CN110252374B - Graphite-phase carbon nitride-loaded porous silica gel particles, paper with same and preparation method of porous silica gel particles - Google Patents
Graphite-phase carbon nitride-loaded porous silica gel particles, paper with same and preparation method of porous silica gel particles Download PDFInfo
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- CN110252374B CN110252374B CN201910544137.6A CN201910544137A CN110252374B CN 110252374 B CN110252374 B CN 110252374B CN 201910544137 A CN201910544137 A CN 201910544137A CN 110252374 B CN110252374 B CN 110252374B
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 170
- 239000002245 particle Substances 0.000 title claims abstract description 107
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000000741 silica gel Substances 0.000 title claims abstract description 89
- 229910002027 silica gel Inorganic materials 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 27
- 239000010439 graphite Substances 0.000 claims abstract description 27
- 239000011148 porous material Substances 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 9
- 239000012071 phase Substances 0.000 claims description 85
- 239000000377 silicon dioxide Substances 0.000 claims description 43
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 229910052681 coesite Inorganic materials 0.000 claims description 25
- 229910052906 cristobalite Inorganic materials 0.000 claims description 25
- 229910052682 stishovite Inorganic materials 0.000 claims description 25
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- 238000003756 stirring Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 235000012239 silicon dioxide Nutrition 0.000 claims description 17
- 229920001131 Pulp (paper) Polymers 0.000 claims description 16
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- 238000004108 freeze drying Methods 0.000 claims description 13
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- 230000001699 photocatalysis Effects 0.000 abstract description 14
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- 239000012752 auxiliary agent Substances 0.000 abstract description 4
- 238000011160 research Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
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- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000003980 solgel method Methods 0.000 abstract description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 111
- 239000000243 solution Substances 0.000 description 20
- 238000007664 blowing Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
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- 239000000835 fiber Substances 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/18—Paper- or board-based structures for surface covering
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/06—Polluted air
Abstract
The invention discloses porous silica gel particles loaded with graphite-phase carbon nitride, paper with the porous silica gel particles and a preparation method of the paper, and belongs to the technical field of environmental catalysis. Mixing ethyl orthosilicate aqueous solution with g-C by adopting a sol-gel method3N4Mixing, and preparing to obtain the porous silica gel particles loaded with the graphite phase carbon nitride, wherein the porous silica gel particles have large specific surface area, controllable pore channel structure size and controllable auxiliary agent particle size. The preparation condition is mild, the process is simple, the raw materials are cheap, the repeatability is good, and the prepared material has good photocatalytic performance. When the photocatalyst is added into the decorative material, the catalytic efficiency of the photocatalytic material can be improved, and the research range of the photocatalytic material is widened.
Description
Technical Field
The invention belongs to the technical field of environmental catalysis, and particularly relates to porous silica gel particles loaded with graphite-phase carbon nitride, paper with the porous silica gel particles and a preparation method of the porous silica gel particles.
Background
The environmental pollution is a prominent problem faced by our country and the world, formaldehyde is colorless and gas with strong pungent smell, 37% aqueous solution of formaldehyde is called formalin, and the formaldehyde is commonly used for preserving specimens in medical and scientific research departments. In order to prevent the corrosion of interior decoration materials and furniture, the wood is also soaked in formaldehyde solution before processing so as to prevent the corrosion and damage of wood borers. The boiling point of the formaldehyde is 19.5 ℃, the formaldehyde is very easy to volatilize at room temperature, and the volatilization speed is accelerated along with the rise of the temperature. The second place listed in the priority control list of toxic chemicals in China, the toxic chemicals are determined to be carcinogenic and teratogenic substances by the world health organization. The formaldehyde in the synthetic boards used for interior decoration, such as plywood, blockboard, high-density board, shaving board, wooden furniture and other materials, acts as an adhesive and a preservative, and is released slowly into the room all the time, and the release amount is particularly prominent in the last years. How to effectively control the release of formaldehyde is a difficult point and research hotspot for solving the problem.
Graphite phase carbon nitride (g-C)3N4) As a non-metal photocatalyst, a photocatalytic hydrogen production reaction by water splitting is attracting attention because of its appropriate band gap (2.7eV) under visible light irradiation. In addition, the photocatalyst has the characteristics of good thermal stability and chemical stability, low price of raw materials and the like, and is widely applied to the field of photocatalytic water photolysis. g-C3N4The photocatalyst is a block photocatalytic material formed by stacking two-dimensional layered materials, and due to the special two-dimensional layered structure, the transfer resistance of excited electrons in a layer is small, and the resistance between layers is large, so that the activity of an edge position ((100) crystal face) is far higher than that of a ((002) crystal face) on a two-dimensional plane. The conventional powdered catalyst is fully mixed with reactants (such as hydrogen produced by photolysis of water, CO)2Reduction of NOxRemoval, etc.) can play a role in high-efficiency photocatalysis, but pure g-C3N4Due to its own powder properties, the formaldehyde released from the interior of the furniture cannot be controlled and completely degraded. Therefore, it is necessary to use a certain carrier as a skeleton structure for g-C3N4Dispersing uniformly and carrying out the photocatalytic degradation reaction of formaldehyde.
The traditional wallpaper is used as a framework carrier to disperse g-C due to poor air permeability3N4Not only can not enable overflowing formaldehyde molecules to smoothly penetrate through the wallpaper and g-C3N4The formaldehyde molecules can not be emitted for a long time due to the blockage of the pore channel structure by the catalyst, and the formaldehyde molecules still overflow for several years or even longer. The sponge can be used as a good carrier to uniformly disperse g-C due to good pore structure and mechanical strength3N4The formaldehyde is degraded, but as the pore channel structure in the sponge is too much and the pore diameter is too large, most of formaldehyde molecules are not adsorbed by the catalyst when overflowing, and are directly emitted indoors, and the formaldehyde removing effect is not good.
Thus, a mounting g-C was manufactured3N4The porous channel material is a problem to be solved at present.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention discloses porous silica gel particles loaded with graphite-phase carbon nitride, paper with the porous silica gel particles and a preparation method of the porous silica gel particles, the preparation conditions are mild, the process is simple, the raw materials are cheap, the repeatability is good, and the prepared material has good photocatalytic performance.
The invention is realized by the following technical scheme:
the invention discloses a preparation method of porous silica gel particles loaded with graphite-phase carbon nitride, which comprises the following steps:
step 1: respectively weighing the following materials in a liquid-to-solid ratio of (0.2-1.0): 100mL of g-C3N4And ethyl orthosilicate water solution, the ethyl orthosilicate water solution is placed in the dispersing agent and stirred, and then mixed with the mixture of g-C3N4Mixing to obtain reaction system A, and adding into the reaction body while continuously stirringAdding curing agent dropwise into the system A until the mixture is viscous, standing and aging to obtain SiO2/g-C3N4A gel system;
step 2: mixing SiO2/g-C3N4Freeze-drying the gel system to obtain porous silicon dioxide gel loaded with graphite phase carbon nitride;
and step 3: and (3) calcining the porous silica gel loaded with the graphite-phase carbon nitride obtained in the step (2) at the temperature of 450-650 ℃, and naturally cooling to room temperature to obtain porous silica gel particles loaded with the graphite-phase carbon nitride.
Preferably, the specific steps of step 1 are:
step 1.1: dispersing ethyl orthosilicate water solution into absolute ethyl alcohol, stirring for 30min, and mixing with g-C3N4Mixing and stirring uniformly to obtain a system A;
step 1.2: dripping the solution with the concentration less than 1mol L into the system A in the process of continuous stirring-1When the ammonia water is dripped, the previous drop of ammonia water is stirred and mixed evenly in the system A, then the next drop of ammonia water is dripped until the ammonia water is viscous, and SiO is obtained after standing and aging2/g-C3N4A gel system.
Further preferably, in step 2, before freeze-drying, the SiO is dissolved by using deionized water, an ethanol-miscible solvent or ethanol2/g-C3N4The liquid phase in the gel system is singulated.
Preferably, in step 2, the time for freezing to be solid during freeze drying is less than 1min, and the time for freeze drying is more than 20 h.
The invention also discloses porous silica gel particles loaded with graphite-phase carbon nitride, which are prepared by the preparation method and have the aperture of 20-30 nm.
The invention discloses a method for preparing paper by adopting the porous silica gel particles loaded with graphite-phase carbon nitride, which comprises the following steps:
step 1: sieving the porous silica gel particles loaded with graphite-phase carbon nitride, and screening out particles with uniform mass distribution for later use;
step 2: defibering base paper pulp according to the mass concentration of 0.5-5.0%, adding porous silica gel particles loaded with graphite-phase carbon nitride, and stirring until the porous silica gel particles loaded with graphite-phase carbon nitride are stably suspended in a solution to obtain a system B;
and step 3: and (3) making paper sheets by using the system B, and drying the obtained paper sheets under ventilation conditions to obtain the paper with the porous silica gel particles loaded with the graphite-phase carbon nitride.
Preferably, in step 1, the particle size obtained by sieving is 1 to 1.5 times of the paper thickness.
Preferably, in the step 2, the mass ratio of the porous silica gel particles loaded with graphite-phase carbon nitride to the raw paper pulp is (0.1-10): 100.
preferably, in the step 3, the drying temperature is 50-80 ℃, the drying time is more than 24 hours, and the ventilation air volume is more than 2.0m3/min。
The invention also discloses paper with porous silica gel particles loaded with graphite-phase carbon nitride, which is prepared by the method for preparing the paper.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention discloses a preparation method of porous silicon dioxide gel particles loaded with graphite-phase carbon nitride, which adopts a sol-gel method to mix tetraethoxysilane aqueous solution with g-C3N4And mixing to prepare the porous silica gel particles loaded with the graphite phase carbon nitride. High-temperature calcination can ensure g-C3N4In SiO2Stability in the pore channels, removal of substances which are easy to decompose and block the pore channels, ensuring SiO2The cell structure of (2) is not plugged. SiO 22The aerogel is a porous solid material formed by mutually coalescing nano particles, has the advantages of low density, high porosity, uniform pore distribution, good light transmittance and the like, can provide a specific pore channel structure, realizes the control of the diffusion rate of formaldehyde in the pore channel, and enables the carried photocatalyst g-C3N4Can effectively oxidize formaldehyde into nontoxic harmless formic acid or reduce the formaldehyde into methanol with less harm, and the energy source of the formaldehyde is diffuseThe sunlight entering the room is reflected without additional energy supply. Furthermore, g-C3N4The photocatalyst has rich nitrogen active sites, can not be consumed in the formaldehyde removing process, can ensure the continuous and high-efficiency utilization of the nitrogen active sites, and can continuously treat overflowed formaldehyde molecules. Theoretically, the photocatalytic formaldehyde removal performance can ensure that the formaldehyde release amount is still effective within five years (the maximum formaldehyde release amount) as long as the pore structure of the silica is not blocked. The method has the advantages of mild preparation conditions, simple process, cheap raw materials and good repeatability.
Further, the concentration is less than 1mol L-1The ammonia water is used as a curing agent, the reaction is rapid, and the reaction rate controllability is good; and the last drop of ammonia water is ensured to be fully stirred and uniformly mixed in the reaction system A during the dropping, and then the next drop of ammonia water is dropped, so that the ammonia water can be uniformly dispersed in the solution, the cross-linking rate of the ethyl orthosilicate is the same, and the pore structure of the silicon dioxide after cross-linking is ensured to be uniform.
Furthermore, the freeze drying time is more than 20h, the moisture in the pore channels can be ensured to be completely volatilized, and SiO can not be blocked2The pore structure of (1).
Further, before freeze-drying, the liquid phase in the system comprises the residual water and unreacted ethanol, and the SiO is prepared by using deionized water, ethanol-miscible solvent or ethanol2/g-C3N4The liquid phase in the gel system is simplified, so that the pore size of the obtained silicon dioxide is ensured to be relatively uniform, otherwise, the system contains a dispersing agent and a polymerization reaction product, the surface energy is different, and the pore size and the particle size distribution are not uniform.
The porous silica gel particles loaded with graphite-phase carbon nitride, which are obtained by the preparation method, have the advantages of large specific surface area, controllable pore structure size and controllable particle size of the auxiliary agent. When the photocatalyst is added into the decorative material, the catalytic efficiency of the photocatalytic material can be improved, and the research range of the photocatalytic material is widened.
The invention discloses a preparation method of paper of porous silica gel particles loaded with graphite-phase carbon nitride, which comprises the steps of sieving the porous silica gel particles loaded with graphite-phase carbon nitride to obtain particles with approximate particle sizes, and removing a sample with too small or too large pore channels by adopting a blast screening method to ensure the integral air permeability of the subsequent obtained paper. And then the porous silicon dioxide gel particles are used as a paper assistant for papermaking, the prepared paper contains the porous silicon dioxide gel particles loaded with the graphite-phase carbon nitride, and formaldehyde can be photo-catalyzed by the graphite-phase carbon nitride when passing through the pore channel structure.
Furthermore, the particle size of the particles obtained by sieving is 1-1.5 times of the thickness of the paper, so that the porous silica gel particles loaded with the graphite-phase carbon nitride can penetrate through the paper, and a good ventilation effect is achieved. If the particle size is too large, the flatness of the paper is affected; if the particle size is too small, the pore structure of the porous silica is blocked, and the reaction rate is affected.
Furthermore, the mass ratio of the porous silica gel particles loaded with the graphite phase carbon nitride to the original paper pulp is (0.1-10): 100, the addition amount of the porous silica gel particles loaded with the graphite phase carbon nitride is too small to achieve the optimal catalytic performance, and the addition amount is too large to influence the strength of the paper.
Further, the drying temperature is 50-80 ℃, the drying time is more than 24 hours, and the ventilation air volume is more than 2.0m3And min, ensuring thorough drying, preventing the pore structure of the silica gel from being blocked by paper fibers, and avoiding influencing the formaldehyde passing performance due to process reasons.
The paper loaded with the porous silica gel particles of graphite-phase carbon nitride disclosed by the invention can be used as decorative materials such as wallpaper, decorative stickers and the like, and takes light which is diffusely reflected indoors as energy, so that formaldehyde molecules overflowing from furniture are loaded with g-C3N4The porous silica pore channels are treated by the photocatalyst, and the indoor air quality is solved from the source of formaldehyde overflow. The scheme does not need additional energy sources, and the used catalyst and carrier are non-toxic and harmless, so that the air quality is not reduced due to the introduction of the catalyst.
Drawings
In FIG. 1, a to e are the stones loaded with the materials obtained in examples 1 to 5, respectivelyA physical representation of a porous silica gel of ink phase carbon nitride; f is pure SiO2Physical picture of gel;
in FIG. 2, a to e are diagrams of the papers having porous silica gel particles supporting graphite-phase carbon nitride, which were obtained in examples 1 to 5, respectively; f is pure SiO2A physical diagram of the paper made by using the gel as an auxiliary agent;
FIG. 3 is an SEM image (200nm) of graphite phase carbon nitride-loaded porous silica gel particles obtained in example 1 of the present invention;
FIG. 4 is an SEM photograph (2 μm) of graphite phase carbon nitride-loaded porous silica gel particles obtained in example 1 of the present invention;
FIG. 5 is an SEM image (10 μm) of graphite phase carbon nitride-loaded porous silica gel particles obtained in example 1 of the present invention;
FIG. 6 is a graph showing photocatalytic formaldehyde removal performance curves for papers having porous silica gel particles supporting graphite-phase carbon nitride and papers having pure silica gel particles prepared in examples 1 to 5.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The preparation method of the porous silica gel particles loaded with graphite phase carbon nitride comprises the following steps:
example 1
Dispersing 100mL of ethyl orthosilicate aqueous solution into absolute ethyl alcohol at room temperature, stirring for 30min for full hydrolysis, and adding 0.2g of g-C3N4After being stirred evenly, the mixture is dripped into the mixture by drops with the concentration of less than 1mol L-1Continuously stirring the ammonia water for 1h until the solution becomes viscous, standing and aging, replacing absolute ethyl alcohol in the system by deionized water for multiple times, and pouring out the deionized water to obtain SiO2/g-C3N4A gel system. Mixing SiO2/g-C3N4The gel system is frozen into solid within 1min, and is frozen and dried for 20h, then is calcined for 2h in a muffle furnace at 550 ℃, and is naturally cooled to room temperature to obtain the porous silicon dioxide gel particles loaded with graphite phase carbon nitride.
Sieving the obtained porous silica gel particles loaded with graphite-phase carbon nitride, screening out silica microspheres with the particle size of 50 mu m and ensuring the uniform mass distribution of the silica microspheres. Defibering original paper pulp in a fiber standard defibering device according to the concentration of 1.5 percent, adding 5g of porous silica gel particles loaded with graphite phase carbon nitride into 100g of defibered paper pulp, stirring until the porous silica gel particles loaded with graphite phase carbon nitride are stably suspended in a solution, making paper by using the obtained suspension on a paper sample former, setting the thickness of the paper to be 40 mu m, drying the obtained paper at 50 ℃, and blowing air with the air volume of more than 2.0m under the condition of air blowing3Ventilating for more than 24h at/min to obtain the paper with the porous silica gel particles loaded with graphite-phase carbon nitride.
Example 2
Dispersing 100mL of ethyl orthosilicate aqueous solution into absolute ethyl alcohol at room temperature, stirring for 30min for full hydrolysis, and adding 0.4g of g-C3N4After being stirred evenly, the mixture is dripped into the mixture by drops with the concentration of less than 1mol L-1Continuously stirring the ammonia water for 1h until the solution becomes viscous, standing and aging, replacing absolute ethyl alcohol and water in the system by adopting methanol for multiple times, and pouring out the methanol to obtain SiO2/g-C3N4A gel system. Mixing SiO2/g-C3N4The gel system is frozen into solid within 1min, and is subjected to freeze drying for 21h, then is calcined for 2h at 550 ℃ in a muffle furnace, and is naturally cooled to room temperature to obtain the porous silicon dioxide gel particles loaded with graphite phase carbon nitride.
Sieving the obtained porous silica gel particles loaded with graphite-phase carbon nitride, screening out silica microspheres with the particle size of 50 mu m and ensuring the uniform mass distribution of the silica microspheres. Defibering original paper pulp in a fiber standard defibering device according to the concentration of 1.5 percent, adding 5g of porous silica gel particles loaded with graphite phase carbon nitride into 100g of defibered paper pulp, stirring until the porous silica gel particles loaded with graphite phase carbon nitride are stably suspended in a solution, making paper by using the obtained suspension on a paper sample former, setting the thickness of the paper to be 40 mu m, drying the obtained paper at 60 ℃, and blowing air with the air volume of more than 2.0m under the condition of air blowing3Ventilating for more than 24h at/min to obtain the paper with the porous silica gel particles loaded with graphite-phase carbon nitride.
Example 3
Dispersing 100mL of ethyl orthosilicate aqueous solution into absolute ethyl alcohol at room temperature, stirring for 30min for full hydrolysis, and adding 0.6g of g-C3N4After being stirred evenly, the mixture is dripped into the mixture by drops with the concentration of less than 1mol L-1Continuously stirring the ammonia water for 1h until the solution becomes viscous, standing and aging, replacing absolute ethyl alcohol in the system by deionized water for multiple times, and pouring out the deionized water to obtain SiO2/g-C3N4A gel system. Mixing SiO2/g-C3N4The gel system is frozen into solid within 1min, and is subjected to freeze drying for 22h, then is calcined for 2h at 550 ℃ in a muffle furnace, and is naturally cooled to room temperature to obtain the porous silicon dioxide gel particles loaded with graphite phase carbon nitride.
Sieving the obtained porous silica gel particles loaded with graphite-phase carbon nitride, screening out silica microspheres with the particle size of 50 mu m and ensuring the uniform mass distribution of the silica microspheres. Defibering original paper pulp in a fiber standard defibering device according to the concentration of 1.5 percent, adding 5g of porous silica gel particles loaded with graphite phase carbon nitride into 100g of defibered paper pulp, stirring until the porous silica gel particles loaded with graphite phase carbon nitride are stably suspended in a solution, making paper by using the obtained suspension on a paper sample former, setting the thickness of the paper to be 40 mu m, drying the obtained paper at 70 ℃, and blowing air with the air volume of more than 2.0m under the condition of air blowing3Ventilating for more than 24h at/min to obtain the paper with the porous silica gel particles loaded with graphite-phase carbon nitride.
Example 4
At room temperature, 100mL of ethyl orthosilicate water solution is dispersed into absolute ethyl alcohol, stirred for 30min for full hydrolysis, and then 0.8g of g-C is added3N4After being stirred evenly, the mixture is dripped into the mixture by drops with the concentration of less than 1mol L-1Continuously stirring the ammonia water for 1h until the solution becomes viscous, standing and aging, replacing water in the system with ethanol for multiple times, and pouring out the ethanol to obtain SiO2/g-C3N4A gel system. Mixing SiO2/g-C3N4The gel system is frozen into solid within 1min, and is frozen and dried for 20h, then is calcined for 2h in a muffle furnace at 450 ℃, and is naturally cooled to room temperature to obtain the porous silicon dioxide gel particles loaded with graphite phase carbon nitride.
Sieving the obtained porous silica gel particles loaded with graphite-phase carbon nitride, screening out silica microspheres with the particle size of 40 mu m and ensuring the uniform mass distribution of the silica microspheres. Defibering original paper pulp in a fiber standard defibering device according to the concentration of 0.5 percent, adding 3g of porous silica gel particles loaded with graphite phase carbon nitride into 100g of defibered paper pulp, stirring until the porous silica gel particles loaded with the graphite phase carbon nitride are stably suspended in the solution, making paper by using the obtained suspension on a paper sample former, setting the thickness of the paper to be 40 mu m, drying the obtained paper at 50 ℃, and blowing air with the air volume of more than 2.0m under the condition of air blowing3Ventilating for more than 24h at/min to obtain the paper with the porous silica gel particles loaded with graphite-phase carbon nitride.
Example 5
Dispersing 100mL of ethyl orthosilicate aqueous solution into absolute ethyl alcohol at room temperature, stirring for 30min for full hydrolysis, and adding 1.0g of g-C3N4After being stirred evenly, the mixture is dripped into the mixture by drops with the concentration of less than 1mol L-1Continuously stirring the ammonia water for 1h until the solution becomes viscous, standing and aging, replacing absolute ethyl alcohol in the system by deionized water for multiple times, and pouring out the deionized water to obtain SiO2/g-C3N4A gel system. Mixing SiO2/g-C3N4The gel system is frozen into solid within 1min, and is frozen and dried for 20h, then is calcined for 2h in a muffle furnace at 650 ℃, and is naturally cooled to room temperature to obtain the porous silicon dioxide gel particles loaded with graphite phase carbon nitride.
Sieving the obtained porous silica gel particles loaded with graphite-phase carbon nitride, screening out silica microspheres with the particle size of 60 mu m and ensuring the uniform mass distribution of the silica microspheres. Defibering original paper pulp in a fiber standard defibering device according to the concentration of 5.0 percent, adding 10g of porous silica gel particles loaded with graphite phase carbon nitride into 100g of defibered paper pulp, and stirring until the mixture is stirredSuspending porous silica gel particles loaded with graphite phase carbon nitride in solution stably, making paper from the obtained suspension on a paper pattern former, setting the thickness of the paper to be 50 μm, drying the obtained paper at 80 ℃, and blowing air with the air volume of more than 2.0m under the condition of air blast3Ventilating for more than 24h at/min to obtain the paper with the porous silica gel particles loaded with graphite-phase carbon nitride.
Example 6
Dispersing 100mL of ethyl orthosilicate aqueous solution into acetone at room temperature, stirring for 30min for sufficient hydrolysis, and adding 0.6g of g-C3N4After being stirred evenly, the mixture is dripped into the mixture by drops with the concentration of less than 1mol L-1Continuously stirring the ethylenediamine for 1h until the solution becomes viscous, standing and aging, replacing unreacted water in the system with acetone, and pouring off the acetone to obtain SiO2/g-C3N4A gel system. Mixing SiO2/g-C3N4And (3) quickly freezing the gel system, carrying out freeze drying for 20h, then calcining for 2h in a muffle furnace at 550 ℃, and naturally cooling to room temperature to obtain the porous silica gel particles loaded with graphite-phase carbon nitride.
Sieving the obtained porous silica gel particles loaded with graphite-phase carbon nitride, screening out silica microspheres with the particle size of 50 mu m and ensuring the uniform mass distribution of the silica microspheres. Defibering original paper pulp in a fiber standard defibering device according to the concentration of 1.5 percent, adding 0.1g of porous silica gel particles loaded with graphite-phase carbon nitride into 100g of defibered paper pulp, stirring until the porous silica gel particles loaded with graphite-phase carbon nitride are stably suspended in a solution, making paper by using the obtained suspension on a paper sample former, setting the thickness of the paper to be 30 mu m, drying the obtained paper at 50 ℃, and enabling the air volume to be more than 2.0m under the condition of air blowing3Ventilating for more than 24h at/min to obtain the paper with the porous silica gel particles loaded with graphite-phase carbon nitride.
In FIG. 1, a to e are diagrams of the porous silica gel loaded with graphite-phase carbon nitride obtained in examples 1 to 5, respectively, and f is pure SiO2The physical picture of the gel can be seen from the figure: pure SiO2The gel was white. Yellow g-C3N4The powder is uniformly dispersed in the solution after being added to form stable suspension, and the phenomenon of bottom precipitation does not occur after the gel is formed, which indicates that the photocatalyst g-C3N4Uniformly dispersed in SiO2In the gel.
In FIG. 2, a to e are physical diagrams of papers having porous silica gel particles supporting graphite-phase carbon nitride prepared in examples 1 to 5, respectively, and f is pure SiO2The physical picture of the paper made by using the gel as the auxiliary agent can be seen from the picture: prepared g-C with different loads3N4The color of the paper is gradually deepened, which shows that SiO is generated2/g-C3N4The particles are uniformly dispersed in the paper. Furthermore, with g-C3N4Increase in content of SiO2/g-C3N4The more uniform the particles are dispersed on the surface of the paper, the more favorable the formaldehyde molecules are diffused in the pore channels, and the processing capacity of the formaldehyde is enhanced.
FIGS. 3 to 5 are SEM images at 10 μm, 2 μm and 200nm of the porous silica gel particles supporting graphite-phase carbon nitride prepared in example 1, respectively, and it can be seen that: the magnification is 800 times, so that a plurality of pore channel structures exist in the silicon dioxide particles, the magnification is continued to 8000 times, and the g-C can be more clearly seen3N4The pore channel structure in the silicon dioxide is more obvious through the crosslinking of the silicon dioxide, and the size distribution of the pore channel is more obvious and is about 20-30nm when the amplification is continued by 25000 times.
FIG. 6 is a graph showing photocatalytic formaldehyde removal performance curves of the papers having porous silica gel particles supporting graphite-phase carbon nitride and the papers having pure silica gel particles prepared in examples 1 to 5, in which the initial concentration of formaldehyde is 100ppm and pure SiO is used2The paper sample made by the gel has little change of formaldehyde concentration before and after illumination, and is loaded with photocatalyst g-C3N4Then, the concentration of formaldehyde after illumination is greatly reduced to below 10ppm, which shows that the load is g-C3N4The photocatalytic formaldehyde removal performance of the wallpaper is excellent.
It is noted that the porous silica gel particles loaded with graphite phase carbon nitride prepared in the present invention can be added into any surface layer, including but not limited to: wallpaper, wall cloth, decorative stickers, woodwork veneers, finish paint and the like only need to be prepared by corresponding raw materials and process adjustment according to the preparation method of the paper loaded with the graphite-phase carbon nitride porous silica gel particles.
Claims (8)
1. A method for preparing paper by using porous silica gel particles loaded with graphite-phase carbon nitride is characterized by comprising the following steps:
step 1: respectively weighing the following materials in a liquid-to-solid ratio of (0.2-1.0): 100mL of g-C3N4And ethyl orthosilicate water solution, the ethyl orthosilicate water solution is placed in the dispersing agent and stirred, and then mixed with the mixture of g-C3N4Mixing to obtain a reaction system A, dropwise adding a curing agent into the reaction system A in the process of continuously stirring until the mixture is viscous, standing and aging to obtain SiO2/g-C3N4A gel system;
step 2: mixing SiO2/g-C3N4Freeze-drying the gel system to obtain porous silicon dioxide gel loaded with graphite phase carbon nitride;
and step 3: calcining the porous silica gel loaded with the graphite-phase carbon nitride obtained in the step 2 at 450-650 ℃, and naturally cooling to room temperature to obtain porous silica gel particles loaded with the graphite-phase carbon nitride, wherein the pore diameter of the porous silica gel particles is 20-30 nm;
and 4, step 4: sieving the porous silica gel particles loaded with graphite-phase carbon nitride, and screening out particles with uniform mass distribution for later use;
and 5: defibering base paper pulp according to the mass concentration of 0.5-5.0%, adding porous silica gel particles loaded with graphite-phase carbon nitride, and stirring until the porous silica gel particles loaded with graphite-phase carbon nitride are stably suspended in a solution to obtain a system B;
step 6: and (3) making paper sheets by using the system B, and drying the obtained paper sheets under ventilation conditions to obtain the paper with the porous silica gel particles loaded with the graphite-phase carbon nitride.
2. The method for producing paper using porous silica gel particles supporting graphite-phase carbon nitride according to claim 1, wherein the specific steps of step 1 are:
step 1.1: dispersing ethyl orthosilicate water solution into absolute ethyl alcohol, stirring for 30min, and mixing with g-C3N4Mixing and stirring uniformly to obtain a system A;
step 1.2: dripping the solution with the concentration less than 1mol L into the system A in the process of continuous stirring-1When the ammonia water is dripped, the previous drop of ammonia water is stirred and mixed evenly in the system A, then the next drop of ammonia water is dripped until the ammonia water is viscous, and SiO is obtained after standing and aging2/g-C3N4A gel system.
3. The method of preparing paper using porous silica gel particles loaded with graphite-phase carbon nitride according to claim 2, wherein in step 2, before freeze-drying, SiO is subjected to deionized water, an ethanol-miscible solvent or ethanol2/g-C3N4The liquid phase in the gel system is singulated.
4. The method of making paper using porous silica gel particles loaded with graphite-phase carbon nitride according to claim 1, wherein in step 2, the freeze-drying time for freezing to a solid is < 1min and the freeze-drying time is > 20 h.
5. The method for producing paper using porous silica gel particles supporting graphite-phase carbon nitride according to claim 1, wherein the particle size of the particles obtained by sieving in step 4 is 1 to 1.5 times the thickness of the paper.
6. The method for producing paper according to claim 1, wherein in the step 5, the mass ratio of the graphite-phase carbon nitride-loaded porous silica gel particles to the raw pulp is (0.1 to 10): 100.
7. the method for preparing paper using porous silica gel particles supporting graphite-phase carbon nitride according to claim 1, wherein in step 6, the drying temperature is 50 to 80 ℃, the drying time is longer than 24 hours, and the ventilation air volume is longer than 2.0m3/min。
8. Paper having porous silica gel particles supporting graphite-phase carbon nitride, produced by the production method according to any one of claims 1 to 7.
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