CN113952983B - Preparation method of paper-supported noble metal nanoparticle catalyst - Google Patents
Preparation method of paper-supported noble metal nanoparticle catalyst Download PDFInfo
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- CN113952983B CN113952983B CN202111305592.4A CN202111305592A CN113952983B CN 113952983 B CN113952983 B CN 113952983B CN 202111305592 A CN202111305592 A CN 202111305592A CN 113952983 B CN113952983 B CN 113952983B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002082 metal nanoparticle Substances 0.000 title claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 6
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- 230000003197 catalytic effect Effects 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000004587 chromatography analysis Methods 0.000 claims description 8
- 239000003223 protective agent Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical group [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000001632 sodium acetate Substances 0.000 claims description 6
- 235000017281 sodium acetate Nutrition 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 5
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 229920001131 Pulp (paper) Polymers 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- KIDBBTHHMJOMAU-UHFFFAOYSA-N propan-1-ol;hydrate Chemical compound O.CCCO KIDBBTHHMJOMAU-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052753 mercury Inorganic materials 0.000 claims description 2
- 229910001507 metal halide Inorganic materials 0.000 claims description 2
- 150000005309 metal halides Chemical class 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N n-Butanol Substances CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 claims 1
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 11
- 239000002815 homogeneous catalyst Substances 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000006722 reduction reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 37
- 239000002253 acid Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000006555 catalytic reaction Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000000084 colloidal system Substances 0.000 description 7
- 102000004190 Enzymes Human genes 0.000 description 5
- 108090000790 Enzymes Proteins 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000002608 ionic liquid Substances 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 238000007172 homogeneous catalysis Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- KTUQUZJOVNIKNZ-UHFFFAOYSA-N butan-1-ol;hydrate Chemical compound O.CCCCO KTUQUZJOVNIKNZ-UHFFFAOYSA-N 0.000 description 1
- VZHHNBNSMNNUAD-UHFFFAOYSA-N cobalt 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound [Co].OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VZHHNBNSMNNUAD-UHFFFAOYSA-N 0.000 description 1
- 238000000366 colloid method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- 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
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the field of synthesis of catalyst materials, and provides a preparation method of a paper-supported noble metal nanoparticle catalyst. The invention can prepare a novel catalyst with the characteristics of easy separation of a heterogeneous catalyst and high activity of a homogeneous catalyst, and the performance of the catalyst is investigated by respectively using dehydrogenation oxidation reaction and hydrogenation reduction reaction.
Description
Technical Field
The invention belongs to the field of synthesis of catalyst materials, and particularly relates to a method for synthesizing a paper-supported noble metal nanoparticle catalyst.
Background
The catalytic action and the catalyst have important effects on the development of human society. At present, more than 90% of chemical industrial processes are not separated from catalysis and catalysts. In the catalytic reaction, the catalyst reacts with the reactant to change the reaction pathway, thereby lowering the activation energy of the reaction, which is why the catalyst increases the reaction rate. Catalysis plays a very critical role in the development of the world civilization and the advancement of human society. The method can convert easily available and cheap raw materials into chemical products with high added values, high-energy density fuels and the like through chemical changes in a high-cost performance, high-efficiency, green and environment-friendly mode, and the materials not only relate to human clothes, eating and housing, and the like, but also relate to modern high-tech and high-new fields, such as network technology, information transmission, bioengineering, aerospace, military industry and the like, so that the catalysis is called the heart of the modern industry. The catalysts are mainly divided into three types: heterogeneous catalysts, homogeneous catalysts and enzymatic catalysts. Heterogeneous catalysts are widely used in industrial production due to their characteristics of easy separation, high stability, etc., while homogeneous catalysts and enzyme catalysts are difficult to be industrially applied due to their disadvantages of high cost, difficult separation, etc., but heterogeneous catalysts do not have the characteristics of high selectivity and high activity of homogeneous catalysts. Establishing a bridge between heterogeneous catalysis and homogeneous catalysis/enzyme catalysis, it is a very challenging task to have heterogeneous catalysts with the superior performance of homogeneous catalysts and enzyme catalysts. Therefore, the development of a novel green, efficient, low-cost, high-selectivity and environment-friendly heterogeneous catalyst is the core of the development of chemical, catalysis and other subjects.
Noble metal catalysts are known to exhibit high catalytic activity and selectivity in many reactions. Therefore, the noble metal catalyst is widely applied, and the search for a proper noble metal carrier ensures that the noble metal catalyst breaks through the original performance of the noble metal catalyst and is very important. The paper catalyst can integrate the characteristics of easy separation, stability, independent single clear active center, high selectivity and high activity of a heterogeneous catalyst. This is because the paper catalyst can have the characteristics of a homogeneous catalyst by forming a state of pulp in a liquid phase chemical reaction system, exist in a state of paper at the time of separation and recovery, and have the characteristics of a heterogeneous catalyst. Meanwhile, the paper catalyst is simpler to separate and recover than the traditional heterogeneous catalyst. Therefore, the preparation research of the paper catalyst is very important, and even hopefully establishes a large unified theory of catalysis.
In summary, when special paper such as porous chromatography paper, filter paper, etc. is used as a catalyst carrier, besides noble metal nanoparticles can be carried, because the surface of the special paper has abundant hydroxyl groups, the special paper does not need to be functionalized, can be well combined with the noble metal nanoparticles, and is cheap and easy to obtain. The paper is used as the catalyst carrier, so that the unique phase transition characteristic of the paper can be utilized, and the transition between the liquid phase and the solid phase can be easily and reversibly carried out. Meanwhile, a colloid method is used for colloidizing and depositing the noble metal on paper, the hydroxyl group shown by the paper is used for adsorbing the noble metal, the particle size of the noble metal can be adjusted by adjusting the concentration of a protective agent, the reaction time for preparing the colloid and the like, uniform noble metal nano particles are prepared, and when the noble metal/paper catalyst is in a paper pulp state, the structure and the performance of the noble metal/paper catalyst are similar to those of a homogeneous catalyst and even an enzyme catalyst.
At present, the preparation method of the paper catalyst has some defects:
chinese patent, application number: CN201910955378.X, which discloses polyimide composite paper with catalytic performance and SERS performance and a preparation method thereof. Directly papermaking by using the fibrid loaded with the metal nano particles; or mixing the metal nanoparticle-loaded fibrids and the polyimide chopped fibers and papermaking to obtain the polyimide composite paper. But the preparation conditions are more complicated, the raw materials are more expensive, particularly, the price of the polyimide even reaches 9000-15000 yuan/kg, and the economic benefit is not obvious.
Chinese patent, application number: CN201610569319.5, which describes a process for liquefying biomass by catalyzing paper with m (salen) in ionic liquid. In the presence of ionic liquid and M (salen) catalytic paper, biomass compounds are subjected to catalytic liquefaction treatment, and because ionic liquid catalysis is introduced, the ionic liquid is difficult to separate from pulp, so that the catalyst is difficult to recycle, and the application of the catalyst is limited.
Chinese patent, application number: CN201510130919.7, which describes the application of co (salen) catalytic paper in lignin oxidation. The Co complex synthesized by the patent is mixed with ceramic fiber, polyacrylamide and the like, and the mixture is made into the catalyst-ceramic fiber-polymer composite paper through papermaking, so that the problems of complex process and high cost are solved, and the morphology and particle size of Co are not controllable, so that the performance of Co is influenced.
Chinese patent, application number: CN202110485155.9, discloses a photocatalytic paper and a preparation method thereof. The prepared photocatalytic paper is used for photocatalysis, and is only limited to application of photocatalysis although the process is simple and the cost is low, so that the method has limitations.
Chinese patent, application number: CN200420022026.8, discloses a transfer catalytic paper for all cotton printing. The utility model discloses a constitute by paper and dyestuff layer, this processingequipment includes parts such as pressurization rubber roller, inflation balance roll and catalysis padding rubber roller, is equipped with the isolation layer on the surface of being printed paper, and the back is equipped with the catalyst layer, is equipped with on the isolation layer or scribbles the dyestuff layer of transfer catalysis paper intaglio printing. The method is an environment-friendly and green technology, but the process is complicated, and large-scale production is difficult to realize.
Disclosure of Invention
The invention discloses a preparation method of a paper-supported noble metal nanoparticle catalyst, and belongs to the field of synthesis of catalyst materials. The invention aims to provide a novel catalyst preparation method, which aims to communicate heterogeneous catalysis and homogeneous catalysis, and has the characteristics of easy separation and high activity by utilizing the characteristic that paper can carry out reversible phase change.
The technical scheme of the invention is as follows:
dissolving precursor salt of noble metal with water or alcohol organic solvent to obtain noble metal precursorThe concentration of the salt solution is 0.001-0.1mol/L, the precursor salt of the noble metal is completely dissolved by stirring, then the protective agent is added, the solubility of the protective agent in the system is controlled to be 0.01-0.1mol/L, after the stirring and the dissolution, the solution is heated for 5-120 minutes under the temperature condition of 100-140 ℃, and the noble metal colloidal solution is prepared. Then adding the paper into the noble metal colloidal solution, adjusting the pH to be less than 3, heating to 100-140 ℃, and keeping the temperature for 5-120 minutes; at the moment, the solution is in a paper pulp state, then is cooled to room temperature, is filtered and washed to be neutral, and is dried for 6 to 12 hours at the temperature of 60 to 100 ℃ to prepare the paper supported noble metal nanoparticle catalyst; wherein the noble metal accounts for 0.01 to 10 weight percent of the paper. Water or alcohol organic solvent, wherein the alcohol organic solvent is water-methanol, water-ethanol, water-glycol, water-n-propanol or water-n-butanol, and the volume fraction of the organic solvent is not more than 100%. The noble metal is one or more than two of noble metals such as platinum, palladium, gold, rhodium, iridium and the like. The metal salt solution is one or more of nitrate, chloride, acetate and chlorhydric acid. The protective agent is inorganic salt such as sodium acetate, and polymer such as polyvinylpyrrolidone. The paper used as the catalyst carrier is a paper-based material having a fiber or paper-like structure, such as chromatography paper, filter paper, and carbon paper. Using external lamps or electromagnetic waves with a power of 0-2 w.m -2 The paper can be irradiated for 12-100 hours, and the physical and chemical properties of the paper can be adjusted. The external lamp source is one or the combination of more than two of common lamp sources such as mercury lamps, xenon lamps, metal halide lamps and the like. The electromagnetic wave is one or combination of more than two of invisible light such as visible light, ultraviolet ray, infrared ray, X ray and the like.
Compared with the known paper catalyst preparation technology, the preparation method has the following advantages:
1. the ceramic fiber, a large amount of high molecular polymer and other expensive materials are not needed, and the cost is low.
2. The complicated paper technology such as papermaking and the like is not needed.
3. The method is not limited to photoelectrocatalysis, can be used in the field of thermocatalysis, and has potential industrial application prospect.
4. When the catalytic reaction is carried out, the catalyst exists in a paper pulp state in the solution, so that the active center of the catalyst is uniform, and the catalytic performance of the catalyst can be comparable to that of a homogeneous catalyst or even an enzyme catalyst theoretically. The catalyst can be reformed into paper by simple separation means after reaction, and the catalyst has the characteristic of recycling of heterogeneous catalyst.
5. Cheap and easily available, and simultaneously, because the surface of the material is rich in hydroxyl, the pretreatment of a carrier is not needed. Has the advantages of homogeneous catalysts and heterogeneous catalysts, and even hopefully establishes a large unified theory of catalysis.
Detailed Description
To further illustrate the present invention, the following examples are set forth without limiting the scope of the invention as defined by the various appended claims.
Example 1: dissolving a certain amount of chloroplatinic acid in 10mL of glycol solution to ensure that the concentration of the chloroplatinic acid is 0.0025mol/L, fully stirring the solution until the chloroplatinic acid is completely dissolved, then adding a certain amount of sodium acetate to ensure that the concentration of the sodium acetate is 0.04mol/L, stirring the solution for dissolution, and heating the solution at 120 ℃ for 20 minutes to prepare the Pt colloid solution. Then 8 pieces of chromatography paper (1cm × 1cm, 97.5mg) were added to the colloidal solution, the acid-base environment was adjusted to pH less than 3 using dilute hydrochloric acid, heated to 120 degrees, and kept at constant temperature for 60 minutes. At this time, the solution was in a pulp state, and then cooled to room temperature, filtered and washed 5 times, and dried at 80 ℃ for 12 hours to prepare a Pt/paper catalyst in which the noble metal was 5 wt% of the carrier.
Example 2: dissolving a certain amount of chloroplatinic acid in 10mL of glycol solution to ensure that the concentration of the chloroplatinic acid is 0.0025mol/L, fully stirring the solution until the chloroplatinic acid is completely dissolved, then adding a certain amount of sodium acetate to ensure that the concentration of the sodium acetate is 0.04mol/L, stirring the solution for dissolution, and heating the solution at 120 ℃ for 20 minutes to prepare the Pt colloid solution. Then 97.5mg of activated carbon is added into the colloid, diluted hydrochloric acid is used for adjusting the pH value of the acid-base environment to be less than 3, the temperature is heated to 120 ℃, and the constant temperature is kept for 60 minutes. Filtering and washing for 5 times, and drying at 80 ℃ for 12 hours to obtain the Pt/activated carbon catalyst, wherein the mass percent of the noble metal in the carrier is 5 wt%.
Example 3: irradiating the chromatographic paper with ultraviolet light: a UVA-340 type ultraviolet lamp tube is adopted, and the wavelength of ultraviolet light is selected to be 340 nm; irradiance of 0.76 w.m -2 (ii) a Temperature ofIs (30 +/-3) DEG C; the humidity is not controlled; the front side of the paper was irradiated directly for 12 hours and then the back side of the paper was irradiated for 12 hours. The catalyst was then prepared according to the method of example 1. Is recorded as Pt/L paper catalyst.
Example 4: taking 50mL of methanol-water solution, wherein the ratio of alcohol to water is 1: 1, adding 0.15g of polyvinylpyrrolidone, adding a certain amount of chloroplatinic acid to make the concentration of the chloroplatinic acid be 0.0005ml/L, stirring to dissolve, and heating at 120 ℃ for 180 minutes to prepare a Pt colloid solution. Then 8 pieces of chromatography paper (1cm × 1cm, 97.5mg) were added to the colloidal solution, the acid-base environment was adjusted to pH less than 3 using dilute hydrochloric acid, heated to 120 degrees, and kept at constant temperature for 60 minutes. At this time, the solution was in a pulp state, and then cooled to room temperature, filtered and washed 5 times, and dried at 80 ℃ for 12 hours to obtain Pt/paper catalyst-4 in which the noble metal was 5 wt% based on the mass of the support.
Example 5: taking 50mL of ethanol-water solution, wherein the ratio of alcohol to water is 1: 1, adding 0.15g of polyvinylpyrrolidone, adding a certain amount of chloroplatinic acid to make the concentration of the chloroplatinic acid be 0.0005ml/L, stirring to dissolve, and heating at 120 ℃ for 120 minutes to prepare a Pt colloid solution. Then 8 pieces of chromatography paper (1cm × 1cm, 97.5mg) were added to the colloidal solution, the acid-base environment was adjusted to pH less than 3 using dilute hydrochloric acid, heated to 120 degrees, and kept at constant temperature for 60 minutes. At this time, the solution was in a pulp state, and then cooled to room temperature, filtered and washed 5 times, and dried at 80 ℃ for 12 hours to obtain Pt/paper catalyst-5 in which the noble metal was 5 wt% based on the mass of the support.
Example 6: taking 50mL of an n-propanol-water solution, wherein the ratio of alcohol to water is 1: 1, adding 0.146g of polyvinylpyrrolidone, adding a certain amount of chloroplatinic acid to make the concentration of the chloroplatinic acid be 0.0005ml/L, stirring to dissolve the mixture, and heating at 120 ℃ for 120 minutes to prepare a Pt colloidal solution. Then 8 pieces of chromatography paper (1cm × 1cm, 97.5mg) were added to the colloidal solution, the acid-base environment was adjusted to pH less than 3 using dilute hydrochloric acid, heated to 120 ℃ and kept at constant temperature for 60 minutes. At this time, the solution was in a pulp state, and then cooled to room temperature, filtered and washed 5 times, and dried at 80 ℃ for 12 hours to obtain Pt/paper catalyst-6 in which the noble metal was 5 wt% based on the mass of the carrier.
Example 7: taking 50mL of n-butanol-water solution, wherein the ratio of alcohol to water is 1: 1, adding 0.15g of polyvinylpyrrolidone, adding a certain amount of chloroplatinic acid to make the concentration of the chloroplatinic acid be 0.0005ml/L, stirring to dissolve, and heating at 120 ℃ for 120 minutes to prepare a Pt colloid solution. Then 8 pieces of chromatography paper (1cm × 1cm, 97.5mg) were added to the colloidal solution, the acid-base environment was adjusted to pH less than 3 using dilute hydrochloric acid, heated to 120 degrees, and kept at constant temperature for 60 minutes. At this time, the solution was in a pulp state, and then cooled to room temperature, filtered and washed 5 times, and dried at 80 ℃ for 12 hours to obtain Pt/paper catalyst-7 in which the noble metal was 5 wt% based on the mass of the support.
Example 8: the performance of the Pt/paper catalyst was compared to the Pt/activated carbon catalyst. The catalysts prepared in examples 1-3 were used to catalyze the dehydro-oxidation of glucose. Firstly, 0.4324g of glucose is dissolved in 40mL of water-methanol solution, the volume fraction of water is 40%, 0.7405g of KOH is added, the gas in a reactor is replaced by Ar atmosphere, the reaction temperature is 30 ℃, the reaction pressure is normal pressure, the dehydrogenation oxidation catalyst is Pt/activated carbon, Pt/paper or Pt/L paper catalyst, the collected product gas is analyzed by gas chromatography, the detector is a thermal conductivity detector, the chromatographic column is TDX-01, the gas chromatography shows the generation of hydrogen, and the reaction result is shown in Table 1.
Example 9: the performance of Pt/paper catalysts prepared from different solvents was compared. The catalysts prepared in examples 4 to 7 were used in the nitrobenzene reductive hydrogenation reaction. Firstly, 5mmol of nitrobenzene is dissolved in 20mL of cyclohexane solution, the hydrogenation reduction catalyst is Pd/paper catalyst 4-7, the adding amount of the catalyst is 20mg, and then the solution is transferred to a tank reactor. The air in the reactor was replaced 5 times with hydrogen, the reactor was heated to 60 degrees at 700rpm, and then hydrogen gas at a set pressure of 1Mpa was introduced. The composition of the product was analyzed by gas chromatography and the results are shown in Table 2.
Example 10: evaluation of catalyst recycle. Three catalysts obtained in example 8 after 4 hours of reaction were centrifuged and recovered by vacuum drying. 0.4324g of glucose is dissolved in 40mL of water-methanol solution, the volume fraction of water is 40%, 0.7405g of KOH is added, Ar atmosphere is used for replacing gas in a reactor, the reaction temperature is 30 ℃, the reaction pressure is normal pressure, the dehydrogenation oxidation catalyst is Pt/activated carbon, Pt/paper or Pt/L paper catalyst, the collected product gas is analyzed by gas chromatography, the detector is a thermal conductivity detector, a chromatographic column is TDX-01, the gas chromatography shows the generation of hydrogen, and the reaction result is shown in Table 1. The catalyst was recycled 5 times and the reaction results are shown in table 3.
Table 1 evaluation of the performance of the catalysts of examples 1 to 3
| Catalyst and process for preparing same | Hydrogen yield (mol%) |
| Pt/paper | 90 |
| Pt/activated carbon | 84 |
| Pt/L paper | 93 |
Table 2 evaluation of catalyst Performance of examples 4-7
Table 3 catalyst stability testing
| Catalyst and process for preparing same | Number of cycles | Hydrogen yield (mol%) |
| Pt/paper | 1 | 89 |
| Pt/paper | 2 | 88 |
| Pt/paper | 3 | 87 |
| Pt/paper | 4 | 88 |
| Pt/paper | 5 | 86 |
| Pt/L paper | 1 | 93 |
| Pt/L paper | 2 | 90 |
| Pt/L paper | 3 | 85 |
| Pt/L paper | 4 | 80 |
| Pt/L paper | 5 | 78 |
| Pt/activated carbon | 1 | 82 |
| Pt/activated carbon | 2 | 83 |
| Pt/activated carbon | 3 | 83 |
| Pt/activated carbon | 4 | 83 |
| Pt/activated carbon | 5 | 82 |
Claims (6)
1. A preparation method of a paper supported noble metal nanoparticle catalyst for catalytic dehydrogenation and glucose oxidation reaction is characterized by comprising the following steps:
dissolving precursor salt of noble metal by using water-methanol, water-ethanol, water-ethylene glycol, water-n-propanol or water-n-butanol to obtain the solution of the precursor salt of noble metal with the concentration of 0.001-0.1mol/L, stirring to completely dissolve the precursor salt of noble metal, then adding a protective agent, controlling the solubility of the protective agent in the system to be 0.01-0.1mol/L, stirring and dissolving, and then heating the solution for 5-120 minutes at the temperature of 140 ℃ to prepare a noble metal colloidal solution; then adding the paper into the noble metal colloidal solution, adjusting the pH to be less than 3, heating to 100-140 ℃, and keeping the temperature for 5-120 minutes; at the moment, the solution is in a paper pulp state, then is cooled to room temperature, is filtered and washed to be neutral, and is dried for 6 to 12 hours at the temperature of 60 to 100 ℃ to prepare the paper supported noble metal nanoparticle catalyst; wherein the noble metal accounts for 0.01 to 10 weight percent of the paper; the paper used as the catalyst support is chromatography paper, filter paper or carbon paper.
2. The method according to claim 1, wherein the noble metal is one or more of platinum, palladium, gold, rhodium and iridium; the precursor salt of the noble metal is one or the mixture of more than two of nitrate, chloride, acetate and chlorhydric acid.
3. The method according to claim 1 or 2, wherein the protective agent is sodium acetate or polyvinylpyrrolidone.
4. The method of claim 1 or 2, wherein an external lamp or electromagnetic waves are used at a power of 0-2w ∙ m -2 Irradiating the paper for 12-100 hours, wherein the power is not zero, and adjusting the physical and chemical properties of the paper catalyst.
5. The preparation method according to claim 3, wherein an external lamp or electromagnetic waves are used at a power of 0-2w ∙ m -2 Irradiating the paper for 12-100 hours, wherein the power is not zero, and adjusting the physical and chemical properties of the paper catalyst.
6. The method according to claim 4, wherein the external lamp source is one or two of a mercury lamp, a xenon lamp and a metal halide lamp; the electromagnetic wave is one or two of visible light, ultraviolet ray, infrared ray and X ray.
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