CN108993468B - Hollow spherical photocatalyst, preparation method and application thereof - Google Patents
Hollow spherical photocatalyst, preparation method and application thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 22
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 20
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 20
- 239000011701 zinc Substances 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 19
- 230000001699 photocatalysis Effects 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 48
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- 229910021529 ammonia Inorganic materials 0.000 claims description 24
- 229910052799 carbon Inorganic materials 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 22
- 238000001354 calcination Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 150000001721 carbon Chemical class 0.000 claims description 15
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 11
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 8
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 7
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 claims description 6
- 229910003450 rhodium oxide Inorganic materials 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000003426 co-catalyst Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 235000010265 sodium sulphite Nutrition 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 230000006798 recombination Effects 0.000 abstract description 4
- 238000005215 recombination Methods 0.000 abstract description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 6
- 239000008103 glucose Substances 0.000 description 6
- 238000001027 hydrothermal synthesis Methods 0.000 description 6
- 238000001132 ultrasonic dispersion Methods 0.000 description 6
- -1 modified zinc titanate Chemical class 0.000 description 5
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 229910003122 ZnTiO3 Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- 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
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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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- 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
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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
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- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention relates to a hollow spherical photocatalyst, a preparation method and application thereof, wherein the photocatalyst is hollow spherical zinc titanate, and when in preparation, the coordination capability of a template is improved through ammoniation of the template, so that porous hollow spherical zinc titanate is successfully prepared, a cocatalyst can be successfully modified inside and outside a shell, the photocatalytic hydrogen production rate is greatly improved, and the rate of catalyzing water decomposition by the structured photocatalyst is promoted. Compared with the prior art, the hollow structure can enable the reduction type cocatalyst and the oxidation type cocatalyst to be respectively modified on the inner surface and the outer surface of the catalyst material, so that the directional flow of a light-induced electron hole is facilitated, the recombination probability is reduced, and the photocatalytic water decomposition efficiency is improved.
Description
Technical Field
The invention relates to the technical field of photocatalysis, in particular to a hollow spherical photocatalyst, a preparation method and application thereof.
Background
With the development of society, the problem of environmental pollution caused by energy crisis and fossil energy combustion is becoming more serious, and the search for new renewable energy becomes an urgent need. Hydrogen energy has a high combustion value and the combustion product is water, which is an excellent alternative energy source. At present, the hydrogen production mode adopted by the industry is petroleum heat cracking or natural gas hydrogen production, and a large amount of non-renewable fossil energy is still needed and causes the problem of environmental pollution. The photocatalytic water splitting hydrogen production technology becomes an effective way for solving energy and environmental problems due to the characteristics of high efficiency and environmental protection, so the application of the material is directly influenced by the advantages and disadvantages of the performance of the semiconductor catalyst for photocatalytic water splitting.
Recent researches show that the hollow structure can effectively improve the photocatalytic water decomposition rate of the catalyst, and a reduction promoter (platinum, palladium and the like) and an oxidation promoter (rhodium oxide, cobalt oxide and the like) can be respectively modified on the inner surface and the outer surface of the catalyst, so that the directional flow of a light-induced electron hole is facilitated, and the recombination probability is reduced.
For example: a problem group is avoided, a novel and simple template method is adopted to prepare a Ta3N5 photocatalyst with a core-shell structure, a platinum nano cluster is modified inside a shell, and iridium oxide or cobalt oxide is modified outside the shell, so that the water decomposition activity is enhanced, see ANGEW CHEM INT EDIT, 2013, 52, 11252-11256 pages; manganese oxide and cobalt phosphide are respectively modified on the inner surface and the outer surface of a CdS spherical shell by the Zhang Jinlong topic group, so that the hydrogen production performance and the photocatalytic activity for degrading rhodamine B are improved, see ADV FUNCT MATER, 2017, 27, page 1702624. Platinum and manganese oxide are respectively modified on the inner surface and the outer surface of a titanium dioxide shell by the Jingulong project group, so that the photocatalytic oxidation water activity is improved, see CHEM SCI, 2016, 7, 890-895.
However, the hollow spherical catalyst with the co-catalyst modified inside and outside prepared by the template method is only suitable for binary materials, and the main reason is that the template has different adsorption capacities for metal ions in a multi-element compound, so that the metal ions cannot be adsorbed on the template according to molar proportions, and synthesis failure is caused, thereby greatly limiting the selectivity of the photocatalyst types. Therefore, the adsorption capacity of the template is improved, and the structure can be popularized to more multi-element materials.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a hollow spherical photocatalyst with high hydrogen production rate, a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme: the hollow spherical photocatalyst is hollow spherical zinc titanate. The hollow structure can enable the reduction type cocatalyst and the oxidation type cocatalyst to be respectively modified on the inner surface and the outer surface of the catalyst material, so that the directional flow of a light-excited electron hole is facilitated, the recombination probability is reduced, and the photocatalytic water decomposition efficiency is improved.
Preferably, the inside surface or/and the outside surface of the hollow spherical zinc titanate is/are modified with a cocatalyst, wherein the cocatalyst modified on the inside surface is platinum, and the cocatalyst modified on the outside surface is rhodium oxide. Namely, the hollow spherical catalyst of the present invention comprises four forms: pure zinc titanate, zinc titanate with only platinum modified on the inside, zinc titanate with only rhodium oxide modified on the outside, and zinc titanate with platinum modified on the inside and rhodium oxide modified on the outside. Platinum is favorable for collecting electrons as a reduction promoter, rhodium oxide is favorable for collecting holes as an oxidation promoter, and separation modification of the promoters greatly promotes the flow of electron holes to different directions and reduces the recombination rate. The hydrogen production rate also corresponds to that: the hydrogen production performance of the zinc titanate of the internal and external modified cocatalyst is superior to that of single-side modified zinc titanate, and the single-side modified zinc titanate is superior to that of pure zinc titanate.
A preparation method of the hollow spherical photocatalyst comprises the following steps:
(1) placing the carbon spheres in an ammonia atmosphere, and performing high-temperature treatment to obtain ammoniated carbon spheres;
(2) dissolving zinc acetate dihydrate in N, N-dimethylformamide, stirring, then adding tetrabutyl titanate and absolute ethyl alcohol, and stirring until a transparent solution is obtained;
(3) and (3) soaking the aminated carbon sphere obtained in the step (1) in the transparent solution obtained in the step (2), performing ultrasonic treatment, then stirring, centrifuging, cleaning, drying and calcining to obtain the hollow spherical photocatalyst.
Preferably, the temperature of the high-temperature treatment of the carbon spheres in the ammonia atmosphere is not less than 300 ℃, and the time is 2-5 h. After the carbon spheres are subjected to anhua reaction, amino groups are formed on the surfaces of the carbon spheres, the coordination capacity of the amino groups is higher than that of carboxyl groups, and the carboxyl groups on the carbon spheres are substituted by the amino groups through ammoniation, so that the coordination capacity is improved
Preferably, chloroplatinic acid is dropwise added on the surface of the ammoniated carbon sphere, and then the mixture is dried and treated at a high temperature of more than or equal to 300 ℃ for 2-5 hours in an ammonia atmosphere, so that the hollow spherical photocatalyst with the cocatalyst modified on the inner surface is finally obtained.
Meanwhile, if rhodium trichloride is dripped on the outer surface of the hollow spherical photocatalyst of which the inner side surface is modified with the cocatalyst, the hollow spherical photocatalyst of which the inner side surface and the outer side surface are modified with the cocatalyst is obtained by drying and then carrying out high-temperature treatment at the temperature of more than or equal to 250 ℃ for 2-5 hours.
And (3) if rhodium trichloride is dripped on the outer surface of the hollow spherical photocatalyst of pure zinc titanate, drying, and then carrying out high-temperature treatment at the temperature of more than or equal to 250 ℃ for 2-5 h to finally obtain the hollow spherical photocatalyst with the outer surface modified with the cocatalyst.
The molar ratio of the zinc acetate dihydrate to tetrabutyl titanate is 1: 1.
And (3) carrying out ultrasonic treatment for 20-50 min, wherein the calcination sequentially comprises two stages of air atmosphere calcination and ammonia atmosphere calcination, the temperature of the air atmosphere calcination is 450-550 ℃, the calcination time is 3-6 h, the temperature of the ammonia atmosphere calcination is 600-650 ℃, and the calcination time is 2-3 h. The un-ammoniated sample has only ultraviolet light catalytic hydrogen production performance, and after 600-degree ammoniation treatment, the sample has visible light photocatalytic hydrogen production performance.
The application of the hollow spherical photocatalyst is used for preparing hydrogen by water photocatalysis, and sodium sulfite is used as a sacrificial agent. Under the irradiation of light, photoexcited electrons and holes are generated, the holes are consumed by the sacrificial agent, and the electrons reduce water to generate hydrogen.
Compared with the prior art, the invention has the beneficial effects that: the ammoniation of the carbon spheres improves the coordination capacity of the carbon spheres, increases the adsorption capacity to zinc ions, and prepares pure-phase zinc titanate ZnTiO3The hollow structure of the internally and externally modified cocatalyst is favorably expanded to other series of multi-component compounds, the photocatalytic hydrogen production rate is greatly improved, and the application of the photocatalytic material with the structure is promoted.
Drawings
FIG. 1 is an XRD pattern of the product of example 1;
FIG. 2 is an XRD pattern of the product of example 2;
FIG. 3 is an XRD pattern of the product of example 3;
FIG. 4 is a SEM image of a product of example 1;
FIG. 5 is a SEM image of a product of example 2;
FIG. 6 is a TEM image of the product of example 2;
FIG. 7 is a SEM image of a product obtained in example 3;
FIG. 8 is a high resolution TEM image of the product of example 5;
FIG. 9 is a graph of the photocatalytic hydrogen production rate by visible light (λ ≥ 400nm) for the products of examples 2-5;
FIG. 10 is a graph of the photocatalytic hydrogen production rate of the mercury lamp of example 1 and example 7 by means of total spectrum.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
Adding 6g of glucose into 60ml of water, carrying out hydrothermal reaction for 24 hours at 180 ℃, cleaning and drying to obtain the conventional carbon spheres. The obtained conventional carbon spheres were treated at 300 ℃ for 2 hours under an ammonia atmosphere. Zinc acetate dihydrate (0.2217g, AR) was dissolved in N, N-dimethylformamide (50ml, AR), after stirring for several minutes, tetrabutyl titanate (0.3438g, 99%) and absolute ethanol (50ml, AR) were added, the solution became transparent after stirring for several hours, then the above-mentioned aminated carbon spheres (0.35g) were added to the transparent solution, dispersed by ultrasound for about half an hour, after stirring for several hours, centrifuged and washed once with absolute ethanol, and dried at about 80 ℃. Then calcined at 500 ℃ for 5 hours to give a white sample.
The XRD test and the electron microscope scan of the sample were carried out, and the results are shown in fig. 1 and fig. 4, respectively, from which we can see that the sample is pure phase zinc titanate and has a spherical structure.
Example 2
Adding 6g of glucose into 60ml of water, carrying out hydrothermal reaction for 24 hours at 180 ℃, cleaning and drying to obtain the conventional carbon spheres. The obtained conventional carbon spheres were treated at 300 ℃ for 5 hours under an ammonia atmosphere. Zinc acetate dihydrate (0.2217g, AR) was dissolved in N, N-dimethylformamide (50ml, AR), after stirring for several minutes, tetrabutyl titanate (0.3438g, 99%) and absolute ethanol (50ml, AR) were added, the solution became transparent after stirring for several hours, then the above-mentioned aminated carbon spheres (0.35g) were added to the transparent solution, dispersed by ultrasound for about half an hour, after stirring for several hours, centrifuged and washed once with absolute ethanol, and dried at about 80 ℃. Then calcined at 500 ℃ for 5 hours. The obtained sample was calcined at 600 ℃ for 2 hours in an ammonia atmosphere to obtain a yellow sample.
The XRD test, the electron microscope scanning and the transmission electron microscope scanning are carried out on the sample, the obtained results are respectively shown in figure 2, figure 5 and figure 6, and the sample is pure-phase zinc titanate and has a hollow spherical structure.
Example 3
Adding 6g of glucose into 60ml of water, carrying out hydrothermal reaction for 24 hours at 180 ℃, cleaning and drying to obtain the conventional carbon spheres. The obtained conventional carbon spheres were treated at 300 ℃ for 3 hours under an ammonia atmosphere. And adding 0.35g of the aminated carbon ball into 500 mul of chloroplatinic acid solution (1mg/ml) and 4ml of deionized water, drying after ultrasonic dispersion, and calcining for 2 hours at 300 ℃ in an ammonia atmosphere to obtain the aminated carbon ball deposited with the Pt nanocluster. Zinc acetate dihydrate (0.2217g, AR) was dissolved in N, N-dimethylformamide (50ml, AR), after stirring for several minutes, tetrabutyl titanate (0.3438g, 99%) and absolute ethanol (50ml, AR) were added, the solution became transparent after stirring for several hours, then the above-mentioned aminated carbon spheres with deposited Pt nanoclusters were added to the transparent solution, dispersed by ultrasound for about half an hour, after stirring for several hours, centrifuged and washed once with absolute ethanol, and dried at about 80 ℃. Then calcined at 500 ℃ for 5 hours. And calcining the obtained sample at 600 ℃ for 2 hours in an ammonia atmosphere to obtain a yellow sample internally deposited with the cocatalyst.
The XRD test and the electron microscope scan were performed on the sample, and the results are shown in fig. 3 and fig. 7, respectively, from which we can see that the sample has a spherical structure.
Example 4
Adding 6g of glucose into 60ml of water, carrying out hydrothermal reaction for 24 hours at 180 ℃, cleaning and drying to obtain the conventional carbon spheres. The obtained conventional carbon spheres were treated at 300 ℃ for 3 hours under an ammonia atmosphere. Zinc acetate dihydrate (0.2217g, AR) was dissolved in N, N-dimethylformamide (50ml, AR), after stirring for several minutes, tetrabutyl titanate (0.3438g, 99%) and absolute ethanol (50ml, AR) were added, the solution became transparent after stirring for several hours, then the above-mentioned aminated carbon spheres (0.35g) were added to the transparent solution, dispersed by ultrasound for about half an hour, after stirring for several hours, centrifuged and washed once with absolute ethanol, and dried at about 80 ℃. Then calcined at 500 ℃ for 5 hours. The obtained sample was calcined at 600 ℃ for 2 hours in an ammonia atmosphere to obtain a yellow sample. 1ml of rhodium trichloride solution (1mg/ml) was added to the obtained yellow sample, and after ultrasonic dispersion and drying, heating was carried out at 250 ℃ for two hours to obtain a yellow sample with an external deposited cocatalyst.
Example 5
Adding 6g of glucose into 60ml of water, carrying out hydrothermal reaction for 24 hours at 180 ℃, cleaning and drying to obtain the conventional carbon spheres. The obtained conventional carbon spheres were treated at 300 ℃ for 3 hours under an ammonia atmosphere. And adding 0.35g of the aminated carbon ball into 500 mul of chloroplatinic acid solution (1mg/ml) and 4ml of deionized water, drying after ultrasonic dispersion, and calcining for 1 hour at 300 ℃ in an ammonia atmosphere to obtain the aminated carbon ball deposited with the Pt nanocluster. Zinc acetate dihydrate (0.2217g, AR) was dissolved in N, N-dimethylformamide (50ml, AR), after stirring for several minutes, tetrabutyl titanate (0.3438g, 99%) and absolute ethanol (50ml, AR) were added, the solution became transparent after stirring for several hours, then the above-mentioned aminated carbon spheres with deposited Pt nanoclusters were added to the transparent solution, dispersed by ultrasound for about half an hour, after stirring for several hours, centrifuged and washed once with absolute ethanol, and dried at about 80 ℃. Then calcined at 500 ℃ for 5 hours. The obtained sample was calcined at 600 ℃ for 2 hours in an ammonia atmosphere to obtain a yellow sample. 1ml of rhodium trichloride solution (1mg/ml) was added to the obtained yellow sample, and after ultrasonic dispersion and drying, the mixture was heated at 250 ℃ for two hours to obtain yellow samples of the internal and external deposition promoters.
The sample is scanned by a high-resolution transmission electron microscope, the obtained results are respectively shown in fig. 8, and we can see that the inside and the outside of the hollow spherical shell are both beneficial to catalyst modification.
The samples obtained in the embodiments 2 to 5 are applied to photocatalytic water decomposition to prepare hydrogen, and the reaction conditions are as follows: the 10mg sample is added into 100mL water, sodium sulfite is used as a sacrificial agent, and the hydrogen production rate is researched under the illumination of visible light, and the obtained result is shown in figure 9, and it can be seen from the figure that the hydrogen production rate of the inside and outside modified cocatalyst zinc titanate is superior to that of the single-side modified zinc titanate, and the single-side modified zinc titanate is superior to that of the unmodified zinc titanate.
Comparative example 1
Preparation of non-spherical zinc titanate: zinc acetate dihydrate (0.2217g, AR) was dissolved in N, N-dimethylformamide (50ml, AR), stirred for several minutes, then tetrabutyl titanate (0.3438g, 99%) and absolute ethanol (50ml, AR) were added, stirred for several hours, the solution became transparent, stirred and dried, then calcined at 500 ℃ for 5 hours, and washed with dilute hydrochloric acid to give a white sample. The samples obtained in example 1 and example 7 were applied to photocatalytic water splitting for hydrogen production under the following reaction conditions: the result of the study on the hydrogen production rate under the full spectrum irradiation of the mercury lamp by adding 10mg of the sample into 100mL of water and using sodium sulfite as a sacrificial agent is shown in FIG. 10, and it can be seen from the figure that the hydrogen production rate of the spherical zinc titanate is far superior to that of the non-spherical zinc titanate.
Example 6
Adding 6g of glucose into 60ml of water, carrying out hydrothermal reaction for 24 hours at 180 ℃, cleaning and drying to obtain the conventional carbon spheres. The obtained conventional carbon spheres were treated at 300 ℃ for 3 hours under an ammonia atmosphere. And adding 0.35g of the aminated carbon ball into 1ml of chloroplatinic acid solution (1mg/ml) and 4ml of deionized water, drying after ultrasonic dispersion, and calcining for 1 hour at 300 ℃ in an ammonia atmosphere to obtain the aminated carbon ball deposited with the Pt nanocluster. Zinc acetate dihydrate (0.2217g, AR) was dissolved in N, N-dimethylformamide (50ml, AR), after stirring for several minutes, tetrabutyl titanate (0.3438g, 99%) and absolute ethanol (50ml, AR) were added, the solution became transparent after stirring for several hours, then the above-mentioned aminated carbon spheres with deposited Pt nanoclusters were added to the transparent solution, dispersed by ultrasound for about half an hour, after stirring for several hours, centrifuged and washed once with absolute ethanol, and dried at about 80 ℃. Then calcined at 500 ℃ for 5 hours. The obtained sample was calcined at 600 ℃ for 2 hours in an ammonia atmosphere to obtain a yellow sample. 1ml of rhodium trichloride solution (1mg/ml) was added to the obtained yellow sample, and after ultrasonic dispersion and drying, the mixture was heated at 300 ℃ for two hours to obtain yellow samples of the internal and external deposition promoters.
Claims (8)
1. A preparation method of a hollow spherical photocatalyst is characterized by comprising the following steps:
(1) placing the carbon spheres in an ammonia atmosphere, and performing high-temperature treatment to obtain ammoniated carbon spheres; the temperature of the high-temperature treatment of the carbon spheres in the ammonia atmosphere is not less than 300 ℃, and the time is 2-5 h;
(2) dissolving zinc acetate dihydrate in N, N-dimethylformamide, stirring, then adding tetrabutyl titanate and absolute ethyl alcohol, and stirring until a transparent solution is obtained; the molar ratio of the zinc acetate dihydrate to tetrabutyl titanate is 1: 1;
(3) and (3) soaking the aminated carbon spheres obtained in the step (1) in the transparent solution obtained in the step (2), performing ultrasonic treatment, then stirring, centrifuging, cleaning, drying and calcining to obtain the hollow spherical zinc titanate.
2. The preparation method of the hollow spherical photocatalyst according to claim 1, wherein chloroplatinic acid is dropwise added on the surface of the aminated carbon sphere, and after dropwise addition, the hollow spherical photocatalyst is dried and then treated at a high temperature of not less than 300 ℃ for 2-5 hours in an ammonia atmosphere, so that the hollow spherical photocatalyst with the cocatalyst modified on the inner surface is finally obtained.
3. The preparation method of the hollow spherical photocatalyst according to claim 2, characterized in that rhodium trichloride is dripped on the outer surface of the hollow spherical photocatalyst with the cocatalyst modified on the inner side surface, and after drying, the hollow spherical photocatalyst with the cocatalyst modified on the inner side surface and the outer side surface is obtained by high-temperature treatment at a temperature of more than or equal to 250 ℃ for 2-5 h.
4. The preparation method of the hollow spherical photocatalyst according to claim 1, characterized in that rhodium trichloride is dripped on the outer surface of the hollow spherical photocatalyst, and after drying, the hollow spherical photocatalyst is treated at a temperature of not less than 250 ℃ for 2-5 h to finally obtain the hollow spherical photocatalyst with the cocatalyst modified on the outer surface.
5. The method for preparing a hollow spherical photocatalyst according to claim 1, wherein the time of the ultrasound in step (3) is 20-50 min, the calcination sequentially comprises two stages of air atmosphere calcination and ammonia atmosphere calcination, the air atmosphere calcination temperature is 450-550 ℃, the calcination time is 3-6 h, the ammonia atmosphere calcination temperature is 600-650 ℃, and the calcination time is 2-3 h.
6. A hollow sphere photocatalyst prepared by the method of any one of claims 1 to 5.
7. The hollow spherical photocatalyst according to claim 6, wherein the inside surface or/and the outside surface of the hollow spherical zinc titanate is modified with a co-catalyst, wherein the co-catalyst for the inside surface modification is platinum and the co-catalyst for the outside surface modification is rhodium oxide.
8. Use of a hollow sphere photocatalyst as claimed in claim 6 or 7, wherein the catalyst is used for the photocatalytic production of hydrogen from water, using sodium sulfite as a sacrificial agent.
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