CN104489922A - Preparation and application of graphene oxide-bonded silica gel composite - Google Patents

Preparation and application of graphene oxide-bonded silica gel composite Download PDF

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Publication number
CN104489922A
CN104489922A CN201410766164.5A CN201410766164A CN104489922A CN 104489922 A CN104489922 A CN 104489922A CN 201410766164 A CN201410766164 A CN 201410766164A CN 104489922 A CN104489922 A CN 104489922A
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silica gel
graphene oxide
gel composite
bonded silica
cleaning
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CN104489922B (en
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石睿
徐同广
严莉红
张�杰
王巍巍
刘冬烨
周骏
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Shanghai Tobacco Group Co Ltd
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BEIJING CIGARETTE FACTORY SHANGHAI TOBACCO GROUP
Shanghai Tobacco Group Co Ltd
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    • AHUMAN NECESSITIES
    • A24TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24DCIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06Use of materials for tobacco smoke filters
    • A24D3/14Use of materials for tobacco smoke filters of organic materials as additive

Abstract

The invention provides a reparation method for a graphene oxide-bonded silica gel composite, which includes the following steps: (1) sodium nitrate and concentrated sulfuric acid are added into graphite powder for pre-oxidation treatment, potassium permanganate is added into the mixture and agitated, water is added for dilution, agitation is then continued, warm water and hydrogen peroxide are added into the mixture, uniformly agitated, centrifuged and filtered, and finally, after cleaning and drying, graphene oxide powder is produced; (2) the graphene oxide powder is added into N, N dimethylformamide and ultrasonically dispersed, amino silica gel and dicyclohexylcarbodiimide are added into the mixture and heated for reflux, and after centrifugation, filtration, cleaning and drying, the graphene oxide-bonded silica gel composite is produced. The invention also further provides a cigarette filter into which the graphene oxide-bonded silica gel composite is added. The graphene oxide-bonded silica gel composite provided by the invention can effectively reduce the content of TSNAs in the mainstream smoke of cigarettes, and has an excellent effect.

Description

A kind of preparations and applicatio of graphene oxide bonded silica gel composite
Technical field
The invention belongs to cigarette material technical field, relate in a kind of cigarette field functional material preparation and application, be specifically related to a kind of preparation of graphene oxide bonded silica gel composite and add in cigarette filter rod the application reducing nitrosamine in cigarette mainstream flue gas to.
Background technology
Cigarette can produce short cancer and carcinogen in combustion, as condensed-nuclei aromatics, aldehydes matter, tobacco-specific nitrosamine (TSNAs) and free radical etc.Wherein, tobacco-specific nitrosamine (TSNAs) it is reported, has identified 8 kinds at present.But main in cigarette have 4 kinds: N-nitrosonornicotine (NNN), 4-(methyl nitrous ammonia)-1-(3-pyridine radicals)-1-butanone (NNK), N-nitrosoanatabine (NAT), N-nitroso anabasine (NAB).Wherein NNN and NNK has been proved to be and has had animal carcinogenicity, brings out lung cancer to mouse, rat and Syria gold vole.In metabolic activity, NNN and NNK can make the DNA methylation in living animal and in vitro tissue, and this result can be proven in isolated 07-methyl guanine and 06-methyl guanine from tissue.
At present, the method reducing harmful substance in cigarette has a lot, comprises in filter stick punching, formula and adds expanded cut tobacco, expanded cut stem and mix reconstituted tobacoo etc.But these methods great majority are while harmful substance such as reduction releasing content of coke tar or nicotine content etc., the fragrance of cigarette and mouthfeel are had a great impact.
Recent years, nano material has due to it absorption property that unique texture brings, and is regarded as can be used as additive of cigarette filter stick.Wherein, Graphene is a kind of two-dimension nano materials only having a carbon atom thickness, form cellular regular hexagon lattice configuration by carbon atom with sp2 hybridized orbit, except there is the character of common nano material, also there is high electron mobility, unique π key conjugation suction-operated.Graphene oxide (GO) is the presoma that chemical method prepares Graphene, and its surface is containing abundant hydroxyl, carboxyl and epoxy functionality, and easy and other polar groups form chemical bond, and have good hydrophily.Therefore, be necessary very much to grapheme material Harm reduction techniques fall burnt in application carry out further investigated and research.
Summary of the invention
The shortcoming of prior art in view of the above, the object of the present invention is to provide a kind of preparations and applicatio of graphene oxide bonded silica gel composite, by graphene oxide (GO) is loaded on silica-gel carrier, prepare graphene oxide bonded silica gel (GO/ silica gel) composite, add in cigarette filter rod, can effectively reduce TSNAs content in cigarette mainstream flue gas.
For achieving the above object and other relevant objects, the invention provides a kind of preparation method of graphene oxide bonded silica gel composite, comprise the following steps:
1) in graphite powder, sodium nitrate is added and the concentrated sulfuric acid carries out pre-oxidation treatment, add after potassium permanganate stirs again, be diluted with water rear continuations and stir, then add warm water and hydrogen peroxide stir after centrifugal, filtration, finally clean post-drying, obtain graphene oxide (GO) powder;
Preferably, described graphite powder with the ratio adding weight of sodium nitrate is: 2:0.9-1.1.
Preferably, described graphite powder with the ratio adding weight of sodium nitrate is: 2:1.
Preferably, the solid-to-liquid ratio adding volume adding weight and the concentrated sulfuric acid of described graphite powder is: 1:21-25 (g/ml).
Preferably, the solid-to-liquid ratio adding volume adding weight and the concentrated sulfuric acid of described graphite powder is: 1:23 (g/ml).
Preferably, described pre-oxidation treatment condition is: reaction temperature: 0-5 DEG C; Reaction time: 20-40 minute; Stir number of times: 150-250 beat/min.
Preferably, described pre-oxidation treatment condition is: reaction temperature: 0 DEG C; Reaction time: 30 minutes; Stir number of times: 200 beats/min.
Preferably, described graphite powder with the ratio adding weight of potassium permanganate is: 1:2.8-3.2.
Preferably, described graphite powder with the ratio adding weight of potassium permanganate is: 1:3.
Preferably, the stirring condition of described potassium permanganate is: whipping temp: room temperature; Mixing time: 110-130 minute; Stir number of times: 100-150 beat/min.
Preferably, the stirring condition of described potassium permanganate is: whipping temp: 20-25 DEG C; Mixing time: 120 minutes; Stir number of times: 120 beats/min.
Described add potassium permanganate stir after, mixture can become brown slurry.The principle of described generation brown slurry is that graphite powder is oxidized, and the functional groups such as Surface Creation hydroxyl, carboxyl, epoxy radicals, large conjugatedπbond system is broken, and spectral absorption changes, and therefore color is become brown from black.
Preferably, the solid-to-liquid ratio adding volume adding weight and water of described graphite powder is: 1:48-52 (g/ml).Described being diluted with water is conducive to release heat, is convenient to oxidation.
Preferably, the solid-to-liquid ratio adding volume adding weight and water of described graphite powder is: 1:50 (g/ml).
Preferably, the stirring condition that adds water described in is: mixing time is 110-130 minute; Stir number of times: 150-250 beat/min.
Preferably, the stirring condition that adds water described in is: mixing time is 120 minutes; Stir number of times: 200 beats/min.
Preferably, described warm water is the deionized water of water temperature 30-50 DEG C.Described warm water adds and is conducive to preventing from precipitating in reaction regenerating, and increases solute effect.
Preferably, the solid-to-liquid ratio adding volume adding weight and warm water of described graphite powder is: 1:95-105 (g/ml).
Preferably, the solid-to-liquid ratio adding volume adding weight and warm water of described graphite powder is: 1:100 (g/ml).
Preferably, described hydrogen peroxide is 30% hydrogen peroxide (v/v).
Preferably, the solid-to-liquid ratio adding volume adding weight and hydrogen peroxide of described graphite powder is: 1:9.5-10.5 (g/ml).
Preferably, the solid-to-liquid ratio adding volume adding weight and hydrogen peroxide of described graphite powder is: 1:10 (g/ml).
Preferably, warm water and hydrogen peroxide stirring condition are: mixing time is 15-25 minute; Stir number of times: 150-250 beat/min.
Preferably, warm water and hydrogen peroxide stirring condition are: mixing time is 20 minutes; Stir number of times: 200 beats/min.
Preferably, described centrifugal, filter and refer to and filter out solvent by after centrifugal for reactant layering, retain pressed powder.
Preferably, described centrifugal condition is: centrifugation time: 9.5-10.5min; Rotating speed: 4800-5200rpm/min.
More excellent, described centrifugal condition is: centrifugation time: 10min; Rotating speed: 5000rpm/min.
Preferably, described cleaning filters out cleaning agent by after centrifugal for the reactant adding cleaning agent layering, retains pressed powder.
Preferably, described cleaning agent is watery hydrochloric acid or water.
Preferably, described cleaning way is: first carry out cleaning twice with watery hydrochloric acid, then carry out cleaning twice with water.The described metal oxide adding watery hydrochloric acid cleaning and be conducive to removing material surface.
More excellent, described watery hydrochloric acid is the watery hydrochloric acid (v/v) of 5%.
More excellent, each cleaning volumetric usage of described watery hydrochloric acid with the ratio adding weight of graphite powder is: 95-105:1 (ml/g).
Optimum, each cleaning volumetric usage of described watery hydrochloric acid with the ratio adding weight of graphite powder is: 100:1 (ml/g).
More excellent, each cleaning volumetric usage of described water with the ratio adding weight of graphite powder is: 95-105:1 (ml/g).
Optimum, each cleaning volumetric usage of described water with the ratio adding weight of graphite powder is: 100:1 (ml/g).
Preferably, described drying mode is at room temperature to dry sample with vacuum drying oven.
Preferably, described drying condition is: reaction temperature: room temperature; Reaction vessel: vacuum drying oven; Container power: 1.8-2.0kW; Drying time: 23.5-24.5 hour.
More excellent, described drying condition is: reaction temperature: 20-25 DEG C; Reaction vessel: vacuum drying oven; Container power: 1.9kW; Drying time: 24 hours.
2) graphene oxide powder is joined N, carry out ultrasonic disperse in dinethylformamide, then add after alkylamino silica gel and dicyclohexylcarbodiimide carry out adding hot reflux, centrifugal, filter, cleaning post-drying, obtains graphene oxide bonded silica gel composite.
Preferably, the solid-to-liquid ratio adding volume adding weight and DMF of described graphene oxide powder is: 2:4.8-5.2 (g/ml).
Preferably, the solid-to-liquid ratio adding volume adding weight and DMF of described graphene oxide powder is: 2:5 (g/ml).
Preferably, described ultrasound condition is: ultrasonic time: 20-40 minute; Ultrasonic power: 480-520W; Ultrasonic temperature: room temperature.
Preferably, described ultrasound condition is: ultrasonic time: 30 minutes; Ultrasonic power: 500W; Ultrasonic temperature: 20-25 DEG C.
Preferably, described graphene oxide powder, alkylamino silica gel, dicyclohexylcarbodiimide add the ratio of weight and are: 1:23-27:0.9-1.1.
Preferably, described graphene oxide powder, alkylamino silica gel, dicyclohexylcarbodiimide add the ratio of weight and are: 1:25:1.
Preferably, described heated reflux condition: heating-up temperature: 50 ± 0.5 DEG C; Return time: 30 ± 0.1 hours.
Preferably, described heated reflux condition: heating-up temperature: 50 DEG C; Return time: 30 hours.
Preferably, described centrifugal, filter and refer to and filter out solvent by after centrifugal for reactant layering, retain pressed powder.
Preferably, described centrifugal condition is: centrifugation time: 9.5-10.5min; Rotating speed: 4800-5200rpm/min.
More excellent, described centrifugal condition is: centrifugation time: 10min; Rotating speed: 5000rpm/min.
Preferably, described cleaning filters out cleaning agent by after centrifugal for the reactant adding cleaning agent layering, retains pressed powder.
Preferably, described cleaning agent is methyl alcohol or water.
Preferably, described cleaning way is: first carry out eccentric cleaning twice with water, then carry out eccentric cleaning twice with methyl alcohol.
More excellent, each cleaning volumetric usage of described water with the ratio adding weight of graphite powder is: 2300-2700:1 (ml/g).
Optimum, each cleaning volumetric usage of described water with the ratio adding weight of graphite powder is: 2500:1 (ml/g).
More excellent, each cleaning volumetric usage of described methyl alcohol with the ratio adding weight of graphite powder is: 2300-2700:1 (ml/g).
Optimum, each cleaning volumetric usage of described methyl alcohol with the ratio adding weight of graphite powder is: 2500:1 (ml/g).
More excellent, described methyl alcohol is absolute methanol.
Preferably, described drying mode is at room temperature to dry sample with vacuum drying oven.
Preferably, described drying condition is: reaction temperature: room temperature; Reaction vessel: vacuum drying oven; Container power: 1.8-2.0kW; Drying time: 29.5-30.5 hour.
More excellent, described drying condition is: reaction temperature: 20-25 DEG C; Reaction vessel: vacuum drying oven; Container power: 1.9kW; Drying time: 30 hours.
Preferably, the described water used in the present invention is deionized water.
The invention also discloses a kind of graphene oxide bonded silica gel composite adopting said method to obtain.
Preferably, the specific area of described graphene oxide composite material is 280-295m 2/ g.
Preferably, the specific area of described graphene oxide composite material is 287m 2/ g.
Preferably, the specific area of described graphene oxide bonded silica gel composite is 330-340m 2/ g.
Preferably, the specific area of described graphene oxide bonded silica gel composite is 336m 2/ g.
The present invention further discloses the cigarette filter rod that with the addition of graphene oxide bonded silica gel composite as described above.
Preferably, the graphene oxide bonded silica gel composite that 3-8mg/ props up is contained in described cigarette filter rod.Preferably, the graphene oxide bonded silica gel composite that 5mg/ props up is contained in described cigarette filter rod.
Preferably, described cigarette filter rod comprises the two sections of acetate fiber sections being positioned at pipe tobacco end and mouth end and the graphene oxide bonded silica gel composite section be positioned in the middle of described two sections of acetate fiber sections.
Present invention also offers a kind of cigarette filter rod that with the addition of graphene oxide bonded silica gel composite and reduce the application in cigarette mainstream flue gas in nitrosamine.
As mentioned above, a kind of preparations and applicatio reducing the graphene oxide bonded silica gel composite of nitrosamine in cigarette mainstream flue gas of the present invention, graphene oxide (GO) is prepared by adopting Hummer method principle, again according to the carboxyl on GO surface and the amino bonded route of Silica Surface, graphene oxide (GO) is loaded on silica-gel carrier, prepare graphene oxide bonded silica gel (GO/ silica gel) composite, add in cigarette filter rod, have studied the filtering effect that it reduces TSNAs in cigarette mainstream flue gas, for up-to-date nanometer technology Harm reduction techniques fall burnt in deep application effective reference is provided.
The GO/ material silica gel composite that preparation method of the present invention obtains has larger specific area, easily fully contacts with the TSNAs in flue gas, has very strong adsorption capacity.Simultaneously, GO/ material silica gel composite also has carboxyl functional group, nitrogen-atoms in TSNAs molecule can by the carbon atom in nucleophilic substitution attack carboxyl, final formation amido link, thus be effectively adsorbed on GO/ material silica gel composite surface, and can not be entered in smoker's body by cigarette filter rod.GO/ material silica gel composite prepared by the present invention effectively can reduce NAB, NAT, NNK, NNN in main flume and reach 18.95%, 16.33%, 26.55%, 6.43% respectively, has very good effect.
Accompanying drawing explanation
Fig. 1 is shown as the X-ray diffractogram of a kind of GO/ material silica gel composite of the present invention
Fig. 2 is shown as the Raman spectrogram of a kind of GO/ material silica gel composite of the present invention
Fig. 3 is shown as the N2 adsorption isothermal curve figure of a kind of GO/ material silica gel composite of the present invention
Fig. 4 is shown as the transmission electron microscope picture of a kind of GO/ material silica gel composite of the present invention
Detailed description of the invention
Set forth the present invention further below in conjunction with specific embodiment, should be understood that these embodiments are only not used in for illustration of the present invention and limit the scope of the invention.
Below by way of specific instantiation, embodiments of the present invention are described, those skilled in the art the content disclosed by this description can understand other advantages of the present invention and effect easily.The present invention can also be implemented or be applied by detailed description of the invention different in addition, and the every details in this description also can based on different viewpoints and application, carries out various modification or change not deviating under spirit of the present invention.
The following reagent that following examples use and equipment
1. reagent
Graphite powder (commercially available); The concentrated sulfuric acid, sodium nitrate, potassium permanganate, hydrogen peroxide, methyl alcohol, hydrochloric acid, ammonium acetate (analyzing pure, traditional Chinese medicines company); DMF, alkylamino silica gel, dicyclohexylcarbodiimide (analyzing pure, Agilent company); Deionized water (water purification machine self-control)
2. equipment
D8 type X-ray diffractometer (X-ray be Cu target, bruker company of Germany); RM2000 type spectrometer (Renishw company of Britain); JEM 2010 type high resolution transmission electron microscopy (Japanese JEOL company); ASAP2010 type N2 adsorption specific surface tester (Merck & Co., Inc); SM450 orthoscopic smoking machine (Cerulean company of Britain); VD-115 type vacuum drying oven (BINDER company); KH5200DE type ultrasonic washing instrument (Kunshan He Chuan company); 2487 type high performance liquid chromatography GC-MSs (Water company)
Embodiment 1
The preparation of 1.GO
By 10g graphite powder, 5gNaNO 3being added to volume with the 230ml concentrated sulfuric acid is in the large beaker of 2L, within 30 minutes, carries out pre-oxidation treatment 0 DEG C of stirring.After pre-oxidation treatment, by the KMnO of 30g 4slowly add, then mixture in stirring at room temperature until become brown slurry.After stirring 120 minutes, in brown slurry, slowly add 500ml deionized water, now reaction temperature sharply rises, and continues stirring 120 minutes.Add warm water and the 100ml30%H of 1L again 2o 2, centrifugal after stirring, filtration.The sample obtained after filtering first with watery hydrochloric acid cleaning twice, then uses washed with de-ionized water twice, at room temperature uses vacuum drying oven dry, finally obtains GO powder.
The preparation of 2.GO/ material silica gel composite
Get 200mgGO powder dispersion to 500mlN, in N-dimethylformamide, after ultrasonic 30 minutes, add alkylamino silica gel and the 200mg dicyclohexylcarbodiimide of 5g, at 50 DEG C, add hot reflux 30 hours.Reaction terminates rear centrifugal, filtration, and washed with de-ionized water twice first used by the sample obtained after filtering, and then uses washed with methanol twice, at room temperature uses vacuum drying oven dry, finally obtains GO/ material silica gel composite.
3. the preparation of cigarette filter rod
By the GO/ material silica gel composite obtained, add in cigarette filter rod with the content that 5mg/ props up, then be prepared into cigarette sample (interpolation sample), to be measured.Described cigarette filter rod comprises the two sections of acetate fiber sections being positioned at pipe tobacco end and mouth end and the graphene oxide bonded silica gel composite section be positioned in the middle of described two sections of acetate fiber sections.Meanwhile, preparation contains the cigarette sample (control sample) of the cigarette filter rod not being added with graphene oxide bonded silica gel composite, to be measured.
Embodiment 2
The preparation of 1.GO
By 10g graphite powder, 4.5gNaNO 3being added to volume with the 210ml concentrated sulfuric acid is in the large beaker of 2L, within 20 minutes, carries out pre-oxidation treatment 0 DEG C of stirring.After pre-oxidation treatment, by the KMnO of 28g 4slowly add, then mixture in stirring at room temperature until become brown slurry.After stirring 110 minutes, in brown slurry, slowly add 480ml deionized water, now reaction temperature sharply rises, and continues stirring 110 minutes.Add warm water and the 95ml30%H of 950ml again 2o 2, centrifugal after stirring, filtration.The sample obtained after filtering first with watery hydrochloric acid cleaning twice, then uses washed with de-ionized water twice, at room temperature uses vacuum drying oven dry, finally obtains GO powder.
The preparation of 2.GO/ material silica gel composite
Get 200mgGO powder dispersion to 480mlN, in N-dimethylformamide, after ultrasonic 20 minutes, add alkylamino silica gel and the 180mg dicyclohexylcarbodiimide of 4.6g, at 49.5 DEG C, add hot reflux 29.9 hours.Reaction terminates rear centrifugal, filtration, and washed with de-ionized water twice first used by the sample obtained after filtering, and then uses washed with methanol twice, at room temperature uses vacuum drying oven dry, finally obtains GO/ material silica gel composite.
3. the preparation of cigarette filter rod
By the GO/ material silica gel composite obtained, add in cigarette filter rod with the content that 3mg/ props up, then be prepared into cigarette sample (interpolation sample), to be measured.Described cigarette filter rod comprises the two sections of acetate fiber sections being positioned at pipe tobacco end and mouth end and the graphene oxide bonded silica gel composite section be positioned in the middle of described two sections of acetate fiber sections.Meanwhile, preparation contains the cigarette sample (control sample) of the cigarette filter rod not being added with graphene oxide bonded silica gel composite, to be measured.
Embodiment 3
The preparation of 1.GO
By 10g graphite powder, 5.5gNaNO 3being added to volume with the 250ml concentrated sulfuric acid is in the large beaker of 2L, within 40 minutes, carries out pre-oxidation treatment 5 DEG C of stirrings.After pre-oxidation treatment, by the KMnO of 32g 4slowly add, then mixture in stirring at room temperature until become brown slurry.After stirring 130 minutes, in brown slurry, slowly add 520ml deionized water, now reaction temperature sharply rises, and continues stirring 130 minutes.Add warm water and the 105ml30%H of 1L again 2o 2, centrifugal after stirring, filtration.The sample obtained after filtering first with watery hydrochloric acid cleaning twice, then uses washed with de-ionized water twice, at room temperature uses vacuum drying oven dry, finally obtains GO powder.
The preparation of 2.GO/ material silica gel composite
Get 200mgGO powder dispersion to 520mlN, in N-dimethylformamide, after ultrasonic 40 minutes, add alkylamino silica gel and the 220mg dicyclohexylcarbodiimide of 5.4g, at 50.5 DEG C, add hot reflux 30.1 hours.Reaction terminates rear centrifugal, filtration, and washed with de-ionized water twice first used by the sample obtained after filtering, and then uses washed with methanol twice, at room temperature uses vacuum drying oven dry, finally obtains GO/ material silica gel composite.
3. the preparation of cigarette filter rod
By the GO/ material silica gel composite obtained, add in cigarette filter rod with the content that 8mg/ props up, then be prepared into cigarette sample (interpolation sample), to be measured.Described cigarette filter rod comprises the two sections of acetate fiber sections being positioned at pipe tobacco end and mouth end and the graphene oxide bonded silica gel composite section be positioned in the middle of described two sections of acetate fiber sections.Meanwhile, preparation contains the cigarette sample (control sample) of the cigarette filter rod not being added with graphene oxide bonded silica gel composite, to be measured.
Embodiment 4
1. constituent analysis
1.1 testing sample process
Interpolation sample prepared by clause 3 in above-described embodiment 1, according to standard ISO 3308-2000 " cigarette smoke conventional analysis device. definition and standard conditions ", SM450 orthoscopic smoking machine is used to carry out aspirating (pumping volume 35ml/min), and the TPM in the glass fiber filter using diameter to be Φ 44mm trapping cigarette mainstream flue gas, often open the Smoke Particulate that filter disc collects 5 cigarettes, each sample answers parallel determination 2 times.
After cigarette smoking, glass fiber filter is placed in 50ml conical flask, accurately adds the ammonium acetate solution of the 100mM (mol/L) of 20ml, under room temperature, ultrasonic extraction is after 30 minutes, then extract is crossed aqueous phase membrane filtration, get 1ml filtrate, to be measured.
1.2 instruments detect
High performance liquid chromatography GC-MS (HPLC-MS/MS) filtrate is adopted to measure.
Wherein, the analysis condition of high performance liquid chromatography is: chromatographic column: C18 post (3.2 × 100mm i.d.1.7 μm); Flow velocity: 0.25ml/min; Column temperature: 50 DEG C; Sample size: 10 μ l; Mobile phase: A phase is 10mM Acetic Acid-Water solution, B phase is 10mM acetic acid-methanol solution; Analysis time: 10min; Linear gradient elution.
Described A phase: the graded wash-out of B phase meets following condition:
0-4min A phase: B phase volume ratio: 92:8-40:60;
4-5min A phase: B phase volume ratio: 40:60-40:60;
5-8min A phase: B phase volume ratio: 40:60-5:95;
8-10min A phase: B phase volume ratio: 5:95-92:8.
Wherein, Mass Spectrometry Conditions is:
Mass ions source dates: ion gun: electron spray ionisation source; Scan mode: cation scans; Detection mode: multiple-reaction monitoring; Electron spray voltage: 5000V; Ion source temperature: 600 DEG C; Assisted gas Gas1 pressure: 35psi; Assisted gas Gas2 pressure: 35psi.
In addition, object mass spectrometry parameters is in table 1.
Table 1 is mass spectrometer parameters setting value
2. result and discussion
The detection of 2.1GO/ material silica gel composite
Adopt D8 type X-ray diffractometer to measure GO/ material silica gel composite, obtain X-ray diffraction Fig. 1 of GO/ material silica gel composite.As shown in Figure 1, near 10 DEG C, occur diffraction maximum, illustrate that original graphite powder is oxidized, generate oxygen-containing functional group, cause interplanar distance to expand, GO is successfully synthesized.
Adopt RM2000 type spectrophotometer GO/ material silica gel composite, obtain the Raman spectrogram 2 of GO/ material silica gel composite.As shown in Figure 2, there are D band and G etc. in Raman spectrum, further illustrated GO and be successfully synthesized.
Adopt ASAP 2010 type N2 adsorption specific surface tester to measure GO/ material silica gel composite, obtain N2 adsorption isothermal curve Fig. 3 of GO/ material silica gel composite.As shown in Figure 3, GO/ material silica gel composite has large specific area, is excellent sorbing material in theory.
Adopt JEM 2010 type high resolution transmission electron microscopy to measure GO/ material silica gel composite, obtain transmission electron microscope Fig. 4 of GO/ material silica gel composite.As shown in Figure 4, GO is incorporated into Silica Surface with the formal bond of monolithic, maintains large specific area, is suitable for absorption.
The detection of 2.2TSNAs content
HPLC-MS/MS is adopted to measure the cigarette sample (interpolation sample) adding GO/ material silica gel composite in the filter stick of preparation in above-described embodiment 1 according to above-mentioned 1.2.In like manner, HPLC-MS/MS is adopted to measure the cigarette sample (control sample) not adding GO/ material silica gel composite in the filter stick of preparation in above-described embodiment 1 according to above-mentioned 1.2.Concrete testing result is in table 2.
Table 2 composite filter reduces the result of 4 kinds of TSNAs in main flume
As shown in Table 2, GO/ material silica gel composite is added in cigarette filter rod as adsorbent, the composite filter cigarette prepared, obviously can reduce the TSNAs in cigarette mainstream flue gas.This filter stick reaches 18.95%, 16.33%, 26.55%, 6.43% respectively to the range of decrease of NAB, NAT, NNK, NNN in cigarette mainstream flue gas.
2.3 sensory evaluating smoking
In addition, show preparing sensory evaluating smoking's result that sample carries out in embodiment 1, this filter stick has no adverse effects to smoking property of cigarette quality, the results are shown in Table 3.As shown in Table 3, compare the cigarette sample (control sample) not adding GO/ material silica gel composite in filter stick, cigarette sample (interpolation sample) smoking result adding GO/ material silica gel composite in filter stick is close with it, visible interpolation GO/ material silica gel composite, smoking property of cigarette quality is not affected substantially, can apply in practice.
Table 3 Sensory Quality of Cigarette inspection record table
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not for limiting the present invention.Any person skilled in the art scholar all without prejudice under spirit of the present invention and category, can modify above-described embodiment or changes.Therefore, such as have in art usually know the knowledgeable do not depart from complete under disclosed spirit and technological thought all equivalence modify or change, must be contained by claim of the present invention.

Claims (10)

1. a preparation method for graphene oxide bonded silica gel composite, comprises the following steps:
1) in graphite powder, sodium nitrate is added and the concentrated sulfuric acid carries out pre-oxidation treatment, add after potassium permanganate stirs again, be diluted with water rear continuations and stir, then add warm water and hydrogen peroxide stir after centrifugal, filtration, finally clean post-drying, obtain graphene oxide powder;
2) graphene oxide powder is joined N, carry out ultrasonic disperse in dinethylformamide, then add after alkylamino silica gel and dicyclohexylcarbodiimide carry out adding hot reflux, centrifugal, filter, cleaning post-drying, obtains graphene oxide bonded silica gel composite.
2. the preparation method of a kind of graphene oxide bonded silica gel composite according to claim 1, is characterized in that, step 1) in, described pre-oxidation treatment condition is: reaction temperature: 0-5 DEG C; Reaction time: 20-40 minute; Stir number of times: 150-250 beat/min.
3. the preparation method of a kind of graphene oxide bonded silica gel composite according to claim 1, is characterized in that, step 1) in, the stirring condition of described potassium permanganate is: whipping temp: room temperature; Mixing time: 110-130 minute; Stir number of times: 100-150 beat/min; The described stirring condition that adds water is: mixing time is 110-130 minute; Stir number of times: 150-250 beat/min; Warm water and hydrogen peroxide stirring condition are: warm water and hydrogen peroxide stirring condition are: mixing time is 15-25 minute; Stir number of times: 150-250 beat/min.
4. the preparation method of a kind of graphene oxide bonded silica gel composite according to claim 1, is characterized in that, step 1) in, described cleaning filters out cleaning agent by after centrifugal for the reactant adding cleaning agent layering, retains pressed powder; Described cleaning agent is watery hydrochloric acid or water; Described cleaning way is: first carry out cleaning twice with watery hydrochloric acid, then carry out cleaning twice with water.
5. the preparation method of a kind of graphene oxide bonded silica gel composite according to claim 1, is characterized in that, step 2) in, described ultrasound condition is: ultrasonic time: 20-40 minute; Ultrasonic power: 480-520W; Ultrasonic temperature: room temperature; Described heated reflux condition: heating-up temperature: 49.5-50.5 DEG C; Return time: 29.9-30.1 hour.
6. the preparation method of a kind of graphene oxide bonded silica gel composite according to claim 1, is characterized in that, step 2) in, described cleaning filters out cleaning agent by after centrifugal for the reactant adding cleaning agent layering, retains pressed powder; Described cleaning agent is methyl alcohol or water; Described cleaning way is: first carry out eccentric cleaning twice with water, then carry out eccentric cleaning twice with methyl alcohol.
7. a graphene oxide bonded silica gel composite, is obtained by described method arbitrary in claim 1-6.
8. a cigarette filter rod, is added with graphene oxide bonded silica gel composite as claimed in claim 7.
9. a kind of cigarette filter rod according to claim 8, is characterized in that, containing the graphene oxide bonded silica gel composite that 3-8mg/ props up in described cigarette filter rod; Described cigarette filter rod comprises the two sections of acetate fiber sections being positioned at pipe tobacco end and mouth end and the graphene oxide bonded silica gel composite section be positioned in the middle of described two sections of acetate fiber sections.
10. a kind of cigarette filter rod that with the addition of graphene oxide bonded silica gel composite according to Claim 8 described in-9 is reducing the application in cigarette mainstream flue gas in nitrosamine.
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