying for 20 hours to obtain solid C, namely NiV-LDH;
5) grinding the solid C for 100min, mixing the solid C with the powder A according to the mass ratio of 1.5:10, placing the mixture into 40mL of ultrapure water, performing ultrasonic treatment for 240min, placing the mixture on a magnetic stirrer, stirring for 36h, performing centrifugation to obtain a precipitate, drying, and grinding for 120min to obtain powder D;
6) firstly, mixing the powder D and ammonium thiocyanate according to the mass ratio of 2.5:8, then pumping the tubular furnace to a vacuum state, slowly introducing argon, and repeatedly operating for three times until all air in the tubular furnace is discharged;
7) then the temperature of the tube furnace is raised to 580 ℃ at the heating rate of 4 ℃/min, the temperature is kept for 6h, and after the product is cooled, the product is taken out and ground for 100min, thus obtaining VS4-NiS/g-C3N4A photocatalyst;
8) VS obtained by adopting LabSolar 6A type equipment pair4-NiS/g-C3N4And testing the photocatalytic effect of the photocatalyst. The specific test process comprises weighing 60mg of VS4-NiS/g-C3N4The photocatalyst and 10mL of EDTA (ethylene diamine tetraacetic acid) were sequentially placed in a glass reaction vessel containing 90mL of ultrapure water, and irradiated with light for 4 hours.
Comparative example 1:
placing 16g of cyanamide into a white porcelain boat, calcining at 450 ℃, keeping the temperature for 4h, and raising the temperature at 8 ℃/min to obtain a yellow blocky substance A after the reaction is finished, taking out a sample, and grinding to obtain g-C3N4。
Comparative example 2:
1) mixing nickel chloride, vanadium chloride, urea, ammonium chloride and polyvinylpyrrolidone according to a feeding ratio of 3mmol:1mmol:2mmol:3mmol:0.01g, wherein the addition amount of polyvinylpyrrolidone is 0.02g, obtaining mixed powder B, adding 30-100mL of ultrapure water, firstly carrying out ultrasonic treatment for 100min, then adding 0.003mol/L hydrochloric acid solution, adjusting the pH value of the solution to 4, then placing the solution on a magnetic stirrer to stir for 100min, and then quickly pouring the mixed solution into a 50mL reaction kettle;
2) setting the working temperature of the oven to 140 ℃, putting the reaction kettle into the oven when the temperature in the oven is raised to the set temperature, preserving the heat for 14 hours, and taking out the reaction kettle for cooling after the temperature in the oven is reduced to room temperature;
3) pouring the cooled reaction solution out, centrifuging, washing with ultrapure water-removed water and absolute ethyl alcohol for more than three times respectively to obtain precipitates, and drying in a vacuum drying oven for 14 hours to obtain solid C, namely NiV-LDH;
4) grinding the solid C for 60min, then mixing the solid C with ammonium thiocyanate according to the mass ratio of 1:1, pumping the tubular furnace to a vacuum state, slowly introducing argon, and repeatedly operating for three times until all air in the tubular furnace is discharged;
heating the tube furnace to 550 ℃ at the heating rate of 5 ℃/min, then preserving heat for 4h, taking out and grinding the product for 50min after the product is cooled, and obtaining pure-phase VS4-a NiS photocatalyst.
The invention is described in further detail below with reference to the accompanying drawings:
see FIG. 1 for VS prepared in example 14-NiS/g-C3N4The X-ray diffraction analysis chart of (1), wherein the abscissa is the angle of 2 θ and the ordinate is the diffraction peak intensity. At 13 ℃ and 27 ℃ respectively corresponding to g-C3N4(100) and (002) planes of (a) and (b), and VS4-NiS/g-C3N4Can accurately correspond to g-C3N4PDF #87-1526 and NiS PDF #02-1280, indicating successful preparation of VS4-NiS/g-C3N4A photocatalyst.
See FIG. 2 for g-C prepared in this comparative example 13N4The X-ray diffraction analysis chart of (1) shows that the positions of the small square pieces are 13 DEG and 27 DEG, respectively corresponding to g-C3N4The (100) crystal face and the (002) crystal face of the crystal and can accurately correspond to g-C3N4Standard cards (PDF #87-1526), indicating successful preparation of phase-pure g-C3N4。
FIG. 3 is a pure phase VS prepared in comparative example 24X-ray diffraction analysis of NiS, VS4NiS cocatalyst VS4Standard cards (PDF #72-1294) and NiS Standard cards (PDF #02-1280), indicating that a pure-phase VS was successfully prepared4-NiS。
See FIG. 4 for VS prepared in this comparative example 24Scanning of NiS at 5 μm, enabling a clear observation of VS4NiS is a ball cactus-shaped nanosphere structure formed by stacking nanosheets。
See FIG. 5 for VS prepared in example 14-NiS/g-C3N4The scanned image of (a). Can be clearly seen, g-C is added3N4No later change in VS4The original nanospherical structure of NiS. Nanospheres are composed of VS4-NiS nanosheets stacked, the larger nanosheets on the nanospheres being the resulting sheet g-C3N4。
The above contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention should not be limited thereby, and any modification made on the basis of the technical idea proposed by the present invention falls within the protection scope of the claims of the present invention.

Claims (8)

1. A preparation method of vanadium tetrasulfide-nickel sulfide/graphite phase carbon nitride photocatalyst is characterized by comprising the following steps:
a) in an inert atmosphere, performing one-step calcination treatment on cyanamide to obtain a calcined sample, naturally cooling the calcined sample along with a furnace, and grinding to obtain g-C3N4；
b) Mixing nickel chloride, vanadium chloride, urea and ammonium chloride to obtain mixed powder B, uniformly dispersing the mixed powder B in water for ultrasonic treatment, continuously adding polyvinylpyrrolidone, uniformly stirring to obtain mixed liquid, carrying out hydrothermal reaction on the obtained mixed liquid, cooling to obtain reaction solution, washing the obtained reaction solution to obtain precipitate, and drying the obtained precipitate to obtain NiV-LDH;
mixing nickel chloride, vanadium chloride, urea, ammonium chloride and polyvinylpyrrolidone according to a feed ratio of (0.5-5) mmol, (1-3) mmol, (1-5) mmol, (0.003-0.02) g;
c) grinding the NiV-LDH, and mixing with g-C3N4Uniformly mixing the raw materials according to the mass ratio of (0.1-3) to (1-10) to obtain a mixed reaction system, carrying out composite reaction on the obtained mixed reaction system, centrifuging the obtained product after the reaction is finished to obtain a precipitate, drying the obtained precipitate, and grinding the dried precipitate to obtain powder D;
d) and in an inert atmosphere, calcining the mixture obtained by mixing the powder D and ammonium thiocyanate, and cooling and grinding the calcined mixture to obtain the vanadium tetrasulfide-nickel sulfide/graphite phase carbon nitride photocatalyst.
2. The method for preparing vanadium tetrasulfide-nickel sulfide/graphite phase carbon nitride photocatalyst according to claim 1, wherein in step a), the technological parameters of one-step calcination treatment include: the calcination temperature is 450-600 ℃, the heat preservation time is 2-4h, and the temperature rise speed is 2-10 ℃/min.
3. The method for preparing vanadium tetrasulfide-nickel sulfide/graphite phase carbon nitride photocatalyst according to claim 1, characterized in that in step b), the ultrasonic treatment time is 60-150 min; stirring for 60-250 min;
in the step b), the temperature of the hydrothermal reaction is 100-.
4. The method for preparing vanadium tetrasulfide-nickel sulfide/graphite phase carbon nitride photocatalyst according to claim 1, wherein in step c), the process parameters of the composite reaction include: stirring for 15-36h after ultrasonic treatment for 80-240 min.
5. The method for preparing vanadium tetrasulfide-nickel sulfide/graphite phase carbon nitride photocatalyst according to claim 1, wherein in step D), the powder D and the ammonium thiocyanate are mixed according to the mass ratio of (1-10) to (0.5-8).
6. The method for preparing a vanadium tetrasulfide-nickel sulfide/graphite phase carbon nitride photocatalyst as claimed in claim 1, wherein in step d), the calcination treatment comprises: raising the temperature to 650 ℃ at the temperature raising speed of 2-10 ℃/min, and then preserving the heat for 2-6 h.
7. The method for preparing a vanadium tetrasulfide-nickel sulfide/graphite phase carbon nitride photocatalyst according to claim 1, characterized in that in step a), the grinding time of the calcined sample is 20-60 min;
in the step c), the grinding time of the NiV-LDH is 30-120 min;
in the step c), the grinding time of the dried precipitate is 30-120 min;
in the step d), the grinding time after the calcination treatment is 40-100 min.
8. The vanadium tetrasulfide-nickel sulfide/graphite phase carbon nitride photocatalyst prepared by the preparation method of any one of claims 1 to 7.
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