CN107185591A - 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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- CN107185591A CN107185591A CN201710341121.6A CN201710341121A CN107185591A CN 107185591 A CN107185591 A CN 107185591A CN 201710341121 A CN201710341121 A CN 201710341121A CN 107185591 A CN107185591 A CN 107185591A
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- cellulose paper
- paper base
- catalysis material
- cellulose
- silver
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 237
- 239000001913 cellulose Substances 0.000 title claims abstract description 237
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 176
- 239000000463 material Substances 0.000 title claims abstract description 144
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 229910052709 silver Inorganic materials 0.000 claims abstract description 96
- 239000004332 silver Substances 0.000 claims abstract description 96
- 239000002105 nanoparticle Substances 0.000 claims abstract description 82
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 239000003054 catalyst Substances 0.000 claims abstract description 41
- 230000003197 catalytic effect Effects 0.000 claims abstract description 40
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910000077 silane Inorganic materials 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
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 29
- 150000002500 ions Chemical class 0.000 claims abstract description 25
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 16
- 230000004048 modification Effects 0.000 claims abstract description 6
- 238000012986 modification Methods 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 45
- 238000007639 printing Methods 0.000 claims description 40
- 239000007864 aqueous solution Substances 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 26
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical class OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 19
- 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
- 238000001035 drying Methods 0.000 claims description 18
- 230000004913 activation Effects 0.000 claims description 15
- 238000007306 functionalization reaction Methods 0.000 claims description 13
- 125000003277 amino group Chemical group 0.000 claims description 12
- 238000001914 filtration 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
- 238000001291 vacuum drying Methods 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 class CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 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
- 238000010521 absorption reaction Methods 0.000 claims description 8
- 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
- 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
- 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
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 241000416536 Euproctis pseudoconspersa Species 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 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 23
- 239000002184 metal Substances 0.000 abstract description 23
- 238000000034 method Methods 0.000 abstract description 8
- 239000000356 contaminant Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 abstract 1
- RBXVOQPAMPBADW-UHFFFAOYSA-N nitrous acid;phenol Chemical class ON=O.OC1=CC=CC=C1 RBXVOQPAMPBADW-UHFFFAOYSA-N 0.000 abstract 1
- 235000010980 cellulose Nutrition 0.000 description 202
- 239000013522 chelant Substances 0.000 description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- 239000000835 fiber Substances 0.000 description 11
- 230000006641 stabilisation Effects 0.000 description 11
- 230000009286 beneficial effect Effects 0.000 description 10
- 230000009920 chelation Effects 0.000 description 10
- 239000011943 nanocatalyst Substances 0.000 description 10
- 238000011105 stabilization Methods 0.000 description 10
- 238000009792 diffusion process Methods 0.000 description 9
- 238000011534 incubation Methods 0.000 description 9
- 229910021645 metal ion Inorganic materials 0.000 description 9
- 239000000376 reactant Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 229910021529 ammonia Inorganic materials 0.000 description 8
- 229910000510 noble metal Inorganic materials 0.000 description 8
- 238000005859 coupling reaction Methods 0.000 description 7
- 238000011065 in-situ storage Methods 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 230000008878 coupling Effects 0.000 description 6
- 238000010168 coupling process Methods 0.000 description 6
- 235000013339 cereals Nutrition 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000000969 carrier Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000003993 interaction Effects 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
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 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
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 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
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000016507 interphase 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
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum 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 a kind of preparation method and applications of the silver-colored catalysis material of loaded nano that can be recycled, 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.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 coupler 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 being reduced through additional reducing agent.Cellulose paper base silver nanoparticle catalysis material prepared by the present invention is reduced to the catalyst of 4 amino-phenols reaction as 4 nitrophenols, catalytic activity is high, carrier and silver nanoparticle stability are high, catalyst is easily reclaimed, repeatable utility is good, and continuous recycle more than 20 times remains to keep higher catalytic activity.
Description
Technical field
The invention belongs to technical field of nano material, it is related to a kind of silver-colored catalysis material of loaded nano 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
It circulates the application of catalyzed conversion environmental contaminants.
Background technology
Metal nano material is with a wide range of applications in fields such as the energy, catalysis, biological medicine, sensing detections,
As the focus for studying concern in the world.Wherein, the noble metal nanometer material such as gold, silver, platinum because its higher specific surface area and solely
Special surface electronic characteristic and with excellent catalytic performance, 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, led because particle diameter is small, surface energy is high
Catalytic activity reduction is caused, and the catalyst of nanoscale is difficult to separate and recover from reaction system, reused.To solve these
Problem, is often carried on polymeric matrix by noble metal nano catalyst（J. Phys. Chem. C 2009, 113,5157−
5163）, mesoporous silicon（ACS Catal. 2011, 1, 207−211）, metal oxide（Green Chem., 2005,7,
768-770）Deng on carrier, to improve the dispersiveness 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 generally pre-treatment and preparation of these carriers
Method is complex.Therefore, explore new simple and effective metal nano catalyst carrier class and promote nanocatalyst in reality
In application.
Cellulosic-based material（Such as microcrystalline cellulose, bacteria cellulose film and laboratory ordinary filter paper）Because its resource is rich
Rich, biodegradable and cheap the advantages of can as noble metal nano catalyst excellent carrier.Document report with cellulose
Sill is that carrier synthesis noble metal nano catalyst has：Silver nanoparticle is grown 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
Ethene imido coats golden nanometer particle（RSC Adv., 2015, 5, 104239–104244）Deng.In addition, Application No.
201210184589.6 Chinese invention patent discloses a kind of method in cellulose-containing material silver nanoparticles loaded, mainly
Step includes the material of containing cellulose being soaked in the silver ammino solution being pre-configured with, and is reacted in 30 DEG C -100 DEG C of water-bath
10 min-24 h, cellulosic material cleaning is dried and produces area load and has the cellulosic material of Nano silver grain.Above-mentioned document
Or the method described in patent is to utilize physical absorption or electrostatic force between Nano silver grain and cellulosic material surface real mostly
The fixation of existing nano material, adhesion is not strong, and catalyst easily comes 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 substrate is easily disintegrated after water suction.Therefore, explore and utilize cellulose
The three-dimensional netted loose structure of paper base material, enhancing noble metal nanometer material and carrier interphase interaction, realize nanocatalyst
Stabilisation it is immobilized, while strengthen the mechanical strength of porous paper substrate, for developing the cellulose paper with high circulation catalytic activity
Base nano-catalyst seems particularly necessary.
The content of the invention
The present invention is in order to solve the above technical problems, there is provided a kind of using the plain paper substrate of functional fiber as carrier steady load silver
The preparation approach of nanocatalyst, this method is simple and easy to apply, and cellulose paper base used is cheap and easy to get, and wide material sources, silver nanoparticle is urged
Agent particle diameter is small, size uniformity, immobilized stabilization, also resides in a kind of cellulose paper base argentum nano composite material of offer in catalysis 4- nitre
Base phenol is reduced to the cycle applications in PAP reaction, and the composite 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 present invention uses following technical scheme：
A kind of preparation method for the cellulose paper base Nano Silver catalysis material that can be recycled, using cellulose paper sill as load
Body, amido modified, the amino of carrier surface and metal precursor ions phase after modification are carried out using silane coupler to carrier surface
Chelating, forms cellulose paper base Nano Silver catalysis material after being reduced through additional reducing agent.
The preparation method of the described cellulose paper base Nano Silver catalysis material that can be recycled, step is as follows：
（1）Cellulose paper sill it is surface-functionalized：Silane coupler is dissolved in ethanol/water system, after 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, activation 2 ~ 4 hours, the cellulose paper base material after activation in 110 ~ 130 DEG C of baking oven are placed in
Material is the cellulose paper sill I for obtaining surface amino groups functionalization through water and ethanol cleaning, drying at room temperature respectively；
（2）The absorption of silver nanoparticle precursor ion：Cellulose paper sill I is immersed in silver nanoparticle precursor solution, 25 ~ 40 DEG C of perseverances
Temperature is cleaned after being incubated 0.5 ~ 2 hour with water, is removed the unnecessary silver ion that surface is not chelated, is produced 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, added under stirring condition additional
Reducing agent, 25 ~ 50 DEG C of isothermal reactions 0.5 ~ 2 hour, you can 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.
The preparation method of the described cellulose paper base Nano Silver catalysis material that can be recycled, the cellulose paper base material
Expect for filter paper, printing paper or corrugated paper.
The step（1）In, silane coupler be 3- aminopropyl trimethoxysilanes or 3- aminopropyl triethoxysilanes,
The concentration of silane coupler solution is 0.4 ~ 2.5 mg/mL；The volume ratio of ethanol and water is 7 in the ethanol/water system:3.
The step（2）In, silver nanoparticle precursor is silver nitrate, silver acetate or silver orthophosphate, the concentration of silver nanoparticle precursor solution
For 5mM ~ 100mM.
The step（3）In, 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 is urged
Change material, the cycle applications in PAP reaction are reduced in catalytic environment pollutant 4- nitrophenols.
The application of the described cellulose paper base Nano Silver catalysis material that can be recycled, step is as follows：
A. cellulose paper base Nano Silver catalysis material is added in the 4- nitrophenol aqueous solution under the conditions of 25 ~ 60 DEG C, stirring is equal
After even, NaBH is added4The aqueous solution is reacted, and after 3 ~ 20min of reaction, that is, obtains product PAP；
B. after step a reactions terminate, cellulose paper base Nano Silver catalysis material is taken out from system through filtering, it is dry in vacuum
Dried in dry case, the cellulose paper base Nano Silver catalysis material can realize reuse 20 ~ 40 times.
In the step a, 4- nitro phenol concentrations are 0.02 ~ 0.50 mM, cellulose paper base Nano Silver catalysis material quality
For 10 ~ 50 mg, the NaBH4The concentration of the 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 the cellulose paper base silver nanoparticle catalysis material preparation method of the reusable edible of the present invention is as follows：With common
Laboratory filter paper is exemplified by cellulose paper sill, cellulosic filter paper has tridimensional network, and fiber surface is rich in hydroxyl, adopted
It is amino by hydroxyl modified, with reinforcing fiber chelant absorption silver ion and stable silver with silane coupled technology to its surface modification
The ability of nanometer；Amido modified cellulosic filter paper is immersed in silver ion solution, electronics is passed to shared and fiber
The amino strong bonded on surface；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：
1st, in cellulose paper base silver nanoparticle catalysis material prepared by the present invention, carrier material is cheap and easy to get, wide material sources, paper substrate table
Face functionalization and Nano silver grain restoring method are simple, and surface modification enhances the mechanical strength of paper substrate, the nano grain of silver of synthesis
Sub- size is small, active high, uniform particle diameter, and adhesion is strong especially between carrier, and stability is good.
2nd, cellulose paper base silver nanoparticle catalysis material prepared by the present invention is reduced to PAP as 4- nitrophenols
The catalyst of reaction, catalytic activity is high, and carrier and silver nanoparticle stability are high, and catalyst is easily reclaimed, and repeatable utility is good, even
Continuous recycle more than 20 times remains to keep higher catalytic activity.
3rd, cellulose paper sill（Such as ordinary filter paper, printing paper, corrugated paper）Cheap and wide material sources, show three-dimensional
Reticulated porous structures, cellulose fiber surface is rich in hydroxyl, and it is modified by silane coupled technology, on the one hand can be strengthened
The mechanical strength of paper base material, on the other hand introduces the functional group that energy chelant adsorbs noble metal precursor, can strengthen nanometer and urge
Agent and paper substrate carrier Interaction Force, therefore, carry out cellulose paper base functionalizing material surface and silver nanoparticle catalyst
Stabilize immobilized, the recyclable catalytic conversion applications of realization to environmental pollutants, for widening having for noble metal nano catalyst
Imitate load carriers scope and reduction environmental pollution is significant.
Brief description of the drawings
Fig. 1 is the infrared spectrogram that silane coupler prepared by embodiment 1 modifies filter paper.
Fig. 2 is the silver nanoparticle high power transmission electron micrograph based on cellulosic filter paper prepared by embodiment 2.
Fig. 3 is the XRD spectrum of amido modified filter paper prepared by embodiment 2 and the filter paper of load silver nanoparticle.
Fig. 4 is that composite prepared by embodiment 3 makees catalyst 4- p-nitrophenol reduction reaction course figures.
Fig. 5 is that composite prepared by embodiment 3 makees the cycle-index of catalyst and the graph of a relation of reaction conversion ratio.
Embodiment
A kind of preparation method for the cellulose paper base Nano Silver catalysis material that can be recycled, using cellulose paper sill as
Carrier, amido modified, the amino and metal precursor ions of carrier surface after modification is carried out using silane coupler to carrier surface
Mutually chelate, cellulose paper base Nano Silver catalysis material is formed after being reduced through additional reducing agent.
The preparation method of the described cellulose paper base Nano Silver catalysis material that can be recycled, step is as follows：
（1）Cellulose paper sill it is surface-functionalized：Silane coupler is dissolved in ethanol/water system, after 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, activation 2 ~ 4 hours, the cellulose paper base material after activation in 110 ~ 130 DEG C of baking oven are placed in
Material is the cellulose paper sill I for obtaining surface amino groups functionalization through water and ethanol cleaning, drying at room temperature respectively；
（2）The absorption of silver nanoparticle precursor ion：Cellulose paper sill I is immersed in silver nanoparticle precursor solution, 25 ~ 40 DEG C of perseverances
Temperature is cleaned after being incubated 0.5 ~ 2 hour with water, is removed the unnecessary silver ion that surface is not chelated, is produced 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, added under stirring condition additional
Reducing agent, 25 ~ 50 DEG C of isothermal reactions 0.5 ~ 2 hour, you can 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.
The preparation method of the described cellulose paper base Nano Silver catalysis material that can be recycled, the cellulose paper base material
Expect for filter paper, printing paper or corrugated paper.
The step（1）In, silane coupler be 3- aminopropyl trimethoxysilanes or 3- aminopropyl triethoxysilanes,
The concentration of silane coupler solution is 0.4 ~ 2.5 mg/mL；The volume ratio of ethanol and water is 7 in the ethanol/water system:3.
The step（2）In, silver nanoparticle precursor is silver nitrate, silver acetate or silver orthophosphate, the concentration of silver nanoparticle precursor solution
For 5mM ~ 100mM.
The step（3）In, 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 is urged
Change material, the cycle applications in PAP reaction are reduced in catalytic environment pollutant 4- nitrophenols.
The application of the described cellulose paper base Nano Silver catalysis material that can be recycled, step is as follows：
A. cellulose paper base Nano Silver catalysis material is added in the 4- nitrophenol aqueous solution under the conditions of 25 ~ 60 DEG C, stirring is equal
After even, NaBH is added4The aqueous solution is reacted, and after 3 ~ 20min of reaction, that is, obtains product PAP；
B. after step a reactions terminate, cellulose paper base Nano Silver catalysis material is taken out from system through filtering, it is dry in vacuum
Dried in dry case, the cellulose paper base Nano Silver catalysis material can realize reuse 20 ~ 40 times.
In the step a, 4- nitro phenol concentrations are 0.02 ~ 0.50 mM, cellulose paper base Nano Silver catalysis material quality
For 10 ~ 50 mg, the NaBH4The concentration of the 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 present invention is described in further detail with specific embodiment below in conjunction with the accompanying drawings, but is not the limitation present invention.
Embodiment 1
1st, cellulose paper is surface-functionalized：With the plain filter paper of laboratory general fibre（Cellulose filter paper, CFP）For
Silver nano material carrier, it is amido modified to the progress of its surface using silane coupling reagent, strengthen it and chelate adsorbing metal ions
Ability.
40mg 3- aminopropyl trimethoxysilanes are dissolved in 100mL ethanol/water system（70/30, v/v）, and stir
Mix scattered；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, it is ammonia to make cellulose surface hydroxyl reaction
Base；Filter paper after activation is cleaned with water and ethanol respectively, room temperature in vacuo is drying to obtain the cellulose filter of surface amino groups functionalization
Paper.
2nd, surface-functionalized paper chelating adsorbing metal precursor ion：Using N in cellulose surface amino lone pair electrons with
The firm adsorbing metal precursor ion of chelation between silver ion.
Surface-functionalized filter paper is dipped in 100mM silver acetate solutions, 40 DEG C of constant-temperature incubations 2 hours, chelant absorption
Silver ion.
3rd, silver nanoparticle is reduced and fixed：Closed using additional reducing agent in amido modified cellulose paper base material surface original position
Into and fixed silver nanoparticle catalyst, enhance nano material and the adhesion of cellulose paper.
Cellulose paper sill is taken out, the unnecessary silver ion of surface attachment is washed with water, chelant has been adsorbed into silver ion
Filter paper be dipped in again in the aqueous solution, a certain amount of ascorbic acid is rapidly injected under stirring, the concentration for making ascorbic acid is
50 mM, 50 DEG C are reacted 0.5 hour, you can in the amido modified immobilized silver nanoparticle catalyst of cellulose paper base surface-stable, are completed
The preparation of cellulose paper base silver nanoparticle catalysis material.
4th, catalytic applications are circulated：It is 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 easy to reclaim characteristic and many
Hole is beneficial to reactant diffusion property, and the stable circulation catalytic applications of catalyst material can be achieved.
A. cellulose paper base Nano Silver catalysis material is added in the 4- nitrophenol aqueous solution under the conditions of 25 DEG C, stirring
After uniform, 0.8M NaBH are added4The aqueous solution is reacted, and after reaction 3min, that is, obtains product PAP；
B. after step a reactions terminate, cellulose paper base Nano Silver catalysis material is taken out from system through filtering, 70 DEG C of conditions
Under dry 2h in vacuum drying chamber, the cellulose paper base Nano Silver catalysis material can realize reuse 20 times.
Embodiment 2
1st, cellulose paper is surface-functionalized：Using laboratory printing paper as silver nano material carrier, using silane coupling reagent to it
Surface progress is amido modified, strengthens its ability for chelating adsorbing metal ions.
250mg 3- aminopropyl triethoxysilanes are dissolved in 100mL ethanol/water system（70/30, v/v）, and
Dispersed with stirring；Take printing paper to be cut into the circle of suitable dimension, be 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, it is ammonia to make printing paper cellulose surface hydroxyl reaction
Base；Printing paper after activation is cleaned with water and ethanol respectively, room temperature in vacuo is drying to obtain the cellulose of surface amino groups functionalization
Printing paper.
2nd, surface-functionalized paper chelating adsorbing metal precursor ion：Using in printing paper cellulose surface amino N it is lonely right
The firm adsorbing metal precursor ion of chelation between electronics and silver ion.
In the silver nitrate solution that surface-functionalized printing paper is dipped in 5 mM, 25 DEG C of constant-temperature incubations 0.5 hour, chelant
Adsorb silver ion.
3rd, silver nanoparticle is reduced and fixed：Synthesized using additional reducing agent in amido modified cellulose printing paper surface in situ
And fixed silver nanoparticle catalyst, enhance nano material and the adhesion of printing paper.
Printing paper is taken out, the unnecessary silver ion of surface attachment is washed with water, chelant has been adsorbed to the printing paper of silver ion
It is dipped in again in the aqueous solution, additional reducing agent NaBH is rapidly injected under stirring4, make NaBH4Concentration be 1mM, 40 DEG C of constant temperature
React 2h, you can in the amido modified immobilized silver nanoparticle catalyst of cellulose paper base surface-stable, complete cellulose paper base silver and receive
The preparation of rice catalysis material.
4th, catalytic applications are circulated：It is 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 easy to reclaim characteristic and many
Hole is beneficial to reactant diffusion property, and the stable circulation catalytic applications of catalyst material can be achieved.
A. cellulose paper base Nano Silver catalysis material is added in the 4- nitrophenol aqueous solution under the conditions of 40 DEG C, stirring
After uniform, 0.5M NaBH are added4The aqueous solution is reacted, and after 12 min of reaction, that is, obtains product PAP；
B. after step a reactions terminate, cellulose paper base Nano Silver catalysis material is taken out from system through filtering, 80 DEG C of conditions
Under dry 1h in vacuum drying chamber, the cellulose paper base Nano Silver catalysis material can realize reuse 40 times.
Embodiment 3
1st, cellulose paper is surface-functionalized：It is even using silane using the plain corrugated paper of laboratory general fibre as silver nano material carrier
Joint-trial agent is amido modified to the progress of its surface, strengthens its ability for chelating adsorbing metal ions.
170mg 3- aminopropyl triethoxysilanes are dissolved in 100mL ethanol/water system（70/30, v/v）, and
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
Answer 2 hours.
Cellulose corrugated paper is taken out, is placed in 120 DEG C of baking ovens and activates 3 hours, it is ammonia to make cellulose surface hydroxyl reaction
Base；Corrugated paper after activation is cleaned with water and ethanol respectively, room temperature in vacuo is drying to obtain the cellulose of surface amino groups functionalization
Corrugated paper.
2nd, surface-functionalized paper chelating adsorbing metal precursor ion：Using N in cellulose surface amino lone pair electrons with
The firm adsorbing metal precursor ion of chelation between silver ion.
Surface-functionalized corrugated paper is dipped in 5 mM silver orthophosphate solution, 35 DEG C of constant-temperature incubations 1.5 hours, chelant is inhaled
Attached silver ion.
3rd, silver nanoparticle is reduced and fixed：Using additional reducing agent NaBH4 in amido modified cellulose paper base material surface
Fabricated in situ and fixed silver nanoparticle catalyst, enhance nano material and the adhesion of cellulose paper.
Cellulose paper sill is taken out, the unnecessary silver ion of surface attachment is washed with water, chelant has been adsorbed into silver ion
Corrugated paper be dipped in again in the aqueous solution, a certain amount of additional reducing agent NaBH is rapidly injected under stirring4Its concentration is set to be
25mM, 25 DEG C of isothermal reaction 2h, you can in the amido modified immobilized silver nanoparticle catalyst of cellulose paper base surface-stable, complete fine
The preparation of the plain paper substrate silver nanoparticle catalysis material of dimension.
4th, catalytic applications are circulated：It is 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 easy to reclaim characteristic and many
Hole is beneficial to reactant diffusion property, and the stable circulation catalytic applications of catalyst material can be achieved.
A. cellulose paper base Nano Silver catalysis material is added in the 4- nitrophenol aqueous solution under the conditions of 60 DEG C, stirring
After uniform, 0.1M NaBH are added4The aqueous solution is reacted, and after reaction 20min, that is, obtains product PAP；
B. after step a reactions terminate, cellulose paper base Nano Silver catalysis material is taken out from system through filtering, 90 DEG C of conditions
Under dry 1h in vacuum drying chamber, the cellulose paper base Nano Silver catalysis material can realize reuse 30 times.
Embodiment 4
1st, cellulose paper is surface-functionalized：It is even using silane using the plain corrugated paper of laboratory general fibre as silver nano material carrier
Joint-trial agent is amido modified to the progress of its surface, strengthens its ability for chelating adsorbing metal ions.
250mg 3- aminopropyl triethoxysilanes are dissolved in 100mL ethanol/water system（70/30, v/v）, and
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
Answer 1 hour.
Cellulose corrugated paper is taken out, is placed in 120 DEG C of baking ovens and activates 3 hours, it is ammonia to make cellulose surface hydroxyl reaction
Base；Corrugated paper after activation is cleaned with water and ethanol respectively, room temperature in vacuo is drying to obtain the cellulose of surface amino groups functionalization
Corrugated paper.
2nd, surface-functionalized paper chelating adsorbing metal precursor ion：Using N in cellulose surface amino lone pair electrons with
The firm adsorbing metal precursor ion of chelation between silver ion.
Surface-functionalized corrugated paper is dipped in 5 mM silver orthophosphate solution, 35 DEG C of constant-temperature incubations 1.5 hours, chelant is inhaled
Attached silver ion.
3rd, silver nanoparticle is reduced and fixed：Utilize additional reducing agent NaBH4In amido modified cellulose paper base material surface
Fabricated in situ and fixed silver nanoparticle catalyst, enhance nano material and the adhesion of cellulose paper.
Cellulose paper sill is taken out, the unnecessary silver ion of surface attachment is washed with water, chelant has been adsorbed into silver ion
Corrugated paper be dipped in again in the aqueous solution, a certain amount of additional reducing agent NaBH is rapidly injected under stirring4Its concentration is set to be
25mM, 50 DEG C of isothermal reaction 0.5h, you can in the amido modified immobilized silver nanoparticle catalyst of cellulose paper base surface-stable, are completed
The preparation of cellulose paper base silver nanoparticle catalysis material.
4th, catalytic applications are circulated：It is 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 easy to reclaim characteristic and many
Hole is beneficial to reactant diffusion property, and the stable circulation catalytic applications of catalyst material can be achieved.
A. cellulose paper base Nano Silver catalysis material is added in the 4- nitrophenol aqueous solution under the conditions of 60 DEG C, stirring
After uniform, 1M NaBH are added4The aqueous solution is reacted, and after reaction 20min, that is, obtains product PAP；
B. after step a reactions terminate, cellulose paper base Nano Silver catalysis material is taken out from system through filtering, 90 DEG C of conditions
Under dry 1h in vacuum drying chamber, the cellulose paper base Nano Silver catalysis material can realize reuse 25 times.
Embodiment 5
1st, cellulose paper is surface-functionalized：It is even using silane using the plain corrugated paper of laboratory general fibre as silver nano material carrier
Joint-trial agent is amido modified to the progress of its surface, strengthens its ability for chelating adsorbing metal ions.
40mg 3- aminopropyl triethoxysilanes are dissolved in 100mL ethanol/water system（70/30, v/v）, and stir
Mix scattered；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, it is ammonia to make cellulose surface hydroxyl reaction
Base；Corrugated paper after activation is cleaned with water and ethanol respectively, room temperature in vacuo is drying to obtain the cellulose of surface amino groups functionalization
Corrugated paper.
2nd, surface-functionalized paper chelating adsorbing metal precursor ion：Using N in cellulose surface amino lone pair electrons with
The firm adsorbing metal precursor ion of chelation between silver ion.
Surface-functionalized corrugated paper is dipped in 100 mM silver orthophosphate solution, 25 DEG C of constant-temperature incubations 2 hours, chelant is inhaled
Attached silver ion.
3rd, silver nanoparticle is reduced and fixed：Utilize additional reducing agent NaBH4In amido modified cellulose paper base material surface
Fabricated in situ and fixed silver nanoparticle catalyst, enhance nano material and the adhesion of cellulose paper.
Cellulose paper sill is taken out, the unnecessary silver ion of surface attachment is washed with water, chelant has been adsorbed into silver ion
Corrugated paper be dipped in again in the aqueous solution, a certain amount of additional reducing agent NaBH is rapidly injected under stirring4Its concentration is set to be
50 mM, 30 DEG C of isothermal reaction 1.5h, you can in the amido modified immobilized silver nanoparticle catalyst of cellulose paper base surface-stable, it is complete
Into the preparation of cellulose paper base silver nanoparticle catalysis material.
4th, catalytic applications are circulated：It is 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 easy to reclaim characteristic and many
Hole is beneficial to reactant diffusion property, and the stable circulation catalytic applications of catalyst material can be achieved.
A. cellulose paper base Nano Silver catalysis material is added in the 4- nitrophenol aqueous solution under the conditions of 25 DEG C, stirring
After uniform, 0.5M NaBH are added4The aqueous solution is reacted, and after 15 min of reaction, that is, obtains product PAP；
B. after step a reactions terminate, cellulose paper base Nano Silver catalysis material is taken out from system through filtering, 90 DEG C of conditions
Under dry 1h in vacuum drying chamber, the cellulose paper base Nano Silver catalysis material can realize reuse 20 times.
Embodiment 6
1st, cellulose paper is surface-functionalized：With the plain filter paper of laboratory general fibre（Cellulose filter paper, CFP）For
Silver nano material carrier, it is amido modified to the progress of its surface using silane coupling reagent, strengthen it and chelate adsorbing metal ions
Ability.
250 mg 3- aminopropyl trimethoxysilanes are dissolved in 100mL ethanol/water system（70/30, v/v）, and
Dispersed with stirring；Cellulose paper base material laboratory filter paper is taken, the rectangle of suitable dimension is cut into, above-mentioned system is immersed in
It is interior, react 1 hour.
Cellulosic filter paper is taken out, is placed in 110 DEG C of baking ovens and activates 2 hours, it is ammonia to make cellulose surface hydroxyl reaction
Base；Filter paper after activation is cleaned with water and ethanol respectively, room temperature in vacuo is drying to obtain the cellulose filter of surface amino groups functionalization
Paper.
2nd, surface-functionalized paper chelating adsorbing metal precursor ion：Using N in cellulose surface amino lone pair electrons with
The firm adsorbing metal precursor ion of chelation between silver ion.
Surface-functionalized filter paper is dipped in 5mM silver orthophosphate solution, 25 DEG C of constant-temperature incubations 1.5 hours, chelant absorption
Silver ion.
3rd, silver nanoparticle is reduced and fixed：Closed using additional reducing agent in amido modified cellulose paper base material surface original position
Into and fixed silver nanoparticle catalyst, enhance nano material and the adhesion of cellulose paper.
Cellulose paper sill is taken out, the unnecessary silver ion of surface attachment is washed with water, chelant has been adsorbed into silver ion
Filter paper be dipped in again in the aqueous solution, a certain amount of ascorbic acid is rapidly injected under stirring, make ascorbic acid concentration be 1
MM, 25 DEG C of isothermal reaction 2h, you can in the amido modified immobilized silver nanoparticle catalyst of cellulose paper base surface-stable, complete fiber
The preparation of plain paper substrate silver nanoparticle catalysis material.
4th, catalytic applications are circulated：It is 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 easy to reclaim characteristic and many
Hole is beneficial to reactant diffusion property, and the stable circulation catalytic applications of catalyst material can be achieved.
A. cellulose paper base Nano Silver catalysis material is added in the 4- nitrophenol aqueous solution under the conditions of 25 DEG C, stirring
After uniform, 0.1M NaBH are added4The aqueous solution is reacted, and after 15 min of reaction, that is, obtains product PAP；
B. after step a reactions terminate, cellulose paper base Nano Silver catalysis material is taken out from system through filtering, 70 DEG C of conditions
Under dry 1h in vacuum drying chamber, the cellulose paper base Nano Silver catalysis material can realize reuse 20 times.
Embodiment 7
1st, cellulose paper is surface-functionalized：With the plain filter paper of laboratory general fibre（Cellulose filter paper, CFP）For
Silver nano material carrier, it is amido modified to the progress of its surface using silane coupling reagent, strengthen it and chelate adsorbing metal ions
Ability.
100 mg 3- aminopropyl trimethoxysilanes are dissolved in 100mL ethanol/water system（70/30, v/v）, and
Dispersed with stirring；Cellulose paper base material laboratory filter paper is taken, the rectangle of suitable dimension is cut into, above-mentioned system is immersed in
It is interior, react 1 hour.
Cellulosic filter paper is taken out, is placed in 130 DEG C of baking ovens and activates 4 hours, it is ammonia to make cellulose surface hydroxyl reaction
Base；Filter paper after activation is cleaned with water and ethanol respectively, room temperature in vacuo is drying to obtain the cellulose filter of surface amino groups functionalization
Paper.
2nd, surface-functionalized paper chelating adsorbing metal precursor ion：Using N in cellulose surface amino lone pair electrons with
The firm adsorbing metal precursor ion of chelation between silver ion.
Surface-functionalized filter paper is dipped in 100mM silver acetate solutions, 40 DEG C of constant-temperature incubations 0.5 hour, chelant is inhaled
Attached silver ion.
3rd, silver nanoparticle is reduced and fixed：Closed using additional reducing agent in amido modified cellulose paper base material surface original position
Into and fixed silver nanoparticle catalyst, enhance nano material and the adhesion of cellulose paper.
Cellulose paper sill is taken out, the unnecessary silver ion of surface attachment is washed with water, chelant has been adsorbed into silver ion
Filter paper be dipped in again in the aqueous solution, a certain amount of ascorbic acid is rapidly injected under stirring, make ascorbic acid concentration be 1
MM, 40 DEG C of isothermal reaction 0.5h, you can in the amido modified immobilized silver nanoparticle catalyst of cellulose paper base surface-stable, complete fine
The preparation of the plain paper substrate silver nanoparticle catalysis material of dimension.
4th, catalytic applications are circulated：It is 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 easy to reclaim characteristic and many
Hole is beneficial to reactant diffusion property, and the stable circulation catalytic applications of catalyst material can be achieved.
A. cellulose paper base Nano Silver catalysis material is added in the 4- nitrophenol aqueous solution under the conditions of 25 DEG C, stirring
After uniform, 0.5M NaBH are added4The aqueous solution is reacted, and after 8 min of reaction, that is, obtains product PAP；
B. after step a reactions terminate, cellulose paper base Nano Silver catalysis material is taken out from system through filtering, 90 DEG C of conditions
Under dry 2h in vacuum drying chamber, the cellulose paper base Nano Silver catalysis material can realize reuse 40 times.
Embodiment 8
1st, cellulose paper is surface-functionalized：Using laboratory printing paper as silver nano material carrier, using silane coupling reagent to it
Surface progress is amido modified, strengthens its ability for chelating adsorbing metal ions.
40mg 3- aminopropyl triethoxysilanes are dissolved in 100mL ethanol/water system（70/30, v/v）, and stir
Mix scattered；Take printing paper to be cut into the circle of suitable dimension, be 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, it is ammonia to make printing paper cellulose surface hydroxyl reaction
Base；Printing paper after activation is cleaned with water and ethanol respectively, room temperature in vacuo is drying to obtain the cellulose of surface amino groups functionalization
Printing paper.
2nd, surface-functionalized paper chelating adsorbing metal precursor ion：Using in printing paper cellulose surface amino N it is lonely right
The firm adsorbing metal precursor ion of chelation between electronics and silver ion.
In the silver nitrate solution that surface-functionalized printing paper is dipped in 50 mM, 40 DEG C of constant-temperature incubations 2 hours, chelant is inhaled
Attached silver ion.
3rd, silver nanoparticle is reduced and fixed：Synthesized using additional reducing agent in amido modified cellulose printing paper surface in situ
And fixed silver nanoparticle catalyst, enhance nano material and the adhesion of printing paper.
Printing paper is taken out, the unnecessary silver ion of surface attachment is washed with water, chelant has been adsorbed to the printing paper of silver ion
It is dipped in again in the aqueous solution, additional reducing agent NaBH is rapidly injected under stirring4, make NaBH4Concentration be 50 mM, 25 DEG C of perseverances
Temperature reaction 0.5h, you can in the amido modified immobilized silver nanoparticle catalyst of cellulose paper base surface-stable, complete cellulose paper base
The preparation of silver nanoparticle catalysis material.
4th, catalytic applications are circulated：It is 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 easy to reclaim characteristic and many
Hole is beneficial to reactant diffusion property, and the stable circulation catalytic applications of catalyst material can be achieved.
A. cellulose paper base Nano Silver catalysis material is added in the 4- nitrophenol aqueous solution under the conditions of 25 DEG C, stirring
After uniform, 0.1M NaBH are added4The aqueous solution is reacted, and after 3 min of reaction, that is, obtains product PAP；
B. after step a reactions terminate, cellulose paper base Nano Silver catalysis material is taken out from system through filtering, 90 DEG C of conditions
Under dry 1h in vacuum drying chamber, the cellulose paper base Nano Silver catalysis material can realize reuse 30 times.
Embodiment 9
1st, cellulose paper is surface-functionalized：Using laboratory printing paper as silver nano material carrier, using silane coupling reagent to it
Surface progress is amido modified, strengthens its ability for chelating adsorbing metal ions.
150 mg 3- aminopropyl triethoxysilanes are dissolved in 100mL ethanol/water system（70/30, v/v）, and
Dispersed with stirring；Take printing paper to be cut into the circle of suitable dimension, be 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 the printing paper cellulose surface hydroxyl reaction be
Amino；Printing paper after activation is cleaned with water and ethanol respectively, room temperature in vacuo is drying to obtain the fiber of surface amino groups functionalization
Plain printing paper.
2nd, surface-functionalized paper chelating adsorbing metal precursor ion：Using in printing paper cellulose surface amino N it is lonely right
The firm adsorbing metal precursor ion of chelation between electronics and silver ion.
Surface-functionalized printing paper is dipped in 100 mM silver orthophosphate solution, 40 DEG C of constant-temperature incubations 2 hours, chelant
Adsorb silver ion.
3rd, silver nanoparticle is reduced and fixed：Synthesized using additional reducing agent in amido modified cellulose printing paper surface in situ
And fixed silver nanoparticle catalyst, enhance nano material and the adhesion of printing paper.
Printing paper is taken out, the unnecessary silver ion of surface attachment is washed with water, chelant has been adsorbed to the printing paper of silver ion
It is dipped in again in the aqueous solution, additional reducing agent NaBH is rapidly injected under stirring4, make NaBH4Concentration be 50 mM, 40 DEG C of perseverances
Temperature reaction 1.5h, you can in the amido modified immobilized silver nanoparticle catalyst of cellulose paper base surface-stable, complete cellulose paper base
The preparation of silver nanoparticle catalysis material.
4th, catalytic applications are circulated：It is 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 easy to reclaim characteristic and many
Hole is beneficial to reactant diffusion property, and the stable circulation catalytic applications of catalyst material can be achieved.
A. cellulose paper base Nano Silver catalysis material is added in the 4- nitrophenol aqueous solution under the conditions of 25 DEG C, stirring
After uniform, 0.5M NaBH are added4The aqueous solution is reacted, and after 3 min of reaction, that is, obtains product PAP；
B. after step a reactions terminate, cellulose paper base Nano Silver catalysis material is taken out from system through filtering, 90 DEG C of conditions
Under dry 1h in vacuum drying chamber, the cellulose paper base Nano Silver catalysis material can realize reuse 25 times.
Claims (10)
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 coupler
Category precursor ion is mutually chelated, and cellulose paper base Nano Silver catalysis material is formed after being reduced through additional reducing agent.
2. the preparation method for the cellulose paper base Nano Silver catalysis material that can be recycled as claimed in claim 1, its feature
It is that step is as follows：
（1）Cellulose paper sill it is surface-functionalized：Silane coupler is dissolved in ethanol/water system, after 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, activation 2 ~ 4 hours, the cellulose paper base material after activation in 110 ~ 130 DEG C of baking oven are placed in
Material is the cellulose paper sill I for obtaining surface amino groups functionalization through water and ethanol cleaning, drying at room temperature respectively；
（2）The absorption of silver nanoparticle precursor ion：Cellulose paper sill I is immersed in silver nanoparticle precursor solution, 25 ~ 40 DEG C of perseverances
Temperature is cleaned after being incubated 0.5 ~ 2 hour with water, is removed the unnecessary silver ion that surface is not chelated, is produced 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, added under stirring condition additional
Reducing agent, 25 ~ 50 DEG C of isothermal reactions 0.5 ~ 2 hour, you can 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.
3. the preparation method for the cellulose paper base Nano Silver catalysis material that can be recycled as claimed in claim 1 or 2, it is special
Levy and be：The cellulose paper sill is filter paper, printing paper or corrugated paper.
4. the preparation method for the cellulose paper base Nano Silver catalysis material that can be recycled as claimed in claim 2, its feature
It is：The step（1）In, silane coupler is 3- aminopropyl trimethoxysilanes or 3- aminopropyl triethoxysilanes, silicon
The concentration of alkane coupling agent solution is 0.4 ~ 2.5 mg/mL；The volume ratio of ethanol and water is 7 in the ethanol/water system:3.
5. the preparation method for the cellulose paper base Nano Silver catalysis material that can be recycled as claimed in claim 2, its feature
It is：The step（2）In, silver nanoparticle precursor is silver nitrate, silver acetate or silver orthophosphate, and the concentration of silver nanoparticle precursor solution is
5mM~100mM。
6. the preparation method for the cellulose paper base Nano Silver catalysis material that can be recycled as claimed in claim 2, its feature
It is：The step（3）In, additional reducing agent is ascorbic acid or NaBH4, the concentration of additional reducing agent is 1mM ~ 50mM.
7. a kind of application for the cellulose paper base Nano Silver catalysis material that can be recycled, it is characterised in that：The cellulose paper
Base Nano Silver catalysis material, the cycle applications in PAP reaction are reduced in catalytic environment pollutant 4- nitrophenols.
8. the application for the cellulose paper base Nano Silver catalysis material that can be recycled as claimed in claim 6, it is characterised in that
Step is as follows：
A. cellulose paper base Nano Silver catalysis material is added in the 4- nitrophenol aqueous solution under the conditions of 25 ~ 60 DEG C, stirring is equal
After even, NaBH is added4The aqueous solution is reacted, and after 3 ~ 20min of reaction, that is, obtains product PAP；
B. after step a reactions terminate, cellulose paper base Nano Silver catalysis material is taken out from system through filtering, it is dry in vacuum
Dried in dry case, the cellulose paper base Nano Silver catalysis material can realize reuse 20 ~ 40 times.
9. the application for the cellulose paper base Nano Silver catalysis material that can be recycled as claimed in claim 8, it is characterised in that：
In the step a, 4- nitro phenol concentrations are 0.02 ~ 0.50 mM, and cellulose paper base Nano Silver catalysis material quality is 10 ~ 50
Mg, the NaBH4The concentration of the aqueous solution is 0.1 M ~ 1M.
10. the application for the cellulose paper base Nano Silver catalysis material that can be recycled as claimed in claim 8, its feature exists
In：In the step b, vacuum drying drying temperature is 70 ~ 90 DEG C, and drying time is 1 ~ 2h.
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| 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 |
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