CN115608400B - Catalyst, preparation method and application thereof - Google Patents
Catalyst, preparation method and application thereof Download PDFInfo
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- CN115608400B CN115608400B CN202211248583.0A CN202211248583A CN115608400B CN 115608400 B CN115608400 B CN 115608400B CN 202211248583 A CN202211248583 A CN 202211248583A CN 115608400 B CN115608400 B CN 115608400B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims description 61
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- 239000000203 mixture Substances 0.000 claims description 46
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 238000002156 mixing Methods 0.000 claims description 35
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 32
- 238000000227 grinding Methods 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 23
- 238000001354 calcination Methods 0.000 claims description 22
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 19
- 239000004202 carbamide Substances 0.000 claims description 19
- 239000012153 distilled water Substances 0.000 claims description 19
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 239000002270 dispersing agent Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- 230000001699 photocatalysis Effects 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 238000002256 photodeposition Methods 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 229910052724 xenon Inorganic materials 0.000 description 10
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 10
- 238000000151 deposition Methods 0.000 description 9
- 230000008021 deposition Effects 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 238000007789 sealing Methods 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 230000000630 rising effect Effects 0.000 description 8
- 238000007873 sieving Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
Classifications
-
- 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
-
- B01J35/39—
-
- 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
- B01J37/34—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
- B01J37/344—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 electromagnetic wave energy
- B01J37/345—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 electromagnetic wave energy of ultraviolet wave energy
-
- 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
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a catalyst, a preparation method and application thereof, wherein the catalyst comprises g-C doped with Pt 3 N 4 /N‑K 2 Ti 4 O 9 . The catalyst of the invention has higher hydrogen production efficiency.
Description
Technical Field
The invention relates to the field of hydrogen production, in particular to a catalyst, a preparation method and application thereof.
Background
The world population growth and the rapid development of industry have led to continuous consumption of energy and serious environmental pollution. Therefore, it is urgent to find various renewable energy sources to replace energy sources such as fossil fuels. And hydrogen energy will play an important role in the future sustainable energy society. The photocatalytic decomposition of water to produce hydrogen utilizes solar energy as a power source and renewable water as a reactant, and is widely focused by researchers. In the process of preparing hydrogen by photocatalytic decomposition of water, a catalyst is required for tasting. But the existing catalyst has lower efficiency of photocatalytic hydrogen evolution.
Disclosure of Invention
The invention aims to provide a catalyst which has higher hydrogen production efficiency.
The invention also aims at providing a preparation method and application of the catalyst.
To achieve the above object, an embodiment of the present invention provides a catalyst comprising g-C doped with Pt 3 N 4 /N-K 2 Ti 4 O 9 。
In one or more embodiments of the present invention, the content of the platinum in the catalyst is 1wt% to 3wt%; and/or the number of the groups of groups,
the g-C 3 N 4 And N-K 2 Ti 4 O 9 The mass ratio of (1-5): 5.
the embodiment of the invention also provides a preparation method of the catalyst, which comprises the following steps:
will g-C 3 N 4 /N-K 2 Ti 4 O 9 Dispersing in a dispersing agent, and adding a platinum source to the dispersing agent to obtain a premix;
stirring in a protective gas atmosphere, and carrying out a photo-deposition reaction on the premix under the irradiation of a light source with the wavelength of 300-380 nm; and
and separating and drying to obtain the catalyst.
In one or more embodiments of the invention, g-C 3 N 4 /N-K 2 Ti 4 O 9 The preparation method of (2) comprises the following steps:
obtaining N-K 2 Ti 4 O 9 Mixing with dicyandiamide and water, heating to react, grinding, separating to obtain g-C 3 N 4 /N-K 2 Ti 4 O 9 。
In one or more embodiments of the invention, N-K is obtained 2 Ti 4 O 9 The method comprises the following steps:
will K 2 CO 3 And TiO 2 Mixing and grinding uniformly, heating to 900-1000 ℃ at a heating rate of 4-6 ℃/min, and calcining for 8-12 h at the temperature to obtain K 2 Ti 4 O 9 ；
Will K 2 Ti 4 O 9 Mixing with urea, calcining at 300-500 deg.C for 3-5 hr to obtain N-K 2 Ti 4 O 9 。
In one or more embodiments of the invention, K is 2 CO 3 And TiO 2 The steps of mixing and grinding uniformly include:
will K 2 CO 3 And TiO 2 Mixing, adding distilled water, grinding, and heating at 120-180 deg.C for 1-3 hr.
In one or more embodiments of the invention, K is 2 Ti 4 O 9 The step of mixing with urea comprises:
will K 2 Ti 4 O 9 Dispersing with urea in ethanol, and heating at 70-90 deg.c for 1-3 hr to eliminate ethanol.
In one or more embodiments of the invention, N-K is 2 Ti 4 O 9 After mixing the dicyandiamide and the water uniformly, the heating reaction comprises the following steps:
N-K 2 Ti 4 O 9 Mixing the dicyandiamide with water, and heating to 65-75 ℃ to completely dissolve the dicyandiamide;
heating the mixture to 550 ℃ at a heating rate of 2-4 ℃/min, and keeping the temperature for reaction for 2.5-3.5 h;
after the reaction was completed, the mixture was cooled to room temperature.
In one or more embodiments of the present invention, the dispersant is at least one of methanol and ethanol; and/or the number of the groups of groups,
the shielding gas is at least one of nitrogen and argon; and/or the number of the groups of groups,
the platinum source is at least one of chloroplatinic acid and platinum nitrate.
The embodiment of the invention also provides application of the catalyst in photocatalytic hydrogen production.
Compared with the prior art, the catalyst according to the embodiment of the invention is prepared by the method of g-C 3 N 4 And N-K 2 Ti 4 O 9 The two semiconductor materials and Pt are combined to cooperate, so that the hydrogen production efficiency of the catalyst is improved, and the catalyst has higher hydrogen production efficiency.
Drawings
FIG. 1 is a flow chart of a method of preparing a catalyst according to an embodiment of the invention;
FIG. 2 is a graph of hydrogen evolution efficiency test data for catalysts obtained in examples and comparative examples according to the present invention;
FIG. 3 is a graph of repeated test data for hydrogen evolution efficiency of a catalyst according to one embodiment of the invention.
Detailed Description
The following detailed description of embodiments of the invention is, therefore, to be taken in conjunction with the accompanying drawings, and it is to be understood that the scope of the invention is not limited to the specific embodiments.
Embodiments of the present invention provide a catalyst.
Wherein the content of platinum in the catalyst is 1-3 wt%. g-C in catalyst 3 N 4 And N-K 2 Ti 4 O 9 The mass ratio of (1-5): 5.
as shown in fig. 1, the method for preparing a catalyst according to a preferred embodiment of the present invention comprises the steps of:
s1, g-C 3 N 4 /N-K 2 Ti 4 O 9 Dispersed in a dispersant and a platinum source was added thereto to obtain a premix.
In a specific embodiment, step S1 may include:
s11, preparation of g-C 3 N 4 /N-K 2 Ti 4 O 9 。
Specifically, g-C 3 N 4 /N-K 2 Ti 4 O 9 The preparation method of (2) can comprise the following steps: obtaining N-K 2 Ti 4 O 9 Mixing with dicyandiamide and water, heating to react, grinding, separating to obtain g-C 3 N 4 /N-K 2 Ti 4 O 9 。
The reason why the dicyandiamide is selected is that the dicyandiamide is soluble in water and can be dispersed well. Secondly, the nitrogen content in the dicyandiamide is higher, and the required addition amount is small.
Wherein N-K is obtained 2 Ti 4 O 9 The method comprises the following steps:
s111, K 2 CO 3 And TiO 2 Mixing and grinding uniformly, heating to 900-1000 ℃ at a heating rate of 4-6 ℃/min, and calcining for 8-12 h at the temperature to obtain K 2 Ti 4 O 9 。
S112, K 2 Ti 4 O 9 Mixing with urea, calcining at 300-500 deg.C for 3-5 hr to obtain N-K 2 Ti 4 O 9 。
In step S111, in one embodiment, K 2 CO 3 And TiO 2 The step of mixing and grinding to homogeneity may comprise:
will K 2 CO 3 And TiO 2 Mixing, adding distilled water, grinding, and heating at 120-180 deg.C for 1-3 hr. Wherein wet grinding can make K 2 CO 3 And TiO 2 The mixing is more uniform. Heating for 1-3 h at 120-180 ℃, firstly, removing water and playing a role of presintering.
In step S112, in one embodiment, K is 2 Ti 4 O 9 The step of mixing with urea comprises:
will K 2 Ti 4 O 9 Dispersing with urea in ethanol, and heating at 70-90 deg.c for 1-3 hr to eliminate ethanol. Wherein the ethanol acts as a dispersion to allow K 2 Ti 4 O 9 Mixing with urea thoroughly.
In step S11, N-K is determined 2 Ti 4 O 9 After mixing the dicyandiamide and the water uniformly, the heating reaction comprises the following steps:
N-K 2 Ti 4 O 9 Mixing the dicyandiamide with water, and heating to 65-75 ℃ to completely dissolve the dicyandiamide;
heating the mixture to 550 ℃ at a heating rate of 3 ℃/min, and keeping the temperature for reaction for 2.5-3.5 hours;
after the reaction was completed, the mixture was cooled to room temperature.
In step S1, the platinum source may be at least one of chloroplatinic acid and platinum nitrate. Preferably, the platinum source is chloroplatinic acid. The dispersing agent can be at least one of methanol and ethanol. Preferably, the dispersing agent is methanol, which facilitates the later drying process to remove the dispersing agent from the product.
S2, stirring in a protective gas atmosphere, and carrying out a photo-deposition reaction on the premix under the irradiation of a light source with the wavelength of 300-380 nm.
Wherein, the light source with the wavelength of 300-380 nm can be a xenon lamp with a 300-380 nm filter.
In step S2, the shielding gas may be at least one of nitrogen and argon.
The time of the photo-deposition reaction may be 2 to 3 hours.
S3, separating and drying to obtain the product.
In step S1, the separating and drying steps may include:
the solid is taken by adopting a centrifugal separation mode, and is dried at the temperature of 70-80 ℃ to remove the dispersing agent.
The embodiment of the invention also provides an application of the catalyst in photocatalytic hydrogen production, and the hydrogen production efficiency can be improved by using the catalyst.
The catalyst of the present invention, its preparation method and its use will be described in detail below in conjunction with specific examples.
Example 1
Preparation of N-K 2 Ti 4 O 9 ：
Step 1, K is taken 2 CO 3 (6.9 g) and TiO 2 (12g) Mixing, adding a small amount of distilled water, and grinding uniformly.
And 2, transferring the mixture into a muffle furnace, and presintering the mixture for 2 hours at 150 ℃.
And step 3, heating to 960 ℃ at a heating rate of 5 ℃/min, and calcining for 10 hours.
Step 4, cooling to room temperature, washing with distilled water, and drying to obtain K 2 Ti 4 O 9 。
Step 5, 1gK 2 Ti 4 O 9 And 2g urea was dispersed in 15mL ethanol.
And 6, heating to 70 ℃ and keeping for 2 hours to volatilize the ethanol completely.
Step 7, calcining the mixture in a muffle furnace at 400 ℃ for 4 hours in an air atmosphere to obtain N-K 2 Ti 4 O 9 。
Preparation of g-C 3 N 4 /N-K 2 Ti 4 O：
Step 1, 1g of dicyandiamide and 5g of N-K are weighed 2 Ti 4 O 9 30mL of water was added to the alumina crucible.
And 2, completely dissolving the dicyandiamide in water bath at 70 ℃.
Step 3, transferring the mixture into a muffle furnace, rising the temperature to 550 ℃ at a heating rate of 3 ℃/min, and maintaining the temperature for 3h.
Step 4, grinding after the mixture is cooled to room temperature, and sieving to obtain g-C 3 N 4 /N-K 2 Ti 4 O。
Preparing a catalyst:
step 1, 1g g-C 3 N 4 /N-K 2 Ti 4 O was dispersed in 100mL of methanol solution.
Step 2, adding 0.02g of chloroplatinic acid.
And step 3, sealing the reactor, and introducing high-purity nitrogen for 30min.
And step 4, under the condition of intense stirring, performing light deposition for 2 hours by using a xenon lamp with a 300nm filter as a light source.
And 5, collecting turbid liquid, centrifuging, and drying at 70 ℃ to obtain the catalyst.
Example 2
Preparation of N-K 2 Ti 4 O 9 ：
Step 1, K is taken 2 CO 3 (6.9 g) and TiO 2 (12g) Mixing, adding a small amount of distilled water, and grinding uniformly.
And 2, transferring the mixture into a muffle furnace, and presintering the mixture for 2 hours at 150 ℃.
And step 3, heating to 960 ℃ at a heating rate of 5 ℃/min, and calcining for 10 hours.
Step 4, cooling to room temperature, washing with distilled water, and drying to obtain K 2 Ti 4 O 9 。
Step 5, 1gK 2 Ti 4 O 9 And 2g urea was dispersed in 15mL ethanol.
And 6, heating to 70 ℃ and keeping for 2 hours to volatilize the ethanol completely.
Step 7, calcining the mixture in a muffle furnace at 400 ℃ for 4 hours in an air atmosphere to obtain N-K 2 Ti 4 O 9 。
Preparation of g-C 3 N 4 /N-K 2 Ti 4 O：
Step 1, weighing 2g of dicyandiamide and 5g of N-K 2 Ti 4 O 9 30mL of water was added to the alumina crucible.
And 2, completely dissolving the dicyandiamide in water bath at 70 ℃.
Step 3, transferring the mixture into a muffle furnace, rising the temperature to 550 ℃ at a heating rate of 3 ℃/min, and maintaining the temperature for 3h.
Step 4, grinding after the mixture is cooled to room temperature, and sieving to obtain g-C 3 N 4 /N-K 2 Ti 4 O。
Preparing a catalyst:
step 1, 1gg-C 3 N 4 /N-K 2 Ti 4 O was dispersed in 100mL of methanol solution.
Step 2, adding 0.02g of chloroplatinic acid.
And step 3, sealing the reactor, and introducing high-purity nitrogen for 30min.
And step 4, under the condition of intense stirring, performing light deposition for 2 hours by using a xenon lamp with a 300nm filter as a light source.
And 5, collecting turbid liquid, centrifuging, and drying at 70 ℃ to obtain the catalyst.
Example 3
Preparation of N-K 2 Ti 4 O 9 ：
Step 1, K is taken 2 CO 3 (6.9 g) and TiO 2 (12g) Mixing, adding a small amount of distilled water, and grinding uniformly.
And 2, transferring the mixture into a muffle furnace, and presintering the mixture for 2 hours at 150 ℃.
And step 3, heating to 960 ℃ at a heating rate of 5 ℃/min, and calcining for 10 hours.
Step 4, cooling to room temperature, washing with distilled water, and drying to obtain K 2 Ti 4 O 9 。
Step 5, 1gK 2 Ti 4 O 9 And 2g urea was dispersed in 15mL ethanol.
And 6, heating to 70 ℃ and keeping for 2 hours to volatilize the ethanol completely.
Step 7, calcining the mixture in a muffle furnace at 400 ℃ for 4 hours in an air atmosphere to obtain N-K 2 Ti 4 O 9 。
Preparation of g-C 3 N 4 /N-K 2 Ti 4 O：
Step 1, weighing 3g of dicyandiamide and 5g of N-K 2 Ti 4 O 9 30mL of water was added to the alumina crucible.
And 2, completely dissolving the dicyandiamide in water bath at 70 ℃.
Step 3, transferring the mixture into a muffle furnace, rising the temperature to 550 ℃ at a heating rate of 3 ℃/min, and maintaining the temperature for 3h.
Step 4, grinding after the mixture is cooled to room temperature, and sieving to obtain g-C 3 N 4 /N-K 2 Ti 4 O。
Preparing a catalyst:
step 1, 1gg-C 3 N 4 /N-K 2 Ti 4 O was dispersed in 100mL of methanol solution.
Step 2, adding 0.02g of chloroplatinic acid.
And step 3, sealing the reactor, and introducing high-purity nitrogen for 30min.
And step 4, under the condition of intense stirring, performing light deposition for 2 hours by using a xenon lamp with a 300nm filter as a light source.
And 5, collecting turbid liquid, centrifuging, and drying at 70 ℃ to obtain the catalyst.
Example 4
Preparation of N-K 2 Ti 4 O 9 ：
Step 1, K is taken 2 CO 3 (6.9 g) and TiO 2 (12g) Mixing, adding small amount of distilled water, and grindingAnd (5) homogenizing.
And 2, transferring the mixture into a muffle furnace, and presintering the mixture for 2 hours at 150 ℃.
And step 3, heating to 960 ℃ at a heating rate of 5 ℃/min, and calcining for 10 hours.
Step 4, cooling to room temperature, washing with distilled water, and drying to obtain K 2 Ti 4 O 9 。
Step 5, 1gK 2 Ti 4 O 9 And 2g urea was dispersed in 15mL ethanol.
And 6, heating to 70 ℃ and keeping for 2 hours to volatilize the ethanol completely.
Step 7, calcining the mixture in a muffle furnace at 400 ℃ for 4 hours in an air atmosphere to obtain N-K 2 Ti 4 O 9 。
Preparation of g-C 3 N 4 /N-K 2 Ti 4 O：
Step 1, weighing 4g of dicyandiamide and 5g of N-K 2 Ti 4 O 9 30mL of water was added to the alumina crucible.
And 2, completely dissolving the dicyandiamide in water bath at 70 ℃.
Step 3, transferring the mixture into a muffle furnace, rising the temperature to 550 ℃ at a heating rate of 3 ℃/min, and maintaining the temperature for 3h.
Step 4, grinding after the mixture is cooled to room temperature, and sieving to obtain g-C 3 N 4 /N-K 2 Ti 4 O。
Preparing a catalyst:
step 1, 1gg-C 3 N 4 /N-K 2 Ti 4 O was dispersed in 100mL of methanol solution.
Step 2, adding 0.02g of chloroplatinic acid.
And step 3, sealing the reactor, and introducing high-purity nitrogen for 30min.
And step 4, under the condition of intense stirring, performing light deposition for 2 hours by using a xenon lamp with a 300nm filter as a light source.
And 5, collecting turbid liquid, centrifuging, and drying at 70 ℃ to obtain the catalyst.
Example 5
Preparation of N-K 2 Ti 4 O 9 ：
Step 1, K is taken 2 CO 3 (6.9 g) and TiO 2 (12g) Mixing, adding a small amount of distilled water, and grinding uniformly.
And 2, transferring the mixture into a muffle furnace, and presintering the mixture for 2 hours at 150 ℃.
And step 3, heating to 960 ℃ at a heating rate of 5 ℃/min, and calcining for 10 hours.
Step 4, cooling to room temperature, washing with distilled water, and drying to obtain K 2 Ti 4 O 9 。
Step 5, 1gK 2 Ti 4 O 9 And 2g urea was dispersed in 15mL ethanol.
And 6, heating to 70 ℃ and keeping for 2 hours to volatilize the ethanol completely.
Step 7, calcining the mixture in a muffle furnace at 400 ℃ for 4 hours in an air atmosphere to obtain N-K 2 Ti 4 O 9 。
Preparation of g-C 3 N 4 /N-K 2 Ti 4 O：
Step 1, weighing 5g of dicyandiamide and 5g of N-K 2 Ti 4 O 9 30mL of water was added to the alumina crucible.
And 2, completely dissolving the dicyandiamide in water bath at 70 ℃.
Step 3, transferring the mixture into a muffle furnace, rising the temperature to 550 ℃ at a heating rate of 3 ℃/min, and maintaining the temperature for 3h.
Step 4, grinding after the mixture is cooled to room temperature, and sieving to obtain g-C 3 N 4 /N-K 2 Ti 4 O。
Preparing a catalyst:
step 1, 1gg-C 3 N 4 /N-K 2 Ti 4 O was dispersed in 100mL of methanol solution.
Step 2, adding 0.02g of chloroplatinic acid.
And step 3, sealing the reactor, and introducing high-purity nitrogen for 30min.
And step 4, under the condition of intense stirring, performing light deposition for 2 hours by using a xenon lamp with a 300nm filter as a light source.
And 5, collecting turbid liquid, centrifuging, and drying at 70 ℃ to obtain the catalyst.
Example 6
Preparation of N-K 2 Ti 4 O 9 ：
Step 1, K is taken 2 CO 3 (6.9 g) and TiO 2 (12g) Mixing, adding a small amount of distilled water, and grinding uniformly.
And 2, transferring the mixture into a muffle furnace, and presintering the mixture for 2 hours at 150 ℃.
And step 3, heating to 960 ℃ at a heating rate of 5 ℃/min, and calcining for 10 hours.
Step 4, cooling to room temperature, washing with distilled water, and drying to obtain K 2 Ti 4 O 9 。
Step 5, 1gK 2 Ti 4 O 9 And 2g urea was dispersed in 15mL ethanol.
And 6, heating to 70 ℃ and keeping for 2 hours to volatilize the ethanol completely.
Step 7, calcining the mixture in a muffle furnace at 400 ℃ for 4 hours in an air atmosphere to obtain N-K 2 Ti 4 O 9 。
Preparation of g-C 3 N 4 /N-K 2 Ti 4 O：
Step 1, weighing 3g of dicyandiamide and 5g of N-K 2 Ti 4 O 9 30mL of water was added to the alumina crucible.
And 2, completely dissolving the dicyandiamide in water bath at 70 ℃.
Step 3, transferring the mixture into a muffle furnace, rising the temperature to 550 ℃ at a heating rate of 3 ℃/min, and maintaining the temperature for 3h.
Step 4, grinding after the mixture is cooled to room temperature, and sieving to obtain g-C 3 N 4 /N-K 2 Ti 4 O。
Preparing a catalyst:
step 1, 1gg-C 3 N 4 /N-K 2 Ti 4 O was dispersed in 100mL of methanol solution.
Step 2, adding 0.04g of chloroplatinic acid.
And step 3, sealing the reactor, and introducing high-purity nitrogen for 30min.
And step 4, under the condition of intense stirring, performing light deposition for 2 hours by using a xenon lamp with a 300nm filter as a light source.
And 5, collecting turbid liquid, centrifuging, and drying at 70 ℃ to obtain the catalyst.
Example 7
Preparation of N-K 2 Ti 4 O 9 ：
Step 1, K is taken 2 CO 3 (6.9 g) and TiO 2 (12g) Mixing, adding a small amount of distilled water, and grinding uniformly.
And 2, transferring the mixture into a muffle furnace, and presintering the mixture for 2 hours at 150 ℃.
And step 3, heating to 960 ℃ at a heating rate of 5 ℃/min, and calcining for 10 hours.
Step 4, cooling to room temperature, washing with distilled water, and drying to obtain K 2 Ti 4 O 9 。
Step 5, 1gK 2 Ti 4 O 9 And 2g urea was dispersed in 15mL ethanol.
And 6, heating to 70 ℃ and keeping for 2 hours to volatilize the ethanol completely.
Step 7, calcining the mixture in a muffle furnace at 400 ℃ for 4 hours in an air atmosphere to obtain N-K 2 Ti 4 O 9 。
Preparation of g-C 3 N 4 /N-K 2 Ti 4 O：
Step 1, weighing 3g of dicyandiamide and 5g of N-K 2 Ti 4 O 9 30mL of water was added to the alumina crucible.
And 2, completely dissolving the dicyandiamide in water bath at 70 ℃.
Step 3, transferring the mixture into a muffle furnace, rising the temperature to 550 ℃ at a heating rate of 3 ℃/min, and maintaining the temperature for 3h.
Step 4, grinding after the mixture is cooled to room temperature, and sieving to obtain g-C 3 N 4 /N-K 2 Ti 4 O。
Preparing a catalyst:
step 1, 1gg-C 3 N 4 /N-K 2 Ti 4 O was dispersed in 100mL of methanol solution.
Step 2, adding 0.06g of chloroplatinic acid.
And step 3, sealing the reactor, and introducing high-purity nitrogen for 30min.
And step 4, under the condition of intense stirring, performing light deposition for 2 hours by using a xenon lamp with a 300nm filter as a light source.
And 5, collecting turbid liquid, centrifuging, and drying at 70 ℃ to obtain the catalyst.
Comparative example 1
Preparation of N-K 2 Ti 4 O 9 ：
Step 1, K is taken 2 CO 3 (6.9 g) and TiO 2 (12g) Mixing, adding a small amount of distilled water, and grinding uniformly.
And 2, transferring the mixture into a muffle furnace, and presintering the mixture for 2 hours at 150 ℃.
And step 3, heating to 960 ℃ at a heating rate of 5 ℃/min, and calcining for 10 hours.
Step 4, cooling to room temperature, washing with distilled water, and drying to obtain K 2 Ti 4 O 9 。
Step 5, 1gK 2 Ti 4 O 9 And 2g urea was dispersed in 15mL ethanol.
And 6, heating to 70 ℃ and keeping for 2 hours to volatilize the ethanol completely.
Step 7, calcining the mixture in a muffle furnace at 400 ℃ for 4 hours in an air atmosphere to obtain N-K 2 Ti 4 O 9 。
Preparation of Pt-N-K 2 Ti 4 O 9 Catalyst:
step 1, 1g N-K 2 Ti 4 O 9 Dispersed in 100mL of methanol solution.
Step 2, adding 0.02g of chloroplatinic acid.
And step 3, sealing the reactor, and introducing high-purity nitrogen for 30min.
And step 4, under the condition of intense stirring, performing light deposition for 2 hours by using a xenon lamp with a 300nm filter as a light source.
Step 5, collectingCollecting turbid liquid, centrifuging, and drying at 70deg.C to obtain Pt-N-K 2 Ti 4 O 9 A catalyst.
Comparative example 2
Preparation of g-C 3 N 4 ：
Step 1, weighing 5g of dicyandiamide and adding 30mL of water into an alumina crucible.
And 2, completely dissolving the dicyandiamide in water bath at 70 ℃.
Step 3, transferring the mixture into a muffle furnace, rising the temperature to 550 ℃ at a heating rate of 3 ℃/min, and maintaining the temperature for 3h.
Step 4, grinding after the mixture is cooled to room temperature, and sieving to obtain g-C 3 N 4 。
Preparation of Pt-g-C 3 N 4 Catalyst:
step 1, 1gg-C 3 N 4 Dispersed in 100mL of methanol solution.
Step 2, adding 0.02g of chloroplatinic acid.
And step 3, sealing the reactor, and introducing high-purity nitrogen for 30min.
And step 4, under the condition of intense stirring, performing light deposition for 2 hours by using a xenon lamp with a 300nm filter as a light source.
Step 5, collecting turbid liquid, centrifuging, drying at 70 ℃ to obtain Pt-g-C 3 N 4 A catalyst.
The following performance tests were carried out on the catalysts obtained in examples 1 to 5 and comparative examples 1 and 2:
1) The hydrogen evolution efficiency test method comprises the following steps:
20mL of photocatalytic solution (2 mL of water, 15mL of acetonitrile, 3mL of triethanolamine) was added to the photocatalytic reactor;
10mg of photocatalyst was added;
using N 2 Purging the reactor to remove air from the reactor and the solution;
a Xe lamp using a 360nm filter as a light source;
the hydrogen content in the reactor was analyzed by GC gas chromatography with timed sampling.
A graph of hydrogen evolution efficiency data is obtained as in fig. 2.
2) Hydrogen evolution efficiency test the test was repeated:
the catalyst obtained in example 3 was repeated 5 times according to the test method in 1). The catalyst from example 3 was removed from the original system at 5 hours intervals, added to a fresh photocatalytic solution and tested in accordance with the test method of 1).
A graph of hydrogen evolution efficiency data as shown in fig. 3 was obtained.
In FIG. 2, the data for comparative example 1 and comparative example 2 are relatively similar, resulting in the possibility of partial overlapping or masking of the data fold lines in the graph. From the data of examples 1 to 7, it can be seen that the catalyst of the present invention has good catalytic hydrogen production effect and hydrogen production efficiency.
As can be seen from the data of fig. 3, the catalyst of the present invention can be reused without significant changes in catalytic hydrogen production efficiency and efficiency.
In summary, the catalyst of the present invention is prepared by reacting g-C 3 N 4 And N-K 2 Ti 4 O 9 The two semiconductor materials and Pt are combined to cooperate, so that the hydrogen production efficiency of the catalyst is improved.
The foregoing descriptions of specific exemplary embodiments of the present invention are presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application to thereby enable one skilled in the art to make and utilize the invention in various exemplary embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (9)
1. A catalyst comprising Pt-doped g-C 3 N 4 /N-K 2 Ti 4 O 9 ；
Wherein the catalysis isIn the agent, the content of platinum is 1-3 wt%; and/or, the g-C 3 N 4 And N-K 2 Ti 4 O 9 The mass ratio of (1-5): 5, a step of;
the preparation method of the catalyst comprises the following steps:
will g-C 3 N 4 /N-K 2 Ti 4 O 9 Dispersing in a dispersing agent, and adding a platinum source to the dispersing agent to obtain a premix;
stirring in a protective gas atmosphere, and carrying out a photo-deposition reaction on the premix under the irradiation of a light source with the wavelength of 300-380 nm; and
separating and drying to obtain the catalyst;
wherein g-C 3 N 4 /N-K 2 Ti 4 O 9 The preparation method of (2) comprises the following steps:
obtaining N-K 2 Ti 4 O 9 Mixing with dicyandiamide and water, heating to react, grinding, separating to obtain g-C 3 N 4 /N-K 2 Ti 4 O 9 。
2. A method for preparing the catalyst according to claim 1, comprising the steps of:
will g-C 3 N 4 /N-K 2 Ti 4 O 9 Dispersing in a dispersing agent, and adding a platinum source to the dispersing agent to obtain a premix;
stirring in a protective gas atmosphere, and carrying out a photo-deposition reaction on the premix under the irradiation of a light source with the wavelength of 300-380 nm; and
and separating and drying to obtain the catalyst.
3. The method for preparing a catalyst according to claim 2, wherein g-C 3 N 4 /N-K 2 Ti 4 O 9 The preparation method of (2) comprises the following steps:
obtaining N-K 2 Ti 4 O 9 Mixing with dicyandiamide and water, heating to react, grindingGrinding and separating to obtain g-C 3 N 4 /N-K 2 Ti 4 O 9 。
4. The process for preparing a catalyst according to claim 3, wherein N-K is obtained 2 Ti 4 O 9 The method comprises the following steps:
will K 2 CO 3 And TiO 2 Mixing and grinding uniformly, heating to 900-1000 ℃ at a heating rate of 4-6 ℃/min, and calcining at the temperature for 8-12 h to obtain K 2 Ti 4 O 9 ；
Will K 2 Ti 4 O 9 Mixing with urea, calcining at 300-500 deg.C for 3-5 hr to obtain N-K 2 Ti 4 O 9 。
5. The method for preparing a catalyst according to claim 4, wherein K is selected from the group consisting of 2 CO 3 And TiO 2 The steps of mixing and grinding uniformly include:
will K 2 CO 3 And TiO 2 Mixing, adding distilled water, grinding uniformly, and heating at 120-180 ℃ for 1-3 h.
6. The method for preparing a catalyst according to claim 4, wherein K is selected from the group consisting of 2 Ti 4 O 9 The step of mixing with urea comprises:
will K 2 Ti 4 O 9 Dispersing the urea and the urea in ethanol, and then heating at 70-90 ℃ for 1-3 hours to remove the ethanol.
7. The method for preparing a catalyst according to claim 3, wherein N-K is selected from the group consisting of 2 Ti 4 O 9 After mixing the dicyandiamide and the water uniformly, the heating reaction comprises the following steps:
N-K 2 Ti 4 O 9 Mixing the dicyandiamide with water, and heating to 65-75 ℃ to completely dissolve the dicyandiamide;
heating the mixture to 550 ℃ at a heating rate of 2-4 ℃/min, and keeping the temperature for reaction for 2.5-3.5 h;
after the reaction was completed, the mixture was cooled to room temperature.
8. The method for preparing the catalyst according to claim 2, wherein the dispersing agent is at least one of methanol and ethanol; and/or the number of the groups of groups,
the shielding gas is at least one of nitrogen and argon; and/or the number of the groups of groups,
the platinum source is at least one of chloroplatinic acid and platinum nitrate.
9. Use of the catalyst of claim 1 for photocatalytic hydrogen production.
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