CN110743596A - Ruthenium nanoparticle/three-dimensional porous carbon nitride composite material, and preparation method and application thereof - Google Patents
Ruthenium nanoparticle/three-dimensional porous carbon nitride composite material, and preparation method and application thereof Download PDFInfo
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- 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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- B01J35/61—
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- C—CHEMISTRY; METALLURGY
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- 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
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- 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
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- 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
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- 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 a superfine ruthenium nanoparticle/three-dimensional porous carbon nitride composite material, a preparation method and application thereof, belonging to the technical field of material preparation and photocatalysis. The invention prepares a ruthenium nano-particle/three-dimensional porous carbon nitride (Ru/3DCN) composite material by a novel solvent heat auxiliary polyol reduction method, which successfully and uniformly divides Ru nano-particles by taking three-dimensional porous carbon nitride as a main catalyst and a substrate, ethylene glycol as a reducing agent and a solvent and CTAB as a surfactantThe Ru nanoparticles are dispersed on the surface of the three-dimensional porous carbon nitride nanosheet, have the size of 1-2nm, can provide more active sites, promote the separation of photogenerated electrons and holes, effectively avoid the agglomeration of the nanoparticles, ensure that the composite photocatalytic material has excellent visible light catalytic hydrogen production performance, and when the loading capacity of the Ru nanoparticles is 1 wt.%, the maximum hydrogen production efficiency can reach 2945.47 umol.h‑1·g‑1。
Description
Technical Field
The invention relates to a superfine ruthenium nanoparticle/three-dimensional porous carbon nitride composite material, a preparation method and application thereof, belonging to the technical field of material preparation and photocatalysis.
Background
The semiconductor photocatalytic water splitting hydrogen production technology can convert solar energy with low energy density into hydrogen energy with high energy density, so that the semiconductor photocatalytic water splitting hydrogen production technology has important application in solving the problems of energy crisis and environmental pollution. Researchers at home and abroad have been continuously working on synthesizing novel efficient semiconductor photocatalytic materials in the past decades. Composite semiconductor photocatalysts comprise two or more components, the properties of which are unique or diverse and therefore have advantages over a single semiconductor material.
Among the numerous semiconductor materials, graphite-like phase carbon nitride (abbreviated as g-C)3N4) The photocatalyst has the advantages of simple preparation, no pollution and low cost, has an energy band structure suitable for decomposing water under visible light, and has a wide application prospect. Most commonly blocky g-C3N4Usually, the photocatalyst is obtained by calcining precursors such as melamine or urea at high temperature, but the photocatalytic performance is limited by the low specific surface area and slow photon-generated carrier transfer capacity. g-C in different structures3N4In addition, the incident photons can be reflected for multiple times between carbon nitride layers, and the maximum utilization of light energy is realized. However, a single g-C3N4The photo-generated electrons and holes generated by the photocatalytic material are easily recombined and quenched, thereby reducing the photocatalytic efficiency. Researches show that a composite material is constructed by loading a cocatalyst on a semiconductor photocatalytic material, a Schottky barrier can be formed at the interface of the semiconductor photocatalytic material and the cocatalyst, so that photoproduction electrons are quickly transferred from the semiconductor photocatalytic material to the surface of the cocatalyst, and the separation of photoproduction electrons and holes is promoted; at the same time, a cocatalystThe surface can be used as a reaction active site, and the formation and desorption of hydrogen are quicker, so that the hydrogen production efficiency is greatly improved.
Among the various promoter materials, the promoter with better performance at present is mainly a noble metal promoter, which has larger work function, lower Fermi level and empty d orbit, is easy to capture photogenerated electrons and serves as a reaction active site. Pt is the most common and effective cocatalyst in the current photocatalytic hydrogen evolution reaction, but the application of Pt is limited by the expensive price. Ru is 25 times cheaper than Pt and the lowest cost among noble metals, but it has excellent activity comparable to Pt and has recently become a new source of hydrogen evolution reaction. Compared with different forms and structures, the Ru nanoparticle catalyst has higher surface atomic ratio, and the smaller the particle size, the higher the surface atomic ratio, which is beneficial to exposing more active sites to improve the performance. The synthesized superfine Ru nanoparticles are used as a cocatalyst to be modified on the surface of carbon nitride, so that interface charge transmission can be promoted, the recombination rate of photon-generated carriers is reduced, and the photocatalytic hydrogen production performance is greatly improved.
So far, no solvent heat-assisted polyol reduction method has been found to be adopted to prepare the superfine ruthenium nanoparticle/three-dimensional porous carbon nitride composite material (abbreviated as Ru/3DCN), the used three-dimensional porous carbon nitride material has stable physicochemical properties, the raw materials are cheap and easy to obtain, the material is nontoxic, the reaction process for preparing the ruthenium nanoparticle/three-dimensional porous carbon nitride composite material by using the material as a carrier is simple, and the obtained product has good photocatalytic activity and high stability.
Disclosure of Invention
The invention aims to provide a method for synthesizing a superfine ruthenium nanoparticle/three-dimensional porous carbon nitride composite material by modifying superfine ruthenium nanoparticles on the surface and layers of three-dimensional porous carbon nitride through a solvothermal assisted polyol reduction method.
The invention is realized by the following technical scheme:
(1) preparing a three-dimensional porous carbon nitride (3DCN) nanosheet: weighing Melamine (Melamine) and Cyanuric acid (Cyanuric acid) in a mortar, grinding and mixing, placing in a beaker, adding deionized water, magnetically stirring at room temperature, centrifuging, and performing vacuum freeze drying to obtain a white Cyanuric acid-Melamine supramolecular precursor (CM); and then, pouring all the obtained CM supramolecular precursors into a crucible with a cover, transferring the crucible into a temperature-rising tube furnace with an automatic program temperature control function, calcining in air, naturally cooling to room temperature, taking out, and grinding into powder by using a mortar to obtain light yellow 3DCN solid powder.
The molar ratio of the melamine to the cyanuric acid is 1: 1.
The magnetic stirring time is 12 h.
The rotating speed of the centrifugal machine is 6000rad/min, and the centrifugal time is 5 min.
The vacuum freeze-drying time is 24 h.
The calcination temperature is 550 ℃, the heating rate is 5 ℃/min, and the calcination time is 4 h.
(2) Preparing an ultrafine ruthenium nanoparticle/three-dimensional porous carbon nitride composite material (Ru/3 DCN): 3DCN is weighed and dispersed in ethylene glycol, and RuCl is removed by using a liquid-removing gun3Adding a CTAB surfactant into the ethylene glycol solution, and performing ultrasonic and magnetic stirring treatment to obtain uniform and stable suspension; then transferring the obtained suspension into a polytetrafluoroethylene lining high-pressure reaction kettle, putting the kettle into a drying oven, and carrying out hydrothermal reaction; and after naturally cooling to room temperature, centrifuging, washing with water and alcohol for 3 times respectively, drying in a vacuum oven, taking out, and grinding into powder by using a mortar to obtain the Ru/3DCN composite material.
In the composite material, Ru accounts for 0.1-5%, preferably 1% of the total mass of the composite material.
The RuCl3The ethylene glycol solution was 5 mg/ml-1。
The RuCl3And CTAB in a molar ratio of 1:2 and a mass ratio of 1: 3.5.
The power of an ultrasonic machine used for ultrasonic treatment is 250W, and the ultrasonic treatment time is 30 min.
The time of the magnetic stirring treatment is 2 hours.
The temperature of the hydrothermal reaction is 140 ℃, and the reaction time is 18 h.
The rotating speed of the centrifugal machine is 6000rad/min, and the centrifugal time is 5 min.
The temperature of the vacuum oven is set to be 60 ℃, and the drying is carried out for 12 h.
The product is subjected to morphological structure analysis by an X-ray diffractometer (XRD), a Scanning Electron Microscope (SEM) and a Transmission Electron Microscope (TEM), and the photocatalytic decomposition efficiency of the water hydrogen is detected by a Labsolar 6A all-glass automatic on-line trace gas analysis system and a gas chromatograph.
Compared with the prior art, the invention has the beneficial effects that: the technical scheme is that the superfine ruthenium nano-particle/three-dimensional porous carbon nitride composite material is prepared by a novel solvent heat-assisted polyol reduction method. The three-dimensional porous carbon nitride is a main catalyst, has reducibility and catalytic performance, can avoid the stacking of nanosheets layer by layer in the three-dimensional porous structure compared with the carbon nitride prepared by the prior art, has a great specific surface area, can realize the maximum utilization of incident photons by multiple reflections between layers, and improves the light energy utilization rate. Compared with other prior art means, the superfine Ru nanoparticles prepared by the technical scheme have smaller and more uniform particle size (1-2nm) and higher surface atomic ratio, are used as a cocatalyst to be modified on the surface of three-dimensional porous carbon nitride, can serve as reactive active sites, promote interface charge transmission, reduce the recombination rate of photon-generated carriers, and greatly improve the photocatalytic hydrogen production performance.
Drawings
FIG. 1 is an XRD diffraction pattern of the prepared three-dimensional porous carbon nitride monomer and ultra-fine ruthenium nanoparticle/three-dimensional porous carbon nitride composite material. As can be seen from the figure, the three-dimensional porous carbon nitride monomer and the superfine ruthenium nano-particle/three-dimensional porous carbon nitride composite material have typical diffraction peaks at the 2 theta values of 13.1 degrees and 27.4 degrees, which are respectively distributed to g-C3N4The (100) and (002) crystal faces (JCPDS card numbers 87-1526); the composite material does not see a characteristic peak of Ru, which shows that the crystal structure of the main catalyst carbon nitride is hardly influenced by a small amount of loaded ultrafine Ru nano particles; the composite material is successfully prepared, and the sample has high crystallinity and no impurities.
FIGS. 2(a-c) are scanning electron microscope and transmission electron microscope photographs of three-dimensional porous carbon nitride monomers at different scales; (d-f) is a scanning electron microscope and transmission electron microscope photographs of different scales of the superfine ruthenium nanoparticle/three-dimensional porous carbon nitride composite material; as can be seen from the graphs (a-e), the three-dimensional porous carbon nitride monomer and the ultra-fine ruthenium nanoparticle/three-dimensional porous carbon nitride composite material both have clearly visible three-dimensional porous structures; from the graph (f), it can be seen that the ultrafine ruthenium nanoparticles with smaller particle size are uniformly dispersed on the surface of the three-dimensional porous carbon nitride nanosheet, indicating that the composite material has been successfully prepared.
FIG. 3 is a graph of hydrogen production efficiency of three-dimensional porous carbon nitride composite materials with different Ru contents after photocatalytic water splitting reaction for 5 hours under visible light (lambda is more than 400nm), the prepared 1% Ru/3DCN composite material has the most excellent photocatalytic hydrogen production activity, and the photocatalytic hydrogen production efficiency reaches 2945.47 umol.h-1·g-1。
Detailed Description
Example 13 preparation of DCN nanoplatelets
The 3DCN nanosheet is prepared by adopting a thermal polymerization method: weighing 2.5224g of melamine and 2.5814g of cyanuric acid in a mortar, grinding and mixing the materials, putting the mixture in a beaker, adding deionized water, magnetically stirring the mixture at room temperature for 12 hours, centrifuging the mixture at 6000rad/min for 5 minutes to obtain a lower-layer solid, and freeze-drying the lower-layer solid in a vacuum freeze-drying machine for 24 hours to obtain a white cyanuric acid-melamine (CM) supramolecular precursor; and then, pouring all the obtained CM supramolecular precursors into a crucible with a cover, transferring the crucible into a temperature-rising tube furnace with an automatic program temperature control function, calcining the crucible for 4 hours at 550 ℃ in air at the temperature-rising rate of 5 ℃/min, naturally cooling the crucible to room temperature, taking the crucible out, and grinding the crucible to powder to obtain light yellow 3DCN solid powder.
EXAMPLE 20.1 preparation of Ru/3DCN composite
The preparation of the superfine Ru nanoparticle/3 DCN composite material adopts a solvent heat-assisted polyol reduction method: 0.0998g of 3DCN were weighed out and dispersed in 60ml of ethylene glycol, and 40. mu.l of 5 mg/ml was pipetted out using a pipette gun-1RuCl3Adding 0.0007g of CTAB into the ethylene glycol solution, and performing ultrasonic treatment for 30min and magnetic stirring treatment for 2h to obtain uniform and stable suspension; then transferring the obtained suspension into a polytetrafluoroethylene lining high-pressure reaction kettle, putting the kettle into a drying oven, and adding water at 140 DEG CCarrying out thermal reaction for 18 h; after naturally cooling to room temperature, centrifuging for 5min at 6000rad/min, washing with deionized water and absolute ethyl alcohol for 3 times respectively, placing in a vacuum oven at 60 ℃, drying for 12h, taking out, and grinding into powder by using a mortar to obtain the 0.1% Ru/3DCN composite material.
EXAMPLE 30.5 preparation of Ru/3DCN composite
The preparation of the superfine Ru nanoparticle/3 DCN composite material adopts a solvent heat-assisted polyol reduction method: 0.0990g of 3DCN were weighed out and dispersed in 60ml of ethylene glycol, and 200. mu.l of 5 mg/ml were pipetted out using a pipette gun-1RuCl3Adding 0.0035g of CTAB into the ethylene glycol solution, and performing ultrasonic treatment for 30min and magnetic stirring treatment for 2h to obtain uniform and stable suspension; then transferring the obtained suspension into a polytetrafluoroethylene lining high-pressure reaction kettle, putting the kettle into a drying oven, and carrying out hydrothermal reaction for 18h at 140 ℃; after naturally cooling to room temperature, centrifuging for 5min at 6000rad/min, washing for 3 times respectively by using deionized water and absolute ethyl alcohol, placing in a vacuum oven at 60 ℃, drying for 12h, taking out, and grinding into powder by using a mortar to obtain the 0.5% Ru/3DCN composite material.
EXAMPLE 41 preparation of Ru/3DCN composite
The preparation of the superfine Ru nanoparticle/3 DCN composite material adopts a solvent heat-assisted polyol reduction method: 0.0980g of 3DCN were weighed out and dispersed in 60ml of ethylene glycol, and 400. mu.l of 5 mg/ml were pipetted out using a pipette gun-1RuCl3Adding 0.0070g of CTAB into the ethylene glycol solution, and performing ultrasonic treatment for 30min and magnetic stirring treatment for 2h to obtain uniform and stable suspension; then transferring the obtained suspension into a polytetrafluoroethylene lining high-pressure reaction kettle, putting the kettle into a drying oven, and carrying out hydrothermal reaction for 18h at 140 ℃; after naturally cooling to room temperature, centrifuging for 5min at 6000rad/min, washing for 3 times respectively by using deionized water and absolute ethyl alcohol, placing in a vacuum oven at 60 ℃, drying for 12h, taking out, and grinding into powder by using a mortar to obtain the 1% Ru/3DCN composite material.
EXAMPLE 53 preparation of Ru/3DCN composite
The preparation of the superfine Ru nanoparticle/3 DCN composite material adopts a solvent heat-assisted polyol reduction method: 0.0940g of 3DCN were weighed out and dispersed in 60ml of ethylene glycol, and 1.2ml of 5 mg/ml was pipetted out using a pipette gun-1RuCl3Adding 0.0210g of CTAB into the ethylene glycol solution, and performing ultrasonic treatment for 30min and magnetic stirring treatment for 2h to obtain uniform and stable suspension; then transferring the obtained suspension into a polytetrafluoroethylene lining high-pressure reaction kettle, putting the kettle into a drying oven, and carrying out hydrothermal reaction for 18h at 140 ℃; after naturally cooling to room temperature, centrifuging for 5min at 6000rad/min, washing with deionized water and absolute ethyl alcohol for 3 times respectively, placing in a vacuum oven at 60 ℃, drying for 12h, taking out, and grinding into powder by using a mortar to obtain the 3% Ru/3DCN composite material.
EXAMPLE preparation of 65% Ru/3DCN composite
The preparation of the superfine Ru nanoparticle/3 DCN composite material adopts a solvent heat-assisted polyol reduction method: 0.0900g of 3DCN was weighed out and dispersed in 60ml of ethylene glycol, and 2.0ml of 5 mg/ml was pipetted out using a pipette gun-1RuCl3Adding 0.0350g of CTAB into the ethylene glycol solution, and performing ultrasonic treatment for 30min and magnetic stirring treatment for 2h to obtain uniform and stable suspension; then transferring the obtained suspension into a polytetrafluoroethylene lining high-pressure reaction kettle, putting the kettle into a drying oven, and carrying out hydrothermal reaction for 18h at 140 ℃; after naturally cooling to room temperature, centrifuging for 5min at 6000rad/min, washing for 3 times respectively by using deionized water and absolute ethyl alcohol, placing in a vacuum oven at 60 ℃, drying for 12h, taking out, and grinding into powder by using a mortar to obtain the 5% Ru/3DCN composite material.
Example 7 photocatalytic Hydrogen production Activity experiment of Ru/3DCN composite Material
(1) Triethanolamine (TEOA) as sacrificial agent: 50ml of a 20 vol% TEOA/water solution was prepared and placed in a photocatalytic reaction flask.
(2) Weighing 0.025g of Ru/3DCN composite material, adding the composite material into the reaction liquid prepared in the step (1), continuously stirring, starting cooling water, vacuumizing a photocatalytic reaction bottle, and performing a catalytic hydrogen production experiment by visible light (lambda is more than 400 nm).
(3) Detecting the gas components in the system by a gas chromatograph every 1 h.
(4) As can be seen from figure 3, the prepared Ru/3DCN composite material has excellent visible light catalytic hydrogen production activity, particularly 1% Ru/3DCN sample, and the hydrogen production efficiency reaches 2945.47 umol.h after 5h of reaction-1·g-1。
Claims (9)
1. The ruthenium nanoparticle/three-dimensional porous carbon nitride composite material is characterized in that three-dimensional porous carbon nitride is used as a main catalyst, and ultrafine Ru nanoparticles are used as a cocatalyst; the three-dimensional porous structure can avoid the stacking of the nano sheets layer by layer, and incident photons can be reflected for multiple times between layers to realize the maximum utilization, thereby improving the utilization rate of light energy; the particle size of the superfine ruthenium nano particles is 1-2nm, the superfine ruthenium nano particles are uniformly dispersed on the surface of the three-dimensional porous carbon nitride nano sheet and can serve as reaction active sites, the interface charge transmission is promoted, the recombination rate of photon-generated carriers is reduced, and the photocatalytic hydrogen production performance is improved.
2. The preparation method of the ruthenium nanoparticle/three-dimensional porous carbon nitride composite material according to claim 1, comprising the following specific steps:
weighing three-dimensional porous carbon nitride nanosheets, dispersing the three-dimensional porous carbon nitride nanosheets in ethylene glycol, and transferring RuCl by using a liquid transferring gun3Adding a CTAB surfactant into the ethylene glycol solution, and performing ultrasonic and magnetic stirring treatment to obtain uniform and stable suspension; then transferring the obtained suspension into a polytetrafluoroethylene lining high-pressure reaction kettle, putting the kettle into a drying oven, and carrying out hydrothermal reaction; and after naturally cooling to room temperature, centrifuging, washing with water and alcohol, drying in a vacuum oven, taking out, and grinding into powder by using a mortar to obtain the ruthenium nanoparticle/three-dimensional porous carbon nitride composite material.
3. The method of claim 1, wherein the Ru comprises 0.1-5% of the total mass of the composite material.
4. The method of claim 3, wherein the Ru comprises 1% of the total mass of the composite material.
5. The method of claim 1, wherein the ruthenium nanoparticle/three-dimensional porous carbon nitride composite is prepared by the following methodCharacterized in that said RuCl3The ethylene glycol solution was 5 mg/ml-1(ii) a The RuCl3And CTAB in a 1:2 molar ratio.
6. The method for preparing the ruthenium nanoparticle/three-dimensional porous carbon nitride composite material according to claim 1, wherein the power of an ultrasonic machine used for ultrasonic treatment is 250W, and the ultrasonic treatment time is 30 min; the time of the magnetic stirring treatment is 2 hours.
7. The method for preparing the ruthenium nanoparticle/three-dimensional porous carbon nitride composite material according to claim 1, wherein the hydrothermal reaction is carried out at 140 ℃ for 18 hours.
8. The method of preparing a ruthenium nanoparticle/three-dimensional porous carbon nitride composite according to claim 1, wherein the centrifuge rotation speed is 6000rad/min, and the centrifugation time is 5 min; the temperature of the vacuum oven is set to be 60 ℃, and the drying is carried out for 12 h.
9. Use of the ruthenium nanoparticle/three-dimensional porous carbon nitride composite material according to claim 1 for photocatalytic decomposition of water to produce hydrogen.
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