CN113522327B - Ternary composite photocatalyst, preparation method and application thereof - Google Patents
Ternary composite photocatalyst, preparation method and application thereof Download PDFInfo
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- CN113522327B CN113522327B CN202010286639.6A CN202010286639A CN113522327B CN 113522327 B CN113522327 B CN 113522327B CN 202010286639 A CN202010286639 A CN 202010286639A CN 113522327 B CN113522327 B CN 113522327B
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Images
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- B01J35/39—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
- C01B2203/107—Platinum catalysts
Abstract
The invention discloses a ternary composite photocatalyst, a preparation method and application thereof. Transition metal particles (TM) are loaded on the surfaces of two-dimensional Black Phosphorus (BP) sheets to serve as a cocatalyst, so that the transition metal particles can serve as capture sites of photon-generated carriers, the dissociation and interface migration efficiency of the carriers is improved, the transition metal particles can serve as active sites of oxidation-reduction reaction, the overpotential of the photocatalytic reaction is reduced, and the photocatalytic efficiency of graphite-phase carbon nitride is effectively improved.
Description
Technical Field
The invention relates to the technical field of photocatalysis, in particular to a ternary composite photocatalyst, and a preparation method and application thereof.
Background
With the rapid increase of population and economy, the consumption of world energy is multiplied, the exhaustion of fossil fuel is accelerated, and the development of new energy for replacing the fossil fuel is not slow. Among new clean energy sources, hydrogen energy is generally considered as an ideal, pollution-free and green energy source because the only product after combustion of hydrogen is water. However, the traditional hydrogen production method has large energy consumption, so that the hydrogen is expensive, and the wide application of the hydrogen in various industries is seriously limited. The sunlight is renewable energy, and the hydrogen obtained from water in a lighting mode returns to the form of water after being used as energy, so that the solar water generating device is clean and environment-friendly and has wide application prospect. The photocatalyst becomes one of the key factors for determining whether the photocatalytic process can be practically applied.
Water is a relatively stable compound, and the process of water decomposition into hydrogen and oxygen is a process of Gibbs free energy increase, that is, the water decomposition reaction is not spontaneous reaction from the thermodynamic point of view and must be carried out by external energy. The reaction for producing hydrogen by photocatalytic water splitting is to utilize the energy of photons to drive the water splitting reaction to occur and then convert the energy into chemical energy. Far ultraviolet rays (with the wavelength less than 190nm) with high energy can directly decompose water, however, the far ultraviolet rays are difficult to reach the earth surface, so that the hydrogen production by water decomposition is difficult to realize by the irradiation of common sunlight. The photocatalytic water splitting hydrogen production is realized by utilizing the light absorption characteristic of a material to carry out a photolytic water splitting reaction. The semiconductor material such as titanium dioxide, carbon nitride and the like has good photocatalytic performance, and can generate photo-generated electrons with strong oxidation capability after being excited by photons, and can reduce protons adsorbed on the surface of the semiconductor into hydrogen, so that hydrogen is produced by photocatalytic water decomposition.
In recent years, the development of non-metal photocatalysts has attracted much attention in order to reduce costs. As one of the most stable structures of the carbon nitride compound, graphite-phase carbon nitride (g-C3N4) is reported to have visible light catalytic activity, but the activity of hydrogen production by water photolysis of pure g-C3N4 is very small, because photo-generated electrons and holes are easily and rapidly recombined in g-C3N4 and released in the form of heat or light energy, so that the activity of hydrogen production by water decomposition of the pure g-C3N4 photocatalyst is very small, and therefore in order to improve the photocatalytic efficiency of g-C3N4, g-C3N4 needs to be modified to improve the photocatalytic efficiency of the material.
Disclosure of Invention
In order to solve the problem that the photocatalytic efficiency of the pure graphite phase carbon nitride photocatalyst in the prior art is too low, the invention provides a novel three-way composite photocatalyst containing graphite phase carbon nitride, and a preparation method and application thereof.
In order to achieve the purpose, the invention provides a three-element composite photocatalyst, which comprises graphite-phase carbon nitride and a two-dimensional black phosphorus/transition metal heterojunction which are mixed with each other, wherein the two-dimensional black phosphorus/transition metal heterojunction comprises a two-dimensional black phosphorus sheet and transition metal particles loaded on the two-dimensional black phosphorus sheet.
Preferably, the mass ratio of the two-dimensional black phosphorus/transition metal heterojunction to the graphite-phase carbon nitride is 1:1 to 1: 100.
Preferably, the transition metal particles are any one of Co, Ni, Fe, Cu, Pd, and Pt.
The invention also provides a preparation method of the ternary composite photocatalyst, which comprises the following steps:
mixing a transition metal salt solution with the two-dimensional black phosphorus sheet to obtain a mixed solution;
illuminating the mixed solution, and depositing transition metal particles on the two-dimensional black phosphorus sheet to obtain a two-dimensional black phosphorus/transition metal heterojunction;
and dispersing the two-dimensional black phosphorus/transition metal heterojunction in graphite-phase carbon nitride in an organic medium, mixing and drying to obtain the ternary composite photocatalyst.
Preferably, the molar concentration of the transition metal cation in the transition metal salt solution is 0.001 to 0.1 mol/L.
Preferably, the ratio of the two-dimensional black phosphorus flakes to the amount of the species of the transition metal cations is 1:0.1 to 1: 10.
Further, the deposition process is controlled to be constant temperature, the temperature range is 10-50 ℃, and the illumination time is 1-500 min.
Further, the mixed solution also comprises an alcohol electron sacrificial agent.
Further preferably, the volume fraction of the alcohol electron sacrifice agent in the mixed solution is 90% or less.
Further, the preparation method of the ternary composite photocatalyst specifically comprises the following steps:
firstly, mixing a transition metal salt solution and two-dimensional black phosphorus sheets, filling the mixture into a reaction container to obtain a mixed solution, sealing the reaction container, and introducing inert gas for 5-300 min;
then, under the constant temperature condition of 10-50 ℃, single-wavelength light is adopted to irradiate the mixed solution for 5-300min, transition metal particles are deposited on the two-dimensional black phosphorus sheet, and the two-dimensional black phosphorus/transition metal heterojunction is obtained after multiple times of cleaning, wherein the wavelength range of the single-wavelength light is 400-635 nm;
and finally, dispersing the two-dimensional black phosphorus/transition metal heterojunction in graphite phase carbon nitride in an organic medium, performing ultrasonic dispersion treatment for 0.01-2h at the power of 100-.
The invention further provides an application of the ternary composite photocatalyst, and the ternary composite photocatalyst is used as a photocatalyst in a hydrogen production process by photolysis of water.
Further, the rate of hydrogen production by photolysis of water of the three-way composite photocatalyst is 31-36.4 mmol/h/g.
The invention provides a three-element composite photocatalyst, which is prepared by mixing a two-dimensional black phosphorus/transition metal heterojunction and graphite-phase carbon nitride (g-C) 3 N 4 ) And (4) compounding to obtain the product. Transition metal particles (TM) are loaded on the surface of a two-dimensional Black Phosphorus (BP) sheet to serve as a cocatalyst, so that the transition metal particles can serve as capture sites of photon-generated carriers, the dissociation and interface migration efficiency of the carriers is improved, the transition metal particles can serve as active sites of redox reaction, and the overpotential of the photocatalytic reaction is reduced.
Drawings
The above and other aspects, features and advantages of embodiments of the present invention will become more apparent from the following description taken in conjunction with the accompanying drawings, in which:
FIGS. 1a and 1b are BP/Ni/g-C of example 1 3 N 4 TEM images of the ternary composite photocatalyst with different magnifications;
FIGS. 2a and 2b are BP/Co/g-C of example 2 3 N 4 TEM images of the ternary composite photocatalyst with different magnifications;
FIGS. 3a and 3b are BP/Pt/g-C of example 3 3 N 4 TEM images of the ternary composite photocatalyst with different magnifications;
FIGS. 4a and 4b are BP/Pd/g-C of example 4 3 N 4 TEM images of the ternary composite photocatalyst at different magnifications.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the specific embodiments set forth herein. Rather, these embodiments are provided to explain the principles of the invention and its practical application to thereby enable others skilled in the art to understand the invention for various embodiments and with various modifications as are suited to the particular use contemplated.
Graphite phase carbon nitride (g-C), one of the most stable structures of carbon nitride compounds 3 N 4 ) Reported to have visible light catalytic activity, g-C 3 N 4 The bandwidth of the photocatalyst is about 2.7eV, and the photocatalyst can absorb visible light below 460 nm. The conduction band is-1.1 eV and the valence band is +1.6eV, which satisfies the requirement of hydrogen production by water decomposition thermodynamically. However, pure g-C3N4 has very little activity in photolyzing water to produce hydrogen, because of the generation of photo-generated electrons and holes at g-C 3 N 4 The interior is easily and rapidly recombined and released in the form of heat or light energy to produce pure g-C 3 N 4 The activity of the photocatalyst for decomposing water to produce hydrogen is very small, so that the g-C with high purity is improved 3 N 4 The photocatalytic efficiency of (2) is required to be modified.
The inventor of the invention researches and provides a novel three-way composite photocatalyst containing graphite-phase carbon nitride, a preparation method and application thereof based on the problem that the existing pure graphite-phase carbon nitride photocatalyst is too low in photocatalytic efficiency.
1. Some embodiments of the invention provide a preparation method of a novel three-way composite photocatalyst containing graphite-phase carbon nitride, which comprises the following steps:
(1) and preparing the two-dimensional black phosphorus/transition metal heterojunction.
(1-1) preparation of two-dimensional black phosphorus flake: the two-dimensional black phosphorus flake is prepared by methods of mechanical stripping, liquid phase stripping, electrochemical stripping, cleaning of blocky black phosphorus crystals and the like.
The method for stripping the black phosphorus block is prior art, therefore, the present invention does not describe this operation too much.
(1-2) mixing the transition metal salt solution with the two-dimensional black phosphorus flakes to obtain a mixed solution.
The transition metal cation in the selected transition metal salt solution is any one of all transition metal cations with different valence states. Transition metals include, but are not limited to, Co, Ni, Fe, Cu, Pd, Pt, and the valence of the transition metal cation includes, but is not limited to, 2 + 、3 + 、5 + (ii) a The concentration of the transition metal salt is 0.001-0.1 mol/L.
The molar ratio of the two-dimensional black phosphorus flakes to the transition metal cations is 1:0.1 to 1: 10.
In a preferred scheme, an alcohol electronic sacrificial agent is further added into the mixed solution, namely, the step (1-2) is replaced by the step (1-2') of mixing a transition metal salt solution, the alcohol electronic sacrificial agent and the two-dimensional black phosphorus flake to obtain the mixed solution.
In the mixed solution, the volume fraction of the alcohol electron sacrificial agent is 0-90%.
The alcohol electron sacrificial body has the functions of avoiding the oxidation of the photo-induced holes to the black phosphorus and preventing the ternary composite structure from being damaged; the alcohol electron-sacrificial agent may preferably be: one of absolute methanol, absolute ethanol and isopropanol.
(1-3) air removal: and (3) introducing inert gas to remove air in the reaction vessel and the mixed solution, wherein the introducing time is 5-300 min.
The inert gas is a gas which does not react with a solute or a solvent and does not affect the subsequent deposition operation. Rare gases such as high purity argon may be selected.
And (1-4) illuminating the mixed solution, depositing transition metal particles on the two-dimensional black phosphorus sheet, and cleaning for multiple times to obtain the two-dimensional black phosphorus/transition metal heterojunction.
The principle of photo-deposition is: the semiconductor material is excited by light to generate photo-generated electrons, the photo-generated electrons and transition metal salt are subjected to reduction reaction, and finally metal particles are deposited on the two-dimensional black phosphorus plate.
The specific operation is as follows: and (3) irradiating the mixed solution for a certain time by adopting single-wavelength light, depositing transition metal particles on the two-dimensional black phosphorus sheet, and cleaning for multiple times to obtain the two-dimensional black phosphorus/transition metal heterojunction, wherein the wavelength range of the single-wavelength light is 400-635nm, and common single-wavelength light sources in the wavelength range can achieve the purpose of deposition.
The temperature is kept constant in the deposition process, and the temperature range is as follows: 10-50 ℃; the stirring speed is 100-5000rpm (stirring can ensure that the black phosphorus nanosheet can keep good dispersibility in the solution); the illumination time is as follows: 1-500 min.
(2) Two-dimensional black phosphorus/transition metal heterojunction and graphite-phase carbon nitride (g-C) 3 N 4 ) Compounding:
two-dimensional black phosphorus/transition metal heterojunction and g-C 3 N 4 Mixing, performing ultrasonic dispersion uniformly, performing ball milling compounding, and performing vacuum drying to obtain the ternary composite photocatalytic material.
Two-dimensional black phosphorus/transition metal heterojunction and g-C 3 N 4 The mass ratio of (A) to (B) is 1:1-1: 100.
The dispersion medium for ultrasonic dispersion treatment is absolute ethyl alcohol, the power is 100-2000W, and the time is 0.01-2 h.
The rotation speed of the ball milling composite treatment is 100 plus 1000rpm, and the ball milling time is 0.1-10 h.
2. Some embodiments of the present invention provide a novel three-way composite photocatalyst including graphite-phase carbon nitride, including graphite-phase carbon nitride and a two-dimensional black phosphorus/transition metal heterojunction mixed with each other, the two-dimensional black phosphorus/transition metal heterojunction including a two-dimensional black phosphorus sheet and transition metal particles supported on the two-dimensional black phosphorus sheet.
The mass ratio of the two-dimensional black phosphorus/transition metal heterojunction to the graphite-phase carbon nitride is 1:1-1: 100.
Transition metal particles include, but are not limited to, Co, Ni, Fe, Cu, Pd, Pt.
3. Some embodiments of the invention provide application of the ternary composite photocatalyst in a hydrogen production process by water photolysis, and the hydrogen production performance by water photolysis of the ternary composite photocatalyst is 31-36.4 mmol/h/g.
The photocatalytic hydrogen production efficiency of pure BP and pure g-C3N4 is very low, about dozens of mu mol/h/g, and the performance of the three-element composite photocatalyst obtained by the invention is smaller by one order of magnitude.
By selecting differentThe semiconductor is used for carrying out heterojunction construction, and the g-C is effectively improved 3 N 4 The strategy of photocatalytic performance utilizes the difference of energy band structures of different semiconductors to construct gradient electron transfer, is favorable for promoting the separation of photogenerated electrons and holes, and improves g-C 3 N 4 Photocatalytic efficiency of the material. The black phosphorus is a novel semiconductor material, has a graphite-like layered structure, is a direct band gap semiconductor material (the forbidden band width of the block black phosphorus is 0.3eV), and the response of the black phosphorus to light can be expanded to an infrared region; meanwhile, the forbidden band width can be changed by regulating the number of layers of the black phosphorus alkene (the forbidden band width of single-layer black phosphorus is 2.1eV), and the black phosphorus has good carrier mobility. The characteristics of the black phosphene are utilized to combine the black phosphene with g-C 3 N 4 The composite catalyst is constructed, so that the carrier mobility and the conductivity of the composite material can be improved, the rapid recombination of photon-generated electrons and holes can be avoided, and the interface migration of photon-generated charges is promoted, so that the photocatalytic efficiency can be obviously improved.
In g-C 3 N 4 The catalytic performance of the material can also be improved by loading transition metal as a cocatalyst on the surface of the material. When the transition metal is in contact with the semiconductor photocatalyst material, the photo-generated electrons will migrate from the conduction band of the semiconductor to the transition metal surface and be trapped. Subsequently, the photo-generated electrons participate in the photocatalytic reduction reaction at the surface thereof, and the remaining photo-generated holes migrate toward the surface of the semiconductor and participate in the photocatalytic oxidation reaction. The process can not only promote the separation of the photoproduction electrons and the holes, but also realize the spatial separation of the oxidation reaction and the reduction reaction, thereby improving the quantum efficiency of the photocatalyst and the efficiency of the photocatalytic reaction. In addition, in addition to promoting the separation of photogenerated electrons and holes, the transition metal may also provide surface active sites for the photocatalytic reaction to reduce the surface reaction overpotential, thereby increasing the surface reaction rate of the photocatalytic reaction.
The above-mentioned three-way composite photocatalyst, the preparation method and the application thereof of the present invention will be described with reference to specific examples, and it will be understood by those skilled in the art that the following examples are only specific examples of the above-mentioned three-way composite photocatalyst, the preparation method and the application thereof of the present invention, and are not intended to limit the entirety thereof. The specific techniques or conditions are not indicated in the examples, and the reagents or apparatuses used are not indicated in the manufacturer's instructions, and are all conventional products commercially available, according to the conventional techniques or conditions in the art or according to the product specifications.
Example 1
(1) Stripping a two-dimensional thin-layer black phosphorus sheet: connecting block black phosphorus as a working electrode with an inert electrode by using a lead, then immersing the working electrode and the inert electrode together into N, N-dimethylformamide electrolyte containing 0.05M (M is a abbreviation of mol/L) tetrabutylammonium cation, continuously electrifying for 3min at 20V, cleaning the expanded block black phosphorus for a plurality of times, ultrasonically oscillating for 2min at 300W, centrifuging for 3min at the rotating speed of 500rpm, taking supernatant after the centrifugation is finished to obtain a two-dimensional black phosphorus sheet, centrifuging the obtained two-dimensional black phosphorus sheet at 12000rpm for 10min, and cleaning the two-dimensional black phosphorus sheet twice by using ultrapure water.
(2) 0.5mg of two-dimensional black phosphorus flakes was added to 1mL of 0.005M NiCl 2 The solution was added with 4mL of ultrapure water to obtain a mixed solution. Adding small magnetons into the quartz tube filled with the mixed solution, and sealing the quartz tube by using a rubber plug and paraffin; and (3) extending a thick long needle into the bottom of the quartz tube, introducing high-purity argon gas into the quartz tube, cooperating with a lower short needle to remove air in the quartz tube and the solution, and sealing the needle hole by paraffin after degassing is finished.
(3) And (3) illuminating the sealed mixed solution obtained in the step (2) for 20min under the conditions of using blue light of 450nm as a light source, keeping the temperature constant at 20 ℃ and stirring at 2500rpm to enable Ni particles to uniformly grow on the two-dimensional thin-layer black phosphorus, and centrifuging and cleaning the two-dimensional thin-layer black phosphorus for multiple times by using absolute ethyl alcohol to obtain the two-dimensional black phosphorus/nickel heterojunction.
(4) Taking the 10mg two-dimensional black phosphorus/nickel heterojunction obtained in the step (3) and g-C 3 N 4 Dispersing the mixture into 30mL of absolute ethyl alcohol solution according to the mass ratio of 1:10, wherein the power of ultrasonic dispersion treatment is 300W, and the time is 0.01 h; the ball milling composite rotating speed is 200rpm, the ball milling time is 5 hours, and BP/Ni/g-C is obtained 3 N 4 A ternary composite photocatalyst.
BP/Ni/g-C 3 N 4 Transmission Electron Microscope (TEM) photographs of the three-way composite photocatalyst are shown in FIGS. 1a and 1b, wherein the black particles are deposited Ni metal ions and are darker and smaller in colorFlakes are g-C 3 N 4 The bottom layer dark large sheet is a two-dimensional black phosphorus sheet.
Example 2
(1) Stripping a two-dimensional thin-layer black phosphorus sheet: connecting block black phosphorus serving as a working electrode with an inert electrode by using a lead, immersing the working electrode and the inert electrode into N, N-dimethylformamide electrolyte containing 0.05M tetrabutylammonium cation, continuously electrifying for 3min at 20V, cleaning the expanded black phosphorus block for a plurality of times, ultrasonically oscillating for 2min at 300W, centrifuging for 3min at the rotating speed of 500rpm, taking supernatant after centrifuging to obtain a two-dimensional black phosphorus sheet, centrifuging the obtained two-dimensional black phosphorus sheet at 12000rpm for 10min, and cleaning the two-dimensional black phosphorus sheet twice by using ultrapure water.
(2) 0.5mg of two-dimensional black phosphorus flake was added to 1mL of 0.005M CoCl 2 The solution was added with 4mL of ultrapure water to obtain a mixed solution. Adding small magnetons into the quartz tube filled with the mixed solution, and sealing the quartz tube by using a rubber plug and paraffin; and (3) extending a thick and long needle into the bottom of the quartz tube, introducing high-purity argon gas to be matched with a lower short needle to remove air in the quartz tube and the solution, and sealing the needle hole by paraffin after degassing is finished.
(3) And (3) taking the blue light of 450nm as a light source, illuminating for 20min under the stirring conditions of constant temperature of 20 ℃ and 2500rpm to enable Co particles to uniformly grow on the two-dimensional thin-layer black phosphorus, and centrifuging and cleaning for multiple times by using absolute ethyl alcohol to obtain the two-dimensional black phosphorus/cobalt heterojunction.
(4) Taking 10mg of the two-dimensional black phosphorus/cobalt heterojunction material obtained in the step (3) and g-C 3 N 4 Dispersing the mixture into 30mL of absolute ethyl alcohol solution according to the mass ratio of 1:10, wherein the power of ultrasonic dispersion treatment is 300W, and the time is 0.01 h; the ball milling composite rotating speed is 200rpm, the ball milling time is 5 hours, and the BP/Co/g-C is obtained 3 N 4 A ternary composite photocatalyst.
BP/Co/g-C 3 N 4 TEM photographs of the ternary composite photocatalyst are shown in FIGS. 2a and 2b, wherein the black particles are deposited Co metal ions, and the darker black platelets are g-C 3 N 4 The bottom layer dark large sheet is a two-dimensional black phosphorus sheet.
Example 3
(1) Stripping a two-dimensional thin-layer black phosphorus sheet: connecting block black phosphorus as a working electrode with an inert electrode by using a lead, then immersing the working electrode and the inert electrode into N, N-dimethylformamide electrolyte containing 0.05M tetrabutylammonium cation, continuously electrifying for 3min at 20V, cleaning the expanded black phosphorus block for several times, ultrasonically oscillating for 2min at 300W, centrifuging for 3min at the rotating speed of 500rpm, taking supernatant after the centrifugation is finished to obtain a two-dimensional black phosphorus sheet, centrifuging the obtained two-dimensional black phosphorus sheet at 12000rpm for 10min, and cleaning twice by using ultrapure water.
(2) 0.5mg of two-dimensional black phosphorus flake was added with 1mL of 0.005M H 2 PtCl 6 The solution was added to 4mL of ultrapure water to form a mixed solution. Adding small magnetons into the quartz tube filled with the mixed solution, and sealing the quartz tube by using a rubber plug and paraffin; the needle is extended into the bottom of the quartz tube by a thick long needle, then high-purity argon is introduced to be matched with a low short needle to remove air in the quartz tube and the solution, and the needle is sealed by paraffin after degassing is finished.
(3) And (3) taking the blue light of 450nm as a light source, illuminating for 20min under the stirring conditions of constant temperature of 20 ℃ and 2500rpm to enable Pt particles to uniformly grow on the two-dimensional thin-layer black phosphorus, and performing multiple centrifugal cleaning by using absolute ethyl alcohol to obtain the two-dimensional black phosphorus/platinum heterojunction.
(4) Taking 10mg of the two-dimensional black phosphorus/platinum heterojunction material obtained in the step (3) and g-C 3 N 4 Dispersing the mixture into 30mL of absolute ethyl alcohol solution according to the mass ratio of 1:10, wherein the power of ultrasonic dispersion treatment is 300W, and the time is 0.01 h; the ball milling composite rotating speed is 200rpm, the ball milling time is 5 hours, and the BP/Pt/g-C can be obtained 3 N 4 A ternary composite photocatalyst.
BP/Pt/g-C 3 N 4 TEM photographs of the ternary composite photocatalyst are shown in FIGS. 3a and 3b, wherein the black particles are deposited Pt metal ions, and the darker black flakes are g-C 3 N 4 The bottom layer dark large sheet is a two-dimensional black phosphorus sheet.
Example 4
(1) Stripping a two-dimensional thin-layer black phosphorus sheet: connecting block black phosphorus as a working electrode with an inert electrode by using a lead, then immersing the working electrode and the inert electrode into N, N-dimethylformamide electrolyte containing 0.05M tetrabutylammonium cation, continuously electrifying for 3min at 20V, cleaning the expanded black phosphorus block for several times, ultrasonically oscillating for 2min at 300W, centrifuging for 3min at the rotating speed of 500rpm, taking supernatant after the centrifugation is finished to obtain a two-dimensional black phosphorus sheet, centrifuging the obtained two-dimensional black phosphorus sheet at 12000rpm for 10min, and cleaning twice by using ultrapure water.
(2) 0.5mg of two-dimensional black phosphorus flake was added with 1mL of 0.005M H 2 PdCl 6 The solution was added with 4mL of ultrapure water to obtain a mixed solution. Adding small magnetons into the quartz tube filled with the mixed solution, and sealing the quartz tube with a rubber plug and paraffin wax; the needle is extended into the bottom of the quartz tube by a thick long needle, then high-purity argon is introduced to be matched with a low short needle to remove air in the quartz tube and the solution, and the needle is sealed by paraffin after degassing is finished.
(3) And (3) taking the blue light of 450nm as a light source, illuminating for 20min under the stirring conditions of constant temperature of 20 ℃ and 2500rpm to enable Pd particles to uniformly grow on the two-dimensional thin-layer black phosphorus, and performing multiple centrifugal cleaning by using absolute ethyl alcohol to obtain the two-dimensional black phosphorus/palladium heterojunction.
(4) Taking 10mg and g-C of the two-dimensional black phosphorus/palladium heterojunction material obtained in the step (3) 3 N 4 Dispersing the mixture in 30mL of absolute ethanol solution according to the mass ratio of 1:10, wherein the power of ultrasonic dispersion treatment is 300W, and the time is 0.01 h; the ball milling composite rotating speed is 200rpm, the ball milling time is 5 hours, and BP/Pd/g-C is obtained 3 N 4 A ternary composite photocatalyst.
BP/Pd/g-C 3 N 4 TEM photographs of the ternary composite photocatalyst are shown in FIGS. 4a and 4b, wherein the black particles are deposited Pd metal ions, and the darker black flakes are g-C 3 N 4 The bottom layer dark large sheet is a two-dimensional black phosphorus sheet.
Example 5
1mg of BP/Ni/g-C prepared in example 1 3 N 4 Dispersed in 3.75mL of ultrapure water, and then 1.25mL of isopropanol was added as an electron sacrificial. Degassing residual oxygen in the tube with argon gas for 30min, sealing the mixture in a quartz tube, and adding 500 μ L CH with a sample injection needle 4 Gas was used as internal standard. And (3) carrying out photocatalytic reaction by using light source illumination of 420nm wave band, and sampling and detecting the hydrogen content after the reaction is finished.
TestingIn this case, the upper gas layer of the quartz tube was sampled by a 1mL sample injector and injected into a Gas Chromatograph (GC) to measure, and the peak area obtained was converted into the standard hydrogen area in the gas chromatograph to obtain BP/Ni/g-C 3 N 4 The rate of hydrogen production by photocatalytic water decomposition is 33.8 mmol/g/h.
Example 6
1mg of BP/Pt/g-C prepared in example 3 3 N 4 Dispersed in 3.75mL of ultrapure water, and then 1.25mL of isopropanol was added as an electron sacrificial. Degassing residual oxygen in the tube with argon gas for 30min, sealing the mixture in a quartz tube, and adding 500 μ L of CH with a sample injection needle 4 Gas was used as internal standard. And (3) carrying out photocatalytic reaction by using light source illumination of 420nm wave band, and sampling and detecting the hydrogen content after the reaction is finished.
In the test, the upper gas of the quartz tube was extracted by a 1mL sample injector and injected into a Gas Chromatograph (GC) to measure, and the BP/Pt/g-C was obtained by converting the obtained peak area with the standard hydrogen area in the gas chromatograph 3 N 4 The rate of hydrogen production by photocatalytic water decomposition is 36.4 mmol/g/h.
Example 7
1mg of BP/Pd/g-C prepared in example 4 3 N 4 Dispersed in 3.75mL of ultrapure water, and then 1.25mL of isopropanol was added as an electron sacrificial. Degassing residual oxygen in the tube with argon gas for 30min, sealing the mixture in a quartz tube, and adding 500 μ L CH with a sample injection needle 4 Gas was used as internal standard. And (3) carrying out photocatalytic reaction by using light source illumination of a 420nm wave band, and sampling and detecting the hydrogen content after the reaction is finished.
During testing, 1mL of sample injector is used for extracting the upper layer gas of the quartz tube and injecting the upper layer gas into a Gas Chromatograph (GC) for measurement, and the obtained peak area is converted with the standard hydrogen area in the gas chromatograph to obtain BP/Pd/g-C 3 N 4 The rate of hydrogen production by photocatalytic water decomposition is 31.9 mmol/g/h.
While the invention has been shown and described with reference to certain embodiments, those skilled in the art will understand that: various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents.
Claims (5)
1. The preparation method of the ternary composite photocatalyst is characterized in that the ternary composite photocatalyst comprises graphite-phase carbon nitride and a two-dimensional black phosphorus/transition metal heterojunction which are mixed with each other, wherein the two-dimensional black phosphorus/transition metal heterojunction comprises a two-dimensional black phosphorus sheet and transition metal particles loaded on the two-dimensional black phosphorus sheet, and the transition metal particles are any one of Co, Ni, Fe, Cu, Pd and Pt; the preparation method comprises the following steps:
mixing a transition metal salt solution, an alcohol electronic sacrificial agent and a two-dimensional black phosphorus sheet to obtain a mixed solution; in the mixed solution, the volume fraction of the alcohol electron sacrificial agent is below 90%;
illuminating the mixed solution, and depositing transition metal particles on the two-dimensional black phosphorus sheet to obtain a two-dimensional black phosphorus/transition metal heterojunction;
and dispersing the two-dimensional black phosphorus/transition metal heterojunction and graphite-phase carbon nitride in an organic medium, mixing and drying to obtain the ternary composite photocatalyst.
2. The method according to claim 1, wherein the transition metal salt solution has a molar concentration of the transition metal cation of 0.001 to 0.1 mol/L.
3. The method according to claim 2, wherein the ratio of the amount of the two-dimensional black flakes to the amount of the species of the transition metal cations is 1:0.1 to 1: 10.
4. The method according to claim 1, wherein the deposition process is controlled to be constant temperature, the temperature range is 10-50 ℃, and the illumination time is 1-500 min.
5. The method according to any one of claims 1 to 4, comprising in particular the steps of:
firstly, mixing a transition metal salt solution, an alcohol electronic sacrificial agent and a two-dimensional black phosphorus sheet, filling the mixture into a reaction container to obtain a mixed solution, sealing the reaction container, and introducing inert gas for 5-300 min;
then, under the constant temperature condition of 10-50 ℃, single-wavelength light is adopted to irradiate the mixed solution for 5-300min, transition metal particles are deposited on the two-dimensional black phosphorus sheet, and the two-dimensional black phosphorus/transition metal heterojunction is obtained after multiple times of cleaning, wherein the wavelength range of the single-wavelength light is 400-635 nm;
and finally, dispersing the two-dimensional black phosphorus/transition metal heterojunction in graphite phase carbon nitride in an organic medium, performing ultrasonic dispersion treatment for 0.01-2h at the power of 100-.
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