CN104891479A - Plant-based graphene and preparation method thereof - Google Patents
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Abstract
The invention provides plant-based graphene and a preparation method thereof. The preparation method comprises the steps of liquefying and filtering plant raw materials to obtain biological oil; mixing the biological oil with a catalyst to obtain a mixture, placing the mixture into a self-pressurizing reactor, sealing the reactor, catalytically calcining for 1 to 12 hours at the temperature of 500 to 1200 DEG C, cooling, washing by utilizing hydrochloric acid to remove the catalyst, rinsing by utilizing deionized water, and drying to obtain the quasi-graphene. According to the preparation method, the plant raw materials are firstly liquefied into biological oil which mainly includes oligosaccharide and a phenolic substance, then the biological oil is mixed with the catalyst, and under the high temperature and high pressure, the biological oil is converted to quasi-graphene on the surface of the catalyst, so that a novel method for preparing the quasi-graphene material in a mass manner by virtue of cheap plant raw materials is provided.
Description
Technical field
The present invention relates to plant base class grapheme material and preparation method thereof, be specifically related to plant resources through the industrial method liquefied, super capacitor active carbon matrix material is prepared in low-temperature catalyzed calcining.
Background technology
Graphene (Graphene) is a kind of Two-dimensional Carbon material, is the general designation of single-layer graphene, bilayer graphene and few layer graphene.Graphene is thin, the hardest nano material in known world, and it is large that it also has specific surface, and electric conductivity is high, the feature that thermomechanical property is excellent, all can play an important role at life science and energy field.At present, the method preparing Graphene has graphite oxide reduction method, epitaxial growth method, chemical Vapor deposition process, mechanically peel method, electrochemical method.The thinking that graphite oxide reduction method is reduced after adopting initial oxidation, concrete steps first prepare graphite oxide, by the method such as ultrasonic wave, thermal expansion, graphene oxide is stripped out as far as possible again, suitable reductive agent is finally adopted to change graphene oxide into Graphene, as adopted hydrazine hydrate to reduce to graphene oxide, be the Graphene that the carbon atom of sp3 becomes sp2 carbon network lattice composition by wherein hybrid form.Carbon is entrained in rare metal with the method for seeping at high temperature and forms interstitial impurity by epitaxial growth method, then makes carbon at metal substrate surface indigenous graphite alkene epitaxial with subzero treatment.When the first layer Graphene not yet completely covering metal substrate time, the second layer has started growth, because the first layer is completely different from the chemical bond kind of second layer Graphene and metal substrate, the gap between weakness coupling and powerful covalent linkage effect makes second layer Graphene be easy to be stripped out.Chemical Vapor deposition process take metal single crystal as substrate, by changing temperature, regulating substrate, controlling the object that the exposed amount etc. of precursor reaches accurately control graphene film thickness.Concrete mode is exposed in methane atmosphere after Ni film thick for 300mm is heated to 1000 degrees Celsius, thus form highly purified graphene film on Ni surface.Micromechanics partition method micromechanics partition method is the method for the most original stripping Graphene.During concrete operations, normal employing makes graphite expansion someway so that be separated, and mono-layer graphite irregularly can appear at graphite surface, and this method is compared chemical stripping method and is more difficult to control Graphene form, is unsuitable for high precision industrial production.
The people such as Yang Rong disclose preparation method's (application number: 201410134804.0) of the conductive carbon material of a kind graphene-structured, sepiolite powder, sucrose are mixed with deionized water, then ultrasonic disperse, microwave heating is again place 24-144h in the vitriol oil moisture eliminator of 98.3% at massfraction; In this step, sucrose heated by microwave is converted into caramel.Carbonization is carried out, caramel carbonization in sepiolite layered framework in protective gas atmosphere.Sepiolite employing hydrofluoric acid after carbonization, hydrochloric acid are replaced acidifying washing, then adopts deionized water to clean sepiolite and fully drying, obtain the conductive carbon material of class graphene-structured.
Burnt odd-numbered prescription (burnt odd-numbered prescription, the preparation of class graphene carbon nanometer fragment and electrocatalysis characteristic thereof, [academic dissertation], South China Normal University, 2013) with waste and old lithium ion battery Carbon anode for raw material, through process such as a series of pre-treatment-chemical oxidation-ultrasonic grinding-dialysis purifying, obtain oxidation state carbon nanometer fragment, result shows: oxidation state carbon nanometer fragment contour is coarse, thickness is 1.5nm, the similar Graphene of profile, size from 5nm ~ 2 μm not etc., and containing a large amount of oxygen-containing functional groups and defect.
Zhu Runliang etc. disclose the preparation method (publication number CN103058168A) of the nano-carbon material of a kind graphene-structured.The wilkinite adsorbing dyestuff is carried out successively drying, pulverizing, carbonization, acidifying washing, drying, obtain the nano-carbon material of class graphene-structured.This invention with discarded wilkinite for raw material, prepare a kind of novel nano stratiform carbon material had compared with bigger serface, recycle for bentonitic resource utilization after solution absorbing dye simultaneously and provide new way, achieve the bentonite resourceization after wastewater treatment to utilize, thus contribute to promoting the application of wilkinite in dyestuff/treatment of dyeing wastewater.
Zhou Xufeng discloses a kind of preparation method and Graphene patent of invention (publication number CN104477901A) of Graphene.Metal catalyst is mixed with water, obtains the aqueous solution of metal catalyst; By the aqueous solution of gel like material and metal catalyst, obtain the hydrogel material being adsorbed with metal catalyst, described gel like material comprises one or more in starchy compounds, cellulose compound and synthetic resins; The hydrogel material being adsorbed with metal catalyst is heat-treated under shielding gas atmosphere or vacuum environment, obtains Graphene.
(the Liang Xuelei such as Liang Xuelei, Li Wei, GuangJun C etc. transfer process is on the impact [J] of the Graphene quality that CVD grows. Science Bulletin, 2014, (33)) Graphene that utilizes the chemical vapor precipitator method (CVD) to grow on the metallic substrate.Utilize Raman spectrum and x-ray photoelectron power spectrum (XPS) to demonstrate metal base corrosive fluid in transfer process and can introduce pollution at graphenic surface, " RCA (radio corporation of America) cleaning (modified RCA clean) of the improvement " shifting process utilizing us to develop can remove this pollution effectively. and this is significant to the performance of the electron device improving follow-up preparation
[the Zou Zhengguang such as the positive light of Guilin University of Technology Zou, Yu Huijiang, Long Fei, Deng. ultrasonic wave added Hummers legal system is for GO [J]. Chinese Journal of Inorganic Chemistry, 2011,27 (09): 1753-1757.] respectively the low temperature (≤10 DEG C) of Hummers method, middle temperature (38 DEG C) and low middle thermophase are carried out to the ultrasonic wave added of different capacity, explore the impact of ultrasonic wave on Hummers method.They find GO interlamellar spacing descending be followed successively by low middle temperature ultrasonic wave added, middle temperature ultrasonic wave added, low temperature ultrasonic assist.Moreover, graphene layer spacing becomes positive correlation with ultrasonic power, and spacing is conducive to more greatly individual layer GO and peels off, so can prepare individual layer GO or intercalation GO according to different experiments demand.
[the Jia Qina such as Jia Qina, Zhao Guangchao. the preparation of Graphene solid-phase micro-extraction fibre and the detection [J] to polychlorobiphenyl. analytical test journal, 2013,32 (05): 541-546.] by solid phase micro-extraction technique, the titanium sol-gel adding Graphene is made fiber, this fiber is made to have all advantages of both Graphene and gel, not only possess quite high specific surface area, stronger thermostability and excellent physical strength, and have three-dimensional structure to provide more adsorption site.
[the Ren little Meng such as Ren little Meng, Wang Yuansheng, the critical process of what special .Hummers method synthesizing graphite alkene and reaction mechanism [J]. material engineering, 2013 (01): 1-5.] classical Hummers method is probed into, by change its temperature of reaction, the temperature control time, reactive material amount etc. and respectively each group of product is detected.The optimum temps in the low-temp reaction stage of discovery Hummers method is close to 0 DEG C, reaction times can suitably increase, and the vitriol oil in the low-temp reaction stage and potassium permanganate can excessively add, the add-on of SODIUMNITRATE can not affect reaction substantially, the temperature of middle thermophase being adjusted to is 30 ~ 45 DEG C, it is best that reaction times increases 90min, and ensure that the oxidation of graphite is more deep with this, lamella peels off more complete.But affect the most productive rate in the temperature rise period, this study group finds that temperature being controlled in 90 ~ 100 DEG C is maximum output scope, by repeatedly adding deionized water on a small quantity, and Reaction time shorten of should trying one's best, prevents product from again reuniting.
Although above method successfully prepares high-quality Graphene, preparation process is with high costs, pollution is large, is difficult to industrialization.Therefore, macroblock quantization is produced and large size is produced and remained obstruction grapheme material and to have high input the main bottleneck of scale commercialization.At present; there is not yet and do not have the preparation method of plant base thunder grapheme material to report; biomass mass-producing liquefaction technology is ripe, therefore, with the low plant base of wide material sources, degree of crystallinity for raw material; class grapheme material is prepared by liquefaction and catalysis calcination; can realize extensive industrialization, cost significantly reduces, and environmental pollution is little; product dispersing property is better, more easily stores.
Summary of the invention
In order to solve the preparation process preparation in macroscopic quantity difficulty that prior art exists, seriously polluted, the problem such as expensive, the present invention carries a kind of plant base liquefied catalytic and prepares class grapheme material and method thereof, can realize extensive industrialization, and preparation process cleans, step is simple, low cost of manufacture, product dispersing property is better, more easily stores.
Technical scheme of the present invention is: the preparation method of plant base class Graphene, comprises the steps:
The first step, plant is liquefied: the agricultural-forestry biomass raw material of oven dry and phenol are liquefied, and filters after removing inorganic impurity and obtains bio oil;
Second step, bio oil and catalyst mix: with iron group nitrate for catalyzer, (0.1 ~ 1.0) ︰ 1.0 mixes according to mass ratio for catalyzer and bio oil;
3rd step, sealing pre-treatment: be placed in spontaneous pressure reactor by a certain amount of said mixture, inventory is no more than 1/3 of reactor volume, carries out airtight pre-treatment;
4th step, calcining: the spontaneous pressure reactor that material is housed is placed in High Temperature Furnaces Heating Apparatus, heat up calcining, after calcining terminates, naturally cooling, take out sample, reclaim catalyzer, by rinsed with deionized water through pickling, after drying, be described plant base class Graphene sample, the specific conductivity 370s/cm of plant base class Graphene, specific surface area 760m
2/ g, thickness 1-3nm.
Plant material described in the first step comprises wood chip, and bamboo is considered to be worth doing, stalk, dries and uses.
Bio oil described in the first step removes solid impurity after filtration.
In second step, iron group comprises iron, nickel, cobalt.
At the uniform velocity stir when in second step, iron group nitrate mixes with bio oil.
In 4th step, calcining temperature is 500 ~ 1200 DEG C, calcination time 1-10h.
The Graphene that the preparation method of described plant base class Graphene obtains, specific conductivity 180 ~ 370s/cm, specific surface area 420 ~ 760m
2/ g, thickness 1-3nm.
The yield of plant base class grapheme material of the present invention, specific surface area, thickness controlled by catalyst loadings, activation temperature, calcining temperature and time.The preparation of plant base class grapheme material: the plant material of oven dry and phenol are liquefied, filters after removing inorganic impurity and obtains bio oil.Bio oil and catalyst mix: with iron group nitrate for catalyzer, according to mass ratio, (0.1 ~ 1.0) ︰ 1.0 mixes with bio oil.Be placed in spontaneous pressure reactor by a certain amount of said mixture, inventory is no more than 1/3 of reactor volume, carries out airtight pre-treatment.The spontaneous pressure reactor that material is housed is placed in High Temperature Furnaces Heating Apparatus, is warming up to 500-1200 DEG C with certain temperature rise rate, keep 1-10h.After calcining terminates, naturally cooling, takes out sample, reclaims catalyzer, by rinsed with deionized water, after drying, be described class Graphene sample through pickling.Specific conductivity 180 ~ the 370s/cm of plant base class Graphene, specific surface area 420 ~ 760m
2/ g, thickness 1-3nm.
Beneficial effect:
1. first plant base raw material to be liquefied pre-treatment.Plant base raw material reduces the degree of crystallinity of vegetable fibre by liquefaction process, obtains oligose and aldehydes matter, reduces graphited activation energy, improves greying transformation efficiency.And liquefaction technology equipment realizes industrialization, the raw material preparing Graphene can be obtained on a large scale.
2. catalyzed graphitization prepares grapheme material.Load iron series catalysts, in spontaneous pressure, obviously can reduce graphitization temperature, improves Graphene yield.The specific conductivity 370s/cm of plant base class Graphene, specific surface area 760m
2/ g, thickness 1-3nm.
Accompanying drawing explanation
Fig. 1 is the embodiment of the present invention 1 plant Graphene Electronic Speculum figure.
Fig. 2 is the XRD figure of embodiment 1.
Fig. 3 is the atomic force microscopy figure of embodiment 1.
Fig. 4 is the schematic diagram of spontaneous pressure reactor.
1 is resistance furnace, and 2 is thermopair, and 3 is resistance wire, and 4 is electrically heated rod, and 5 is stainless steel sealed can, and 6 is ventage.
Embodiment
The testing method of the present invention to prepared plant base class grapheme material performance is as follows:
(1) specific area measuring: under adopting liquid nitrogen condition, gac is to the mensuration of nitrogen adsorption isotherm, according to BET formula calculated specific surface area.
(2) surface topography adopts projection Electronic Speculum (TEM) and atomic force microscope (AFM) test.
(3) conductance measurement: SZT-C type four point probe test board measures.
The preparation method of plant base class Graphene, comprises the steps:
The first step, plant is liquefied: the plant material of oven dry and phenol are liquefied, and filters after removing inorganic impurity and obtains bio oil.By liquefaction, plant material is converted into bio oil, composition is mainly oligose and aldehydes matter.This step can with reference to Wang Yuanyuan, Ye Lei, Shen Huyan, etc. wild rice stem abandoned biomass Liquefaction Products in Phenol and product resin thereof prepare sizing agent [J]. Chemical Industry in Guangzhou, 2014, (23).; Li Gaiyun, Zhu Xianchao, Zou Xianwu, etc. the quick Liquefaction Products in Phenol of microwave-assisted poplar and Characterization of The Products [J]. forest-science, 2014, (11) .DOI:doi:10.11707/j.1001-7488.20141116.; Sun Fengwen, Li little Ke. bamboo wood Liquefaction Products in Phenol and sizing agent preparation technology [J]. chemistry of forest product and industry, 2007,27 (6): 65-70.DOI:doi:10.3321/j.issn:0253-2417.2007.06.014.; Take off refined person of outstanding talent, Zhang Qiuhui, Li Jianzhang. the research [J] of China fir Liquefaction Products in Phenol thing synthesis thermoset phenolic resin. biomass chemical engineering, 2007,41 (5): 9-12.DOI:doi:10.3969/j.issn.1673-5854.2007.05.003.; Qin Tefu, Luo Bei, Li Gaiyun. the Liquefaction Products in Phenol of artificial forest wood and resinifying research II. the preparation of liquefied wood base resol and performance characterization [J]. timber industry, 2006,20 (5): 8-10.DOI:doi:10.3969/j.issn.1001-8654.2006.05.003.; Ma Xiaojun, Zhao Guangjie. the Primary Study [J] of Preparation of Carbon Fiber from Wood-phenol Liquefaction Products. chemistry of forest product and industry, 2007, the method recorded in 27 (2): 29-32.DOI:doi:10.3321/j.issn:0253-2417.2007.02.007..
Second step, bio oil and catalyst mix: with iron group nitrate for catalyzer, according to mass ratio, (0.1 ~ 1.0) ︰ 1.0 mixes with bio oil.
3rd step, sealing pre-treatment: be placed in spontaneous pressure reactor by a certain amount of said mixture, inventory is no more than 1/3 of reactor volume, carries out airtight pre-treatment.
4th step, calcining: the spontaneous pressure reactor that material is housed is placed in High Temperature Furnaces Heating Apparatus, is warming up to 500-1200 DEG C with certain temperature rise rate, keeps 1-10h.After calcining terminates, naturally cooling, takes out sample, reclaims catalyzer, by rinsed with deionized water, after drying, be described class Graphene sample through pickling.The specific conductivity 370s/cm of plant base class Graphene, specific surface area 760m
2/ g, thickness 1-3nm.
Plant material described in the first step comprises wood chip, and bamboo is considered to be worth doing, and the agricultural-forestry biomass raw materials such as stalk, need drying and processing.
Bio oil described in the first step need remove solid impurity after filtration.
In second step, iron group comprises iron, nickel, cobalt.
At the uniform velocity stir when in second step, iron group nitrate mixes with bio oil.
Described spontaneous pressure reaction unit is outer is resistance furnace 1, establish stainless steel sealed can 5 in resistance furnace 1, be provided with resistance wire 3 in resistance furnace 1, spontaneous pressure reactor is heated by electrically heated rod 4, by interior thermopair 2 monitoring temperature established, resistance furnace 1 is also provided with ventage 6.
Embodiment 1
(1) plant liquefaction: liquefied with phenol by the bamboo of oven dry bits, removes inorganic impurity after filtration and obtains bio oil.
(2) bio oil and catalyst mix: take nickelous nitrate as catalyzer, mix according to mass ratio 0.1 ︰ 1.0 with bio oil.
(3) pre-treatment is sealed: be placed in by a certain amount of said mixture in spontaneous pressure reactor, inventory is 1/3 of reactor volume, carries out airtight pre-treatment.
(4) calcine: the spontaneous pressure reactor that material is housed is placed in High Temperature Furnaces Heating Apparatus, is warming up to 500 DEG C with certain temperature rise rate, keep 1h.After calcining terminates, naturally cooling, takes out sample, reclaims catalyzer, by rinsed with deionized water, after drying, be described class Graphene sample through pickling.The specific conductivity 180s/cm of plant base class Graphene, specific surface area 420m
2/ g, thickness 1-3nm.
Embodiment 2
(1) plant liquefaction: liquefied with phenol by the bamboo of oven dry bits, removes inorganic impurity after filtration and obtains bio oil.
(2) bio oil and catalyst mix: take nickelous nitrate as catalyzer, mix according to mass ratio 1.0 ︰ 1.0 with bio oil.
(3) pre-treatment is sealed: be placed in by a certain amount of said mixture in spontaneous pressure reactor, inventory is 1/3 of reactor volume, carries out airtight pre-treatment.
(4) calcine: the spontaneous pressure reactor that material is housed is placed in High Temperature Furnaces Heating Apparatus, is warming up to 1200 DEG C with certain temperature rise rate, keep 10h.After calcining terminates, naturally cooling, takes out sample, reclaims catalyzer, by rinsed with deionized water, after drying, be described class Graphene sample through pickling.The specific conductivity 327s/cm of plant base class Graphene, specific surface area 590m
2/ g, thickness 1-3nm.
Embodiment 3
(1) plant liquefaction: liquefied with phenol by the bamboo of oven dry bits, removes inorganic impurity after filtration and obtains bio oil.
(2) bio oil and catalyst mix: take nickelous nitrate as catalyzer, mix according to mass ratio 0.7 ︰ 1.0 with bio oil.
(3) pre-treatment is sealed: be placed in by a certain amount of said mixture in spontaneous pressure reactor, inventory is 1/3 of reactor volume, carries out airtight pre-treatment.
(4) calcine: the spontaneous pressure reactor that material is housed is placed in High Temperature Furnaces Heating Apparatus, is warming up to 1100 DEG C with certain temperature rise rate, keep 10h.After calcining terminates, naturally cooling, takes out sample, reclaims catalyzer, by rinsed with deionized water, after drying, be described class Graphene sample through pickling.The specific conductivity 370s/cm of plant base class Graphene, specific surface area 760m
2/ g, thickness 1-3nm.
Embodiment 4
(1) plant liquefaction: liquefied with phenol by the bamboo of oven dry bits, removes inorganic impurity after filtration and obtains bio oil.
(2) bio oil and catalyst mix: take nickelous nitrate as catalyzer, mix according to mass ratio 0.7 ︰ 1.0 with bio oil.
(3) pre-treatment is sealed: be placed in by a certain amount of said mixture in spontaneous pressure reactor, inventory is 1/3 of reactor volume, carries out airtight pre-treatment.
(4) calcine: the spontaneous pressure reactor that material is housed is placed in High Temperature Furnaces Heating Apparatus, is warming up to 1200 DEG C with certain temperature rise rate, keep 10h.After calcining terminates, naturally cooling, takes out sample, reclaims catalyzer, by rinsed with deionized water, after drying, be described class Graphene sample through pickling.The specific conductivity 365s/cm of plant base class Graphene, specific surface area 730m
2/ g, thickness 1-3nm.
Embodiment 5
(1) plant liquefaction: liquefied with phenol by the bamboo of oven dry bits, removes inorganic impurity after filtration and obtains bio oil.
(2) bio oil and catalyst mix: with iron group nitrate for catalyzer, mixes according to mass ratio 1.0 ︰ 0.7 with bio oil.
(3) pre-treatment is sealed: be placed in by a certain amount of said mixture in spontaneous pressure reactor, inventory is 1/3 of reactor volume, carries out airtight pre-treatment.
(4) calcine: the spontaneous pressure reactor that material is housed is placed in High Temperature Furnaces Heating Apparatus, is warming up to 1200 DEG C with certain temperature rise rate, keep 5h.After calcining terminates, naturally cooling, takes out sample, reclaims catalyzer, by rinsed with deionized water, after drying, be described class Graphene sample through pickling.The specific conductivity 355s/cm of plant base class Graphene, specific surface area 718m
2/ g, thickness 1-3nm.
Embodiment 6
Change the bamboo bits in embodiment 3 into cedar sawdust, all the other obtain the specific conductivity 369s/cm of plant base class Graphene, specific surface area 751m with embodiment 3
2/ g, thickness 1-3nm.
Embodiment 7
Change the bamboo bits raw material in embodiment 3 into coconut husk, all the other obtain the specific conductivity 325s/cm of plant base class Graphene, specific surface area 728m with embodiment 3
2/ g, thickness 1-3nm.
Embodiment 8
Change the nickelous nitrate in embodiment 3 into iron nitrate, all the other obtain the specific conductivity 285s/cm of plant base class Graphene, specific surface area 672m with embodiment 3
2/ g, thickness 1-3nm.
Embodiment 9
Change the nickelous nitrate in embodiment 3 into Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, all the other obtain the specific conductivity 370s/cm of plant base class Graphene, specific surface area 760m with embodiment 3
2/ g, thickness 1-3nm.
Claims (7)
1. the preparation method of plant base class Graphene, is characterized in that, comprises the steps:
The first step, plant is liquefied: the agricultural-forestry biomass raw material of oven dry and phenol are liquefied, and filters after removing inorganic impurity and obtains bio oil;
Second step, bio oil and catalyst mix: with iron group nitrate for catalyzer, (0.1 ~ 1.0) ︰ 1.0 mixes according to mass ratio for catalyzer and bio oil;
3rd step, sealing pre-treatment: be placed in spontaneous pressure reactor by a certain amount of said mixture, inventory is no more than 1/3 of reactor volume, carries out airtight pre-treatment;
4th step, calcining: the spontaneous pressure reactor that material is housed is placed in High Temperature Furnaces Heating Apparatus, heat up calcining, after calcining terminates, naturally cooling, take out sample, reclaim catalyzer, by rinsed with deionized water through pickling, after drying, be described plant base class Graphene sample, the specific conductivity 370s/cm of plant base class Graphene, specific surface area 760m
2/ g, thickness 1-3nm.
2. the preparation method of plant base class Graphene as claimed in claim 1, it is characterized in that, the plant material described in the first step comprises wood chip, and bamboo is considered to be worth doing, stalk, dries and uses.
3. the preparation method of plant base class Graphene as claimed in claim 1, it is characterized in that, the bio oil described in the first step removes solid impurity after filtration.
4. the preparation method of plant base class Graphene as claimed in claim 1, it is characterized in that, in second step, iron group comprises iron, nickel, cobalt.
5. the preparation method of plant base class Graphene as claimed in claim 1, is characterized in that, at the uniform velocity stir when iron group nitrate mixes with bio oil in second step.
6. the preparation method of plant base class Graphene as claimed in claim 1, it is characterized in that, in the 4th step, calcining temperature is 500 ~ 1200 DEG C, calcination time 1-10h.
7. the Graphene that obtains of the preparation method of the arbitrary described plant base class Graphene of claim 1 ~ 6, is characterized in that, specific conductivity 180 ~ 370s/cm, specific surface area 420 ~ 760m
2/ g, thickness 1-3nm.
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