CN102464981B - Lignin-based carbon nanomaterial having fluorescent performance and preparation method thereof - Google Patents
Lignin-based carbon nanomaterial having fluorescent performance and preparation method thereof Download PDFInfo
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- CN102464981B CN102464981B CN 201010552738 CN201010552738A CN102464981B CN 102464981 B CN102464981 B CN 102464981B CN 201010552738 CN201010552738 CN 201010552738 CN 201010552738 A CN201010552738 A CN 201010552738A CN 102464981 B CN102464981 B CN 102464981B
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Abstract
The invention discloses a lignin-based carbon nanomaterial having fluorescent performance and a preparation method thereof. The preparation method comprises the following steps: a) lignin is extracted from wood flour; b) thermo-synthesis reaction is carried out on the lignin with cerous phosphate or phosphate and cerate solvent to produce the lignin-based carbon nanocomposite material. The preparation method has characteristics such as cheap raw materials, simple process, convenience in operation, controllability of appearance shape of products, controllability of fluorescent efficiency of the prepared lignin-based carbon nanocomposite material having the fluorescent performance and the like.
Description
Technical field
The present invention relates to lignin-base carbon nano-composite material of a kind of phosphoric acid cerium and preparation method thereof, particularly nanostructure lignin-base carbon luminescent material of a kind of phosphoric acid cerium that is widely used in fields such as metallurgy, chemical industry, machinery, electronics, aviation and preparation method thereof.
Background technology
Since 1991 find carbon nanotube (Iijima S.Helical microtubules of grapgitic carbon, Nature, 1991,354,56.), the various countries scientist has produced great interest to carbon material.Numerous studies show that, carbon material have excellent mechanical property, high thermostability, variable electrical properties from the good conductor to the semi-conductor.Therefore, carbon material is considered to the ideal material of aspects such as electronic wire, microelectrode, a ballistic transistor, Chu Qing, drug molecule carrier, has potential application prospect in fields such as light, electricity, magnetic, catalysis, mechanics and biomedicines.In addition, mesopore, meso-porous carbon material can be used for the container of medicine, protein, DNA and catalyzer etc., its research have been become the research focus of material educational circles.
The raw material of carbon material is mainly derived from polyacrylonitrile quasi-fossil raw material.In recent years because fossil feedstock in short supply day by day, utilize the biomass resource xylogen replace polyacrylonitrile quasi-fossil feedstock production carbon material caused widely and paid close attention to (Wu Changlu. the wood based carbon fiber. glass reinforced plastic/matrix material, 2002,6,43.).Lignin conversion is that carbon material can be preserved organic carbon, and alternative fossil resource plays dual CO again
2The reduction of discharging effect promotes the foundation of low-carbon economy pattern, is one of focus of current domestic and international research.
Xylogen (Lignin) lignin that is otherwise known as, be a kind of complexity, amorphous three-dimensional netted class natural polymers, be formed by connecting with forms such as C-C key, ehter bonds by pine and cypress alcohol radical, Syringa oblata Lindl. base and three kinds of monomers of tonka-bean base, basic structural unit is the phenylpropyl alcohol alkyl structure.Xylogen extensively is present in the higher plant cell, is one of basic chemical composition of coniferals, deciduous tree class and straw or like vegetable, also is that occurring in nature is only second to cellulosic second largest renewable resources.
Xylogen is divided into cork, hardwood, careless class xylogen 3 classes according to the difference of raw material sources, wherein carry out the charing processing after hardwood xylogen and the mixed with polymers and can prepare carbon material, heating rate in the charing treating processes, type of polymer have very big influence to form, structure and the mechanical property of carbon material, for example xylogen mixes the carbon material of back preparation with polyethylene terephthalate (PET), because xylogen and PET can be miscible, the carbon material that obtains has smooth surface; And xylogen mixes the carbon material of back preparation with polypropylene (PP), because xylogen and PP immiscible, the carbon material that obtains is the porous shape.Research is also found, the carbon material that carbon material mechanical property ratio xylogen/PP that xylogen/PET obtains obtains will be got well, but they are all than good (the Kubo S of mechanical property of commercial absorbent charcoal material, Kadla JF.Lignin-based carbon fibers:Effect of synthetic polymer blending on fiber properties, Journal of Polymers And The Environment, 2005,13,97.).
Xylogen, lignin-base charcoal and activated carbon are as water conditioner all the time.The method by common-battery spray for example, prepare solid or hollow xylogen micron or nanofiber, form solid or hollow carbon fiber after these fiber charings, the same high specific surface area (the Lallave M with activated carbon of this carbon fiber, Bedia J, et al.Filled and hollow carbon nanofibers by coaxial electrospinning of Alcell lignin without binder polymers, Advanced Materials, 2007,19:4292.), can be used as water conditioner.Adopt KOH that xylogen is carried out the alkali activation, prepare nanostructured carbon material (the Babel K with high hydrogen electro-adsorption ability and high specific surface area then, Jurewicz K.KOH activated lignin based nanostructured carbon exhibiting high hydrogen electrosorption, Carbon, 2008,46,1948.).Polyacrylonitrile and xylogen are at N, mix in the dinethylformamide solution, thermal transition is carbon material (Sazanov YN, Kostycheva DM, et al.Composites of lignin and polyacrylonitrile as carbon precursors, Russian Journal of Applied Chemistry, 2008,81,1220.).Can obtain with platinum or not with the lignin fibre of platinum by EFI xylogen/ethanol/methyl ethyl diketone platinum or xylogen/ethanolic soln, then 600-1000 ℃ of following charing, can obtain carbon fiber (Ruiz-Rosas R, Bedia J, et al.The production of submicron diameter carbon fibers by the electrospinning oflignin, Carbon, 2010,48,696.).With xylogen in the phosphoric acid activation brewer's grains, charing under differing temps then, can prepare carbon material (the Mussatto SI with bigger serface, pore structure and high absorption capacity, Fernandes M, et al.Production, characterization and application of activated carbon from brewer ' s spent grain lignin, Bioresource Technology, 2010,101,2450-2457.).The xylogen carbon material of method for preparing has strong adsorptive power and high specific surface area, all can be used as water conditioner.
Cerium monophosphate can be launched high efficient green fluorescence, uses always and does the luminescent lamp material, and it has two kinds of things of monocline and hexagonal structure mutually, at the high-performance optical electrical part, and sensor, catalyzer, heat-stable material and other functional materials aspect have a wide range of applications.
For example, people such as Shu-hong Yu are carbon source by the synthetic method of hydro-thermal with glucose, the synthetic nano combined cable of TeC (Qian HS, Yu SH, Luo LB, Gong JY, Fei LF, the Liu XM.Chem Mater 2006 that has obtained having fluorescence property; 18:2102-8.); People such as Xian-Luo Hu utilize microwave-hydrothermal method, are carbon source with glucose, synthetic SeC, the Fe that has obtained having nucleocapsid structure
3O
4C, TeC nano composite material (Yu JC, Hu XL, Li Q, Zheng Z, Xu YM.Chem Eur J 2006; 12:548.Hu XL, Yu JC.Chem Asian J 2006; 1:605.Hu XL, Yu JC, Gong JM.J Phys Chem C 2007; 111:5830.).Ming-Guo Ma etc. are carbon source with glucose, have synthesized the CePO with fluorescence property by hydro-thermal reaction
4C nuclear shell structure nano rod (M.G.Ma, J.F.Zhu, R.C.Sun, Y.J.Zhu, Hydrothermal synthesis and characterization of CePO
4/ C core-shell nanorods, Materials Letters, 2009,63,2513).Yet they with glucose are carbon source, and are expensive.
Summary of the invention
The objective of the invention is the problem at the prior art existence, a kind of lignin-base carbon nanomaterial with fluorescence property and preparation method thereof is provided.The present invention replaces traditional carbon source with agricultural-forestry biomass-Mierocrystalline cellulose, and cheap, energy-saving and emission-reduction meet the low-carbon economy Development patterns, and preparation technology is simple, product yield height, and the fluorescence efficiency height of product.
For realizing purpose of the present invention, one aspect of the present invention provides a kind of preparation method with lignin-base carbon nanomaterial of fluorescence, comprises following step in sequence: a) be raw material with the wood powder, make by DeR and contain lignin liquor; B) with lignin liquor and Cerium monophosphate or lignin liquor with after phosphoric acid salt, cerium salt mix, carry out the solvent thermal building-up reactions, namely.
Wherein, the salt of cerium described in the step b) is water-soluble cerium salt; Described phosphoric acid salt is water-soluble phosphate.
Particularly, water-soluble cerium salt is selected from Ce (NO
3)
3, Ce (SO
4)
2, CeF
3, Ce (Ac)
3, Ce
2(CO
3)
3, Ce (NH
4)
2(NO
3)
6, Ce (SO
4)
22 (NH
4)
2SO
42H
2Among the O one or more; Water-soluble phosphate is selected from NaH
2PO
4, Na
2HPO
4, Na
3PO
4, KH
2PO
4, K
2HPO
4, K
3PO
4, (NH
4)
3PO
4In one or more.
Particularly, the mole proportioning of phosphorus is 1 in the cerium in the salt of cerium described in the step b) and the phosphoric acid salt: 1-2 is preferably 1: 1.
Wherein, the step of carrying out in the following order in the described step a) makes the described lignin liquor that contains:
1) wood powder, LiCl are joined in the dimethyl sulfoxide (DMSO), mix, make pre-degradation of mixture;
2) pre-degradation of mixture is carried out the DeR of wood powder under microwave irradiation effect, make degradation of mixture, namely.
Particularly, also comprise step 3): add ethanol in the degradation of mixture, filter then, filtrate is lignin liquor.
The temperature of reaction of the DeR particularly, step 2) is 120-160 ℃, is preferably 140 ℃; Reaction times is 0.5-3 hour, is preferably 1 hour.
Particularly, the mass percent concentration of the ethanol described in the step 3) is 85-100%.
Especially, also comprise step 4): the filtrate that makes in the step 3) is carried out concentration, obtain concentrating xylogen dimethyl sulfoxide (DMSO) (DMSO)/ethanolic soln.
Particularly, the content of xylogen is 0.001-0.003g in every milliliter of described xylogen DMSO/ ethanolic soln, is preferably 0.0017-0.0027g.
Wherein, the temperature of concentration is 50-80 ℃, relative pressure is-0.075～-0.095MPa.
Particularly, the weight part proportioning of the wood powder described in the step 1) and LiCl is 1: 0.3-1 is preferably 1: 0.4; The weight of wood powder is 1 with the ratio of the volume of DMSO: 8-20, and namely when the weight (dry weight) of wood powder was 1g, the volume of DMSO was 8-20ml; When the weight (dry weight) of wood powder was 1kg, the volume of DMSO was 8-20L; The volume of ethanol described in the step 3) is 8-15 with the ratio of the volume of the DMSO described in the step 1): 1, be preferably 10: 1.
Especially, the weight of wood powder is preferably 1: 10 with the ratio of the volume of DMSO.
Wherein, described step b) comprises following step in sequence:
1) lignin liquor that step a) is prepared and Cerium monophosphate or lignin liquor and phosphoric acid salt, cerium salt place in the reactor, stir, and are dispersed into suspension;
2) with after the reactor sealing, heating makes reactor inner suspension liquid carry out the solvent thermal building-up reactions, makes the lignin-base carbon nanomaterial with fluorescence.
Particularly, the mole proportioning of the cerium in the cerium salt described in the step 1) and the phosphorus in the phosphoric acid salt is 1: 1-2 is preferably 1: 1; The ratio of the weight of cerium is 1 in the xylogen that contains in the lignin liquor in the step 1) and the Cerium monophosphate: 1-5, perhaps the ratio of the weight of cerium is 1 in the xylogen that contains in the lignin liquor and the cerium salt: 1-5.
Particularly, step 2) temperature of reaction of solvent thermal building-up reactions is 180-230 ℃ described in, and the reaction times is 3-72 hour, is preferably 24-72 hour.
The volume of the suspension wherein, step 2) in the reactor is the 50-80% of reactor cumulative volume, is preferably 60%.
Particularly, also comprise reaction product is separated, washed and drying, namely get the lignin-base carbon nanomaterial with fluorescence.
Particularly, described separation is adopted centrifugation, is filtered or staticly settle; Adopt dehydrated alcohol and water to carry out described washing.
The present invention provides a kind of lignin-base carbon nanomaterial with fluorescence that is prepared from according to the method described above on the other hand.
The advantage of the inventive method is as follows:
1, the present invention replaces traditional carbon source polyacrylonitrile quasi-fossil raw material with agricultural-forestry biomass----xylogen, the lignin-base carbon nanomaterial with fluorescence of preparation is the matrix material of carbon material and Cerium monophosphate, it is a kind of novel material, this carbon nano-composite material is cheap, energy-saving and emission-reduction meet the low-carbon economy Development patterns.
2, the lignin-base carbon nanomaterial with fluorescence property of the inventive method preparation, fluorescence intensity can be carried out quantitatively regulating and controlling to the solvent thermal building-up reactions according to actual needs, the fluorescence intensity of control lignin-base carbon nanomaterial and the structural performance of material.
3, the inventive method employing ethanol/DMSO is that solvent synthesizes, do not need to add in addition other tensio-active agent in the reaction process, do not need to feed rare gas element yet and carry out deoxygenation, more do not need the pH value of conditioned reaction solution, simplify production process greatly, reduced cost.
4, preparation method's of the present invention technology is simple, and is easy to operate, and easy control of process conditions does not need cost and complex equipment, has reduced production cost, is beneficial to industrialization promotion.
5, preparation method of the present invention adopts compound technology synchronously, the xylogen charing becomes carbon material, cerium salt and phosphoric acid salt generate Cerium monophosphate, carbon material and phosphoric acid salt are combined into the process of lignin-base carbon nanomaterial and finish synchronously, the lignin-base carbon material that forms is compound evenly, and each element evenly distributes in carbon material.
6, the lignin-base carbon nanomaterial with fluorescence of the present invention's preparation has application prospect in fields such as separation, absorption, biological nano technology, especially has huge application potential in separation, absorption and bio-medical fields such as medicine loading and release.
Description of drawings
Fig. 1 has preparation technology's schema of the lignin-base carbon material of fluorescence for the present invention;
Fig. 2 is the electron scanning micrograph of the lignin-base carbon material with fluorescence of embodiment 1 preparation;
Fig. 3 is the energy spectrogram of the lignin-base carbon nanomaterial with fluorescence of embodiment 1 preparation;
Fig. 4 is the fluorescence spectrum figure of the prepared lignin-base carbon nano-composite material of embodiment 1-3, and wherein (a) is the fluorescence spectrum figure of the lignin-base carbon nano-composite material of embodiment 1 preparation; (b) be the fluorescence spectrum figure of the lignin-base carbon nano-composite material of embodiment 2 preparations; (c) be the fluorescence spectrum figure of the lignin-base carbon nano-composite material of embodiment 3 preparations;
Fig. 5 is the electron scanning micrograph of the lignin-base carbon nanomaterial of embodiment 2 preparations;
Fig. 6 is the electron scanning micrograph of the lignin-base carbon nanomaterial of embodiment 3 preparations;
Fig. 7 is the electron scanning micrograph of the lignin-base carbon nanomaterial of embodiment 4 preparations;
Fig. 8 is the electron scanning micrograph of the lignin-base carbon nanomaterial of embodiment 5 preparations;
Fig. 9 is the electron scanning micrograph of the lignin-base carbon nanomaterial of embodiment 6 preparations;
Figure 10 is the fluorescence spectrum figure of the prepared lignin-base carbon nano-composite material of embodiment 4-6, and wherein (a) is the fluorescence spectrum figure of the lignin-base carbon nano-composite material of embodiment 4 preparations; (b) be the fluorescence spectrum figure of the lignin-base carbon nano-composite material of embodiment 5 preparations; (c) be the fluorescence spectrum figure of the lignin-base carbon nano-composite material of embodiment 6 preparations.
Embodiment
Further specify embodiments of the present invention and effect with following indefiniteness embodiment:
Cerium salt is selected Ce (NO for use in the embodiment of the invention
3)
3But the cerium salt described in the present invention is except Ce (NO
3)
3Outside, can also select Ce (SO for use
4)
2, CeF
3, Ce (Ac)
3, Ce
2(CO
3)
3, Ce (NH
4)
2(NO
3)
6, Ce (SO
4)
22 (NH
4)
2SO
42H
2O;
Phosphoric acid salt is selected NaH for use in the embodiment of the invention
2PO
4But the phosphoric acid salt described in the present invention is except NaH
2PO
4Outside, can also select Na for use
2HPO
4, Na
3PO
4, KH
2PO
4, K
2HPO
4, K
3PO
4, (NH
4)
3PO
4
The wood powder that the present invention selects for use is the hardwood wood powder, and wherein the content of xylogen is 20%.
Embodiment 1
1, preparation lignin liquor
1) 3g wood powder, 1.2g LiCl are joined in dimethyl sulfoxide (DMSO) (DMSO) solvent of 30mL, stirred 1 hour down in room temperature (25 ℃), make the pre-degradation of mixture that stirs;
Wood powder is 1: 0.4 with the ratio of the weight of LiCl in the embodiment of the invention, and in addition, wood powder is 1 with the ratio of the weight of LiCl: 0.3-1 all is applicable to the present invention; The weight of wood powder is 1: 10 with the ratio of the volume of DMSO, and in addition, the weight of wood powder is 1 with the ratio of the volume of DMSO: 8-20 all is applicable to the present invention
2) pre-degradation of mixture is placed microwave heater (Beijing XiangHu Science and Technology Development Co., Ltd., model: XH100B), the method for utilizing microwave heating makes the wood powder degraded 140 ℃ of heated and stirred 1 hour, makes degradation of mixture;
3) adding the 300mL mass percent concentration while stirring in the cooled degradation of mixture is 95% ethanol, Mierocrystalline cellulose, hemicellulose precipitation in the degradation of mixture are separated out, carry out suction filtration then, obtain containing the mixed sediment of the filtrate of xylogen and Mierocrystalline cellulose, hemicellulose;
4) utilize Rotary Evaporators (Shanghai Yarong Biochemical Instrument Plant) that filtrate is concentrated, obtain 45ml xylogen DMSO/ ethanolic soln, wherein, contain xylogen 0.1g in the xylogen DMSO/ ethanolic soln of 45mL, carry out heating in water bath in the concentration process, Heating temperature is 45-55 ℃, relative pressure is-0.075～-0.09MPa.
2, solvent thermal synthesize nano carbon material
1) get 30mL xylogen DMSO/ ethanolic soln, and to wherein adding 0.868g Ce (NO
3)
36H
2O and 0.312g NaH
2PO
42H
2O stirs, and the suspension that obtains all is transferred in the withstand voltage reactor of 50ml sealed reactor;
2) reactor is put into baking oven and be heated to 200 ℃, insulation reaction is 24h, after being cooled to room temperature (25 ℃) then, adopting centrifuging to carry out product separates, the precipitation that obtains is washed respectively 2 times with dehydrated alcohol and water successively, under 60 ℃, carry out drying then, make the lignin-base carbon nano-composite material with fluorescence of the present invention.
Adopt scanning electron microscope to detect the form of lignin-base carbon nanomaterial;
Adopting Shimadzu RF-5301 PC fluorescence spectrophotometer instrument is to detect the fluorescence intensity of lignin-base carbon nanomaterial under the 280nm in excitation wavelength, and detected result is as shown in table 1.
Fig. 2 is the electron scanning micrograph of the lignin-base carbon nanomaterial of embodiment 1 preparation, can find out clearly that main form is the micron ball that nanometer sheet is assembled into, micron ball short texture, and specific surface area is bigger than closely knit ball; Also has a spot of laminated structure.
(a) amplifies 2000 times electron scanning micrograph among Fig. 2 for carbon nanomaterial; (b) amplifies 7000 times electron scanning micrograph among Fig. 2 for carbon nanomaterial; (c) amplifies 15000 times electron scanning micrograph among Fig. 2 for carbon nanomaterial.
Fig. 3 is the energy spectrogram of lignin-base carbon nano-composite material, can find out the characteristic peak of Ce, P, O, C clearly, illustrates that resulting product is lignin-base carbon/Cerium monophosphate nano composite material; Can find that by the face scintigram Ce, P, O, C are that big area is equally distributed, illustrate that lignin-base carbon/Cerium monophosphate is evenly compound.
Fig. 3 (a) is the energy spectrogram of lignin-base carbon nano-composite material; Fig. 3 (b) is power spectrum sample area figure; Fig. 3 (c) is the face scanning energy spectrogram of C (carbon) element in the carbon nano-composite material; Fig. 3 (d) is the face scanning energy spectrogram of O (oxygen) element in the carbon nano-composite material; Fig. 3 (e) is the face scanning energy spectrogram of P (phosphorus) element in the carbon nano-composite material; Fig. 3 (f) is the face scanning energy spectrogram of Ce (cerium) element in the carbon nano-composite material;
Can find out that from Fig. 3 (c-f) 4 secondary figure C, O, P, Ce are evenly distributed, illustrate that Cerium monophosphate and lignin-base carbon are compound evenly, each element is evenly distributed in the lignin-base carbon nano-composite material of preparation.
Fig. 4 is the fluorescence spectrum figure of lignin-base carbon nano-composite material, wherein Fig. 4 (c) is the fluorescence spectrum figure of the prepared lignin-base carbon nano-composite material of embodiment 1, fluorescence intensity is 550a.u, shows that the lignin-base carbon nano-composite material of present embodiment gained has high-intensity fluorescence property.
Embodiment 2
Except the temperature of microwave heating in the preparation lignin liquor process is 120 ℃, be 3h heat-up time; The ethanol that joins in the degradation of mixture is dehydrated alcohol; Reactant is 0.434gCe (NO in the preparation carbon nanomaterial process
3)
36H
2O, 0.156g NaH
2PO
42H
2Temperature of reaction in the O, reactor is 180 ℃, and the reaction times is outside the 72h, and all the other are identical with embodiment 1;
Fig. 5 is the electron scanning micrograph of the lignin-base carbon nano-composite material of embodiment 2 preparations, can find out clearly that main form is structure and the micron ball as carnation that nanometer sheet is assembled into.
(a) amplifies 2000 times electron scanning micrograph among Fig. 5 for carbon nanomaterial; (b) amplifies 10000 times electron scanning micrograph among Fig. 5 for carbon nanomaterial; (c) amplifies 10000 times electron scanning micrograph among Fig. 5 for carbon nanomaterial.
(b) is the fluorescence spectrum figure of the prepared lignin-base carbon nano-composite material of embodiment 2 among Fig. 4, and fluorescence intensity is 350a.u, compares with the fluorescence spectrum of embodiment 1, and fluorescence intensity reduces.
Embodiment 3
The temperature that heats except microwave-assisted in the preparation lignin liquor process is 160 ℃, and be 0.5h heat-up time; Reactant is 0.217g Ce (NO in the preparation lignin-base carbon nanomaterial
3)
36H
2O, 0.078g NaH
2PO
42H
2Temperature of reaction in the O, reactor is 230 ℃, and the reaction times is outside the 3h, and all the other are identical with embodiment 1;
Fig. 6 is the electron scanning micrograph of the lignin-base carbon nano-composite material of embodiment 3 preparations, can find out clearly that main form is nanometer sheet and micron ball.
(a) amplifies 2000 times electron scanning micrograph among Fig. 6 for carbon nanomaterial; (b) amplifies 10000 times electron scanning micrograph among Fig. 6 for carbon nanomaterial; (c) amplifies 20000 times electron scanning micrograph among Fig. 6 for carbon nanomaterial.
(a) is the fluorescence spectrum figure of the prepared lignin-base carbon nano-composite material of embodiment 3 among Fig. 4, and fluorescence intensity is 150a.u, compares with the fluorescence spectrum of embodiment 1, and fluorescence intensity greatly reduces.
Embodiment 4
1, preparation lignin liquor
1-1) 3g wood powder, 1.2g LiCl are joined in dimethyl sulfoxide (DMSO) (DMSO) solvent of 30mL, stirred 1 hour down in room temperature (25 ℃), make pre-degradation of mixture;
1-2) pre-degradation of mixture is placed microwave heater (Beijing XiangHu Science and Technology Development Co., Ltd., model: XH100B), the method for utilizing microwave heating makes degradation of mixture 140 ℃ of heated and stirred 1 hour;
1-3) adding the 300mL mass percent concentration while stirring in the cooled degradation of mixture is 95% ethanol, Mierocrystalline cellulose, hemicellulose precipitation in the degradation of mixture are separated out, carry out suction filtration then, obtain containing the mixed sediment of the filtrate of xylogen and Mierocrystalline cellulose, hemicellulose;
1-4) utilize Rotary Evaporators (Shanghai Yarong Biochemical Instrument Plant) that filtrate is concentrated, obtain 45ml xylogen DMSO/ ethanolic soln, wherein, contain xylogen 0.1g in the xylogen DMSO/ ethanolic soln of 45mL, carry out heating in water bath in the concentration process, Heating temperature is 45-55 ℃, relative pressure is-0.075～-0.09MPa.
2, Hydrothermal Preparation CePO
4Powder
2-1) with 0.434g Ce (NO
3)
36H
2O and 0.156g NaH
2PO
42H
2O joins in the 15mL distilled water, stirs, and the suspending liquid A that obtains all is transferred in the withstand voltage reactor of 20ml sealed reactor;
2-2) reactor is put into baking oven and be heated to 100 ℃, behind the insulation reaction 24h, be cooled to 20 ℃, centrifugation makes CePO of the present invention
4Powder.
3, preparation carbon nanomaterial
3-1) taking out weight is the CePO that hydro-thermal reaction generates in the step 2
41/3 CePO of powder gross weight
4Powder contains its 30mL that joins preparation in the step 1 in the DMSO/ ethanolic soln of xylogen, stirs, and the suspension that obtains all is transferred in the withstand voltage reactor of 50ml sealed reactor;
3-2) reactor is put into baking oven and be heated to 200 ℃, insulation reaction is 24h, after being cooled to room temperature (25 ℃) then, adopting centrifuging to carry out product separates, the precipitation that obtains is washed respectively 2 times with dehydrated alcohol and water successively, under 60 ℃, carry out vacuum-drying then, make the lignin-base carbon nano-composite material with fluorescence of the present invention.
Fig. 7 is the electron scanning micrograph of the lignin-base carbon nanomaterial of embodiment 4 preparations, can find out clearly that main form is micron ball and fibrous aggregate, and micron ball size is about 4.5 μ m, and there are a lot of nano particles on the surface.
(a) amplifies 2000 times electron scanning micrograph among Fig. 7 for carbon nanomaterial; (b) amplifies 17000 times electron scanning micrograph for carbon nanomaterial among Fig. 7, and wherein micron ball size is about 4.5 μ m, and there are a lot of nano particles on the surface.
(a) is the fluorescence spectrum figure of the prepared lignin-base carbon nano-composite material of embodiment 4 among Figure 10, and fluorescence intensity is 50a.u, compares with the fluorescence spectrum of embodiment 1, and fluorescence intensity reduces.
Embodiment 5
The temperature that heats except microwave-assisted in the preparation lignin liquor process is 120 ℃, and be 3h heat-up time; The mass percent concentration that joins the ethanol in the degradation of mixture is 85%; Heating temperature is 230 ℃ in the process of Hydrothermal Preparation Cerium monophosphate, and the insulation reaction time is 3h; In the process of preparation lignin-base carbon nanomaterial, the CePO of taking-up
4Weight for the preparation CePO
4Temperature of reaction in 1/2 of the powder gross weight, reactor is 180 ℃, and the reaction times is outside the 72h, and all the other are identical with embodiment 4.
Fig. 8 is the electron scanning micrograph of the lignin-base carbon nano-composite material of embodiment 5 preparations, can find out clearly that main form is micron ball and fibrous aggregate, and micron ball size is about 4.1 μ m, and there is a spot of nano particle on the surface.
(a) amplifies 2000 times electron scanning micrograph among Fig. 8 for carbon nanomaterial; (b) amplifies 20000 times electron scanning micrograph for carbon nanomaterial among Fig. 8, and wherein micron ball size is about 4.1 μ m, and there is a spot of nano particle on the surface.
(b) is the fluorescence spectrum figure of the prepared lignin-base carbon nano-composite material of embodiment 5 among Figure 10, and fluorescence intensity is 125a.u, compares with the fluorescence spectrum of embodiment 1, and fluorescence intensity reduces.
The temperature that heats except microwave-assisted in the preparation lignin liquor process is 160 ℃, and be 0.5h heat-up time; In the process of preparation lignin-base carbon nanomaterial, take out whole CePO
4Temperature of reaction in the powder, reactor is 230 ℃, and the reaction times is outside the 3h, and all the other are identical with embodiment 4.
Fig. 9 is the electron scanning micrograph of the lignin-base carbon nano-composite material of embodiment 6 preparations, can find out clearly that main form is micron ball and fibrous aggregate, and micron ball size is about 3.6 μ m, and the surface does not have nano particle.
(a) amplifies 2000 times electron scanning micrograph among Fig. 9 for carbon nanomaterial; (b) amplifies 20000 times electron scanning micrograph for carbon nanomaterial among Fig. 9, and wherein micron ball size is about 3.6 μ m, and the surface does not have nano particle.
(c) is the fluorescence spectrum figure of the prepared lignin-base carbon nano-composite material of embodiment 6 among Figure 10, and fluorescence intensity is 200a.u, compares with the fluorescence spectrum of embodiment 1, and fluorescence intensity reduces.
Claims (8)
1. preparation method with lignin-base carbon nanomaterial of fluorescence property comprises following step in sequence: a) be raw material with the wood powder, make by DeR and contain lignin liquor; B) lignin liquor and Cerium monophosphate or lignin liquor carry out the solvent thermal building-up reactions with after phosphoric acid salt, cerium salt mix, and wherein, described cerium salt is water-soluble cerium salt, is selected from Ce (NO
3)
3, Ce (SO
4)
2, CeF
3, Ce (Ac)
3, Ce
2(CO
3)
3, Ce (NH
4)
2(NO
3)
6, Ce (SO
4)
22 (NH
4)
2SO
42H
2Among the O one or more; Described phosphoric acid salt is water-soluble phosphate, is selected from NaH
2PO
4, Na
2HPO
4, Na
3PO
4, KH
2PO
4, K
2HPO
4, K
3PO
4, (NH
4)
3PO
4In one or more; Described solvent thermal synthesis reaction temperature is 180-230 ℃, and the reaction times is 3-72 hour.
2. preparation method as claimed in claim 1 is characterized in that the mole proportioning of phosphorus in cerium in the salt of cerium described in the step b) and the phosphoric acid salt is 1:1-2.
3. preparation method as claimed in claim 1 or 2 is characterized in that the step of carrying out in the following order in the step a) makes and contains lignin liquor:
1) wood powder, LiCl are joined in the dimethyl sulfoxide (DMSO), mix, make pre-degradation of mixture;
2) pre-degradation of mixture is carried out the DeR of wood powder under microwave irradiation effect, make degradation of mixture, namely.
4. preparation method as claimed in claim 3 is characterized in that step 2) described in the temperature of reaction of DeR be 120-160 ℃, the reaction times is 0.5-3 hour.
5. preparation method as claimed in claim 3 is characterized in that also comprising step 3): add ethanol in the degradation of mixture, filter then, filtrate is lignin liquor, and the mass percent concentration of wherein said ethanol is 85-100%.
6. preparation method as claimed in claim 1 or 2 is characterized in that step b) comprises following step in sequence:
1) lignin liquor that step a) is prepared and Cerium monophosphate or lignin liquor and phosphoric acid salt, cerium salt place in the reactor, stir, and are dispersed into suspension;
2) with after the reactor sealing, heating makes suspension carry out the solvent thermal building-up reactions, makes the lignin-base carbon nanomaterial with fluorescence.
7. preparation method as claimed in claim 6 is characterized in that step 2) described in the solvent thermal synthesis reaction temperature be 180-230 ℃, the reaction times is 3-72 hour.
8. lignin-base carbon nanomaterial with fluorescence property is characterized in that being prepared from according to method as described in arbitrary as claim 1-7.
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| CN106832327A (en) * | 2015-12-07 | 2017-06-13 | 中国林业科学研究院木材工业研究所 | A kind of fluorescent base nano lignin and preparation method thereof |
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