CN115043431A - General synthesis method of pyrochlore type potassium tantalate photocatalytic material with three-dimensional ordered macroporous structure - Google Patents
General synthesis method of pyrochlore type potassium tantalate photocatalytic material with three-dimensional ordered macroporous structure Download PDFInfo
- Publication number
- CN115043431A CN115043431A CN202210879246.5A CN202210879246A CN115043431A CN 115043431 A CN115043431 A CN 115043431A CN 202210879246 A CN202210879246 A CN 202210879246A CN 115043431 A CN115043431 A CN 115043431A
- Authority
- CN
- China
- Prior art keywords
- dimensional ordered
- ordered macroporous
- template
- synthesis method
- ions
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052700 potassium Inorganic materials 0.000 title claims abstract description 29
- 239000011591 potassium Substances 0.000 title claims abstract description 29
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 title claims abstract description 23
- 238000001308 synthesis method Methods 0.000 title claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 47
- 229910001414 potassium ion Inorganic materials 0.000 claims abstract description 31
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- 229910001460 tantalum ion Inorganic materials 0.000 claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 230000006911 nucleation Effects 0.000 claims abstract description 11
- 238000010899 nucleation Methods 0.000 claims abstract description 10
- 239000011022 opal Substances 0.000 claims abstract description 10
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 7
- 239000011324 bead Substances 0.000 claims abstract description 6
- NGCRLFIYVFOUMZ-UHFFFAOYSA-N 2,3-dichloroquinoxaline-6-carbonyl chloride Chemical compound N1=C(Cl)C(Cl)=NC2=CC(C(=O)Cl)=CC=C21 NGCRLFIYVFOUMZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000013078 crystal Substances 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 25
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 25
- 238000003828 vacuum filtration Methods 0.000 claims description 17
- 238000002791 soaking Methods 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000010189 synthetic method Methods 0.000 claims description 3
- 239000002738 chelating agent Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 238000000967 suction filtration Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 17
- 229920001730 Moisture cure polyurethane Polymers 0.000 abstract description 10
- 238000013508 migration Methods 0.000 abstract description 8
- 230000005012 migration Effects 0.000 abstract description 8
- 239000002245 particle Substances 0.000 abstract description 6
- 239000011941 photocatalyst Substances 0.000 abstract description 6
- 238000012546 transfer Methods 0.000 abstract description 5
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 description 14
- 238000005457 optimization Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000000969 carrier Substances 0.000 description 7
- 239000008188 pellet Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- JVOQKOIQWNPOMI-UHFFFAOYSA-N ethanol;tantalum Chemical compound [Ta].CCO JVOQKOIQWNPOMI-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G35/00—Compounds of tantalum
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1088—Non-supported catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
- C01P2002/36—Three-dimensional structures pyrochlore-type (A2B2O7)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- 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
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
Abstract
The invention discloses pyrochlore type potassium tantalate (K) with a three-dimensional ordered macroporous structure 2 Ta 2 O 6 ) A general synthesis method of a photocatalytic material is characterized in that opal beads are selected as a template agent of a three-dimensional ordered macroporous potassium tantalate material, ethanol solutions of tantalum ethoxide and potassium ions are respectively used as pre-polymers, and the tantalum ions and the potassium ions are respectively introduced into gaps of the template by a two-step crystal nucleation method. In the first step, crystal nucleation sites dominated by tantalum ions are uniformly distributed, and in the second step, the tantalum ion nucleation centers attract potassium ions for nucleation. Then, uniformly calcining the template agent containing the precursor step by step to obtain three-dimensional ordered macropore K 2 Ta 2 O 6 Crystallizing and moldingAnd (5) removing the plate agent. In the field of hydrogen production by photocatalytic decomposition of water, K is prepared 2 Ta 2 O 6 After the three-dimensional ordered macroporous structure is constructed, the photocatalyst K 2 Ta 2 O 6 The specific surface area is obviously increased, the mass transfer efficiency is improved, the carrier migration distance is shortened, and compared with the traditional high-temperature calcined particle K 2 Ta 2 O 6 Compared with the structure, the capability of decomposing water and hydrogen by photocatalysis is obviously improved.
Description
Technical Field
The invention relates to the technical field of hydrogen production by decomposing water with a photocatalyst, in particular to a general synthesis method of a pyrochlore type potassium tantalate material with a three-dimensional ordered macroporous structure.
Background
Today, the social development is high, and the problem of environmental pollution is always accompanied with the production and life of people. The pollution produced by the combustion of fossil energy accounts for a large part, and the fossil fuel is still the main energy used by people until now. In order to develop the economic society of people, a clean, green and efficient energy substitute is urgently needed to be found. The high efficiency and environmental friendliness of hydrogen fuel are being noticed by more and more people. The technology for decomposing water into hydrogen by photocatalysis developed recently is very in line with the expectation of people on future energy conversion. Photocatalysis, which achieves storage of the sun by decomposing water to produce hydrogen using solar energy, is a very promising technology. It is very challenging to achieve high efficiency of hydrogen decomposition, and the photocatalyst of choice becomes critical. However, the existing semiconductor photocatalytic material structure always affects the performance of photocatalytic water splitting for hydrogen production along with some defects, and therefore, the design and preparation of the enhanced photocatalyst are currently important subjects and the greatest challenges.
Pyrochlore potassium tantalate has thermal and chemical stability, excellent dielectric constant and optical isotropy. In addition, K 2 Ta 2 O 6 Being a wide bandgap semiconductor (4.5 eV) has great potential for photocatalytic water splitting due to its conduction band consisting of Ta 5d orbitals, which are more negative in position than typical catalysts such as titanates (Ti 3d) and niobates (Nb 4 d). However, K produced by conventional hydrothermal methods 2 Ta 2 O 6 The low surface area results in fewer reactive active sites and high carrier recombination rate, which further affects photocatalytic activity. And will K 2 Ta 2 O 6 Constructing a three-dimensional ordered macroporous structure would be expected to ameliorate these problems. The high surface area of the three-dimensional ordered macroporous structure can improve more selectable reactive sites, the nano-framework structure can effectively shorten the migration distance of carriers, and the ordered pore channel structure can effectively improve the mass transfer efficiency. Constructing three-dimensional ordered macropore K 2 Ta 2 O 6 （3DOM K 2 Ta 2 O 6 ) Can effectively improve the problems and further improve the efficiency of photocatalytic decomposition of water to produce hydrogen.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a general synthetic method of a three-dimensional ordered macroporous pyrochlore type potassium tantalate photocatalytic hydrogen production material, which is changed from the prior artGood at K 2 Ta 2 O 6 The semiconductor catalyst has the structural defects of small specific surface area, low mass transfer efficiency and long carrier migration distance, so that the hydrogen production efficiency of photocatalytic decomposition water is greatly improved, and the problems in the background art are effectively solved.
In order to achieve the purpose, the invention provides the following technical scheme: a general synthetic method of a three-dimensional ordered macroporous pyrochlore type potassium tantalate photocatalytic hydrogen production material selects proper opal spheres as a template agent of the three-dimensional ordered macroporous pyrochlore type potassium tantalate, and TaCl 5 Dissolving in absolute ethanol solution to form tantalum ion pre-polymer, uniformly distributing the pre-polymer in gaps of opal globules, twice impregnating and introducing potassium ions to obtain a spherical template agent containing tantalum ions and potassium ions, calcining the template agent, gradually solidifying the pre-polymer between the gaps during calcination, crystallizing, and removing the template agent to form three-dimensional ordered macroporous pyrochlore type potassium tantalate ， The method specifically comprises the following steps:
s1, selecting opal globules with proper size as a template agent;
s2, taking TaCl 5 Adding the powder into absolute ethyl alcohol, stirring and dissolving;
s3, naturally filtering the solution obtained in the step S2 to leave a clear solution;
s4, adding the template agent obtained in the step S1 into the clear liquid obtained in the step S3, and soaking for 2-5 hours at room temperature;
s5, carrying out vacuum filtration on the solution obtained in the step S4 to obtain a template agent with gaps containing tantalum ethoxide;
s6, soaking the sample obtained in the step S5 in an ethanol solution containing potassium ions for 2-5 h for the second time;
s7, carrying out vacuum filtration on the standing solution, and drying at room temperature to obtain a template agent with gaps containing tantalum ions and potassium ions;
s8, calcining the sample obtained in the step S7 in a nitrogen atmosphere, heating to 623K, keeping for 1-3h, cooling to room temperature, and taking out;
and S9, calcining the sample obtained in the step S8 in air, heating to 873K, keeping for 0.5-2 h, cooling to room temperature, washing and drying to obtain the sample.
Further optimizing the technical scheme, in the step S1, a suitable template pellet is selected as a template agent of the three-dimensional ordered macroporous potassium tantalate, and the template pellet is polymethyl methacrylate.
In step S1, the template is a highly ordered PMMA bead structure.
Further optimizing the technical scheme, the size of the PMMA pellets is one or more.
Further optimizing the technical scheme, in the step S2, TaCl is taken 5 Adding into absolute ethanol solution, stirring and dissolving for 1-3 h.
Further optimizing the technical scheme, the TaCl in the step S2 5 The dosage of the compound is 0.8-1.1g, and the dosage of the absolute ethyl alcohol is 8-14 mL.
Further optimizing the technical scheme, in the step S4, the template agent is added into the clear solution and dipped for 2-4 h at room temperature.
In step S6, the sample obtained in step S5 is placed in an ethanol solution containing potassium ions, and the sample is dipped for 2 to 4 hours.
In step S8, the sample is calcined in a nitrogen atmosphere, heated to 623K, kept for 1-3h, cooled to room temperature, and then taken out.
Further optimizing the technical scheme, in the step S9, the sample obtained in the step S8 is placed in a muffle furnace, the temperature is raised to 873K, the sample is kept for 0.5 to 2 hours, then the sample is cooled and taken out, and the three-dimensional ordered macroporous K is obtained by washing and drying 2 Ta 2 O 6 。
The invention constructs three-dimensional ordered macropore K by PMMA template agent under the condition of room temperature 2 Ta 2 O 6 . In this process, TaCl 5 Dissolving in absolute ethanol solution to form ethanol solution containing tantalum ions, and filling prepolymer solution by twice impregnation method to introduce potassium ions, TaCl 5 Dissolving in absolute ethanol solution to form tantalum ethoxide precursor, uniformly distributing the precursor in gaps of template pellet, solidifying the precursor in the gaps during calcination, andand (3) crystallizing, wherein the three-dimensional ordered macroporous pyrochlore potassium tantalate is formed along with the removal of the template, the specific surface area of the photocatalytic material is improved by constructing a three-dimensional ordered macroporous pyrochlore potassium tantalate structure, and the carrier migration distance is shortened, so that the hydrogen production efficiency of the pyrochlore potassium tantalate by decomposition water is improved.
Compared with the prior art, the invention provides a general synthesis method of a photocatalytic hydrogen production material of three-dimensional ordered macroporous pyrochlore potassium tantalate, which has the following beneficial effects:
1. the invention uses PMMA template agent to react K 2 Ta 2 O 6 After the three-dimensional ordered macroporous structure is constructed, the specific surface area of the photocatalyst is obviously increased, the reaction active sites are increased, and the reaction is similar to the traditional hydrothermal K 2 Ta 2 O 6 Compared with the structure, the hydrogen generation capacity is greatly improved.
2. According to the invention, the PMMA template agent is used for constructing the catalyst with the three-dimensional ordered macroporous structure, the migration distance of carriers is shortened, the service life of photogenerated carriers is obviously prolonged, and the carriers of reaction transferred to the surface of the catalyst are increased, so that the efficiency of decomposing water of the catalyst to generate hydrogen is improved.
3. According to the invention, PMMA is used as a template agent to construct the catalyst with a three-dimensional ordered macroporous structure, so that the light absorption is increased, and the efficiency of hydrogen generation by photocatalytic decomposition of water is greatly improved.
4. According to the invention, PMMA is used as a template agent to construct the catalyst with a three-dimensional ordered macroporous structure, and the catalyst structure obtains a highly ordered pore structure, so that the gas molecule release efficiency is improved, and the photocatalytic reaction is facilitated.
Drawings
FIG. 1 is three-dimensional ordered macropore K obtained by PMMA template 2 Ta 2 O 6 XRD spectrum compared to (PDF #35-1464) card;
FIG. 2 is a three-dimensional ordered macroporous structure K obtained by using a PMMA template 2 Ta 2 O 6 SEM picture of (1);
FIG. 3 shows three-dimensionally ordered macropores K 2 Ta 2 O 6 The element distribution map of (a);
FIG. 4 shows three-dimensionally ordered macropores K 2 Ta 2 O 6 And hydrothermal K 2 Ta 2 O 6 Performance comparison and hydrogen production stability diagram.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by a person of ordinary skill in the art without creative efforts based on the embodiments of the present invention belong to the protection scope of the present invention.
Example (b):
referring to fig. 1, the invention discloses a general synthesis method of a three-dimensional ordered macroporous pyrochlore potassium tantalate photocatalytic hydrogen production material, and a proper PMMA pellet is selected as a template agent of the three-dimensional ordered macroporous pyrochlore potassium tantalate, TaCl 5 Dissolving in absolute ethanol solution to form tantalum ion pre-polymer, uniformly distributing the pre-polymer in gaps of PMMA pellets, introducing potassium ions by a two-step crystal nucleation method to obtain a spherical template agent containing tantalum ions and potassium ions, calcining the template agent, gradually solidifying the pre-polymer between the gaps during calcination, crystallizing, and forming three-dimensional ordered macropore K along with removal of the template agent 2 Ta 2 O 6 The method specifically comprises the following steps:
s1, selecting opal globules with proper size as a template agent;
s2, taking TaCl 5 Adding the powder into absolute ethyl alcohol, stirring and dissolving;
s3, naturally filtering the solution obtained in the step S2 to leave a clear solution;
s4, adding the template agent obtained in the step S1 into the clear liquid obtained in the step S3, and soaking for 2-5 hours at room temperature;
s5, carrying out vacuum filtration on the solution obtained in the step S4 to obtain a template agent with gaps containing tantalum ethoxide;
s6, soaking the sample obtained in the step S5 in an ethanol solution containing potassium ions for 2-5 h for the second time;
s7, carrying out vacuum filtration on the standing solution, and drying at room temperature to obtain a template agent with gaps containing tantalum ions and potassium ions;
s8, calcining the sample obtained in the step S7 under nitrogen atmosphere, heating to 623K, keeping for 1-3h, cooling to room temperature, and taking out;
s9, calcining the sample obtained in the step S8 in air, heating to 873K, keeping for 0.5-2 h, cooling, taking out, washing and drying to obtain the three-dimensional ordered macroporous K 2 Ta 2 O 6 。
As a specific optimization scheme of this embodiment, in step S1, a suitable PMMA bead is selected as a template agent of the three-dimensional ordered macroporous potassium tantalate, and PMMA is polymethyl methacrylate.
As a specific optimization scheme of this embodiment, in step S1, the template is a highly ordered PMMA bead structure.
As a specific optimization scheme of the embodiment, the size of the PMMA pellets is one or more.
As a specific optimization scheme of this embodiment, in step S2, TaCl is taken 5 Adding into absolute ethanol solution, stirring and dissolving for 1-3 h.
As a specific optimization scheme of this embodiment, TaCl in step S2 is used 5 The dosage of the compound is 0.8-1.1g, and the dosage of the absolute ethyl alcohol is 8-14 mL.
As a specific optimization scheme of this embodiment, in step S4, the template is added to the clear solution and immersed at room temperature for 2-4 h.
As a specific optimization scheme of this embodiment, in the step S6, the sample obtained in S5 is placed in an ethanol solution containing potassium ions, and is immersed for 2-4 h twice.
As a specific optimization scheme of the embodiment, in the step S8, the sample is calcined under a nitrogen atmosphere, heated to 623K, kept for 1-4 h, cooled to room temperature and then taken out.
As a specific optimization scheme of this embodiment, in step S9, the sample obtained in S8 is placed in a muffle furnace, heated to 873K, kept for 0.5-2 h, cooled, taken out, washed, and dried to obtain three-dimensional ordered macroporous K 2 Ta 2 O 6 。
The invention is a strip at room temperatureUnder the condition, a PMMA template agent is used for constructing three-dimensional ordered macropore K 2 Ta 2 O 6 . In this process, a general synthesis method of a method of introducing tantalum ions and potassium ions by a two-step crystal nucleation method. At the first time, TaCl 5 Dissolving in absolute ethanol solution to form ethanol tantalum pre-polymer, uniformly distributing the pre-polymer in the gaps of the template spheres, and introducing the tantalum ion pre-polymer in the first step, wherein the nucleation sites guided by the tantalum ions are uniformly distributed in the gaps of the template spheres. And in the second step, potassium ions are introduced, and the nucleation center attracts the potassium ions to nucleate. Finally, the two cations are uniformly mixed and dissolved. Calcining the template step by step, gradually forming frameworks of the three-dimensional ordered macroporous structures of the two cation sources along with the rise of the temperature, crystallizing, and forming a three-dimensional ordered macroporous structure K along with the removal of the template 2 Ta 2 O 6 . By constructing three-dimensional ordered macropores K 2 Ta 2 O 6 The structure improves the specific surface area of the photocatalytic material, improves the mass transfer efficiency, shortens the migration distance of the current carrier, thereby improving the K 2 Ta 2 O 6 The hydrogen production efficiency of the decomposed water.
The first embodiment is as follows:
firstly, TaCl is taken 5 (0.9 g) adding the mixture into an absolute ethyl alcohol (10 mL) solution, stirring and dissolving, filtering to remove impurities, then adding a PMMA template with the particle size of 200 nm into the filtrate, standing for 2 h, and carrying out vacuum filtration to obtain the template agent with gaps containing tantalum ions. And soaking the template in an ethanol solution containing potassium ions for 4 hours, and performing vacuum filtration to obtain the template agent with gaps containing tantalum ions and potassium ions. Under nitrogen atmosphere, the temperature is increased to 623K and kept for 2 h, and the temperature is reduced to room temperature and then taken out. It was next placed in air, warmed to 873K, and held for 1 h. Obtaining three-dimensional ordered macropore K 2 Ta 2 O 6 。
Example two:
firstly, TaCl is taken 5 (0.9 g) adding the mixture into an absolute ethyl alcohol (10 mL) solution, stirring and dissolving, filtering to remove impurities, then adding a PMMA template with the particle size of 300 nm into the filtrate, standing for 2 h, and carrying out vacuum filtration to obtain the template agent with gaps containing tantalum ions. Then soaking the substrate in ethanol solution containing potassium ions for the second timeAnd soaking for 4 hours, and performing vacuum filtration to obtain the template agent with gaps containing tantalum ions and potassium ions. Under nitrogen atmosphere, the temperature is increased to 623K and kept for 2 h, and the temperature is reduced to room temperature and then taken out. It was next placed in air, warmed to 873K, and held for 1 h. Obtaining three-dimensional ordered macropore K 2 Ta 2 O 6 。
Example three:
firstly, TaCl is taken 5 (0.9 g) adding the mixture into an absolute ethyl alcohol (10 mL) solution, stirring and dissolving, filtering to remove impurities, then adding a PMMA template with the particle size of 200 nm into the filtrate, standing for 2 h, and carrying out vacuum filtration to obtain the template agent with gaps containing tantalum ions. And soaking the template in an ethanol solution containing potassium ions for 4 hours, and performing vacuum filtration to obtain the template agent with gaps containing tantalum ions and potassium ions. Under nitrogen atmosphere, the temperature is increased to 623K and kept for 1 h, and the mixture is taken out after being cooled to room temperature. It was next placed in air, warmed to 873K, and held for 1 h. Obtaining three-dimensional ordered macropore K 2 Ta 2 O 6 。
Example four:
firstly, TaCl is taken 5 (1 g) Adding the mixture into absolute ethyl alcohol (12 mL), stirring and dissolving, filtering to remove impurities, adding a PMMA template with the particle size of 200 nm into the filtrate, standing for 2 hours, and carrying out vacuum filtration to obtain the template agent with gaps containing tantalum ions. And soaking the template in an ethanol solution containing potassium ions for 4 hours, and performing vacuum filtration to obtain the template agent with gaps containing tantalum ions and potassium ions. Under nitrogen atmosphere, the temperature is increased to 623K and kept for 2 h, and the temperature is reduced to room temperature and then taken out. It was next placed in air, warmed to 873K, and held for 1 h. Obtaining three-dimensional ordered macropore K 2 Ta 2 O 6 。
Example five:
firstly, taking TaCl 5 (1 g) Adding the mixture into absolute ethyl alcohol (12 mL), stirring and dissolving, filtering to remove impurities, adding a PMMA template with the particle size of 200 nm into the filtrate, standing for 3h, and carrying out vacuum filtration to obtain the template agent with gaps containing tantalum ions. Then soaking the mixture in ethanol solution containing potassium ions for 4 hours, and performing vacuum filtration to obtain the template agent with gaps containing tantalum ions and potassium ions. Under nitrogen atmosphere, the temperature is increased to 623K and kept for 2 h, and the mixture is taken out after being cooled to room temperature. It was next placed in air, warmed to 873K, and held for 1 h. Obtaining three-dimensional ordered macropore K 2 Ta 2 O 6 。
The morphology and structure, and properties of the product obtained in the comparative example are shown in FIGS. 1-4.
As can be seen from FIG. 1, the three-dimensional ordered macropore K obtained by using PMMA template 2 Ta 2 O 6 Compared with (PDF #35-1464) card, the peak patterns are consistent, and the three-dimensional ordered macropore K is illustrated 2 Ta 2 O 6 Is pure phase K 2 Ta 2 O 6 。
As can be seen from FIG. 2, the three-dimensionally ordered macropores K 2 Ta 2 O 6 Highly ordered, three-dimensionally ordered macropores K 2 Ta 2 O 6 Successfully constructed three-dimensional ordered macropore K of low-magnification SEM picture 2 Ta 2 O 6 High porosity and integrity are maintained.
As can be seen from FIG. 3, the three-dimensionally ordered macropores K 2 Ta 2 O 6 All the constituent elements are uniformly distributed, which indicates the uniform structure of the three-dimensional ordered macropores.
As can be seen from FIG. 4a, the three-dimensionally ordered macropores K 2 Ta 2 O 6 The activity of the generated hydrogen is better than that of hydrothermal K 2 Ta 2 O 6 （H-K 2 Ta 2 O 6 ) FIG. 4b shows three-dimensionally ordered macropores K 2 Ta 2 O 6 Has good stability of decomposing water to produce hydrogen, and the introduction of the three-dimensional ordered macroporous structure proves that the K is greatly improved 2 Ta 2 O 6 The performance of (c).
The results of the examples show that the three-dimensional ordered macropore K prepared by the invention 2 Ta 2 O 6 Has excellent photodecomposition water performance.
The beneficial effects of the invention are:
1. the invention uses opal globule template agent to prepare K 2 Ta 2 O 6 After the three-dimensional ordered macroporous structure is constructed, the specific surface area of the photocatalyst is clearObviously increased mass transfer efficiency, increased selective reaction active sites and traditional hydrothermal K 2 Ta 2 O 6 Compared with the structure, the hydrogen generation capacity is greatly improved.
2. According to the invention, the catalyst with the three-dimensional ordered macroporous structure is constructed by using the opal bead template agent, the migration distance of carriers is shortened, the migration efficiency of photogenerated carriers is improved, and the number of carriers capable of participating in the reaction on the surface of the catalyst is increased, so that the efficiency of decomposing water to generate hydrogen of the catalyst is improved.
3. The catalyst with the three-dimensional ordered macroporous structure is constructed by taking the opal globules as the template agent, and the utilization rate of sunlight is improved due to the slow photon effect of the three-dimensional ordered macroporous structure, so that the efficiency of generating hydrogen by decomposing water through photocatalysis is improved.
4. The catalyst with the three-dimensional ordered macroporous structure is constructed by taking the opal globules as the template agent, and the catalyst structure has a small-tortuous pore passage structure, so that the gas molecule release efficiency is improved, and the photocatalytic reaction is facilitated.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A general synthetic method of a pyrochlore type potassium tantalate photocatalytic material with a three-dimensional ordered macroporous structure is characterized in that a chelating agent which is difficult to remove is not used, a two-step crystal nucleation method is adopted to construct the pyrochlore type potassium tantalate with the three-dimensional ordered macroporous structure, a tantalum ion precursor is introduced in the first step, nucleation sites which are dominated by tantalum ions are uniformly distributed in gaps of template spheres, potassium ions are introduced in the second step, the nucleation centers attract the potassium ions to nucleate, finally, the two cations are uniformly mixed and dissolved, the template is calcined step by step, a framework with the three-dimensional ordered macroporous structure is gradually formed along with the increase of temperature, the framework is crystallized, and the three-dimensional macroporous structure is formed along with the removal of the templateOrdered macroporous structure K 2 Ta 2 O 6， The method specifically comprises the following steps:
s1, selecting opal globules with proper size as a template agent;
s2, taking TaCl 5 Adding the powder into absolute ethyl alcohol, stirring and dissolving;
s3, naturally filtering the solution obtained in the step S2 to leave a clear solution;
s4, adding the template agent obtained in the step S1 into the clear liquid obtained in the step S3, and soaking for 2-5 hours at room temperature;
s5, carrying out vacuum filtration on the solution obtained in the step S4 to obtain a template agent with gaps containing tantalum ethoxide;
s6, soaking the sample obtained in the step S5 in an ethanol solution containing potassium ions for 2-5 h for the second time;
s7, carrying out vacuum filtration on the standing solution, and drying at room temperature to obtain a template agent with gaps containing tantalum ions and potassium ions;
s8, calcining the sample obtained in the step S7 in a nitrogen atmosphere, heating to 623K, cooling to room temperature, and taking out;
and S9, calcining the sample obtained in the step S8 in air, heating to 873K, cooling to room temperature, washing and drying to obtain the sample.
2. The general synthesis method of pyrochlore-type potassium tantalate material with three-dimensional ordered macroporous structure as claimed in claim 1, wherein in step S1, the templating agent is PMMA bead structure with highly ordered arrangement.
3. The general synthesis method of pyrochlore-type potassium tantalate material with three-dimensional ordered macroporous structure as claimed in claim 2, wherein step S4, suction filtration is performed in a closed environment.
4. The general synthesis method of pyrochlore-type potassium tantalate material with three-dimensional ordered macroporous structure as claimed in claim 3, wherein vacuum filtration requires application of suitable negative pressure.
5. The general synthesis method of pyrochlore-type potassium tantalate material with three-dimensional ordered macroporous structure as claimed in claim 1, wherein the material is used in the field of photocatalytic decomposition of hydrogen.
6. The general synthesis method of pyrochlore-type potassium tantalate material with three-dimensional ordered macroporous structure as claimed in claim 1, wherein the negative pressure in step S4 is 0.01-0.05 MPa.
7. The general synthesis method of the three-dimensional ordered macroporous smectite-type potassium tantalate material according to claim 1, wherein in the step S4, the template is added into the clear solution and immersed for 2-5 h at room temperature.
8. The general synthesis method of the three-dimensional ordered macroporous smectite-type potassium tantalate material according to claim 1, wherein the negative pressure in the step S7 is 0.01-0.05 MPa.
9. The general synthesis method of the three-dimensional ordered macroporous smectite-type potassium tantalate photocatalytic hydrogen production material as claimed in claim 1, wherein in step S8, the sample is calcined in nitrogen atmosphere, heated to 623K, kept for 1-3h, cooled to room temperature, and then taken out.
10. The general synthesis method of the three-dimensionally ordered macroporous smectite-type potassium tantalate material according to claim 1, wherein in the step S9, the sample obtained in the step S8 is placed in a muffle furnace, heated to 873K, and kept for 0.5-2 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210879246.5A CN115043431A (en) | 2022-07-25 | 2022-07-25 | General synthesis method of pyrochlore type potassium tantalate photocatalytic material with three-dimensional ordered macroporous structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210879246.5A CN115043431A (en) | 2022-07-25 | 2022-07-25 | General synthesis method of pyrochlore type potassium tantalate photocatalytic material with three-dimensional ordered macroporous structure |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115043431A true CN115043431A (en) | 2022-09-13 |
Family
ID=83167253
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210879246.5A Withdrawn CN115043431A (en) | 2022-07-25 | 2022-07-25 | General synthesis method of pyrochlore type potassium tantalate photocatalytic material with three-dimensional ordered macroporous structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115043431A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101569858A (en) * | 2009-06-04 | 2009-11-04 | 武汉理工大学 | Method for preparing tantalum-potassium composite oxide photocatalyst |
| CN101723600A (en) * | 2009-11-17 | 2010-06-09 | 哈尔滨工业大学 | Method for preparing three-dimensional ordered macroporous (3DOM) film of niobium or tantalum compound |
| CN108993466A (en) * | 2018-08-07 | 2018-12-14 | 中国科学院地球环境研究所 | A kind of three-dimensional ordered macroporous titanate and its sacrifice preparation method certainly in situ |
| CN113070056A (en) * | 2021-03-22 | 2021-07-06 | 南昌大学 | General synthesis method of tantalum pentoxide photocatalytic material with three-dimensional ordered network structure |
| CN113600175A (en) * | 2021-08-02 | 2021-11-05 | 南昌大学 | General synthesis method of three-dimensional ordered macroporous structure sodium tantalate photocatalytic hydrogen production material |
| CN113649026A (en) * | 2021-07-27 | 2021-11-16 | 南昌大学 | General synthesis method of three-dimensional ordered macroporous cadmium sulfide photocatalytic material |
-
2022
- 2022-07-25 CN CN202210879246.5A patent/CN115043431A/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101569858A (en) * | 2009-06-04 | 2009-11-04 | 武汉理工大学 | Method for preparing tantalum-potassium composite oxide photocatalyst |
| CN101723600A (en) * | 2009-11-17 | 2010-06-09 | 哈尔滨工业大学 | Method for preparing three-dimensional ordered macroporous (3DOM) film of niobium or tantalum compound |
| CN108993466A (en) * | 2018-08-07 | 2018-12-14 | 中国科学院地球环境研究所 | A kind of three-dimensional ordered macroporous titanate and its sacrifice preparation method certainly in situ |
| CN113070056A (en) * | 2021-03-22 | 2021-07-06 | 南昌大学 | General synthesis method of tantalum pentoxide photocatalytic material with three-dimensional ordered network structure |
| CN113649026A (en) * | 2021-07-27 | 2021-11-16 | 南昌大学 | General synthesis method of three-dimensional ordered macroporous cadmium sulfide photocatalytic material |
| CN113600175A (en) * | 2021-08-02 | 2021-11-05 | 南昌大学 | General synthesis method of three-dimensional ordered macroporous structure sodium tantalate photocatalytic hydrogen production material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113070056B (en) | General synthesis method of three-dimensional ordered net-shaped tantalum pentoxide photocatalytic material | |
| CN113289653A (en) | g-C of load metal monoatomic3N4Method for preparing photocatalyst | |
| CN109161920B (en) | Preparation method of foamed copper self-supporting nickel-zinc double-metal hydroxide catalyst | |
| CN113600175A (en) | General synthesis method of three-dimensional ordered macroporous structure sodium tantalate photocatalytic hydrogen production material | |
| CN111617780A (en) | Nitrogen-doped nickel-molybdenum-based composite sulfide for stably producing hydrogen by electrolyzing water and preparation method | |
| CN110639585A (en) | Copolymerization modified layered graphite phase carbon nitride photocatalyst and preparation method and application thereof | |
| CN109364927A (en) | A kind of preparation method of prism-shaped copper oxide-zinc oxide catalyst | |
| CN116639729A (en) | Symbiotic bismuth layered ferroelectric Bi 7 Ti 4 NbO 21 Preparation method and application of semiconductor material | |
| CN113713796B (en) | Ni-NiO/C-TiO 2 Preparation method of core-shell structure nanorod-shaped material photocatalyst | |
| CN117512676A (en) | Hierarchical iron doped nickel-carbon structure nanotube and preparation method and application thereof | |
| CN117583001A (en) | BiOBr-Bi 2 O 2 SO 4 Preparation method and application of heterojunction photocatalyst | |
| CN115043431A (en) | General synthesis method of pyrochlore type potassium tantalate photocatalytic material with three-dimensional ordered macroporous structure | |
| CN112897483A (en) | TiN(B)@TiO2Core-shell particle powder material and method of preparation | |
| CN115739157A (en) | 3D hierarchical carbon nitride photocatalyst, preparation method and application thereof | |
| CN111203216A (en) | Selectively depositing Rh @ Cr on surface of ferroelectric photocatalytic material2O3Method for core-shell cocatalyst | |
| KR102587568B1 (en) | Nickel oxide/three dimensional-nickel structure catalyst, a method for manufacturing the same and a electrode for water decomposition comprising the nickel oxide/three dimensional-nickel structure catalyst | |
| Pan et al. | A review on the recent develpoment of bismuth-based catalysts for CO2 photoreduction | |
| CN110876945B (en) | ZnIn grown in limited area in carbon nano hollow sphere2S4Photocatalyst and preparation method thereof | |
| CN114377691A (en) | Doughnut-shaped hollow porous Pt-Ni nanoparticle-loaded titanium oxide material and preparation method thereof | |
| CN1247449C (en) | Method for preparing series of solid solution of metal oxide through carbamide combustion method | |
| CN111659397A (en) | Preparation method of high-performance three-dimensional ordered macroporous mesoporous Ni-Co alloy electrocatalyst | |
| CN115043432A (en) | General synthesis method of three-dimensional ordered macroporous perovskite lithium tantalate photocatalytic hydrogen production material | |
| CN111437847A (en) | Preparation method of layered ordered porous nickel-cobalt bimetallic phosphide nano material | |
| Guo et al. | Hierarchically Periodic Macroporous Niobium Oxide Architecture for Enhanced Hydrogen Evolution | |
| CN112516990B (en) | Synthetic method and application of layered perovskite type photocatalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20220913 |
|
| WW01 | Invention patent application withdrawn after publication |