CN112892572B - Au-PCN-CNT composite material and preparation method and application thereof - Google Patents
Au-PCN-CNT composite material and preparation method and application thereof Download PDFInfo
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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
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- B01J35/39—
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- B01J35/393—
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- B01J35/40—
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- B01J35/613—
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- B01J35/647—
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- 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
- C01B2203/1094—Promotors or activators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention relates to an Au-PCN-CNT composite material and a preparation method and application thereof. The Au nanoparticle, the CNT and the PCN in the Au-PCN-CNT composite material provided by the invention can be firmly combined, and the specific surface area of the composite material is large due to the structure of the PCN porous nanosheet, so that the composite material has outstanding and stable catalytic performance, and the hydrogen production rate reaches 0.95 mmol/g‑1·h‑1。
Description
Technical Field
The invention belongs to the technical field of catalysts containing nitrogen compounds, and particularly relates to an Au-PCN-CNT composite material as well as a preparation method and application thereof.
Background
With the development of the industrial society, the consumption of fossil fuels is increased by the annual increase of the demand of fossil energy for countries in the world nowadays, and the rapid reduction of the reserves of such non-renewable energy seriously threatens the sustainable development of the world in the future. In addition, the ecological environment of the earth is also greatly influenced by greenhouse gases and toxic and harmful substances caused by the combustion of fossil fuels, so that the life and health of people are threatened. Therefore, the exploration and development of new energy become an effective and sustainable development way. Among them, solar energy stands out from a new energy source because of its inexhaustible, clean and environment-friendly properties and no geographical limitation. Rational utilization and conversion of solar energy has therefore been extensively studied in the last decade. Recently, a new chemical energy conversion method has attracted much attention, which directly converts solar energy into clean hydrogen energy through the medium of a semiconductor photocatalyst, has more direct energy conversion efficiency and avoids energy loss compared with other energy conversion methods, and reactants in the system are water with huge reserves on the earth, so that the system has great development potential.
g-C3N4As a polymer semiconductor without metal components, the photocatalyst is considered to be a potential photocatalyst responding to visible light, and g-C is beneficial to the characteristics of proper energy band structure, simple synthesis, physical and chemical stability and the like3N4Is widely applied to the photocatalytic water splitting for producing hydrogen and CO2Reduction and the like. However, the limited visible light absorption range limits its efficiency of solar energy utilization, and the lower specific surface area results in fewer surface active sites. To promoteLet g-C3N4Meets the requirements of practical application, and needs to be modified to improve the performance of the composite material. An effective way is to reasonably construct g-C with an ultrathin two-dimensional sheet structure3N4Therefore, the migration path of the carriers is effectively shortened, the carriers are promoted to be rapidly transferred to the surface to participate in corresponding catalytic reaction, and the inhibition of the recombination of the carriers is facilitated. At the same time, g-C3N4The nano-sheet structure has larger surface area and can provide more reactive sites.
Even so, g-C3N4Is also affected by its inherent disadvantages of lower conductivity and severe carrier recombination, and therefore, in the composition g-C3N4The construction of electron transport channels between triazine rings of the basic unit is a viable approach to overcome this problem. The carbon material has good conductivity and can be used for improving g-C3N4And (4) separating carriers. Among carbon materials, Carbon Nanotubes (CNTs) have excellent mechanical properties due to their particular hexagonal arrangement to form a tube skeleton structure, in addition to good electron conductivity. However, due to CNT and g-C3N4The mismatch of the synthesis temperature is mostly combined together by mechanical mixing in the past work, which causes the interface contact to be not tight, and greatly hinders the migration of the photo-generated electrons between the two. Therefore, suitable methods are sought for reacting CNTs with g-C3N4Promoting g-C while making effective contact3N4The catalytic performance of the catalyst becomes a key to solving the above problems.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, it is an object of the present invention to provide an Au-PCN-CNT composite material.
In order to realize the purpose of the invention, the specific technical scheme is as follows:
an Au-PCN-CNT composite material is obtained by densely stacking ultrathin two-dimensional porous graphite phase PCN (carbon nitride) nanosheets, and Au nanoparticles and in-situ grown CNTs (carbon nanotubes) are uniformly distributed on the surface of the PCN nanosheets.
According to the scheme, the diameter of the PCN nanosheet is 3-6 microns, the thickness of the PCN nanosheet is 1-5 nm, small holes are uniformly distributed on the surface of the PCN nanosheet, and the hole diameter of the PCN nanosheet is 2-20 nm. The PCN nanosheet is a thin-layer porous flaky material, and compared with a block material, the porous two-dimensional thin-layer material has a larger specific surface area, so that more active sites are exposed to participate in catalytic reaction, and the porous lamellar structure is also favorable for rapid diffusion and adsorption of reactants among materials. Compared with the block material, the material has limited specific surface area (about 8-15 m)2·g-1) The specific surface area of the PCN nanosheet can reach 20-30 m2·g-1Correspondingly, the specific surface area of the Au-PCN-CNT composite material is 40-50 m2·g-1。
According to the scheme, the particle size of the Au nano-particles is 5-8 nm. The Au nanoparticles are uniformly loaded on the surface of the PCN, can improve the absorption performance of visible light, and are used as active sites of catalytic reaction. In addition, gold is also used as a catalytic site for preparing the carbon nano tube in situ by a CVD method, and in the process, the low-temperature catalytic cracking of ethylene simultaneously meets the requirements of the stable structure of graphite-phase carbon nitride and the temperature requirement of active carbon atoms for growing the carbon nano tube. The generated carbon nano can improve the photo-excited electron transfer speed of PCN and stabilize the skeleton structure due to good electric conductivity and mechanical property, and Au is used as a connecting point to connect CNT and graphite phase carbon nitride to provide a carrier transfer channel. The Au and the CNT prepared by the method provided by the invention act synergistically to enhance the photocatalytic performance of the PCN.
According to the scheme, the diameter of the CNT is 10-30 nm, and the length of the CNT is 0.1-2 mu m. The carbon nano-tube is generated by catalysis of Au particles and has good contact with Au and PCN.
The second purpose of the invention is to provide a preparation method of the Au-PCN-CNT composite material.
The specific technical scheme is as follows:
the preparation method of the Au-PCN-CNT composite material comprises the following specific steps:
firstly, synthesizing a porous PCN nano sheet:
s1: dispersing melamine in deionized water to obtain uniform melamine dispersion liquid, then adding phosphorous acid serving as an intercalation agent into a melamine mixture, uniformly stirring, heating to 60-90 ℃, keeping for 0.5-3 h to completely dissolve the melamine, transferring the solution into a reaction kettle, carrying out hydrothermal reaction at 150-210 ℃ for 6-12 h after the reaction is finished, and cleaning and drying the obtained solid product to obtain a melamine precursor;
s2: dispersing the melamine precursor obtained in S1 in absolute ethyl alcohol, adding glycerol, carrying out reflux reaction at 70-95 ℃ for 0.5-4 h, violently stirring in the reaction process, separating out a solid product after the reaction is finished, washing and drying to obtain an alcohol intercalation precursor;
s3: placing the alcohol intercalation precursor obtained in the step S2 in a muffle furnace, heating to 400-600 ℃ at a heating rate of 1-15 ℃/min, carrying out thermal polycondensation reaction, carrying out constant-temperature reaction for 0.5-6 h, naturally cooling to room temperature after the reaction is finished, collecting and grinding the product to obtain a porous PCN nano material;
secondly, synthesizing the Au-PCN nano composite material: ultrasonically dispersing the porous PCN nano material obtained in the step one in deionized water to obtain a PCN dispersion liquid, then adding a chloroauric acid aqueous solution into the PCN dispersion liquid, ultrasonically dispersing the chloroauric acid aqueous solution uniformly, then removing solvent water in a system by using a spin dryer, collecting and grinding an obtained product, then placing an obtained sample in a muffle furnace for heat treatment, cooling the sample to room temperature along with the furnace after the heat treatment is finished, and then grinding the sample to obtain the Au-PCN nano composite material;
thirdly, synthesizing the Au-PCN-CNT composite material: heating the Au-PCN nano composite material obtained in the second step to 400-600 ℃ at the heating rate of 50-80 ℃/min in the Ar atmosphere, and then introducing C2H4And H2And keeping for 3-10 min, growing a carbon nano tube on the surface of the Au-PCN nano composite material, then cooling to room temperature, and grinding the product to obtain the Au-PCN-CNT composite material.
According to the scheme, the concentration of the melamine dispersion liquid S1 is 1-20 g/L.
According to the scheme, the mass ratio of the phosphorous acid to the melamine of S1 is 0.5-3: 1.
according to the scheme, the melamine precursor S2 is dispersed in ethanol, and the concentration of the melamine precursor is 20-60 g/L.
According to the scheme, the mass ratio of the glycerol to the melamine precursor of S2 is 5-20: 1.
according to the scheme, the concentration of the PCN dispersion liquid in the step two is 3-10 g/L.
The gold chloride acid (HAuCl) is obtained in the second step according to the scheme4·3H2O) water solution with the concentration of 1-30 g/L, wherein the mass ratio of the chloroauric acid to the porous PCN nano material is 0.001-0.1: 1.
according to the scheme, the heat treatment process conditions in the step two are as follows: in the air atmosphere, the temperature is raised to 100-300 ℃ from room temperature at the speed of 1-10 ℃/min, and the temperature is kept for 0.5-4 h. The heat treatment enables the formation of an effective bond between Au and PCN.
According to the scheme, the flow rate of Ar in the third step is 50-200 sccm, and C2H4The flow rate of (2-20 sccm, H)2The flow rate of (2) is 5 to 30 sccm.
The invention also aims to provide application of the Au-PCN-CNT composite material.
The specific technical scheme is as follows:
an application of the Au-PCN-CNT composite material in the field of photocatalytic hydrogen evolution.
The principle of the invention is as follows:
g-C3N4the band gap is moderate, and the band gap is matched with the solar spectrum, so that the visible light can be absorbed and utilized, and the method is applied to the field of hydrogen production by visible light photocatalysis. But because of the factors of lower specific surface area, serious photo-generated charge recombination, weak visible light absorption performance and the like, the g-C is prepared3N4The photocatalytic performance of (a) is greatly limited. In order to improve the catalytic hydrogen production performance, the invention prepares porous g-C3N4The nanosheet and the method for supporting Au nanoparticles and growing CNT under the catalysis of Au not only greatly improve g-C3N4Specific surface area of (2), Au nanoparticles as catalytic sites in situThe formed CNT and the Au are simultaneously used as photocatalytic active sites and can rapidly conduct light to excite carriers to participate in the hydrogen production reaction of the liquid-solid interface through an electron transmission channel taking the CNT as a medium. The steps of pre-synthesis of the CNT and compounding of various materials are eliminated, the use cost of the CNT is reduced, and the production process is optimized. In addition, the synergistic effect of Au and CNT remarkably increases the capture capability of PCN material to photons, and CNT can be used as g-C3N4The reinforcing agent with the structure and the fast channel for electron transmission effectively separate electrons and holes, and the finally synthesized Au-PCN-CNT composite material not only greatly improves the photocatalytic hydrogen production rate, but also has good circulation stability, and is a high-efficiency and stable photocatalyst.
The invention has the beneficial effects that: 1. in the Au-PCN-CNT composite material provided by the invention, Au nanoparticles are used as dual catalysts, namely Au can be used as a cocatalyst in a photocatalytic reaction system and can be used for catalyzing and thermally cracking C through a plasma resonance effect in the reaction process of preparing the carbon nano tube2H4The synthesis temperature of the carbon nano tube is greatly reduced (from more than 600 ℃ to about 480 ℃), the energy consumption of the synthesized carbon nano tube is reduced, the Au nano particles, CNT and PCN three phases in the Au-PCN-CNT composite material can be firmly combined, the specific surface area of the composite material is large due to the structure of the PCN porous nano sheet, the composite material has outstanding and stable catalytic performance, and the hydrogen production rate reaches 0.95 mmol-g-1·h-1. 2. The preparation method provided by the invention is simple and convenient to operate, low in cost, good in repeatability and suitable for large-scale production.
Drawings
FIG. 1 is a scanning electron microscope image of a porous PCN nanomaterial prepared in example 1 of the present invention;
FIG. 2 is a scanning electron micrograph of the Au-PCN nanocomposite prepared in example 1;
FIG. 3 is a scanning electron microscope image of the Au-PCN-CNT composite prepared in example 1;
FIG. 4 is a transmission electron microscope image of the Au-PCN-CNT composite prepared in example 1;
FIG. 5 is a transmission electron micrograph of Au size distribution of the Au-PCN-CNT composite prepared in example 1;
FIG. 6 is a high resolution TEM image of the Au-PCN-CNT composite prepared in example 1;
FIG. 7 is a nitrogen adsorption-desorption diagram and corresponding pore distribution diagram of the porous PCN nanomaterial, Au-PCN nanocomposite and Au-PCN-CNT composite prepared in example 1;
FIG. 8 is a powder X-ray diffraction pattern of the porous PCN nanomaterial, Au-PCN nanocomposite, and Au-PCN-CNT composite prepared in example 1;
FIG. 9 is a UV diffuse reflectance graph of the porous PCN nanomaterial, Au-PCN nanocomposite, and Au-PCN-CNT composite prepared in example 1;
FIG. 10 is a PL photoluminescence map of the porous PCN nanomaterial, Au-PCN nanocomposite, and Au-PCN-CNT composite prepared in example 1;
FIG. 11 is a graph of photocatalytic hydrogen production rates of the porous PCN nanomaterial, Au-PCN nanocomposite, and Au-PCN-CNT composite prepared in example 1;
FIG. 12 is a graph showing the cycle performance of photocatalytic hydrogen production of Au-PCN-CNT composite prepared in example 1.
Detailed Description
In order to make the technical solutions of the present invention better understood, the present invention is further described in detail below with reference to the accompanying drawings.
The raw materials used in the examples of the present invention were all purchased from Aladdin Chemicals, Inc.
Example 1
An Au-PCN-CNT composite material, wherein the preparation method comprises the following steps:
one, synthesis of porous g-C3N4Nano-materials:
s1: adding 4g of melamine into 400mL of deionized water, stirring to uniformly disperse the melamine to obtain melamine dispersion, then adding 4.8g of phosphorous acid into the melamine dispersion, fully and uniformly stirring until the phosphorous acid is completely dissolved, then placing the mixture into an oil bath kettle at 80 ℃ to stir for reaction for 1h, after the reaction is finished, enabling the solution to become clear and transparent, then transferring the solution into a tetrafluoroethylene reaction kettle to perform constant-temperature reaction for 10h at 180 ℃, naturally cooling to room temperature after the reaction is finished, respectively centrifugally washing the obtained product for 3 times by using the deionized water and ethanol, and then drying the product in a drying oven at 60 ℃ to obtain a melamine precursor;
s2: weighing 6g of melamine precursor obtained in S1, stirring and dispersing in 150mL of absolute ethyl alcohol, then adding 50mL of glycerol, stirring uniformly, carrying out reflux reaction at 90 ℃ for 3h, continuously and violently stirring in the reaction process, centrifugally separating out a solid product after the reaction is finished, centrifugally washing for 3 times by using ethanol, and drying in an oven at 60 ℃ to obtain an alcohol intercalation precursor;
s3: putting 4g of the alcohol intercalation precursor obtained in the step S2 into a muffle furnace, heating to 500 ℃ at the heating rate of 2 ℃/min in the air atmosphere, reacting at constant temperature for 2h, naturally cooling to room temperature after the reaction is finished, collecting and grinding the product to obtain the porous PCN nano material (g-C)3N4)；
Secondly, synthesizing the Au-PCN nano composite material: adding 200mg of the porous PCN nano material obtained in the step one into 30mL of deionized water, performing ultrasonic dispersion for 1h to obtain a PCN dispersion solution, adding 600 mu l of chloroauric acid aqueous solution (with the concentration of 0.02g/mL) into the PCN dispersion solution, performing ultrasonic dispersion for 30min, removing water in a system by using a spin dryer, setting the temperature of the spin dryer to 80 ℃, rotating at 60r/min, adding 10mL of absolute ethyl alcohol into a sample obtained after spin drying, transferring the sample from a round-bottomed flask into a beaker after ultrasonic dispersion, drying and grinding the sample in a 60 ℃ drying oven, placing the sample in a muffle furnace, performing heat treatment in the air atmosphere, heating the sample to 200 ℃ at the speed of 5 ℃/min at room temperature, preserving the heat for 1h, cooling the sample to the room temperature along with the furnace after the heat treatment, and grinding the sample to obtain an Au-PCN nano composite material;
thirdly, synthesizing the Au-PCN-CNT composite material: putting 30mg of the Au-PCN nano composite material obtained in the step two into a quartz ceramic boat, putting the quartz ceramic boat in the center of a quartz tube, connecting the quartz tube with a pipeline of a digital display flowmeter, putting the quartz ceramic boat on a heating core of the tube furnace, firstly opening an Ar switch of the flowmeter to introduce Ar with the flow rate of 105sccm, keeping the flow rate for 20min, and then setting the heat preservation temperature of the tube furnaceHeating at 480 deg.C (temperature rise rate of 70 deg.C/min), and opening C when the instrument reaches the holding temperature2H4And H2Switch, regulation C2H4The flow rate was 7sccm, H2The flow rate was 21sccm and was maintained for 4min, then C was turned off2H4And H2And after the temperature of the tubular furnace is reduced to the room temperature, closing Ar, taking out a sample, grinding and collecting to obtain the Au-PCN-CNT composite material.
The scanning electron microscope image of the porous PCN nanomaterial prepared in the first step of this embodiment is shown in fig. 1, and it can be seen that the porous PCN nanomaterial is obtained by densely stacking ultrathin porous nanosheets having a radius of 2-3 μm and a thickness of 1-5 nm, wherein pores are uniformly distributed on the graphite phase nanosheets, and the pore size is between 2-20 nm, so that the nanomaterial has a rich pore structure.
As shown in fig. 2, a scanning electron microscope image of the Au-PCN nanocomposite prepared in the second step of this embodiment shows that the Au-PCN nanocomposite is similar to the porous PCN nanocomposite in morphology, the diameter and pore size of the nanosheet are close to each other, no obvious structural damage or deformation is caused, and no obvious Au particle is observed in the electron microscope image, which indicates that the size of the loaded Au particle is maintained at a small degree.
FIG. 3 is a scanning electron microscope image of the Au-PCN-CNT composite material prepared in the third step of this example, in which it can be clearly seen that the one-dimensional hollow tubular CNT with a diameter of 10-30 nm and a length of 0.1-2 μm is tightly combined with the two-dimensional porous sheet-like PCN material, which illustrates that the CNT is synthesized in situ during the preparation process and forms a good 1D-2D interface composite with the PCN.
FIG. 4 is a transmission electron micrograph of the Au-PCN-CNT composite prepared in step three of the example, from which it can be observed that Au particles are uniformly dispersed on the surface of the PCN, and the porous sheet morphology of the PCN also conforms to the SEM image, and in addition, a tubular substance appears in the picture, which is a CNT grown in situ at a low temperature.
FIG. 5 is a transmission electron microscope image of the Au size distribution of the Au-PCN-CNT composite material prepared in the third step of the present embodiment, wherein it can be seen that the Au size is 5-8 nm and is uniformly distributed on the PCN.
Fig. 6 is a high-resolution transmission electron microscope image of the Au-PCN-CNT composite material prepared in step three of this embodiment, from which the crystalline phase structure of Au and the PCN of amorphous phase can be clearly distinguished, wherein two distinct lattice fringes appear in the Au crystal, and the interplanar distances thereof are 0.23nm and 0.2nm, respectively, which are consistent with the Au (111) crystal plane and the (200) crystal plane, which proves the existence of Au.
FIG. 7 is a nitrogen adsorption specific surface area diagram and a corresponding pore distribution diagram of the PCN, Au-PCN and Au-PCN-CNT composite materials prepared in this example, and it can be seen from the diagram that all the materials follow the hysteresis curve type IV of H3-type, wherein the adsorption and desorption performance of Au-PCN-CNT on nitrogen is significantly stronger than that of Au-PCN and PCN, and furthermore, the specific surface area of each sample is 48.27m2·g-1(Au-PCN-CNT)、33.12m2·g-1(Au-PCN) and 29.14m2·g-1(PCN) shows that the Au-PCN-CNT composite material sample has the largest specific surface area, and the pore distribution diagram shows that the pore diameters of all the materials are mostly distributed in the range of 0.5-10 nm, so that uniform micropores and mesopores are formed. Therefore, the increased surface area creates more active sites for Au/pCN/CNT, which is beneficial to the transmission and diffusion of reactants among samples, and also provides a plurality of adsorption sites for the reactants, thereby accelerating the progress of catalytic reaction.
FIG. 8 is a powder X-ray diffraction pattern of the PCN, Au-PCN and Au-PCN-CNT composites prepared in this example, all of which have an intense peak at about 27 deg. corresponding to g-C3N4The (002) crystal face of (1) is g-C3N4The layered structure being stacked in the longitudinal direction, and g-C3N4The diffraction peak corresponding to the (100) plane of (A) does not appear, probably due to the destruction of the porous structure to the planar sheet-like spread configuration. In addition, some sharp peaks appear at the positions of 37.9 degrees, 44.1 degrees, 64.4 degrees and 77.3 degrees of 2 theta in a diffraction pattern of the Au-PCN-CNT composite material, the peaks are matched with diffraction peaks of crystal planes of (111), (200), (220) and (311) of Au, and the Au-PCN-CNT is proved to have Au particles, while no Au diffraction peak is observed in the Au-PCN, probably because Au is bonded with PCN in an ionic substance state and the Au content is higher than that of the PCNThe influence of low factors. Furthermore, both Au-PCN and Au-PCN-CNT have a reduced main peak intensity at 27 ℃ relative to the PCN material, which may be caused by a slight amount of deformation of the PCN structure due to the heat treatment process.
FIG. 9 is a graph of the diffuse reflection of ultraviolet light of the PCN, Au-PCN and Au-PCN-CNT composite material prepared in this example, wherein the PCN and Au-PCN have relatively similar absorption edges, which indicates that the two materials have relatively consistent forbidden bandwidth of 2.8 eV. The forbidden band width of the Au-PCN-CNT is not obviously reduced on the basis of the forbidden band widths of PCN and Au-PCN, but the difference is that the light absorption performance of the material is obviously improved in the wavelength range of 200-800 nm, which can be attributed to three factors: 1. the electronic structure of the PCN material is slightly changed after multiple heat treatments; 2. the light absorption capacity of the composite material is enhanced by the metal surface plasma resonance absorption of the Au particles at 580 nm; 3. the in-situ grown CNTs promote absorption of light and capture of photons.
FIG. 10 is a PL photoluminescence spectrum of the PCN, Au-PCN and Au-PCN-CNT composite materials prepared in this example, wherein the PCN, Au-PCN and Au-PCN-CNT composite materials all have an excitation peak at 450nm, and the peak intensity of the PCN is strongest, which indicates that fluorescence excited by recombination of light-excited electrons and holes is strongest, and carriers cannot be effectively separated. The peak intensity of Au-PCN is weaker, which shows that the introduction of Au has certain influence on improving the migration state of carriers. The Au-PCN-CNT composite material has the lowest excitation peak, so that the composite material has less photogenerated charge recombination, and excited electrons can be effectively transferred to the surface to participate in a photocatalytic reaction.
Example 2
Comparison of the photocatalytic performance differences of PCN, Au-PCN and Au-PCN-CNT composites prepared in example 1:
respectively taking 25mg of powder samples (respectively the PCN, Au-PCN and Au-PCN-CNT composite materials prepared in the example 1) to disperse in 100mL of 10% by volume triethanolamine solution, placing the solution into a photocatalytic reaction vessel to be continuously stirred after ultrasonic dispersion for 20min, keeping the temperature of circulating cooling water at 6 ℃, then vacuumizing the reaction vessel by using a vacuum pump until the reaction system is in a similar vacuum state (P is less than or equal to 1.0kpa), and using 3 mg of the circulating cooling waterContinuously illuminating the reactor for 3 hours by a 00W xenon lamp, extracting gas in the reaction tank by an automatic sample injector every 1 hour, sending the gas into a gas chromatograph, carrying out online real-time detection on the gas chromatograph, and judging reaction products and the generation amount according to the peak position and the peak area. The reaction rate chart of the hydrogen production by photocatalytic water decomposition of the PCN, Au-PCN and Au-PCN-CNT composite materials is shown in FIG. 11, and it can be seen that the photocatalytic hydrogen production rates of the three materials are obviously different under the continuous illumination condition of three hours, wherein the PCN material produces hydrogen in a very small amount, and after Au is loaded, the hydrogen production performance of the Au-PCN material can reach 0.32 mmol/g-1·h-1And the hydrogen production rate of the Au-PCN-CNT composite material growing the CNT is further improved to 0.95 mmol/g-1·h-1The performance is far greater than that of a pure-phase PCN material, is about three times that of a single Au-PCN material, and shows excellent photocatalytic hydrogen production performance. In addition, the Au-PCN-CNT composite material sample is subjected to 4 times of circulation experiments in continuous three-hour illumination catalysis experiments, the experiment results are shown in figure 12, the results show that the hydrogen production performance of the Au-PCN-CNT composite material is not obviously reduced, and the composite material is proved to have good circulation stability.
Various corresponding changes and modifications can be made by those skilled in the art based on the above technical solutions and concepts, and all such changes and modifications should be included in the protection scope of the present invention.
Claims (7)
1. An Au-PCN-CNT composite material is characterized in that the Au-PCN-CNT composite material is obtained by densely stacking ultrathin two-dimensional porous graphite phase PCN nanosheets, Au nanoparticles and CNTs grown in situ are uniformly distributed on the surfaces of the PCN nanosheets, the particle size of the Au nanoparticles is 5-8 nm, the diameter of the CNTs is 10-30 nm, and the length of the CNTs is 0.1-2 μm;
the diameter of the PCN nano sheet is 3-6 mu m, the thickness of the PCN nano sheet is 1-5 nm, small holes are uniformly distributed on the surface of the PCN nano sheet, and the aperture of the PCN nano sheet is 2-20 nm.
2. The preparation method of the Au-PCN-CNT composite material as claimed in claim 1, which is characterized by comprising the following specific steps:
firstly, synthesizing a porous PCN nano sheet:
s1: dispersing melamine in deionized water to obtain uniform melamine dispersion liquid, then adding phosphorous acid serving as an intercalation agent into a melamine mixture, uniformly stirring, heating to 60-90 ℃, keeping for 0.5-3 h to completely dissolve the melamine, transferring the solution into a reaction kettle, carrying out hydrothermal reaction at 150-210 ℃ for 6-12 h after the reaction is finished, and cleaning and drying the obtained solid product to obtain a melamine precursor;
s2: dispersing the melamine precursor obtained in S1 in absolute ethyl alcohol, adding glycerol, carrying out reflux reaction at 70-95 ℃ for 0.5-4 h, violently stirring in the reaction process, separating out a solid product after the reaction is finished, washing and drying to obtain an alcohol intercalation precursor;
s3: placing the alcohol intercalation precursor obtained in the step S2 in a muffle furnace, heating to 400-600 ℃ at a heating rate of 1-15 ℃/min, carrying out thermal polycondensation reaction, carrying out constant-temperature reaction for 0.5-6 h, naturally cooling to room temperature after the reaction is finished, collecting and grinding the product to obtain a porous PCN nano material;
secondly, synthesizing the Au-PCN nano composite material: ultrasonically dispersing the porous PCN nano material obtained in the step one in deionized water to obtain a PCN dispersion liquid, then adding a chloroauric acid aqueous solution into the PCN dispersion liquid, ultrasonically dispersing the chloroauric acid aqueous solution uniformly, then removing solvent water in a system by using a spin dryer, collecting and grinding an obtained product, then placing an obtained sample in a muffle furnace for heat treatment, cooling the sample to room temperature along with the furnace after the heat treatment is finished, and then grinding the sample to obtain the Au-PCN nano composite material;
thirdly, synthesizing the Au-PCN-CNT composite material: heating the Au-PCN nano composite material obtained in the second step to 400-600 ℃ at the heating rate of 50-80 ℃/min in the Ar atmosphere, and then introducing C2H4And H2And keeping for 1-10 min, growing a carbon nano tube on the surface of the Au-PCN nano composite material, then cooling to room temperature, and grinding the product to obtain the Au-PCN-CNT composite material.
3. The method for preparing the Au-PCN-CNT composite material as claimed in claim 2, wherein the concentration of the melamine dispersion solution S1 is 1-20 g/L; s1, the mass ratio of the phosphorous acid to the melamine is 0.5-3: 1.
4. the preparation method of the Au-PCN-CNT composite material as claimed in claim 2, wherein S2 melamine precursor is dispersed in ethanol, and the concentration of the melamine precursor is 20-60 g/L; s2, the mass ratio of the glycerol to the melamine precursor is 5-20: 1.
5. the method for preparing Au-PCN-CNT composite material according to claim 2, wherein the concentration of the PCN dispersion liquid in the second step is 3-10 g/L; and step two, the concentration of the chloroauric acid aqueous solution is 1-30 g/L, wherein the mass ratio of the chloroauric acid to the porous PCN nano material is 0.001-0.1: 1; the heat treatment process conditions in the second step are as follows: in the air atmosphere, the temperature is raised to 100-300 ℃ from room temperature at the speed of 1-10 ℃/min, and the temperature is kept for 0.5-4 h.
6. The method of preparing Au-PCN-CNT composite material as claimed in claim 2, wherein the flow rate of Ar in the third step is 50-200 sccm, and the C is2H4The flow rate of (2-20 sccm, H)2The flow rate of (2) is 5 to 30 sccm.
7. Use of the Au-PCN-CNT composite according to claim 1 in the field of photocatalytic hydrogen evolution.
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