CN108686697B - Alginate-based composite carbon nitride photocatalytic aerogel material and preparation method and application thereof - Google Patents
Alginate-based composite carbon nitride photocatalytic aerogel material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 59
- 239000004964 aerogel Substances 0.000 title claims abstract description 45
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229940072056 alginate Drugs 0.000 title claims abstract description 41
- 235000010443 alginic acid Nutrition 0.000 title claims abstract description 41
- 229920000615 alginic acid Polymers 0.000 title claims abstract description 41
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims description 10
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title description 4
- 239000000243 solution Substances 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 26
- 238000004108 freeze drying Methods 0.000 claims abstract description 25
- 239000011259 mixed solution Substances 0.000 claims abstract description 21
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 8
- 239000000919 ceramic Substances 0.000 claims description 21
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- 238000007710 freezing Methods 0.000 claims description 13
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- 238000000605 extraction Methods 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 10
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 9
- 239000002135 nanosheet Substances 0.000 claims description 9
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- 239000000661 sodium alginate Substances 0.000 claims description 9
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- 238000004519 manufacturing process Methods 0.000 claims description 8
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- 238000001035 drying Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine powder Natural products NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
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- MZYRDLHIWXQJCQ-YZOKENDUSA-L potassium alginate Chemical compound [K+].[K+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O MZYRDLHIWXQJCQ-YZOKENDUSA-L 0.000 claims description 3
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- HDSBZMRLPLPFLQ-UHFFFAOYSA-N Propylene glycol alginate Chemical compound OC1C(O)C(OC)OC(C(O)=O)C1OC1C(O)C(O)C(C)C(C(=O)OCC(C)O)O1 HDSBZMRLPLPFLQ-UHFFFAOYSA-N 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
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- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- AEMOLEFTQBMNLQ-AZLKCVHYSA-N (2r,3s,4s,5s,6r)-3,4,5,6-tetrahydroxyoxane-2-carboxylic acid Chemical compound O[C@@H]1O[C@@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H]1O AEMOLEFTQBMNLQ-AZLKCVHYSA-N 0.000 description 1
- AEMOLEFTQBMNLQ-SYJWYVCOSA-N (2s,3s,4s,5s,6r)-3,4,5,6-tetrahydroxyoxane-2-carboxylic acid Chemical compound O[C@@H]1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H]1O AEMOLEFTQBMNLQ-SYJWYVCOSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- B01J35/39—
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
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- C01B2203/1082—Composition of support materials
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses alginate-based composite g-C3N4A photocatalytic aerogel material is prepared by mixing a bulk phase g-C3N4Powder stripping to obtain two-dimensional nano flaky g-C3N4Then, uniformly dispersing the mixture in water by ultrasonic waves to prepare a suspension, adding soluble alginate, and pouring a mixed solution obtained after vigorous stirring into a mould for freeze drying; putting the freeze-dried block material into a curing agent solution for curing, and then further carrying out freeze drying to obtain the alginate-based composite g-C3N4A photocatalytic aerogel material. Alginate-based complex g-C prepared by the invention3N4The photocatalytic aerogel material has the advantages of good strength, low density, large specific surface area and good stability, has high-efficiency photocatalytic activity in a visible light region, and can be used for preparing hydrogen by photolyzing water.
Description
Technical Field
The invention belongs to the field of high-performance photocatalytic composite materials, and particularly relates to alginate-based composite g-C3N4Photocatalytic aerogel materials, and a preparation method and application thereof.
Background
In recent years, it has become possible to provide,with the development of the photocatalytic technology, the photocatalytic technology realized by solar energy has great application potential in the fields of environmental pollution purification and conversion of solar energy into chemical energy. Graphite phase carbon nitride (g-C)3N4) The organic semiconductor is an emerging organic semiconductor with visible light activity, and the special space electron cloud distribution and energy band structure of the organic semiconductor make the organic semiconductor show good catalytic activity for a plurality of important chemical reactions. Meanwhile, the photocatalyst has the advantages of low cost, no toxicity, stable performance and the like, and is gradually the focus in the field of photocatalysis. But g-C3N4In the specific photocatalysis process, certain unsatisfactory points exist, such as low utilization efficiency of sunlight, difficult protection, recovery and reuse, expensive nanofiltration technology and time-consuming separation process, which hinder the industrialization process of the g-C, so that the g-C is subjected to the photocatalysis process3N4The practical application of the photocatalyst in future environmental purification is greatly limited.
Aerogel (Aerogel) is a unique porous structure material due to its high porosity (greater than 90%), low density (0.003-0.5 g/cm)3) High light transmittance and low heat conductivity coefficient (0.0013-0.021W/m.k), and is mainly applied to military affairs, buildings, energy sources, environmental protection and the like. Functionally, aerogel materials are excellent supports for nano-photocatalytic materials. Alginate-based aerogel is prepared by taking alginate as a precursor and performing supercritical drying or freeze drying. Alginate is a natural polysaccharide extracted from brown algae, is a random block copolymer formed by connecting beta-D-mannuronic acid (M unit) and alpha-L-guluronic acid (G unit) through 1-4 glycosidic bonds, and has the excellent performances of rich sources, greenness, no toxicity, easy gelation, reproducibility, degradability, good biocompatibility and the like.
With the development of science and technology, the development trend of compounding multiple materials into new materials is realized, and the composite material with more excellent performance can be prepared by compounding two or more materials in function and mutually compensating and optimizing the performance. Due to the bulk phase g-C3N4Presence ratio tableThe invention has the advantages of small area, poor liquid phase dispersibility, high photoproduction electron hole recombination rate, influence on modification and recombination efficiency and the like, and the two-dimensional nano flaky g-C prepared by adopting the cell crushing method3N4Then two-dimensional nano-sheet g-C is put3N4The composite material is compounded with a natural polysaccharide-based aerogel material to prepare the photocatalytic composite material which has the advantages of high specific surface area, high porosity, strong water resistance, easy molding, easy recovery, good adsorption performance and high visible light catalytic hydrogen generation performance, and has great significance and value.
Disclosure of Invention
Aiming at the problems and defects existing in the application process of the existing nano photocatalytic material, the invention provides the alginate-based composite g-C which has simple process, low production cost, higher stability and photocatalytic activity3N4Photocatalytic aerogel materials, and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
alginate-based composite g-C3N4The preparation method of the photocatalytic aerogel material comprises the following steps:
a) putting melamine powder into a ceramic crucible, covering the ceramic crucible with a cover, putting the ceramic crucible into a muffle furnace, heating to 550 ℃ at the speed of 5 ℃/min, preserving heat for 4 hours, and naturally cooling to obtain a yellow bulk phase g-C3N4Powder;
b) subjecting the bulk phase g-C obtained in step a)3N4Adding into ethanol solution, ultrasonically dispersing in cell pulverizer for 6 hr, centrifuging to remove un-peeled g-C3N4Freeze drying the obtained solution to obtain yellow two-dimensional nano flaky g-C3N4；
c) Subjecting the two-dimensional nano-sheet g-C obtained in the step b)3N4Uniformly dispersing the mixture in water by ultrasonic waves to obtain a suspension;
d) adding soluble alginate into the suspension, stirring vigorously to dissolve the soluble alginate completely, and continuing stirring for 1-4 hours to ensure that the solution is uniformly dispersed;
e) defoaming the mixed solution obtained in the step d), pouring the defoamed mixed solution into a mold, and performing freeze drying treatment to obtain a block material;
f) putting the obtained block material into a curing agent solution for curing, and further freeze-drying to obtain the alginate-based composite g-C3N4A photocatalytic aerogel material.
The concentration of the suspension obtained in the step c) is 0.001-5 g/L.
The concentration of the soluble alginate in the mixed solution in the step e) is 0.5-20 g/L; the soluble alginate comprises one or more of sodium alginate, potassium alginate and propylene glycol alginate.
And e) defoaming by adopting ultrasound in the step e), wherein the ultrasound time is 0-12 h, and the vacuum pumping time after the ultrasound is 0-12 h.
The concentration of the curing agent solution is 5-80 g/L; the curing agent is one or more of alkaline earth metal salts such as Ca and Ba, or trivalent metal salts such as Fe and Al.
The curing time is 1 min-48 h.
The freeze drying is carried out at the speed of 0.1-10 ℃/min, the temperature is reduced to-50 to-10 ℃, the freezing is carried out for 0.5-12 h, and then the drying is carried out for 6-72 h under the conditions of-15 to 25 ℃ and the vacuum degree of 1-2000 Pa.
The resulting alginate-based complex g-C3N4The photocatalytic aerogel material has better photocatalytic activity and can be used for preparing hydrogen by photolyzing water.
Compared with the prior art, the preparation method has the advantages of simple process, low cost, easily-controlled conditions, suitability for large-scale production and the like. In terms of preparation mechanism, the invention obtains the alginate-based aerogel material with higher strength by a stepwise curing method and realizes g-C3N4High dispersion and payload thereon. In performance, the alginate-based complex g-C is prepared3N4The aerogel material has the advantages of high porosity, large specific surface area, strong water resistance, easy molding and recovery, high-efficiency visible light photocatalytic hydrogen production performance, and wide application prospect in the field of clean energy development.
Drawings
FIG. 1 is a two-dimensional nanosheet g-C prepared in example 13N4An atomic force micrograph of (a);
FIG. 2 is the alginate-based complex g-C prepared in example 23N4A sample plot of aerogel material;
FIG. 3 alginate-based complex g-C prepared in example 23N4Scanning electron micrographs of aerogel materials, where a is hypo (100 fold) and B is hyper (10000 fold);
FIG. 4 is the alginate-based complex g-C prepared in examples 1-53N4The gas gel material photolyzes water to produce hydrogen under the irradiation of visible light;
FIG. 5 is the alginate-based complex g-C prepared in example 43N4The photocatalytic aerogel material photolyzes water to produce hydrogen under the irradiation of visible light and is recycled.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1 two-dimensional Nanoplastic g-C3N4Preparation of
a) Putting a certain amount of melamine powder into a ceramic crucible, covering the ceramic crucible with a cover, putting the ceramic crucible into a muffle furnace, heating to 550 ℃ at the speed of 5 ℃/min, preserving heat for 4h, and naturally cooling to obtain a yellow bulk phase g-C3N4Powder;
b) taking 1g of the bulk phase g-C obtained in step a)3N4Adding into 300mL of anhydrous ethanol, ultrasonically dispersing in a cell crusher for 6h, centrifuging to remove the un-peeled bulk phase g-C3N4Freeze drying the obtained solution to obtain yellow two-dimensional nano flaky g-C3N4；
FIG. 1 shows two-dimensional nanosheets g-C prepared in this example3N4Atomic force micrographs of (a).
Example 2
a) Will be fixedPutting melamine powder into a ceramic crucible, covering the ceramic crucible with a cover, putting the ceramic crucible into a muffle furnace, heating to 550 ℃ at the speed of 5 ℃/min, preserving heat for 4 hours, and naturally cooling to obtain a yellow bulk phase g-C3N4Powder;
b) taking 1g of the bulk phase g-C obtained in step a)3N4Adding into 300mL of anhydrous ethanol, ultrasonically dispersing in a cell crusher for 6h, centrifuging to remove the un-peeled bulk phase g-C3N4Freeze drying the obtained solution to obtain yellow two-dimensional nano flaky g-C3N4；
c) Weighing 0.05g of the two-dimensional nanosheet g-C obtained in step b)3N4Adding the suspension into 100mL of deionized water, mechanically stirring and ultrasonically dispersing for 1h to obtain suspension with the concentration of 0.5 g/L;
d) adding 1g of sodium alginate into the suspension under vigorous stirring, and stirring vigorously to dissolve completely, wherein the concentration of sodium alginate in the solution is 10g/L, and then continuing stirring for 1 hour;
e) carrying out ultrasonic defoaming and vacuum air extraction on the mixed solution obtained in the step d), wherein the ultrasonic time is 0.5h, and the air extraction time is 0.5h, so as to discharge gas dissolved in the mixed solution;
f) pouring the mixed solution after exhausting into a culture dish with the diameter of 90mm for freeze drying treatment, wherein the cooling rate is as follows: 1 ℃/min, freezing temperature: -30 ℃, freezing time: 2h, and then drying for 24h at the temperature of minus 5 ℃ and the vacuum degree of 200 Pa to obtain a block material;
g) putting the obtained block material into CaCl with the concentration of 20g/L2Solidifying in the solution for 30min, and further freeze drying to obtain alginate-based complex g-C3N4A photocatalytic aerogel material.
FIG. 2 shows alginate-based complex g-C prepared in this example3N4Sample plots of photocatalytic aerogel materials.
FIG. 3 shows alginate-based complex g-C prepared in this example3N4Scanning electron microscopy of photocatalytic aerogel materials. As can be seen from fig. 3, the prepared aerogel material has a porous structure and uniformly distributed pore channels; negative poleg-C carried on surface of aerogel material3N4Has a sheet structure, is uniformly dispersed and firmly adhered. The volume shrinkage of the obtained cured composite aerogel material is 15%, and the porosity is 98.2%.
Example 3
a) Putting a certain amount of melamine powder into a ceramic crucible, covering the ceramic crucible with a cover, putting the ceramic crucible into a muffle furnace, heating to 550 ℃ at the speed of 5 ℃/min, preserving heat for 4h, and naturally cooling to obtain a yellow bulk phase g-C3N4Powder;
b) taking 1g of the bulk phase g-C obtained in step a)3N4Adding into 300mL of anhydrous ethanol, ultrasonically dispersing in a cell crusher for 6h, centrifuging to remove the un-peeled bulk phase g-C3N4Freeze drying the obtained solution to obtain yellow two-dimensional nano flaky g-C3N4；
c) Weighing 0.1g of the two-dimensional nanosheet g-C obtained in step b)3N4Adding the suspension into 100mL of deionized water, mechanically stirring and ultrasonically dispersing for 4 hours to obtain suspension with the concentration of 1 g/L;
d) adding 0.15g of propylene glycol alginate into the suspension under vigorous stirring, stirring vigorously to dissolve completely, wherein the concentration of sodium alginate in the solution is 1.5g/L, and then continuing stirring for 1 hour;
e) carrying out ultrasonic defoaming and vacuum air extraction on the mixed solution obtained in the step d), wherein the ultrasonic time is 2 hours, and the air extraction time is 2 hours, so as to discharge gas dissolved in the mixed solution;
f) pouring the mixed solution after exhausting into a culture dish with the diameter of 90mm for freeze drying treatment, wherein the cooling rate is as follows: 1 ℃/min, freezing temperature: -30 ℃, freezing time: 2h, and then drying for 24h at the temperature of minus 5 ℃ and the vacuum degree of 200 Pa to obtain a block material;
g) the obtained bulk material was charged into BaCl at a concentration of 20g/L2Solidifying in the solution for 30min, and further freeze drying to obtain alginate-based complex g-C3N4A photocatalytic aerogel material. The volume shrinkage of the obtained cured composite aerogel material is 10.5%, and the porosity is 98.8%.
Example 4
a) Putting a certain amount of melamine powder into a ceramic crucible, covering the ceramic crucible with a cover, putting the ceramic crucible into a muffle furnace, heating to 550 ℃ at the speed of 5 ℃/min, preserving heat for 4h, and naturally cooling to obtain a yellow bulk phase g-C3N4Powder;
b) taking 1g of the bulk phase g-C obtained in step a)3N4Adding into 300mL of anhydrous ethanol, ultrasonically dispersing in a cell crusher for 6h, centrifuging to remove the un-peeled bulk phase g-C3N4Freeze drying the obtained solution to obtain yellow two-dimensional nano flaky g-C3N4；
c) Weighing 0.2g of the two-dimensional nanosheet g-C obtained in step b)3N4Adding the suspension into 100mL of deionized water, mechanically stirring and ultrasonically dispersing for 1h to obtain suspension with the concentration of 2 g/L;
d) adding 0.2g of potassium alginate into the suspension under vigorous stirring, and stirring vigorously to dissolve completely, wherein the concentration of sodium alginate in the solution is 2g/L, and then continuing stirring for 1 hour;
e) carrying out ultrasonic defoaming and vacuum air extraction on the mixed solution obtained in the step d), wherein the ultrasonic time is 3 hours, and the air extraction time is 3 hours, so as to discharge gas dissolved in the mixed solution;
f) pouring the mixed solution after exhausting into a culture dish with the diameter of 90mm for freeze drying treatment, wherein the cooling rate is as follows: 1 ℃/min, freezing temperature: -30 ℃, freezing time: 2h, and then drying for 24h at the temperature of minus 5 ℃ and the vacuum degree of 200 Pa to obtain a block material;
g) the obtained bulk material was charged into BaCl at a concentration of 30g/L2Solidifying in the solution for 1h, and further freeze drying to obtain alginate-based complex g-C3N4A photocatalytic aerogel material. The volume shrinkage of the obtained cured composite aerogel material is 8.96%, and the porosity is 97.5%.
Example 5
a) Putting a certain amount of melamine powder into a ceramic crucible, covering the ceramic crucible with a cover, putting the ceramic crucible into a muffle furnace, heating to 550 ℃ at the speed of 5 ℃/min, and preserving heat for 4hNaturally cooling to obtain a yellow phase g-C3N4Powder;
b) taking 1g of the bulk phase g-C obtained in step a)3N4Adding into 300mL of anhydrous ethanol, ultrasonically dispersing in a cell crusher for 6h, centrifuging to remove the un-peeled bulk phase g-C3N4Freeze drying the obtained solution to obtain yellow two-dimensional nano flaky g-C3N4；
c) Weighing 0.5g of the two-dimensional nanosheet g-C obtained in step b)3N4Adding the suspension into 100mL of deionized water, mechanically stirring and ultrasonically dispersing for 6h to obtain suspension with the concentration of 5 g/L;
d) adding 0.3g of propylene glycol alginate into the suspension under vigorous stirring, stirring vigorously to dissolve completely, wherein the concentration of sodium alginate in the solution is 3g/L, and then continuing stirring for 1 hour;
e) carrying out ultrasonic defoaming and vacuum air extraction on the mixed solution obtained in the step d), wherein the ultrasonic time is 2 hours, and the air extraction time is 2 hours, so as to discharge gas dissolved in the mixed solution;
f) pouring the mixed solution after exhausting into a culture dish with the diameter of 90mm for freeze drying treatment, wherein the cooling rate is as follows: 1 ℃/min, freezing temperature: -30 ℃, freezing time: 2h, and then drying for 24h at the temperature of minus 5 ℃ and the vacuum degree of 200 Pa to obtain a block material;
g) placing the obtained block material into BaCl2With Fe (NO)3)3Solidifying for 1h in 30g/L mixed solution prepared according to the mol ratio of 2:1, and further freeze-drying to obtain alginate-based composite g-C3N4A photocatalytic aerogel material. The volume shrinkage of the obtained cured composite aerogel material is 8.77%, and the porosity is 96.8%.
Comparative example blank alginate aerogel
a) Under vigorous stirring, 0.1g of sodium alginate is added into 100mL of deionized water, the mixture is vigorously stirred to be completely dissolved, the concentration of the sodium alginate in the solution is 1g/L, and then the stirring is continued for 1 hour;
b) carrying out ultrasonic defoaming and vacuum air extraction on the alginate solution obtained in the step a), wherein the ultrasonic time is 0.5h, and the air extraction time is 0.5h, so as to discharge dissolved gas in the mixed solution;
c) pouring the alginate solution after air exhaust into a culture dish with the diameter of 90mm for freeze drying treatment, wherein the cooling rate is as follows: 1 ℃/min, freezing temperature: -30 ℃, freezing time: 2h, and then drying for 24h at the temperature of minus 5 ℃ and the vacuum degree of 200 Pa to obtain a block material;
d) putting the obtained block material into CaCl with the concentration of 20g/L2Solidifying the solution for 30min, and further freeze-drying to obtain the alginate aerogel material. The volume shrinkage of the cured aerogel is 17.94%, and the porosity reaches 97.1%.
Example 6 preparation of Hydrogen by photolysis of Water with alginate-based composite g-C3N4 aerogel-Material catalyst
The reactants were placed in a cylindrical jacketed glass reactor of about 250 mL volume in the following proportions: alginate-based complex g-C3N4Aerogel material: methanol solution: deionized water =0.8 g: 20 ml: 100ml, coating vacuum grease at the interface of the reactor and the device for sealing, and stirring by a magnetic stirrer to uniformly mix the gas in the reaction system. Vacuumizing the system before reaction by a mechanical pump, turning off the system when the system is in a vacuum state, turning on a xenon lamp light source (300W xenon lamp and 420 nm optical filter), extracting gas at regular intervals, and quantitatively measuring H at different times by using a Shimadzu (GC-8A) gas chromatograph2The amount of (a) released.
For g-C prepared in examples 1-53N4Sample and alginate-based complex g-C3N4The photolytic water-hydrogen production performance of the photocatalytic aerogel material is characterized, and the result is shown in fig. 4. As can be seen in FIG. 4, g-C was prepared3N4Both the sample and the composite aerogel have certain photolysis water hydrogen production activity, and are compared with pure g-C3N4Sample (Hydrogen production rate 256. mu. mol. g)-1 h-1) g-C synthesized in example 53N4The composite aerogel material has the highest hydrogen production rate (up to 364 mu mol g)-1 h-1) And the catalyst is easy to recover.
The alginate base prepared in example 4 was complexed with g-C3N4The photocatalytic aerogel materials were subjected to cyclic photolysis experiments and the results are shown in figure 5. As can be seen from the figure, after 4 hours of light irradiation, alginate-based complex g-C3N4The photocatalytic hydrogen production rate of the photocatalytic aerogel material is 58.24 mu mol, and the photocatalytic aerogel material shows better stability in 3 times of cycle life.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (1)
1. Alginate-based composite g-C for hydrogen production by photolysis of water3N4Photocatalytic aerogel materials, characterized by: the preparation method comprises the following steps:
a) putting a certain amount of melamine powder into a ceramic crucible, covering the ceramic crucible with a cover, putting the ceramic crucible into a muffle furnace, heating to 550 ℃ at the speed of 5 ℃/min, preserving heat for 4h, and naturally cooling to obtain a yellow bulk phase g-C3N4Powder;
b) taking 1g of the bulk phase g-C obtained in step a)3N4Adding into 300mL of anhydrous ethanol, ultrasonically dispersing in a cell crusher for 6h, centrifuging to remove the un-peeled bulk phase g-C3N4Freeze drying the obtained solution to obtain yellow two-dimensional nano flaky g-C3N4；
c) Weighing 0.2g of the two-dimensional nanosheet g-C obtained in step b)3N4Adding the suspension into 100mL of deionized water, mechanically stirring and ultrasonically dispersing for 1h to obtain suspension with the concentration of 2 g/L;
d) adding 0.2g of potassium alginate into the suspension under vigorous stirring, and stirring vigorously to dissolve completely, wherein the concentration of sodium alginate in the solution is 2g/L, and then continuing stirring for 1 hour;
e) carrying out ultrasonic defoaming and vacuum air extraction on the mixed solution obtained in the step d), wherein the ultrasonic time is 3 hours, and the air extraction time is 3 hours, so as to discharge gas dissolved in the mixed solution;
f) pouring the mixed solution after exhausting into a culture dish with the diameter of 90mm for freeze drying treatment, wherein the cooling rate is as follows: 1 ℃/min, freezing temperature: -30 ℃, freezing time: 2h, and then drying for 24h at the temperature of minus 5 ℃ and the vacuum degree of 200 Pa to obtain a block material;
g) the obtained bulk material was charged into BaCl at a concentration of 30g/L2Solidifying in the solution for 1h, and further freeze drying to obtain alginate-based complex g-C3N4A photocatalytic aerogel material;
the volume shrinkage of the obtained cured composite aerogel material is 8.96%, and the porosity is 97.5%.
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