CN107185591B - A kind of preparation method and applications for the cellulose paper base nano silver catalysis material that can be recycled - Google Patents
A kind of preparation method and applications for the cellulose paper base nano silver catalysis material that can be recycled Download PDFInfo
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- CN107185591B CN107185591B CN201710341121.6A CN201710341121A CN107185591B CN 107185591 B CN107185591 B CN 107185591B CN 201710341121 A CN201710341121 A CN 201710341121A CN 107185591 B CN107185591 B CN 107185591B
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- cellulose paper
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- cellulose
- catalysis material
- silver
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 233
- 239000001913 cellulose Substances 0.000 title claims abstract description 233
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 175
- 239000000463 material Substances 0.000 title claims abstract description 135
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229910052709 silver Inorganic materials 0.000 claims abstract description 95
- 239000004332 silver Substances 0.000 claims abstract description 95
- 239000002105 nanoparticle Substances 0.000 claims abstract description 81
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 230000003197 catalytic effect Effects 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- 125000003368 amide group Chemical group 0.000 claims abstract description 36
- 239000002243 precursor Substances 0.000 claims abstract description 35
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 29
- 150000002500 ions Chemical class 0.000 claims abstract description 28
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 16
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 11
- 230000004048 modification Effects 0.000 claims abstract description 7
- 238000012986 modification Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 72
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 238000007639 printing Methods 0.000 claims description 40
- 239000007864 aqueous solution Substances 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 31
- 235000019441 ethanol Nutrition 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 27
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 25
- 229910000077 silane Inorganic materials 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 20
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 18
- 230000004913 activation Effects 0.000 claims description 15
- 125000003277 amino group Chemical group 0.000 claims description 12
- 238000007306 functionalization reaction Methods 0.000 claims description 12
- 239000012279 sodium borohydride Substances 0.000 claims description 12
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 9
- 238000010521 absorption reaction Methods 0.000 claims description 9
- 229960005070 ascorbic acid Drugs 0.000 claims description 9
- 235000010323 ascorbic acid Nutrition 0.000 claims description 9
- 239000011668 ascorbic acid Substances 0.000 claims description 9
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 claims description 8
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical group CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 5
- 229940071536 silver acetate Drugs 0.000 claims description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- 239000013522 chelant Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000003344 environmental pollutant Substances 0.000 claims description 4
- 231100000719 pollutant Toxicity 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims 1
- 241000416536 Euproctis pseudoconspersa Species 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 239000007822 coupling agent Substances 0.000 claims 1
- 239000002086 nanomaterial Substances 0.000 abstract description 31
- 229910052751 metal Inorganic materials 0.000 abstract description 26
- 239000002184 metal Substances 0.000 abstract description 26
- 238000000034 method Methods 0.000 abstract description 9
- 239000000356 contaminant Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 235000010980 cellulose Nutrition 0.000 description 200
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- 239000000835 fiber Substances 0.000 description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- 239000011943 nanocatalyst Substances 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- 238000011534 incubation Methods 0.000 description 11
- 238000004064 recycling Methods 0.000 description 11
- 230000006641 stabilisation Effects 0.000 description 11
- 230000009920 chelation Effects 0.000 description 10
- 238000005859 coupling reaction Methods 0.000 description 10
- 238000011065 in-situ storage Methods 0.000 description 10
- 238000011105 stabilization Methods 0.000 description 10
- 239000003153 chemical reaction reagent Substances 0.000 description 9
- 230000008878 coupling Effects 0.000 description 9
- 238000010168 coupling process Methods 0.000 description 9
- 238000009792 diffusion process Methods 0.000 description 9
- 239000000376 reactant Substances 0.000 description 9
- 229910021529 ammonia Inorganic materials 0.000 description 8
- 229910000510 noble metal Inorganic materials 0.000 description 8
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 239000000969 carrier Substances 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- -1 silicon Alkane Chemical class 0.000 description 3
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 2
- 239000008108 microcrystalline cellulose Substances 0.000 description 2
- 229940016286 microcrystalline cellulose Drugs 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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
- 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
-
- B01J35/56—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- 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
- Y02P20/584—Recycling of catalysts
Abstract
The invention belongs to technical field of nano material, it is related to the preparation method and applications more particularly to a kind of application of silver nanoparticle method for preparing catalyst and its circulation catalyzed conversion environmental contaminants based on surface-functionalized cellulose paper base of a kind of loaded nano silver catalysis material that can be recycled.The preparation method of the cellulose paper base nano silver catalysis material that can be recycled, using cellulose paper sill as carrier, carrier surface is carried out using silane coupling agent amido modified, the amino of carrier surface is mutually chelated with metal precursor ions after modification, and cellulose paper base nano silver catalysis material is formed after additional reducing agent restores.Cellulose paper base silver nanoparticle catalysis material prepared by the present invention is reduced to the catalyst of 4-aminophenol reaction as 4- nitrophenol, catalytic activity is high, carrier and silver nanoparticle stability are high, catalyst easily recycles, reusable performance is good, and continuous be recycled 20 times or more is still able to maintain higher catalytic activity.
Description
Technical field
The invention belongs to technical field of nano material, it is related to a kind of loaded nano silver catalysis material that can be recycled
Preparation method and applications more particularly to a kind of silver nanoparticle method for preparing catalyst based on surface-functionalized cellulose paper base and
Its application for recycling catalyzed conversion environmental contaminants.
Background technique
Metal nano material is with a wide range of applications in fields such as the energy, catalysis, biological medicine, sensing detections,
As the hot spot for studying concern in the world.Wherein, the noble metal nanometer materials such as gold, silver, platinum because its higher specific surface area and solely
Special surface electronic characteristic and have excellent catalytic properties, in the reaction such as hydrogenating reduction, coupling reaction and catalysis oxidation all
Show higher catalytic activity.However, sequestered noble metal nano particles are easily reunited, are led because partial size is small, surface energy is high
Catalytic activity is caused to reduce, and the catalyst of nanoscale is difficult to separate and recover from reaction system, reuse.To solve these
Noble metal nano catalyst is often carried on polymeric matrix (J. Phys. Chem. C 2009,113,5157 by problem
5163), mesoporous silicon (ACS Catal. 2011,1,207 211), metal oxide (Green Chem., 2005,7,
768-770) etc. on carriers, to improve the dispersibility and stability of nanocatalyst.These carriers can by electrostatic adsorption,
The chelation of space confinement effect or surface functional group fixes nano particle, but the pre-treatment and preparation of usually these carriers
Method is complex.Therefore, exploring new simple and effective metal nano catalyst carrier class pushes nanocatalyst in reality
In application.
Cellulosic-based material (such as microcrystalline cellulose, bacteria cellulose film and laboratory ordinary filter paper) is rich because of its resource
The advantages that rich, biodegradable and cheap, can be used as the excellent carrier of noble metal nano catalyst.It is reported in the literature with cellulose
Sill is that carrier synthesis noble metal nano catalyst has: growing silver nanoparticle on microcrystalline cellulose matrix by microwave process for synthesizing
Particle (Carbohydr. Polym., 2011,86:441-447)；It is fixed poly- by electrostatic interaction absorption using filter paper as carrier
Ethylene imido coats gold nanoparticle (RSC Adv., 2015,5,104239-104244) etc..In addition, application No. is
201210184589.6 Chinese invention patent discloses a kind of method in cellulose-containing material silver nanoparticles loaded, mainly
Step includes that cellulose-containing material is soaked in preconfigured silver ammino solution, is reacted in 30 DEG C -100 DEG C of water-bath
Cellulosic material cleaning is dried the cellulosic material for having Nano silver grain up to area load by 10 min-24 h.Above-mentioned document
Or method described in patent is mostly real using physical absorption between Nano silver grain and cellulosic material surface or electrostatic force
The fixation of existing nano material, binding force is not strong, and catalyst easily falls off from carrier surface in catalystic converter system；And it is original
Cellulose paper base mechanical strength is not high, and the macrostructure of porous paper base is easily disintegrated after water suction.Therefore, it explores and utilizes cellulose
The three-dimensional netted porous structure of paper base material enhances and interacts between noble metal nanometer material and carrier, realizes nanocatalyst
Stabilisation it is immobilized, while enhancing the mechanical strength of porous paper base, there is the cellulose paper of high circulation catalytic activity for developing
Base nano-catalyst seems particularly necessary.
Summary of the invention
The present invention is in order to solve the above technical problems, provide a kind of using functional fiber element paper base as carrier steady load silver
The preparation approach of nanocatalyst, this method is simple and easy, and cellulose paper base used is cheap and easy to get, and from a wealth of sources, silver nanoparticle is urged
Agent partial size is small, size uniformity, immobilized stabilization, also resides in and provides a kind of cellulose paper base argentum nano composite material in catalysis 4- nitre
Base phenol is reduced to the cycle applications in 4-aminophenol reaction, and composite material catalytic activity is high, and it is good to recycle performance,
Catalyzed conversion field application potential is wide.
In order to solve the above technical problems, the invention adopts the following technical scheme:
A kind of preparation method for the cellulose paper base nano silver catalysis material that can be recycled is with cellulose paper sill
Carrier carries out amido modified, the amino and metal precursor ions of carrier surface after modification to carrier surface using silane coupling agent
It mutually chelates, forms cellulose paper base nano silver catalysis material after additional reducing agent restores.
The preparation method of the cellulose paper base nano silver catalysis material that can be recycled, steps are as follows:
(1) cellulose paper sill is surface-functionalized: silane coupling agent being dissolved in ethanol/water system, stirring point
Silane coupler solution is obtained after dissipating, cellulose paper sill is immersed into silane coupler solution, reaction 1 ~ 4 hour, instead
Cellulose paper sill is taken out after answering, and is placed in activation 2 ~ 4 hours, the cellulose paper after activation in 110 ~ 130 DEG C of baking oven
Sill obtains the cellulose paper sill I of surface amino groups functionalization through water and ethyl alcohol cleaning, drying at room temperature respectively；
(2) absorption of silver nanoparticle precursor ion: cellulose paper sill I is immersed in silver nanoparticle precursor solution, 25 ~ 40
It DEG C is washed with water after constant-temperature incubation 0.5 ~ 2 hour, the extra silver ion that removal surface does not chelate is to get the fibre for having adsorbed silver ion
Tie up plain paper base material II；
(3) cellulose paper base nano silver catalysis material: cellulose paper sill II is immersed in the water, and is added under stirring condition
Additional reducing agent, 25 ~ 50 DEG C isothermal reaction 0.5 ~ 2 hour, can be in the amido modified immobilized silver of cellulose paper base surface-stable
Nanocatalyst completes the preparation of cellulose paper base nano silver catalysis material.
The preparation method of the cellulose paper base nano silver catalysis material that can be recycled, the cellulose paper substrate
Material is filter paper, printing paper or corrugated paper.
In the step (1), silane coupling agent be 3- aminopropyl trimethoxysilane or 3- aminopropyl triethoxysilane,
The concentration of silane coupler solution is 0.4 ~ 2.5 mg/mL；The volume ratio of ethyl alcohol and water is 7:3 in the ethanol/water system.
In the step (2), silver nanoparticle precursor is silver nitrate, silver acetate or silver orthophosphate, the concentration of silver nanoparticle precursor solution
For 5mM ~ 100mM.
In the step (3), additional reducing agent is ascorbic acid or NaBH4, the concentration of additional reducing agent is 1mM ~ 50mM.
A kind of application for the cellulose paper base nano silver catalysis material that can be recycled, the cellulose paper base nano silver are urged
Change material, is reduced to the cycle applications in 4-aminophenol reaction in catalytic environment pollutant 4- nitrophenol.
The application of the cellulose paper base nano silver catalysis material that can be recycled, steps are as follows:
A. cellulose paper base nano silver catalysis material is added in 4- nitrophenol aqueous solution under the conditions of 25 ~ 60 DEG C, is stirred
After mixing uniformly, NaBH is added4Aqueous solution is reacted, and after reacting 3 ~ 20min, that is, obtains product 4-aminophenol；
B. step a after reaction, is filtered and is taken out cellulose paper base nano silver catalysis material from system, true
Dry in empty drying box, the cellulose paper base nano silver catalysis material can be realized reuse 20 ~ 40 times.
In the step a, 4- nitro phenol concentration is 0.02 ~ 0.50 mM, cellulose paper base nano silver catalysis material quality
For 10 ~ 50 mg, the NaBH4The concentration of aqueous solution is 0.1 M ~ 1M.
In the step b, vacuum drying drying temperature is 70 ~ 90 DEG C, and drying time is 1 ~ 2h.
The principle of recyclable cellulose paper base silver nanoparticle catalysis material preparation method of the invention is as follows: with common
For for cellulose paper sill, cellulosic filter paper has tridimensional network, fiber surface is rich in hydroxyl, adopts laboratory filter paper
It is amino by hydroxyl modified with silane coupled technology to its surface modification, with reinforcing fiber chelating absorption silver ion and stablizes silver
The ability of nanometer；Amido modified cellulosic filter paper is immersed in silver ion solution, makes it through electronics to shared and fiber
The amino on surface is firmly combined；Additional reducing agent fabricated in situ Nano silver grain is introduced, and realizes it on cellulosic filter paper
Stablize immobilized.
The beneficial effects of the present invention are:
1, in cellulose paper base silver nanoparticle catalysis material prepared by the present invention, carrier material is cheap and easy to get, from a wealth of sources, paper
Primary surface functionalization and Nano silver grain restoring method are simple, and surface modification enhances the mechanical strength of paper base, the Yin Na of synthesis
Rice corpuscles size is small, active high, uniform particle diameter, and especially binding force is strong between carrier, and stability is good.
2, cellulose paper base silver nanoparticle catalysis material prepared by the present invention is reduced to 4-aminophenol as 4- nitrophenol
The catalyst of reaction, catalytic activity is high, and carrier and silver nanoparticle stability are high, and catalyst easily recycles, and reusable performance is good, even
Continue recycling 20 times or more and is still able to maintain higher catalytic activity.
3, cellulose paper sill (such as ordinary filter paper, printing paper, corrugated paper) is cheap and from a wealth of sources, shows three-dimensional
Reticulated porous structures, cellulose fiber surface are rich in hydroxyl, are modified by silane coupled technology it, on the one hand can be enhanced
On the other hand the mechanical strength of paper base material introduces the functional group of energy chelating absorption noble metal precursor, can enhance nanometer and urge
Therefore interaction force between agent and paper base carrier carries out cellulose paper base functionalizing material surface and silver nanoparticle catalyst
It stabilizes immobilized, recyclable catalytic conversion applications to environmental pollutants is realized, for widening having for noble metal nano catalyst
It imitates load carriers range and reduces environmental pollution and be of great significance.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of silane coupling agent modification filter paper prepared by embodiment 1.
Fig. 2 is the silver nanoparticle high power transmission electron microscope picture based on cellulosic filter paper prepared by embodiment 2.
Fig. 3 is the XRD spectrum of the filter paper of amido modified filter paper prepared by embodiment 2 and load silver nanoparticle.
Fig. 4 is that composite material prepared by embodiment 3 makees catalyst 4- p-nitrophenol reduction reaction course figure.
Fig. 5 is that composite material prepared by embodiment 3 makees the cycle-index of catalyst and the relational graph of reaction conversion ratio.
Specific embodiment
A kind of preparation method for the cellulose paper base nano silver catalysis material that can be recycled is with cellulose paper sill
Carrier carries out amido modified, the amino and metal precursor ions of carrier surface after modification to carrier surface using silane coupling agent
It mutually chelates, forms cellulose paper base nano silver catalysis material after additional reducing agent restores.
The preparation method of the cellulose paper base nano silver catalysis material that can be recycled, steps are as follows:
(1) cellulose paper sill is surface-functionalized: silane coupling agent being dissolved in ethanol/water system, stirring point
Silane coupler solution is obtained after dissipating, cellulose paper sill is immersed into silane coupler solution, reaction 1 ~ 4 hour, instead
Cellulose paper sill is taken out after answering, and is placed in activation 2 ~ 4 hours, the cellulose paper after activation in 110 ~ 130 DEG C of baking oven
Sill obtains the cellulose paper sill I of surface amino groups functionalization through water and ethyl alcohol cleaning, drying at room temperature respectively；
(2) absorption of silver nanoparticle precursor ion: cellulose paper sill I is immersed in silver nanoparticle precursor solution, 25 ~ 40
It DEG C is washed with water after constant-temperature incubation 0.5 ~ 2 hour, the extra silver ion that removal surface does not chelate is to get the fibre for having adsorbed silver ion
Tie up plain paper base material II；
(3) cellulose paper base nano silver catalysis material: cellulose paper sill II is immersed in the water, and is added under stirring condition
Additional reducing agent, 25 ~ 50 DEG C isothermal reaction 0.5 ~ 2 hour, can be in the amido modified immobilized silver of cellulose paper base surface-stable
Nanocatalyst completes the preparation of cellulose paper base nano silver catalysis material.
The preparation method of the cellulose paper base nano silver catalysis material that can be recycled, the cellulose paper substrate
Material is filter paper, printing paper or corrugated paper.
In the step (1), silane coupling agent be 3- aminopropyl trimethoxysilane or 3- aminopropyl triethoxysilane,
The concentration of silane coupler solution is 0.4 ~ 2.5 mg/mL；The volume ratio of ethyl alcohol and water is 7:3 in the ethanol/water system.
In the step (2), silver nanoparticle precursor is silver nitrate, silver acetate or silver orthophosphate, the concentration of silver nanoparticle precursor solution
For 5mM ~ 100mM.
In the step (3), additional reducing agent is ascorbic acid or NaBH4, the concentration of additional reducing agent is 1mM ~ 50mM.
A kind of application for the cellulose paper base nano silver catalysis material that can be recycled, the cellulose paper base nano silver are urged
Change material, is reduced to the cycle applications in 4-aminophenol reaction in catalytic environment pollutant 4- nitrophenol.
The application of the cellulose paper base nano silver catalysis material that can be recycled, steps are as follows:
A. cellulose paper base nano silver catalysis material is added in 4- nitrophenol aqueous solution under the conditions of 25 ~ 60 DEG C, is stirred
After mixing uniformly, NaBH is added4Aqueous solution is reacted, and after reacting 3 ~ 20min, that is, obtains product 4-aminophenol；
B. step a after reaction, is filtered and is taken out cellulose paper base nano silver catalysis material from system, true
Dry in empty drying box, the cellulose paper base nano silver catalysis material can be realized reuse 20 ~ 40 times.
In the step a, 4- nitro phenol concentration is 0.02 ~ 0.50 mM, cellulose paper base nano silver catalysis material quality
For 10 ~ 50 mg, the NaBH4The concentration of aqueous solution is 0.1 M ~ 1M.
In the step b, vacuum drying drying temperature is 70 ~ 90 DEG C, and drying time is 1 ~ 2h.
Present invention is further described in detail with specific embodiment with reference to the accompanying drawing, but is not the limitation present invention.
Embodiment 1
1, cellulose paper is surface-functionalized: with laboratory general fibre element filter paper (cellulose filter paper,
It CFP) is silver nano material carrier, it is amido modified to the progress of its surface using silane coupling reagent, enhance its and chelates adsorbing metal
The ability of ion.
40mg 3- aminopropyl trimethoxysilane is dissolved in the ethanol/water system of 100mL (70/30, v/v), and is stirred
Mix dispersion；Cellulose paper base material laboratory filter paper is taken, the rectangle of suitable dimension is cut into, is immersed in above-mentioned system,
Reaction 4 hours.
Cellulosic filter paper is taken out, is placed in 130 DEG C of baking ovens and activates 4 hours, making the reaction of cellulose surface hydroxyl is ammonia
Base；Filter paper after activation is cleaned with water and ethyl alcohol respectively, room temperature in vacuo is drying to obtain the cellulose filter of surface amino groups functionalization
Paper.
2, surface-functionalized paper chelates adsorbing metal precursor ion: using N in cellulose surface amino lone pair electrons with
The secured adsorbing metal precursor ion of chelation between silver ion.
Surface-functionalized filter paper is dipped in the silver acetate solutions of 100mM, 40 DEG C constant-temperature incubation 2 hours, chelating absorption
Silver ion.
3, silver nanoparticle is restored and is fixed: being closed in situ using additional reducing agent in amido modified cellulose paper base material surface
At and fixed silver nanoparticle catalyst, enhance the binding force of nano material and cellulose paper.
Cellulose paper sill is taken out, the extra silver ion of surface attachment is washed with water, chelating has been adsorbed into silver ion
Filter paper be dipped in aqueous solution again, a certain amount of ascorbic acid is rapidly injected under stirring, makes the concentration of ascorbic acid
50 mM, 50 DEG C are reacted 0.5 hour, can be completed in the amido modified immobilized silver nanoparticle catalyst of cellulose paper base surface-stable
The preparation of cellulose paper base silver nanoparticle catalysis material.
4, catalytic applications are recycled: even using the catalytic capability and silane of silver nanoparticle in cellulose paper base silver nanoparticle catalysis material
Joint-trial agent modified cellulose paper is to the stabilization of nano material, in addition, cellulose-binding paper macroscopic view is convenient for recycling characteristic and more
Hole is conducive to reactant diffusion property, it can be achieved that catalyst material stablizes circulation catalytic applications.
A. cellulose paper base nano silver catalysis material is added in 4- nitrophenol aqueous solution under the conditions of 25 DEG C, stirring
After uniformly, 0.8M NaBH is added4Aqueous solution is reacted, and after reacting 3min, that is, obtains product 4-aminophenol；
B. step a after reaction, is filtered and is taken out cellulose paper base nano silver catalysis material from system, and 70 DEG C
Under the conditions of dry 2h in vacuum oven, the cellulose paper base nano silver catalysis material can realize reuse 20 times.
Embodiment 2
1, cellulose paper is surface-functionalized: using laboratory printing paper as silver nano material carrier, using silane coupling reagent
It is amido modified to the progress of its surface, enhance its ability for chelating adsorbing metal ions.
250mg 3- aminopropyl triethoxysilane is dissolved in the ethanol/water system of 100mL (70/30, v/v), and
It is dispersed with stirring；It takes printing paper to be cut into the circle of suitable dimension, is immersed in above-mentioned system, react 2.5 hours.
Printing paper is taken out, is placed in 110 DEG C of baking ovens and activates 2 hours, making the reaction of printing paper cellulose surface hydroxyl is ammonia
Base；Printing paper after activation is cleaned with water and ethyl alcohol respectively, room temperature in vacuo is drying to obtain the cellulose of surface amino groups functionalization
Printing paper.
2, surface-functionalized paper chelates adsorbing metal precursor ion: the orphan using N in printing paper cellulose surface amino is right
The secured adsorbing metal precursor ion of chelation between electronics and silver ion.
Surface-functionalized printing paper is dipped in the silver nitrate solution of 5 mM, 25 DEG C constant-temperature incubation 0.5 hour, chelating
Adsorb silver ion.
3, silver nanoparticle is restored and is fixed: being synthesized using additional reducing agent in amido modified cellulose printing paper surface in situ
And fixed silver nanoparticle catalyst, enhance the binding force of nano material and printing paper.
Printing paper is taken out, the extra silver ion of surface attachment is washed with water, chelating has been adsorbed to the printing paper of silver ion
It is dipped in aqueous solution again, additional reducing agent NaBH is rapidly injected under stirring4, make NaBH4Concentration be 1mM, 40 DEG C of constant temperature
2h is reacted, cellulose paper base silver can be completed in the amido modified immobilized silver nanoparticle catalyst of cellulose paper base surface-stable and receive
The preparation of rice catalysis material.
4, catalytic applications are recycled: even using the catalytic capability and silane of silver nanoparticle in cellulose paper base silver nanoparticle catalysis material
Joint-trial agent modified cellulose paper is to the stabilization of nano material, in addition, cellulose-binding paper macroscopic view is convenient for recycling characteristic and more
Hole is conducive to reactant diffusion property, it can be achieved that catalyst material stablizes circulation catalytic applications.
A. cellulose paper base nano silver catalysis material is added in 4- nitrophenol aqueous solution under the conditions of 40 DEG C, stirring
After uniformly, 0.5M NaBH is added4Aqueous solution is reacted, and after reacting 12 min, that is, obtains product 4-aminophenol；
B. step a after reaction, is filtered and is taken out cellulose paper base nano silver catalysis material from system, and 80 DEG C
Under the conditions of dry 1h in vacuum oven, the cellulose paper base nano silver catalysis material can realize reuse 40 times.
Embodiment 3
1, cellulose paper is surface-functionalized: using laboratory general fibre element corrugated paper as silver nano material carrier, using silicon
Alkane coupling reagent is amido modified to the progress of its surface, enhances its ability for chelating adsorbing metal ions.
170mg 3- aminopropyl triethoxysilane is dissolved in the ethanol/water system of 100mL (70/30, v/v), and
It is dispersed with stirring；Cellulose paper sill corrugated paper is taken, the circle of suitable dimension is cut into, is immersed in above-mentioned system, instead
It answers 2 hours.
Cellulose corrugated paper is taken out, is placed in 120 DEG C of baking ovens and activates 3 hours, making the reaction of cellulose surface hydroxyl is ammonia
Base；Corrugated paper after activation is cleaned with water and ethyl alcohol respectively, room temperature in vacuo is drying to obtain the cellulose of surface amino groups functionalization
Corrugated paper.
2, surface-functionalized paper chelates adsorbing metal precursor ion: using N in cellulose surface amino lone pair electrons with
The secured adsorbing metal precursor ion of chelation between silver ion.
Surface-functionalized corrugated paper is dipped in the silver orthophosphate solution of 5 mM, 35 DEG C constant-temperature incubation 1.5 hours, chelating inhale
Attached silver ion.
3, silver nanoparticle is restored and is fixed: using additional reducing agent NaBH4 in amido modified cellulose paper base material surface
Fabricated in situ and fixed silver nanoparticle catalyst, enhance the binding force of nano material and cellulose paper.
Cellulose paper sill is taken out, the extra silver ion of surface attachment is washed with water, chelating has been adsorbed into silver ion
Corrugated paper be dipped in aqueous solution again, a certain amount of additional reducing agent NaBH is rapidly injected under stirring4Make its concentration
25mM, 25 DEG C of isothermal reaction 2h can be completed fine in the amido modified immobilized silver nanoparticle catalyst of cellulose paper base surface-stable
Tie up the preparation of plain paper base silver nanoparticle catalysis material.
4, catalytic applications are recycled: even using the catalytic capability and silane of silver nanoparticle in cellulose paper base silver nanoparticle catalysis material
Joint-trial agent modified cellulose paper is to the stabilization of nano material, in addition, cellulose-binding paper macroscopic view is convenient for recycling characteristic and more
Hole is conducive to reactant diffusion property, it can be achieved that catalyst material stablizes circulation catalytic applications.
A. cellulose paper base nano silver catalysis material is added in 4- nitrophenol aqueous solution under the conditions of 60 DEG C, stirring
After uniformly, 0.1M NaBH is added4Aqueous solution is reacted, and after reacting 20min, that is, obtains product 4-aminophenol；
B. step a after reaction, is filtered and is taken out cellulose paper base nano silver catalysis material from system, and 90 DEG C
Under the conditions of dry 1h in vacuum oven, the cellulose paper base nano silver catalysis material can realize reuse 30 times.
Embodiment 4
1, cellulose paper is surface-functionalized: using laboratory general fibre element corrugated paper as silver nano material carrier, using silicon
Alkane coupling reagent is amido modified to the progress of its surface, enhances its ability for chelating adsorbing metal ions.
250mg 3- aminopropyl triethoxysilane is dissolved in the ethanol/water system of 100mL (70/30, v/v), and
It is dispersed with stirring；Cellulose paper sill corrugated paper is taken, the circle of suitable dimension is cut into, is immersed in above-mentioned system, instead
It answers 1 hour.
Cellulose corrugated paper is taken out, is placed in 120 DEG C of baking ovens and activates 3 hours, making the reaction of cellulose surface hydroxyl is ammonia
Base；Corrugated paper after activation is cleaned with water and ethyl alcohol respectively, room temperature in vacuo is drying to obtain the cellulose of surface amino groups functionalization
Corrugated paper.
2, surface-functionalized paper chelates adsorbing metal precursor ion: using N in cellulose surface amino lone pair electrons with
The secured adsorbing metal precursor ion of chelation between silver ion.
Surface-functionalized corrugated paper is dipped in the silver orthophosphate solution of 5 mM, 35 DEG C constant-temperature incubation 1.5 hours, chelating inhale
Attached silver ion.
3, silver nanoparticle is restored and is fixed: utilizing additional reducing agent NaBH4In amido modified cellulose paper base material surface
Fabricated in situ and fixed silver nanoparticle catalyst, enhance the binding force of nano material and cellulose paper.
Cellulose paper sill is taken out, the extra silver ion of surface attachment is washed with water, chelating has been adsorbed into silver ion
Corrugated paper be dipped in aqueous solution again, a certain amount of additional reducing agent NaBH is rapidly injected under stirring4Make its concentration
25mM, 50 DEG C of isothermal reaction 0.5h can be completed in the amido modified immobilized silver nanoparticle catalyst of cellulose paper base surface-stable
The preparation of cellulose paper base silver nanoparticle catalysis material.
4, catalytic applications are recycled: even using the catalytic capability and silane of silver nanoparticle in cellulose paper base silver nanoparticle catalysis material
Joint-trial agent modified cellulose paper is to the stabilization of nano material, in addition, cellulose-binding paper macroscopic view is convenient for recycling characteristic and more
Hole is conducive to reactant diffusion property, it can be achieved that catalyst material stablizes circulation catalytic applications.
A. cellulose paper base nano silver catalysis material is added in 4- nitrophenol aqueous solution under the conditions of 60 DEG C, stirring
After uniformly, 1M NaBH is added4Aqueous solution is reacted, and after reacting 20min, that is, obtains product 4-aminophenol；
B. step a after reaction, is filtered and is taken out cellulose paper base nano silver catalysis material from system, and 90 DEG C
Under the conditions of dry 1h in vacuum oven, the cellulose paper base nano silver catalysis material can realize reuse 25 times.
Embodiment 5
1, cellulose paper is surface-functionalized: using laboratory general fibre element corrugated paper as silver nano material carrier, using silicon
Alkane coupling reagent is amido modified to the progress of its surface, enhances its ability for chelating adsorbing metal ions.
40mg 3- aminopropyl triethoxysilane is dissolved in the ethanol/water system of 100mL (70/30, v/v), and is stirred
Mix dispersion；Cellulose paper sill corrugated paper is taken, the circle of suitable dimension is cut into, is immersed in above-mentioned system, reaction 4
Hour.
Cellulose corrugated paper is taken out, is placed in 130 DEG C of baking ovens and activates 2 hours, making the reaction of cellulose surface hydroxyl is ammonia
Base；Corrugated paper after activation is cleaned with water and ethyl alcohol respectively, room temperature in vacuo is drying to obtain the cellulose of surface amino groups functionalization
Corrugated paper.
2, surface-functionalized paper chelates adsorbing metal precursor ion: using N in cellulose surface amino lone pair electrons with
The secured adsorbing metal precursor ion of chelation between silver ion.
Surface-functionalized corrugated paper is dipped in the silver orthophosphate solution of 100 mM, 25 DEG C constant-temperature incubation 2 hours, chelating inhale
Attached silver ion.
3, silver nanoparticle is restored and is fixed: utilizing additional reducing agent NaBH4In amido modified cellulose paper base material surface
Fabricated in situ and fixed silver nanoparticle catalyst, enhance the binding force of nano material and cellulose paper.
Cellulose paper sill is taken out, the extra silver ion of surface attachment is washed with water, chelating has been adsorbed into silver ion
Corrugated paper be dipped in aqueous solution again, a certain amount of additional reducing agent NaBH is rapidly injected under stirring4Make its concentration
50 mM, 30 DEG C of isothermal reaction 1.5h, can be complete in the amido modified immobilized silver nanoparticle catalyst of cellulose paper base surface-stable
At the preparation of cellulose paper base silver nanoparticle catalysis material.
4, catalytic applications are recycled: even using the catalytic capability and silane of silver nanoparticle in cellulose paper base silver nanoparticle catalysis material
Joint-trial agent modified cellulose paper is to the stabilization of nano material, in addition, cellulose-binding paper macroscopic view is convenient for recycling characteristic and more
Hole is conducive to reactant diffusion property, it can be achieved that catalyst material stablizes circulation catalytic applications.
A. cellulose paper base nano silver catalysis material is added in 4- nitrophenol aqueous solution under the conditions of 25 DEG C, stirring
After uniformly, 0.5M NaBH is added4Aqueous solution is reacted, and after reacting 15 min, that is, obtains product 4-aminophenol；
B. step a after reaction, is filtered and is taken out cellulose paper base nano silver catalysis material from system, and 90 DEG C
Under the conditions of dry 1h in vacuum oven, the cellulose paper base nano silver catalysis material can realize reuse 20 times.
Embodiment 6
1, cellulose paper is surface-functionalized: with laboratory general fibre element filter paper (cellulose filter paper,
It CFP) is silver nano material carrier, it is amido modified to the progress of its surface using silane coupling reagent, enhance its and chelates adsorbing metal
The ability of ion.
250 mg 3- aminopropyl trimethoxysilanes are dissolved in the ethanol/water system of 100mL (70/30, v/v), and
It is dispersed with stirring；Cellulose paper base material laboratory filter paper is taken, the rectangle of suitable dimension is cut into, is immersed in above-mentioned system
It is interior, it reacts 1 hour.
Cellulosic filter paper is taken out, is placed in 110 DEG C of baking ovens and activates 2 hours, making the reaction of cellulose surface hydroxyl is ammonia
Base；Filter paper after activation is cleaned with water and ethyl alcohol respectively, room temperature in vacuo is drying to obtain the cellulose filter of surface amino groups functionalization
Paper.
2, surface-functionalized paper chelates adsorbing metal precursor ion: using N in cellulose surface amino lone pair electrons with
The secured adsorbing metal precursor ion of chelation between silver ion.
Surface-functionalized filter paper is dipped in the silver orthophosphate solution of 5mM, 25 DEG C constant-temperature incubation 1.5 hours, chelating absorption
Silver ion.
3, silver nanoparticle is restored and is fixed: being closed in situ using additional reducing agent in amido modified cellulose paper base material surface
At and fixed silver nanoparticle catalyst, enhance the binding force of nano material and cellulose paper.
Cellulose paper sill is taken out, the extra silver ion of surface attachment is washed with water, chelating has been adsorbed into silver ion
Filter paper be dipped in aqueous solution again, a certain amount of ascorbic acid is rapidly injected under stirring, makes the concentration 1 of ascorbic acid
MM, 25 DEG C of isothermal reaction 2h can complete fiber in the amido modified immobilized silver nanoparticle catalyst of cellulose paper base surface-stable
The preparation of plain paper base silver nanoparticle catalysis material.
4, catalytic applications are recycled: even using the catalytic capability and silane of silver nanoparticle in cellulose paper base silver nanoparticle catalysis material
Joint-trial agent modified cellulose paper is to the stabilization of nano material, in addition, cellulose-binding paper macroscopic view is convenient for recycling characteristic and more
Hole is conducive to reactant diffusion property, it can be achieved that catalyst material stablizes circulation catalytic applications.
A. cellulose paper base nano silver catalysis material is added in 4- nitrophenol aqueous solution under the conditions of 25 DEG C, stirring
After uniformly, 0.1M NaBH is added4Aqueous solution is reacted, and after reacting 15 min, that is, obtains product 4-aminophenol；
B. step a after reaction, is filtered and is taken out cellulose paper base nano silver catalysis material from system, and 70 DEG C
Under the conditions of dry 1h in vacuum oven, the cellulose paper base nano silver catalysis material can realize reuse 20 times.
Embodiment 7
1, cellulose paper is surface-functionalized: with laboratory general fibre element filter paper (cellulose filter paper,
It CFP) is silver nano material carrier, it is amido modified to the progress of its surface using silane coupling reagent, enhance its and chelates adsorbing metal
The ability of ion.
100 mg 3- aminopropyl trimethoxysilanes are dissolved in the ethanol/water system of 100mL (70/30, v/v), and
It is dispersed with stirring；Cellulose paper base material laboratory filter paper is taken, the rectangle of suitable dimension is cut into, is immersed in above-mentioned system
It is interior, it reacts 1 hour.
Cellulosic filter paper is taken out, is placed in 130 DEG C of baking ovens and activates 4 hours, making the reaction of cellulose surface hydroxyl is ammonia
Base；Filter paper after activation is cleaned with water and ethyl alcohol respectively, room temperature in vacuo is drying to obtain the cellulose filter of surface amino groups functionalization
Paper.
2, surface-functionalized paper chelates adsorbing metal precursor ion: using N in cellulose surface amino lone pair electrons with
The secured adsorbing metal precursor ion of chelation between silver ion.
Surface-functionalized filter paper is dipped in the silver acetate solutions of 100mM, 40 DEG C constant-temperature incubation 0.5 hour, chelating inhale
Attached silver ion.
3, silver nanoparticle is restored and is fixed: being closed in situ using additional reducing agent in amido modified cellulose paper base material surface
At and fixed silver nanoparticle catalyst, enhance the binding force of nano material and cellulose paper.
Cellulose paper sill is taken out, the extra silver ion of surface attachment is washed with water, chelating has been adsorbed into silver ion
Filter paper be dipped in aqueous solution again, a certain amount of ascorbic acid is rapidly injected under stirring, makes the concentration 1 of ascorbic acid
MM, 40 DEG C of isothermal reaction 0.5h can be completed fine in the amido modified immobilized silver nanoparticle catalyst of cellulose paper base surface-stable
Tie up the preparation of plain paper base silver nanoparticle catalysis material.
4, catalytic applications are recycled: even using the catalytic capability and silane of silver nanoparticle in cellulose paper base silver nanoparticle catalysis material
Joint-trial agent modified cellulose paper is to the stabilization of nano material, in addition, cellulose-binding paper macroscopic view is convenient for recycling characteristic and more
Hole is conducive to reactant diffusion property, it can be achieved that catalyst material stablizes circulation catalytic applications.
A. cellulose paper base nano silver catalysis material is added in 4- nitrophenol aqueous solution under the conditions of 25 DEG C, stirring
After uniformly, 0.5M NaBH is added4Aqueous solution is reacted, and after reacting 8 min, that is, obtains product 4-aminophenol；
B. step a after reaction, is filtered and is taken out cellulose paper base nano silver catalysis material from system, and 90 DEG C
Under the conditions of dry 2h in vacuum oven, the cellulose paper base nano silver catalysis material can realize reuse 40 times.
Embodiment 8
1, cellulose paper is surface-functionalized: using laboratory printing paper as silver nano material carrier, using silane coupling reagent
It is amido modified to the progress of its surface, enhance its ability for chelating adsorbing metal ions.
40mg 3- aminopropyl triethoxysilane is dissolved in the ethanol/water system of 100mL (70/30, v/v), and is stirred
Mix dispersion；It takes printing paper to be cut into the circle of suitable dimension, is immersed in above-mentioned system, react 1 hour.
Printing paper is taken out, is placed in 130 DEG C of baking ovens and activates 2 hours, making the reaction of printing paper cellulose surface hydroxyl is ammonia
Base；Printing paper after activation is cleaned with water and ethyl alcohol respectively, room temperature in vacuo is drying to obtain the cellulose of surface amino groups functionalization
Printing paper.
2, surface-functionalized paper chelates adsorbing metal precursor ion: the orphan using N in printing paper cellulose surface amino is right
The secured adsorbing metal precursor ion of chelation between electronics and silver ion.
Surface-functionalized printing paper is dipped in the silver nitrate solution of 50 mM, 40 DEG C constant-temperature incubation 2 hours, chelating inhale
Attached silver ion.
3, silver nanoparticle is restored and is fixed: being synthesized using additional reducing agent in amido modified cellulose printing paper surface in situ
And fixed silver nanoparticle catalyst, enhance the binding force of nano material and printing paper.
Printing paper is taken out, the extra silver ion of surface attachment is washed with water, chelating has been adsorbed to the printing paper of silver ion
It is dipped in aqueous solution again, additional reducing agent NaBH is rapidly injected under stirring4, make NaBH4Concentration be 50 mM, 25 DEG C of perseverances
Temperature reaction 0.5h can complete cellulose paper base in the amido modified immobilized silver nanoparticle catalyst of cellulose paper base surface-stable
The preparation of silver nanoparticle catalysis material.
4, catalytic applications are recycled: even using the catalytic capability and silane of silver nanoparticle in cellulose paper base silver nanoparticle catalysis material
Joint-trial agent modified cellulose paper is to the stabilization of nano material, in addition, cellulose-binding paper macroscopic view is convenient for recycling characteristic and more
Hole is conducive to reactant diffusion property, it can be achieved that catalyst material stablizes circulation catalytic applications.
A. cellulose paper base nano silver catalysis material is added in 4- nitrophenol aqueous solution under the conditions of 25 DEG C, stirring
After uniformly, 0.1M NaBH is added4Aqueous solution is reacted, and after reacting 3 min, that is, obtains product 4-aminophenol；
B. step a after reaction, is filtered and is taken out cellulose paper base nano silver catalysis material from system, and 90 DEG C
Under the conditions of dry 1h in vacuum oven, the cellulose paper base nano silver catalysis material can realize reuse 30 times.
Embodiment 9
1, cellulose paper is surface-functionalized: using laboratory printing paper as silver nano material carrier, using silane coupling reagent
It is amido modified to the progress of its surface, enhance its ability for chelating adsorbing metal ions.
150 mg 3- aminopropyl triethoxysilanes are dissolved in the ethanol/water system of 100mL (70/30, v/v), and
It is dispersed with stirring；It takes printing paper to be cut into the circle of suitable dimension, is immersed in above-mentioned system, react 1 hour.
Printing paper is taken out, is placed in 120 DEG C of baking ovens and activates 0.9 hour, make printing paper cellulose surface hydroxyl reaction be
Amino；Printing paper after activation is cleaned with water and ethyl alcohol respectively, room temperature in vacuo is drying to obtain the fiber of surface amino groups functionalization
Plain printing paper.
2, surface-functionalized paper chelates adsorbing metal precursor ion: the orphan using N in printing paper cellulose surface amino is right
The secured adsorbing metal precursor ion of chelation between electronics and silver ion.
Surface-functionalized printing paper is dipped in the silver orthophosphate solution of 100 mM, 40 DEG C constant-temperature incubation 2 hours, chelating
Adsorb silver ion.
3, silver nanoparticle is restored and is fixed: being synthesized using additional reducing agent in amido modified cellulose printing paper surface in situ
And fixed silver nanoparticle catalyst, enhance the binding force of nano material and printing paper.
Printing paper is taken out, the extra silver ion of surface attachment is washed with water, chelating has been adsorbed to the printing paper of silver ion
It is dipped in aqueous solution again, additional reducing agent NaBH is rapidly injected under stirring4, make NaBH4Concentration be 50 mM, 40 DEG C of perseverances
Temperature reaction 1.5h can complete cellulose paper base in the amido modified immobilized silver nanoparticle catalyst of cellulose paper base surface-stable
The preparation of silver nanoparticle catalysis material.
4, catalytic applications are recycled: even using the catalytic capability and silane of silver nanoparticle in cellulose paper base silver nanoparticle catalysis material
Joint-trial agent modified cellulose paper is to the stabilization of nano material, in addition, cellulose-binding paper macroscopic view is convenient for recycling characteristic and more
Hole is conducive to reactant diffusion property, it can be achieved that catalyst material stablizes circulation catalytic applications.
A. cellulose paper base nano silver catalysis material is added in 4- nitrophenol aqueous solution under the conditions of 25 DEG C, stirring
After uniformly, 0.5M NaBH is added4Aqueous solution is reacted, and after reacting 3 min, that is, obtains product 4-aminophenol；
B. step a after reaction, is filtered and is taken out cellulose paper base nano silver catalysis material from system, and 90 DEG C
Under the conditions of dry 1h in vacuum oven, the cellulose paper base nano silver catalysis material can realize reuse 25 times.
Claims (9)
1. a kind of preparation method for the cellulose paper base nano silver catalysis material that can be recycled, it is characterised in that: with cellulose
Paper base material is carrier, carries out amido modified, the amino of carrier surface and gold after modification to carrier surface using silane coupling agent
Belong to precursor ion mutually to chelate, forms cellulose paper base nano silver catalysis material after additional reducing agent restores；
Specific step is as follows:
(1) cellulose paper sill is surface-functionalized: silane coupling agent being dissolved in ethanol/water system, after being dispersed with stirring
Silane coupler solution is obtained, cellulose paper sill is immersed into silane coupler solution, is reacted 1 ~ 4 hour, reaction knot
Cellulose paper sill is taken out after beam, is placed in activation 2 ~ 4 hours, the cellulose paper substrate after activation in 110 ~ 130 DEG C of baking oven
Material obtains the cellulose paper sill I of surface amino groups functionalization through water and ethyl alcohol cleaning, drying at room temperature respectively；
(2) absorption of silver nanoparticle precursor ion: cellulose paper sill I is immersed in silver nanoparticle precursor solution, 25 ~ 40 DEG C of perseverances
Temperature washes with water after being incubated for 0.5 ~ 2 hour, and the extra silver ion that removal surface does not chelate is to get the cellulose for having adsorbed silver ion
Paper base material II；
(3) cellulose paper base nano silver catalysis material: cellulose paper sill II is immersed in the water, and is added under stirring condition additional
Reducing agent, 25 ~ 50 DEG C isothermal reaction 0.5 ~ 2 hour, can be in the amido modified immobilized silver nanoparticle of cellulose paper base surface-stable
Catalyst completes the preparation of cellulose paper base nano silver catalysis material.
2. the preparation method for the cellulose paper base nano silver catalysis material that can be recycled as described in claim 1, feature
Be: the cellulose paper sill is filter paper, printing paper or corrugated paper.
3. the preparation method for the cellulose paper base nano silver catalysis material that can be recycled as described in claim 1, feature
Be: in the step (1), silane coupling agent is 3- aminopropyl trimethoxysilane or 3- aminopropyl triethoxysilane, silicon
The concentration of alkane coupling agent solution is 0.4 ~ 2.5 mg/mL；The volume ratio of ethyl alcohol and water is 7:3 in the ethanol/water system.
4. the preparation method for the cellulose paper base nano silver catalysis material that can be recycled as described in claim 1, feature
Be: in the step (2), silver nanoparticle precursor is silver nitrate, silver acetate or silver orthophosphate, and the concentration of silver nanoparticle precursor solution is
5mM~100mM。
5. the preparation method for the cellulose paper base nano silver catalysis material that can be recycled as described in claim 1, feature
Be: in the step (3), additional reducing agent is ascorbic acid or NaBH4, the concentration of additional reducing agent is 1mM ~ 50mM.
6. the application of the described in any item cellulose paper base nano silver catalysis materials that can be recycled of claim 1-5, special
Sign is: the cellulose paper base nano silver catalysis material, is reduced to 4- aminobenzene in catalytic environment pollutant 4- nitrophenol
Cycle applications in phenol reaction.
7. the application for the cellulose paper base nano silver catalysis material that can be recycled as claimed in claim 6, which is characterized in that
Steps are as follows:
A. cellulose paper base nano silver catalysis material is added in 4- nitrophenol aqueous solution under the conditions of 25 ~ 60 DEG C, stirring is equal
After even, NaBH is added4Aqueous solution is reacted, and after reacting 3 ~ 20min, that is, obtains product 4-aminophenol；
B. step a after reaction, is filtered and is taken out cellulose paper base nano silver catalysis material from system, dry in vacuum
Dry in dry case, the cellulose paper base nano silver catalysis material can be realized reuse 20 ~ 40 times.
8. the application for the cellulose paper base nano silver catalysis material that can be recycled as claimed in claim 7, it is characterised in that:
In the step a, 4- nitro phenol concentration is 0.02 ~ 0.50 mM, and catalysis material quality is 10 ~ 50 mg, the NaBH4Water
The concentration of solution is 0.1 M ~ 1M.
9. the application for the cellulose paper base nano silver catalysis material that can be recycled as claimed in claim 7, it is characterised in that:
In the step b, vacuum drying drying temperature is 70 ~ 90 DEG C, and drying time is 1 ~ 2h.
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| CN108543547B (en) * | 2018-03-19 | 2019-06-18 | 华南理工大学 | A kind of the catalysis test paper and its method of bacteria cellulose carrying metal particles and the compound preparation of plant fiber |
| CN109603920B (en) * | 2018-12-18 | 2020-04-07 | 同济大学 | Visible light excited cellulose-TiO2Composite photocatalyst |
| CN110339859A (en) * | 2019-07-12 | 2019-10-18 | 河南省口岸食品检验检测所 | A kind of preparation method and applications of the highmulti paper based composites of supported bi-metallic nanometer |
| CN110681415B (en) * | 2019-10-09 | 2021-10-15 | 齐鲁工业大学 | Modified CNF membrane capable of catalytically degrading 4-nitrophenol and preparation method and application thereof |
| CN111485448B (en) * | 2020-05-05 | 2021-07-30 | 东阳市聚冉电子科技有限公司 | Preparation method of paper-based photoelectrocatalysis material for catalyzing oxidation of xylose |
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| "原位还原制备滤纸载纳米银粒子复合材料及其催化特性";吴贺君等;《化工进展》;20160531;第35卷(第5期);第1466-1470页 |
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