CN113398990A - Polyimide/cotton fiber hydrogen peroxide synthesis photocatalyst and preparation and application thereof - Google Patents
Polyimide/cotton fiber hydrogen peroxide synthesis photocatalyst and preparation and application thereof Download PDFInfo
- Publication number
- CN113398990A CN113398990A CN202110652694.7A CN202110652694A CN113398990A CN 113398990 A CN113398990 A CN 113398990A CN 202110652694 A CN202110652694 A CN 202110652694A CN 113398990 A CN113398990 A CN 113398990A
- Authority
- CN
- China
- Prior art keywords
- hydrogen peroxide
- polyimide
- cotton fiber
- photocatalyst
- polyamic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 176
- 229920000742 Cotton Polymers 0.000 title claims abstract description 104
- 239000004642 Polyimide Substances 0.000 title claims abstract description 74
- 229920001721 polyimide Polymers 0.000 title claims abstract description 74
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 70
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 39
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000011248 coating agent Substances 0.000 claims abstract description 21
- 238000000576 coating method Methods 0.000 claims abstract description 21
- 239000002105 nanoparticle Substances 0.000 claims abstract description 21
- 238000005286 illumination Methods 0.000 claims abstract description 19
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 238000002791 soaking Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 31
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 24
- 150000004985 diamines Chemical class 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- 239000002798 polar solvent Substances 0.000 claims description 6
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 5
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 5
- QHQSCKLPDVSEBJ-UHFFFAOYSA-N 1,3,5-tri(4-aminophenyl)benzene Chemical compound C1=CC(N)=CC=C1C1=CC(C=2C=CC(N)=CC=2)=CC(C=2C=CC(N)=CC=2)=C1 QHQSCKLPDVSEBJ-UHFFFAOYSA-N 0.000 claims description 3
- WHSQATVVMVBGNS-UHFFFAOYSA-N 4-[4,6-bis(4-aminophenyl)-1,3,5-triazin-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C1=NC(C=2C=CC(N)=CC=2)=NC(C=2C=CC(N)=CC=2)=N1 WHSQATVVMVBGNS-UHFFFAOYSA-N 0.000 claims description 3
- SNLFYGIUTYKKOE-UHFFFAOYSA-N 4-n,4-n-bis(4-aminophenyl)benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1N(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 SNLFYGIUTYKKOE-UHFFFAOYSA-N 0.000 claims description 3
- OPDZOUPGXXSCNF-UHFFFAOYSA-N anthracene-1,2,8,9-tetracarboxylic acid Chemical compound C1=CC=C(C(O)=O)C2=C(C(O)=O)C3=C(C(O)=O)C(C(=O)O)=CC=C3C=C21 OPDZOUPGXXSCNF-UHFFFAOYSA-N 0.000 claims description 3
- RPHKINMPYFJSCF-UHFFFAOYSA-N benzene-1,3,5-triamine Chemical compound NC1=CC(N)=CC(N)=C1 RPHKINMPYFJSCF-UHFFFAOYSA-N 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- BBYQSYQIKWRMOE-UHFFFAOYSA-N naphthalene-1,2,6,7-tetracarboxylic acid Chemical compound C1=C(C(O)=O)C(C(O)=O)=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 BBYQSYQIKWRMOE-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- BLYOXQBERINFDU-UHFFFAOYSA-N pyrene-1,8-diamine Chemical compound C1=C2C(N)=CC=C(C=C3)C2=C2C3=CC=C(N)C2=C1 BLYOXQBERINFDU-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 3
- 238000002834 transmittance Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000002253 acid Substances 0.000 description 28
- 239000004952 Polyamide Substances 0.000 description 27
- 229920002647 polyamide Polymers 0.000 description 27
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 230000005484 gravity Effects 0.000 description 11
- 238000001816 cooling Methods 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000004577 artificial photosynthesis Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical class N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- -1 anthraquinone compounds Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
- B01J35/58—Fabrics or filaments
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/027—Preparation from water
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a polyimide/cotton fiber hydrogen peroxide synthesis photocatalyst and preparation and application thereof, wherein the photocatalyst comprises cotton fibers and a polyimide nanoparticle coating loaded on the cotton fibers; the preparation method comprises the following steps: soaking cotton fibers in a polyamic acid solution, and carrying out closed-loop polymerization reaction to obtain a polyimide nano particle coating loaded on the cotton fibers; the photocatalyst is used for catalyzing water and oxygen to react under illumination to prepare hydrogen peroxide. Compared with the prior art, the photocatalyst has good activity and stability and good processability, can be used for efficiently catalyzing the reaction of water and oxygen under illumination to prepare hydrogen peroxide, has simple preparation process, is green, safe and low in cost, is easy to control, and can realize large-scale production.
Description
Technical Field
The invention belongs to the technical field of hydrogen peroxide continuous synthesis, and relates to a polyimide/cotton fiber hydrogen peroxide synthesis photocatalyst, and preparation and application thereof.
Background
Hydrogen peroxide is a very common and widely used chemical, and is often applied to the fields of bleaching, disinfection, chemical synthesis and the like; at the same time, it is also a very green reagent, since from an atomic point of view it releases only water and oxygen in use, hardly generating waste harmful to the environment, and requiring no secondary treatment. However, the synthesis of hydrogen peroxide is always a difficult problem in the chemical industry, and the most widely used industrial synthesis mode at present is to perform hydrogen catalytic hydrogenation on anthraquinone compounds, combine with subsequent oxygen oxidation, and obtain high-concentration hydrogen peroxide through an extraction tower and a concentration tower. The method relates to a step-by-step chemical reaction, which can not only fail to continuously produce, but also consume a large amount of unnecessary energy, and simultaneously discharge a large amount of organic solvent and acid waste liquid and use a large amount of noble metal catalysts. In addition, in the production process, the production atmosphere of oxygen and hydrogen is very dangerous, and has great potential safety hazard. The transportation cost can be reduced by concentrating the hydrogen peroxide to a high concentration (more than 40%), but the hydrogen peroxide is not needed in practical application (for example, the concentration of < 3% is needed for medical treatment and livestock disinfection), and the high-concentration hydrogen peroxide is very explosive, so that the transportation risk of hazardous chemicals is greatly increased.
In recent years, with research and development of various clean energy sources and requirements for sustainable development, many researchers focus on the aspect of converting solar energy into chemical energy, such as photocatalytic water splitting hydrogen production, photocatalytic nitrogen fixation, artificial photosynthesis and the like. Theoretically, under a proper catalytic system, water and oxygen can be converted into hydrogen peroxide by natural illumination, and the problem of hydrogen peroxide preparation can be well solved. At present, some catalysts for hydrogen peroxide photosynthesis have been developed, such as TiO2Series, graphite phase carbon nitride series.
Some extensively studied TiO2The series of hydrogen peroxide synthesis photocatalysts comprise Cu2+/TiO2、Au/TiO2、AuAg/TiO2The composite system of titanium dioxide and metal, the metal compound of which is taken as a catalyst, is necessarily accompanied with a series of environmental problems, particularly for the water environmental system. Moreover, if faced with mass production, the price cost is not dominant either. Graphite phase carbon nitride is used as a photocatalyst, and often needs the composite action of metal, and the material itself needs high temperature of more than 500 ℃ to be prepared, so that the application of the material is limited.The ideal hydrogen peroxide synthesis photocatalyst should have the following characteristics: 1. low cost and good processability. 2. Good stability and catalytic efficiency, and can maintain working performance for a long time under illumination. 3. No toxicity, no pollution and no harm to environment. However, the existing hydrogen peroxide synthesis photocatalyst still far does not meet the requirements.
If a material with excellent photocatalytic hydrogen peroxide production catalytic activity can be found from common non-metal organic semiconductor polymers, the synthesis method of the polymer material is simple and cheap, the industrial preparation conditions are mature, the stability is good, meanwhile, the continuous production of hydrogen peroxide under solar illumination can be realized through some chemical equipment and carrier designs, and the industrial production requirement is met, so that the development of the polymer hydrogen peroxide synthesis photocatalyst not only has important application in the fields of chemical industry, energy sources and the like, revolutionarily replaces the original production technology, but also provides a new idea for various artificial photosynthesis and conversion from solar energy to chemical energy.
Disclosure of Invention
The invention aims to provide a polyimide/cotton fiber hydrogen peroxide synthesis photocatalyst, and preparation and application thereof, and direct synthesis of hydrogen peroxide can be realized through a high-efficiency, low-cost and practical hydrogen peroxide synthesis photocatalyst.
The purpose of the invention can be realized by the following technical scheme:
the polyimide/cotton fiber hydrogen peroxide synthesis photocatalyst comprises cotton fibers and a polyimide nanoparticle coating loaded on the cotton fibers.
Further, every 2-5g of cotton fiber is loaded with 0.2-3g of polyimide nano particle coating.
The preparation method of the polyimide/cotton fiber hydrogen peroxide synthetic photocatalyst comprises the following steps: and soaking the cotton fiber in the polyamic acid solution, and performing closed-loop polymerization to obtain the polyimide nano-particle coating loaded on the cotton fiber.
Further, the method comprises the steps of:
1) preparation of a polyamic acid solution: dissolving a polyamic acid monomer in a polar solvent, and carrying out polymerization reaction to obtain a polyamic acid solution;
2) soaking cotton fiber in the polyamic acid solution and stirring uniformly;
3) and raising the temperature to perform closed-loop polymerization reaction on the polyamic acid on the surface of the cotton fiber so as to form a polyimide nano-particle coating on the surface of the cotton fiber.
Further, in step 1), the polyamic acid monomer includes diamine and dianhydride, the diamine includes one or more of 1, 4-phenylenediamine, 1,3, 5-benzenetriamine, 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, tris (4-aminophenyl) amine, 1,3, 5-tris (4-aminophenyl) benzene, diethylamine or 1, 8-pyrene diamine, the dianhydride comprises one or more of benzene-1, 2,4, 5-tetracarboxylic dianhydride, naphthalene-1, 2,6, 7-tetracarboxylic dianhydride or anthracene-1, 2,8, 9-tetracarboxylic dianhydride, the polar solvent comprises one or more of N, N-dimethylformamide, dimethyl sulfoxide or m-hydroxyphenol. Isoquinoline may be added as a catalyst to obtain a polyamic acid solution.
Further, in the step 2), the concentration of the polyamic acid solution is 0.2-3g/120mL, and the dosage ratio of the cotton fiber to the polyamic acid solution is 2-5 g/120 mL.
Further, in the step 3), in the ring-closing polymerization process, the reaction temperature is 120-300 ℃, and the reaction time is 8-72 hours. The polyamic acid is subjected to ring-closing polycondensation reaction on the surface of the cotton fiber to form a stable polyimide nano-particle coating on the surface of the cotton fiber.
The application of the polyimide/cotton fiber hydrogen peroxide to synthesize the photocatalyst is used for catalyzing water to react with oxygen under the illumination to prepare hydrogen peroxide.
A natural light continuous reaction device for preparing hydrogen peroxide is based on polyimide/cotton fiber hydrogen peroxide synthesis photocatalyst, the device include drip ware, reactor and the collector that communicates in proper order, the height of drip ware be greater than the height of reactor, the height of reactor be greater than the height of collector, photocatalyst place in the reactor. The device is a natural light continuous reaction device with zero additional energy consumption.
Further, the reactor comprises a container with an open top and a top cover arranged on the top of the container, wherein the top cover is an unsealed high-light-transmission top cover. The reactor is preferably a quartz/glass reactor.
In the invention, the photocatalyst is the combination of cotton fibers and a polyimide nano particle coating, wherein the polyimide nano particles have the activity of photocatalytic synthesis of hydrogen peroxide, and the structure of the polyimide can generate charge separation under the action of light excitation to form a hole-electron pair, thereby catalyzing the redox effect in the reaction. The polyimide of the present invention has excellent catalytic selectivity for the reaction of synthesizing hydrogen peroxide due to the intrinsic band structure. The cotton fiber does not have any activity of photocatalytic synthesis of the hydrogen peroxide, but has high whiteness, low light absorbance, good hydrophilicity, no decomposition effect on the hydrogen peroxide, and is a very ideal catalyst carrier, and the catalyst can be fixed in flowing water to avoid reaction loss. The photocatalyst has good property stability and processability, and the preparation process is simple, green, safe, low in cost, easy to control and capable of realizing large-scale production. And the continuous production of hydrogen peroxide under natural illumination can be realized by combining a natural light continuous reaction device with zero external energy consumption.
Compared with the prior art, the invention has the following characteristics:
1) the photocatalyst has good activity and stability and good processability, can be used for efficiently catalyzing the reaction of water and oxygen under illumination to prepare hydrogen peroxide, has simple preparation process, is green and safe, has low cost and easy control, and can realize large-scale production.
2) The natural light continuous reaction device adopts a gravity dropping mode, can realize continuous photocatalytic reaction with zero additional energy consumption by combining the photocatalyst and the reaction device, and has very wide application potential in a plurality of fields such as solar energy conversion, storage, hydrogen peroxide production and the like.
Drawings
FIG. 1 is a digital photograph of a polyimide/cotton fiber photocatalyst synthesized with hydrogen peroxide in example 1;
FIG. 2 is a scanning electron micrograph of the polyimide/cotton fiber photocatalyst synthesized with hydrogen peroxide obtained in example 1;
FIG. 3 is a TEM photograph of a polyimide/cotton fiber photocatalyst synthesized with hydrogen peroxide in example 1;
fig. 4 is a hydrogen peroxide generation curve diagram obtained by a 4-hour cycle test of the polyimide/cotton fiber hydrogen peroxide synthesis photocatalyst prepared in example 1 when the photocatalyst is used for preparing hydrogen peroxide;
fig. 5 is a graph showing the change of the concentration of hydrogen peroxide in a collector of a reaction apparatus with time when the polyimide/cotton fiber hydrogen peroxide synthesis photocatalyst prepared in example 1 is used for continuously preparing hydrogen peroxide;
FIG. 6 is a schematic view of the structure of a reaction apparatus in the present invention;
the notation in the figure is:
1-dropping liquid device, 2-reactor, 201-container, 202-top cover, 3-collector.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
The invention provides a polyimide/cotton fiber hydrogen peroxide synthesis photocatalyst, which comprises cotton fibers and a polyimide nanoparticle coating loaded on the cotton fibers.
Wherein, every 2 to 5g of cotton fiber is loaded with 0.2 to 3g of polyimide nano-particle coating. That is, the polyimide/cotton loading is 0.04 to 1.5g/g, preferably about 0.1 g/g.
The invention also provides a preparation method of the polyimide/cotton fiber hydrogen peroxide synthesis photocatalyst, which comprises the following steps: and soaking the cotton fiber in the polyamic acid solution, and performing closed-loop polymerization to obtain the polyimide nano-particle coating loaded on the cotton fiber.
The method comprises the following steps:
1) preparation of a polyamic acid solution: dissolving a polyamic acid monomer in a polar solvent, and carrying out polymerization reaction to obtain a polyamic acid solution;
2) soaking cotton fiber in the polyamic acid solution and stirring uniformly;
3) and raising the temperature to perform closed-loop polymerization reaction on the polyamic acid on the surface of the cotton fiber so as to form a polyimide nano-particle coating on the surface of the cotton fiber.
Wherein, in the step 1), the polyamic acid monomer comprises diamine and dianhydride, the diamine comprises 1, 4-phenylenediamine, 1,3, 5-benzenetriamine, 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine and tri (4-aminophenyl) amine, one or more of 1,3, 5-tris (4-aminophenyl) benzene, diethylamine or 1, 8-pyrenediamine, the dianhydride comprising one or more of benzene-1, 2,4, 5-tetracarboxylic dianhydride, naphthalene-1, 2,6, 7-tetracarboxylic dianhydride or anthracene-1, 2,8, 9-tetracarboxylic dianhydride, the polar solvent comprising one or more of N, N-dimethylformamide, dimethyl sulfoxide or m-hydroxyphenol. The polyamic acid monomer can be a precursor of the diamine and the dianhydride, an incomplete ring-closing polymer, and a modification of other functional groups on the molecular skeleton. The polyamic acid monomer is dissolved in a common high-polarity solvent, and is catalyzed by isoquinoline to form a polyamic acid solution (namely, a polyimide prepolymer) which is used as a coating liquid of cotton fibers.
In the step 2), the concentration of the polyamic acid solution is 0.2-3g/120mL, and the dosage ratio of the cotton fiber to the polyamic acid solution is 2-5 g/120 mL. Soaking cotton fibers with required weight in the polyamic acid solution, and mechanically stirring uniformly to ensure that the polyamic acid solution is absorbed and saturated by the cotton fibers. The cotton fibers can be various types of cotton fibers. The cotton fibers used in the following examples were purchased from medical absorbent cotton fibers for medical use, and were cut into small pieces for use as required.
In the step 3), the reaction temperature is 120-300 ℃ (preferably 120 ℃) during the ring-closing polymerization reaction, and the reaction time is 8-72 hours (preferably 16 hours). And heating the solution system soaked with the cotton fibers in the nitrogen atmosphere to perform high-temperature ring-closing polycondensation reaction, and forming a polyimide nanoparticle coating on the surface of the cotton fibers. And finally, naturally cooling, filtering, washing with ethanol and water to obtain the polyimide/cotton fiber hydrogen peroxide synthesis photocatalyst.
The invention also provides application of the polyimide/cotton fiber hydrogen peroxide synthesis photocatalyst, and the photocatalyst is used for catalyzing water and oxygen to react under illumination to prepare hydrogen peroxide.
The invention further provides a natural light continuous reaction device for preparing hydrogen peroxide, as shown in fig. 6, the device synthesizes the photocatalyst based on the polyimide/cotton fiber hydrogen peroxide, the device comprises a dropping device 1, a reactor 2 and a collector 3 which are sequentially communicated, the height of the dropping device 1 is larger than that of the reactor 2, the height of the reactor 2 is larger than that of the collector 3, and the photocatalyst is placed in the reactor 2. The reactor 2 comprises a vessel 201 with an open top and a top cover 202 arranged on top of the vessel 201, the top cover 202 being a non-sealed, highly light-transmitting top cover.
In the reaction device, firstly, the flow rate is controllable, the gravity dropping device can also be a dropping device driven by other energy, the flow rate can be controlled to be 20-2000mL/h, other various flow rates can also be adopted, and 100mL/h is preferred in the embodiment. The dropping device is connected with a glass/quartz reactor, the diameter of the reactor is preferably 30 cm in the embodiment, and the reactor can be in any other shape and thickness, the holding of the catalyst and the passing of water flow are mainly realized, and an unsealed high-light-transmittance photoreaction top cover is arranged on the upper part of the reactor, so that the air flow displacement and the light irradiation reaction system are realized. The water flow is received by a collector after reaction in the reactor, and the collector can be a container with any type to realize the collection and storage of the hydrogen peroxide solution.
In the following examples, the diamine is 1, 4-phenylenediamine and the dianhydride is benzene-1, 2,4, 5-tetracarboxylic dianhydride.
Example 1:
successively stirring and dissolving polyamide acid monomer diamine and dianhydride in a molar ratio of 1:1(0.01mol:0.01mol) in 120mL of N, N-dimethylformamide, adding a few drops of isoquinoline, stirring and reacting overnight to form polyamide acid solution, then placing cotton fiber (5g) with clean surface in the polyamide acid solution, mechanically stirring uniformly, then placing the reaction system under the protection of nitrogen flow, controlling the reaction temperature range to be 120 ℃, reacting for 16 hours, naturally cooling, filtering, washing with ethanol and water to obtain the polyimide/cotton fiber hydrogen peroxide synthesis photocatalyst, wherein the polyimide/cotton load is 0.6 g/g.
In this embodiment, the reaction formula of polyamic acid monomer (diamine is 1, 4-phenylenediamine, and dianhydride is benzene-1, 2,4, 5-tetracarboxylic dianhydride) to form polyamic acid, and then ring-closing polycondensation is performed to form polyimide is as follows:
fig. 1 is a digital photograph of the prepared polyimide/cotton fiber photocatalyst synthesized by hydrogen peroxide. As can be seen from FIG. 1, the polyimide nanoparticle coating is uniformly attached to the cotton fiber, and the process is stable.
FIG. 2 is a scanning electron micrograph of the prepared polyimide/cotton fiber photocatalyst synthesized by hydrogen peroxide. As can be seen from fig. 2, the polyimide nanoparticle coating is uniformly distributed on the cotton fiber.
FIG. 3 is a transmission electron micrograph of the prepared polyimide/cotton fiber photocatalyst synthesized by hydrogen peroxide. From FIG. 3, the distribution of the polyimide nanoparticle coating can be seen from the side view, and the particle size is about 200-800 nm.
20g of the photocatalyst is placed in a reactor in the figure 6, water is fully added, the flow rate of a gravity dropping device is adjusted to be 100mL/h, and the photocatalytic reaction is carried out to prepare hydrogen peroxide.
Fig. 4 is a hydrogen peroxide generation curve diagram obtained by a 4-hour cyclic test of the photocatalyst when the photocatalyst is used for preparing hydrogen peroxide. As can be seen from FIG. 4, the catalyst has stable reaction activity and can be repeatedly used.
Fig. 5 is a graph showing the change of the concentration of hydrogen peroxide in the collector with time when the photocatalyst is used for continuously preparing hydrogen peroxide. As can be seen from FIG. 5, the catalyst can stably produce hydrogen peroxide products by combining with a continuous reaction device with zero external energy consumption, and stable hydrogen peroxide solution with the concentration of about 110mg/L is generated from 8 hours of solar illumination.
Example 2:
successively stirring and dissolving polyamide acid monomer diamine and dianhydride in a molar ratio of 1:1(0.01mol:0.01mol) in 120mL of dimethyl sulfoxide, adding a few drops of isoquinoline, stirring and reacting overnight to form polyamide acid solution, then placing cotton fibers (5g) with clean surfaces in the polyamide acid solution, mechanically stirring uniformly, placing a reaction system under the protection of nitrogen flow, controlling the reaction temperature range to be 180 ℃ for 8 hours, naturally cooling, filtering, washing with ethanol and water to obtain the polyimide/cotton fiber hydrogen peroxide synthesis photocatalyst, wherein the polyimide/cotton load is 0.6 g/g.
20g of the photocatalyst is placed in a reactor, water is added, the flow rate of a gravity dropping device is adjusted to be 100mL/h, and stable hydrogen peroxide solution with the concentration of about 79mg/L is generated from 8 hours of solar illumination.
Example 3:
successively stirring and dissolving polyamide acid monomer diamine and dianhydride in a molar ratio of 1:1(0.005mol:0.005mol) in 120mL of m-methylphenol, adding a few drops of isoquinoline, stirring and reacting overnight to form polyamide acid solution, then placing cotton fiber (5g) with a clean surface in the polyamide acid solution, mechanically stirring uniformly, placing the reaction system under the protection of nitrogen flow, controlling the reaction temperature to be 190 ℃ for 16 hours, naturally cooling, filtering, washing with ethanol and water to obtain the polyimide/cotton fiber hydrogen peroxide synthesis photocatalyst, wherein the polyimide/cotton load is 0.3 g/g.
20g of the photocatalyst is placed in a reactor, water is added, the flow rate of a gravity dropping device is adjusted to be 100mL/h, and stable hydrogen peroxide solution with the concentration of about 65mg/L is generated from 8 hours of solar illumination.
Example 4:
sequentially stirring and dissolving polyamide acid monomer diamine and dianhydride in a molar ratio of 1:1(0.0033mol:0.0033mol) in 120mL of dimethyl sulfoxide, adding a few drops of isoquinoline, stirring and reacting overnight to form polyamide acid solution, then placing cotton fiber (2g) with a clean surface in the polyamide acid solution, mechanically stirring uniformly, then placing the reaction system under the protection of nitrogen flow, controlling the reaction temperature range to be 180 ℃ for 8 hours, naturally cooling, filtering, washing with ethanol and water to obtain the polyimide/cotton fiber hydrogen peroxide synthesis photocatalyst, wherein the polyimide/cotton load is 0.5 g/g.
20g of the photocatalyst is placed in a reactor, water is added, the flow rate of a gravity dropping device is adjusted to be 100mL/h, and stable hydrogen peroxide solution with the concentration of about 102mg/L is generated from 8 hours of solar illumination.
Example 5:
successively stirring and dissolving polyamide acid monomer diamine and dianhydride in a molar ratio of 1:1(0.01mol:0.01mol) in 120mL of dimethyl sulfoxide, adding a few drops of isoquinoline, stirring and reacting overnight to form polyamide acid solution, then placing cotton fiber (2g) with a clean surface in the polyamide acid solution, mechanically stirring uniformly, then placing the reaction system under the protection of nitrogen flow, controlling the reaction temperature range to be 220 ℃ for 16 hours, naturally cooling, filtering, washing with ethanol and water to obtain the polyimide/cotton fiber hydrogen peroxide synthesis photocatalyst, wherein the polyimide/cotton load is 1.5 g/g.
20g of the photocatalyst is placed in a reactor, water is added, the flow rate of a gravity dropping device is adjusted to be 100mL/h, and stable hydrogen peroxide solution with the concentration of about 69mg/L is generated from 8 hours of solar illumination.
Example 6:
successively stirring and dissolving polyamide acid monomer diamine and dianhydride in a molar ratio of 1:1(0.01mol:0.01mol) in 120mL of m-methylphenol, adding a few drops of isoquinoline, stirring and reacting overnight to form polyamide acid solution, then placing cotton fibers (5g) with clean surfaces in the polyamide acid solution, mechanically stirring uniformly, placing a reaction system under the protection of nitrogen flow, controlling the reaction temperature range to be 180 ℃ for 8 hours, naturally cooling, filtering, washing with ethanol and water to obtain the polyimide/cotton fiber hydrogen peroxide synthesis photocatalyst, wherein the polyimide/cotton load is 0.6 g/g.
20g of the photocatalyst is placed in a reactor, water is added, the flow rate of a gravity dropping device is adjusted to be 80mL/h, and stable hydrogen peroxide solution with the concentration of about 79mg/L is generated from 8 hours of solar illumination.
Example 7:
successively stirring and dissolving polyamide acid monomer diamine and dianhydride in a molar ratio of 1:1(0.01mol:0.01mol) in 120mL of dimethyl sulfoxide, adding a few drops of isoquinoline, stirring and reacting overnight to form polyamide acid solution, then placing cotton fibers (5g) with clean surfaces in the polyamide acid solution, mechanically stirring uniformly, placing a reaction system under the protection of nitrogen flow, controlling the reaction temperature range to be 300 ℃ for 72 hours, naturally cooling, filtering, washing with ethanol and water to obtain the polyimide/cotton fiber hydrogen peroxide synthesis photocatalyst, wherein the polyimide/cotton load is 0.6 g/g.
20g of the photocatalyst is placed in a reactor, water is added, the flow rate of a gravity dropping device is adjusted to be 80mL/h, and stable hydrogen peroxide solution with the concentration of about 92mg/L is generated from 8 hours of solar illumination.
Example 8:
successively stirring and dissolving polyamide acid monomer diamine and dianhydride in a molar ratio of 1:1(0.01mol:0.01mol) in 120mL of dimethyl sulfoxide, adding a few drops of isoquinoline, stirring and reacting overnight to form polyamide acid solution, then placing cotton fibers (5g) with clean surfaces in the polyamide acid solution, mechanically stirring uniformly, placing a reaction system under the protection of nitrogen flow, controlling the reaction temperature range to be 250 ℃ for 24 hours, naturally cooling, filtering, washing with ethanol and water to obtain the polyimide/cotton fiber hydrogen peroxide synthesis photocatalyst, wherein the polyimide/cotton load is 0.6 g/g.
20g of the photocatalyst is placed in a reactor, water is added, the flow rate of a gravity dropping device is adjusted to be 100mL/h, and stable hydrogen peroxide solution with the concentration of about 32mg/L is generated from 8 hours of solar illumination.
Example 9:
successively stirring and dissolving polyamide acid monomer diamine and dianhydride in a molar ratio of 1:1(0.00066mol:0.00066mol) in 120mL of m-methylphenol, adding a few drops of isoquinoline, stirring and reacting overnight to form polyamide acid solution, then placing cotton fibers (5g) with clean surfaces in the polyamide acid solution, mechanically stirring uniformly, placing the reaction system under the protection of nitrogen flow, controlling the reaction temperature range to be 180 ℃ for 8 hours, naturally cooling, filtering, washing with ethanol and water to obtain the polyimide/cotton fiber hydrogen peroxide synthesis photocatalyst, wherein the polyimide/cotton load is 0.04 g/g.
20g of the photocatalyst is placed in a reactor, water is added, the flow rate of a gravity dropping device is adjusted to be 100mL/h, and stable hydrogen peroxide solution with the concentration of about 12mg/L is generated from 8 hours of solar illumination.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. The polyimide/cotton fiber hydrogen peroxide synthesis photocatalyst is characterized by comprising cotton fibers and a polyimide nanoparticle coating loaded on the cotton fibers.
2. The polyimide/cotton fiber hydrogen peroxide synthesis photocatalyst as claimed in claim 1, wherein 0.2-3g of polyimide nanoparticle coating is loaded on each 2-5g of cotton fiber.
3. The preparation method of the polyimide/cotton fiber hydrogen peroxide synthesis photocatalyst as claimed in claim 1 or 2, wherein the method comprises the following steps: and soaking the cotton fiber in the polyamic acid solution, and performing closed-loop polymerization to obtain the polyimide nano-particle coating loaded on the cotton fiber.
4. The preparation method of the polyimide/cotton fiber photocatalyst synthesized by hydrogen peroxide is characterized by comprising the following steps:
1) preparation of a polyamic acid solution: dissolving a polyamic acid monomer in a polar solvent, and carrying out polymerization reaction to obtain a polyamic acid solution;
2) soaking cotton fiber in the polyamic acid solution and stirring uniformly;
3) and raising the temperature to perform closed-loop polymerization reaction on the polyamic acid on the surface of the cotton fiber so as to form a polyimide nano-particle coating on the surface of the cotton fiber.
5. The method of claim 4, wherein in step 1), the polyamic acid monomer comprises diamine and dianhydride, the diamine comprises one or more of 1, 4-phenylenediamine, 1,3, 5-benzenetriamine, 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, tris (4-aminophenyl) amine, 1,3, 5-tris (4-aminophenyl) benzene, diethylamine or 1, 8-pyrenediamine, and the dianhydride comprises one or more of benzene-1, 2,4, 5-tetracarboxylic dianhydride, naphthalene-1, 2,6, 7-tetracarboxylic dianhydride or anthracene-1, 2,8, 9-tetracarboxylic dianhydride, the polar solvent comprises one or more of N, N-dimethylformamide, dimethyl sulfoxide or m-hydroxyphenol.
6. The preparation method of the polyimide/cotton fiber hydrogen peroxide synthesis photocatalyst according to claim 4, wherein in the step 2), the concentration of the polyamic acid solution is 0.2-3g/120mL, and the dosage ratio of the cotton fiber to the polyamic acid solution is 2-5g:120 mL.
7. The method for preparing a polyimide/cotton fiber photocatalyst synthesized by hydrogen peroxide according to claim 4, wherein in the step 3), the reaction temperature is 120-300 ℃ and the reaction time is 8-72 hours in the ring-closing polymerization reaction process.
8. The application of the polyimide/cotton fiber hydrogen peroxide synthetic photocatalyst as claimed in claim 1 or 2, wherein the photocatalyst is used for catalyzing water to react with oxygen under illumination to prepare hydrogen peroxide.
9. The natural light continuous reaction device for preparing hydrogen peroxide is based on the polyimide/cotton fiber hydrogen peroxide synthesis photocatalyst as claimed in claim 1 or 2, and is characterized by comprising a dropping device (1), a reactor (2) and a collector (3) which are sequentially communicated, wherein the height of the dropping device (1) is greater than that of the reactor (2), the height of the reactor (2) is greater than that of the collector (3), and the photocatalyst is placed in the reactor (2).
10. The natural light continuous reaction device for preparing hydrogen peroxide according to claim 9, wherein the reactor (2) comprises a container (201) with an open top and a top cover (202) arranged on the top of the container (201), and the top cover (202) is an unsealed top cover with high light transmittance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110652694.7A CN113398990A (en) | 2021-06-11 | 2021-06-11 | Polyimide/cotton fiber hydrogen peroxide synthesis photocatalyst and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110652694.7A CN113398990A (en) | 2021-06-11 | 2021-06-11 | Polyimide/cotton fiber hydrogen peroxide synthesis photocatalyst and preparation and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113398990A true CN113398990A (en) | 2021-09-17 |
Family
ID=77683587
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110652694.7A Pending CN113398990A (en) | 2021-06-11 | 2021-06-11 | Polyimide/cotton fiber hydrogen peroxide synthesis photocatalyst and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113398990A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102180553A (en) * | 2011-03-15 | 2011-09-14 | 南京林业大学 | Photo-catalytic oxidation water treatment device based on solar fixed film double-layer thin plate |
| US20140004929A1 (en) * | 1996-11-14 | 2014-01-02 | Bally Gaming International, Inc. | Network gaming system |
| CN105417830A (en) * | 2014-11-15 | 2016-03-23 | 深圳市芭田生态工程股份有限公司 | Method for producing organic carbon fertilizer through photocatalytic and oxidized organic wastewater |
| CN109364994A (en) * | 2018-09-10 | 2019-02-22 | 深圳大学 | Loaded photocatalyst and its application |
-
2021
- 2021-06-11 CN CN202110652694.7A patent/CN113398990A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140004929A1 (en) * | 1996-11-14 | 2014-01-02 | Bally Gaming International, Inc. | Network gaming system |
| CN102180553A (en) * | 2011-03-15 | 2011-09-14 | 南京林业大学 | Photo-catalytic oxidation water treatment device based on solar fixed film double-layer thin plate |
| CN105417830A (en) * | 2014-11-15 | 2016-03-23 | 深圳市芭田生态工程股份有限公司 | Method for producing organic carbon fertilizer through photocatalytic and oxidized organic wastewater |
| CN109364994A (en) * | 2018-09-10 | 2019-02-22 | 深圳大学 | Loaded photocatalyst and its application |
Non-Patent Citations (3)
| Title |
|---|
| KELIAN ZHANG等: "Polyimide with enhanced π stacking for efficient visible-light-driven photocatalysis", 《CATALYSIS SCIENCE & TECHNOLOGY》 * |
| 钱立军等: "《高分子材料》", 31 July 2020, 中国轻工业出版社 * |
| 高樱等: "改性光催化剂的制备与表征及其在光芬顿中的应用", 《西安工业大学学报》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107552033B (en) | Preparation method of oxygen vacancy-containing strontium titanate photocatalyst | |
| CN111454459B (en) | Bionic photosystem I covalent organic framework material, preparation and application thereof | |
| CN102527420A (en) | Bismuth subcarbonate photocatalyst and preparation method thereof | |
| CN111036285A (en) | Photocatalyst of nitrogen modified perovskite composite molecular sieve and preparation method and application method thereof | |
| CN105562093A (en) | Photocatalyst and preparation method thereof, catalyst for hydrogen production from photocatalytic decomposition and preparation method thereof, and preparation method of hydrogen | |
| CN115181265B (en) | Methylene modified covalent triazine framework material and preparation method and application thereof | |
| CN111530490A (en) | Co3O4-TiO2Heterojunction loaded carbon nanotube photocatalytic degradation material and preparation method thereof | |
| CN114225957A (en) | Carbon-doped supermolecule polymeric carbon nitride visible-light-induced photocatalyst and application thereof | |
| CN115318291A (en) | Preparation method and application of copper nanoparticle-carbon nitride photocatalytic sterilization composite material | |
| CN108479812B (en) | AgInS2/Bi2WO6Preparation method and application of heterojunction nanosheet | |
| Lin et al. | A polyimide-based photocatalyst for continuous hydrogen peroxide production using air and water under solar light | |
| CN112774703A (en) | Elemental red phosphorus-loaded titanium dioxide composite catalyst for efficient photocatalytic decomposition of water to produce hydrogen | |
| CN113398990A (en) | Polyimide/cotton fiber hydrogen peroxide synthesis photocatalyst and preparation and application thereof | |
| CN116651500A (en) | Novel TpTz-COF photocatalytic material and preparation method thereof | |
| CN115970765B (en) | Bionic floatable photocatalytic material with 3D three-phase interface, preparation method and application thereof in photocatalytic nitrogen reduction synthesis of ammonia | |
| CN114308126B (en) | K (K)4Nb6O17Micron flower/Co-TCPP MOF hydrogen evolution catalyst and preparation method and application thereof | |
| CN113861496B (en) | Polyimide/carbon quantum dot/zinc sulfide quantum dot composite aerogel and preparation method thereof | |
| CN112246256B (en) | Piezoelectric catalytic degradation and ammonia synthesis catalyst, and preparation method and application thereof | |
| Venditto et al. | Monolithic Porous Organic Polymer‐Photocatalyst Composites for Applications in Catalysis | |
| CN113171791A (en) | Composite catalyst capable of efficiently producing hydrogen peroxide and preparation method thereof | |
| CN113634279A (en) | Oil-water amphiphilic titanium-based Ag/TiO2Preparation and application of @ PANI photocatalyst | |
| CN100519656C (en) | Poly furfuryl alcohol /TiO2 nano composite material and preparation method thereof | |
| CN111137920A (en) | Black Ta2O5And preparation method and application thereof | |
| Guayaquil-Sosa | Photocatalytic Hydrogen Production using a Mesoporous TiO2 Doped with Pt: Semiconductor Synthesis, Oxidation-Reduction Network and Quantum Efficiencies | |
| Zhang et al. | Oxygen and Nitrogen Vacancies in a BiOBr/g-C3N4 Heterojunction for Sustainable Solar Ammonia Fertilizer Synthesis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210917 |