CN106241780A - A kind of method preparing Graphene for raw material with lignin - Google Patents
A kind of method preparing Graphene for raw material with lignin Download PDFInfo
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Abstract
The invention belongs to material with carbon element Manufacturing Techniques field, specifically disclose a kind of method preparing Graphene for raw material with lignin.Lignin and catalyst precursor successively alternate group, with stratiform or powdered substance as base material, by the method for Self assembly, are loaded on substrate surface by described method；Then lignin/catalyst precursor/substrate composite is placed in double temperature-area tubular furnace, is passed through H with certain speed2/ Ar mixed gas, heats up with certain program in stove simultaneously, after being heated to target temperature, and constant temperature certain time, treat that double temperature-area tubular furnace is down to room temperature, sample is taken out, removes catalyst through acid soak, washing several times, is vacuum dried, i.e. can get Graphene.Present invention process is simple, and easy to operate, the graphene growth of preparation is good, the number of plies is controlled, and productivity is considerable.
Description
Technical field
The invention belongs to material with carbon element Manufacturing Techniques field, be specifically related to one and prepare Graphene with lignin for raw material
Method.
Background technology
Lignin, as the substantial amounts of natural organic matter of nature second, is widely present in major part land plant xylem
In, the annual yield in the whole world is up to 150,000,000,000 tons.It has many uses general, can be used as surfactant, reinforcing agent, binding agent,
Water reducer, scale preventative, corrosion inhibiter and dispersant etc., cover a lot of fields of industry agricultural, have the highest value.So
And, the utilization ratio of current lignin is low, and the overwhelming majority is used for burning, and the response rate is low, pollutes again environment.As can be seen here,
Need exploitation lignin clean and effective utilizes technology.Herein by the method for Self assembly by lignin conversion Cheng Xin
Type graphene material, had both utilized resource, had protected again environment.
Graphene is the nano-carbon material that known world is the thinnest, the hardest, and it is made up of one layer of carbon atom, the most thoroughly
Bright, there is the highest light transmission (up to 97.7%)；Its resistivity ratio copper or silver are lower, for world resistivity minimum
Material, the speed of electron transfer is exceedingly fast.Graphene is with its superior electricity, calorifics, mechanical performance, at lithium ion battery, super
There is potential huge application prospect in the fields such as capacitor, electrically conductive ink, quasiconductor.About answering in field of lithium ion battery
With, Graphene forms composite ratio with metal or oxide particle and is used alone Graphene as ion cathode material lithium
Advantage becomes apparent from.But, although Graphene possesses above many merits, how low cost prepares Graphene is numerous application
Major premise.
So far, the preparation method of Graphene is broadly divided into two big classes, and a class is synthetic method from large to small, i.e. with
Native graphite is carbon source, obtains monolayer or form the few-layer graphene alkene, such as mechanical stripping by the method physically or chemically peeled off/shear
Method, chemistry redox method and arc process etc.；Another kind of is synthetic method from small to large, with little molecule carbon compound is i.e.
The monolayer of Material synthesis macromole or form the few-layer graphene alkene, such as chemical vapour deposition technique, organic synthesis method etc..Wherein, chemistry gas
Phase sedimentation is simple to operate, grows controlled, but condition is harsh, high cost, is difficult to commercialization；The preparation letter of chemistry redox method
Single, material is cheap, is expected to batch production, but reaction time is long, and gained graphene product quality is relatively low, introduces defect and functional group
Too much；Additive method also remains in problems.Thus, also need to attempt novel, controlled graphene preparation technology.
Polyelectrolyte Self assembly is to prepare many with polyanion and polycation at substrate surface alternating sorbent
The new technique of tunic.This technology is simple because of its operation, structure-controllable, and quality of forming film is high, and base material requiring, the feature such as low becomes
The study hotspot of functional polymer nano film applications.
In terms of the Self assembly of lignin, Paterno L G and Mattoso L finds lignosulfonates
Self assembly can be well carried out, by the surface shape of atomic force microscope research self-assembled film with poly-O-ethoxyl amine
Looks, find that lignin sulfonic acid salt deposit compares poly-O-ethoxyl amine layer more smooth (Polymer.2001,42:5239-5245).Quiet
Lignin polyelectrolyte nanometer film prepared by electricity LBL self assembly may be used for surface and waits (Ind with the modified of interface
Crop.Prod.2009,30:287-291).Have not yet to see and utilize lignin polyelectrolyte LBL self assembly technology to prepare stone
The report of ink alkene.
Summary of the invention
It is an object of the invention to provide a kind of with lignin as raw material, by Self assembly and catalysis carbonization,
The method preparing Graphene.
Utilize the molecular separating force of lignin polyelectrolyte, induce its aggregation micro structure to change from " unordered " to " in order ",
" from bottom to top " construct the Self assembly nanometer film of lignin polyelectrolyte, effectively suppress lignin polyelectrolyte
Random reunion.Catalyst precursor is successively introduced in the LBL self-assembly nanometer film of lignin solid-state carbon source, stratiform or
Surface " from bottom to top " growth in situ such as particulate substrates even electrode material go out the graphene coated layer of structure-controllable, its graphite
Alkene preparation method is different from the method for conventional CVD method or other preparing graphene by utilizing solid carbon source.
The object of the invention is achieved through the following technical solutions:
A kind of method preparing the controlled Graphene of the number of plies for raw material with lignin, comprises the following steps:
(1) lignin is made into certain density aqueous solution, claims a certain amount of catalyst precursor to be made into aqueous solution；Described
Catalyst precursor is FeCl3、FeSO4·7H2O、Fe(NO3)3·9H2O、CuSO4·5H2O、Co(NO3)2And NiSO4·6H2O
In one；
(2) pretreated base material is first sufficiently impregnated with a period of time, after taking-up in ultra-pure water in lignin liquor
Soak a period of time, then with ultrapure water for several times, and cold drying in the range of 10～25 DEG C；Place into complex catalyst precursor
Time of infusion in liquid solution, first soaks with ultra-pure water after taking-up and rinses for several times, and low temperature is done in the range of 10～25 DEG C
Dry, i.e. obtain one layer of lignin polyelectrolyte and the self-assembled film of catalyst precursor；Repeat above lignin liquor dipping, surpass
Pure water immersion, milli-Q water, Catalyst precursor solutions dipping, ultra-pure water immersion, the operation of milli-Q water, the most available
The self-assembled film that the number of plies is controlled；
(3) sample that step (2) obtains is placed in vacuum tube furnace, is passed through H with given pace2/ Ar (5:95, V/V)
Mixed gas, as protection gas and reducing gases, heats up with certain speed simultaneously, and after being heated to target temperature, constant temperature is certain
Time, treat that double temperature-area tubular furnace temperature is down to room temperature, sample is taken out, removes catalyst through acid soak, wash several times, vacuum
After drying, the controlled Graphene of the number of plies.
For realizing goal of the invention further, step (1) described lignin liquor concentration range is 0.05～10g/L, catalysis
Agent precursor solution concentration range is 0.01～0.5mol/L, and in lignin, carbon controls with the mol ratio of catalyst precursor
10～400.
Step (1) described lignin is in alkali lignin, sodium lignin sulfonate, Milled wood lignin and organosolv lignin
A kind of.
Step (2) described base material can be stratiform, such as the one in quartz slide, copper sheet, iron plate；It can also be granule
Shape, such as NaCl, graphite powder, LiFePO4 etc..
Preferably, the preprocess method of quartz slide is: quartz slide is used dense H2SO4With H2O2Mixed liquid dipping 1h,
10min is soaked with ultra-pure water after taking-up, then with ultra-pure water drip washing quartz slide 3～4 times, then with ammonia, H2O2With H2O's is mixed
Close solution soaking 1h, with ultra-pure water drip washing 3～4 times, be soaked in ultra-pure water standby.
Preferably, step (3) is passed through the speed range of gaseous mixture is 20～100mL/min.
Preferably, step (3) described heating rate is 2～8 DEG C/min, and target temperature is 600～800 DEG C, the retention time
It is 1～6h.
A kind of method being prepared Graphene by lignin, is realized by above-mentioned steps；Gained Graphene is that monolayer arrives multilamellar
, growth is uniformly.
The present invention uses the method for polyelectrolyte Self assembly, is usually made by transition metal-catalyzed carbonized woody
Standby Graphene, simple to operate, abundant raw material, grow controlled, the cycle is shorter, and gained Graphene high-quality is uniform, holistic cost
Low, it is a kind of the most novel but also the most feasible method.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) present invention is directly with industrial lignin as raw material, and abundance is cheap.Both can drop to a certain extent
Low production cost, can reduce again the pollution that papermaking wastewater brings, the higher value application realizing natural resources.
(2) Self assembly of the present invention, is referred to as " technology in beaker ", and equipment is simple, and operation is held
Easily；Solvent is the water of environmental protection the most, and whole process never relates to poisonous and hazardous organic solvent；Self-assembled film quality height,
Controllability is good, low to substrate surface character and shape need.It is embodied everywhere energy-saving and environmental protection, economy, efficient theory.
(3), in the present invention, during self-assembled film catalysis carbonization, set temperature is only 500～800 DEG C, relative to conventional high-temperature
Carbonization (2500～2900 DEG C), mild condition, low-carbon environment-friendly.
(4) products therefrom Graphene of the present invention, uniformly, the number of plies is controlled, with its superior electricity, calorifics, mechanicalness in growth
Can, there is potential huge application prospect in fields such as lithium ion battery, ultracapacitor, electrically conductive ink, quasiconductors.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscopic picture of the Graphene of the inventive method embodiment 1 preparation.
Fig. 2 is the Raman spectrum of the Graphene of the inventive method embodiment 1 preparation.
The X-ray diffraction spectrogram of the Graphene of Fig. 3 position the inventive method embodiment 1 preparation.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention do not limit
In this.
Embodiment 1
(1) sodium lignin sulfonate (sodium lignosulfonate, hereinafter referred to as SL) SL is made into the water-soluble of 1g/L
Liquid, claims 20.20gFe (NO3)3·9H2O solid, is dissolved in water and is made into the solution of 0.1mol/L.
(2) pretreated quartz slide is first sufficiently impregnated with 10min in SL solution, soaks in ultra-pure water after taking-up
5min, then with ultrapure water for several times, and dries up with cold wind；Place into dipping 10min in iron nitrate solution, after taking-up, first
Soak 5min with ultra-pure water, then rinse for several times, and dry up with cold wind；I.e. can get one layer of SL/Fe3+Electrostatic self-assembled film；Repeat
More than operate, prepare 10 layers of SL/Fe3+Electrostatic self-assembled film.
(3) sample that step (2) obtains is placed in double temperature-area tubular furnace, is passed through H with the speed of 70mL/min2/Ar(5:
95, V/V) mixed gas is as protection gas and reducing gases, carries out temperature programming with the speed of 5 DEG C/min simultaneously, is heated to target
After temperature 750 DEG C, constant temperature 3h, then cool the temperature to room temperature with the speed of 5 DEG C/min；Sample is taken out, soaks through dilute hydrochloric acid
Remove catalyst ferrum simple substance, with milli-Q water several times, after vacuum drying, the controlled Graphene of the number of plies.
Fig. 1 is to be produced by the embodiment of the present invention 1 of Germany's Carl Zeiss AG-Merlin field emission scanning electron microscope shooting
The SEM figure of product, shows that graphene film layer thickness is about 3nm.
Fig. 2 is to be produced by the present embodiment 1 of France's HORIBA JobinYvon-LabRAMAramis Raman spectrometer test
The Raman spectrum of product, Raman D peak and G peak-to-peak are by force than ID/IGValue be 0.13, show preparation Graphene the most high-graphitized.
Fig. 3 is that the X-ray of the present embodiment 1 product by Germany's Bruker-D8ADVANCE X-ray diffractometer test is spread out
Penetrating collection of illustrative plates, sharp-pointed (002) crystal face peak shows that prepared Graphene degree of crystallinity is good.
Embodiment 2
(1) SL is made into the aqueous solution of 2g/L, claims 26.28g NiSO4·6H2O solid, is dissolved in water and is made into 0.2mol/L's
Solution.
(2) pretreated quartz slide is first sufficiently impregnated with 10min in SL solution, soaks in ultra-pure water after taking-up
5min, then with ultrapure water for several times, and dries up with cold wind；Place into dipping 10min in nickel sulfate solution, after taking-up, first
Soak 5min with ultra-pure water to rinse for several times again, and dry up with cold wind；I.e. can get one layer of SL/Ni2+Electrostatic self-assembled film；Repeat with
Upper operation, prepares 10 layers of SL/Ni2+Electrostatic self-assembled film.
(3) sample that step (2) obtains is placed in double temperature-area tubular furnace, is passed through H with the speed of 20mL/min2/Ar(5:
95, V/V) mixed gas is as protection gas and reducing gases, carries out temperature programming with the speed of 8 DEG C/min simultaneously, is heated to target
After temperature 600 DEG C, constant temperature 4h, then cool the temperature to room temperature with the speed of 6 DEG C/min；Sample is taken out, removes through acid treatment
Catalyst nickel simple substance with milli-Q water several times, after vacuum drying, the controlled Graphene of the number of plies.
Scanning electron microscope, Raman spectrum and X-ray diffractometer same as in Example 1 is used to measure product pattern, carbonization journey
Degree and crystallization degree, result is essentially identical with Fig. 1, Fig. 2 and Fig. 3.
Embodiment 3
(1) SL is made into the aqueous solution of 4g/L, claims 12.48gCuSO4·5H2O solid, is dissolved in water and is made into the molten of 0.1mol/L
Liquid.
(2) pretreated copper sheet is first sufficiently impregnated with 10min in SL solution, soaks in ultra-pure water after taking-up
5min, then with ultrapure water for several times, and dries up with cold wind；Place into dipping 10min in copper-bath, after taking-up, first
Soak 5min with ultra-pure water, then rinse for several times, and dry up with cold wind；I.e. can get one layer of SL/Cu2+Electrostatic self-assembled film；Repeat
More than operate, prepare 10 layers of SL/Cu2+Electrostatic self-assembled film.
(3) sample that step (2) obtains is placed in double temperature-area tubular furnace, is passed through H with the speed of 100mL/min2/Ar
(5:95, V/V) mixed gas, as protection gas and reducing gases, carries out temperature programming with the speed of 8 DEG C/min simultaneously, is heated to mesh
After mark temperature 600 DEG C, constant temperature 5h, then cool the temperature to room temperature with the speed of 10 DEG C/min；Sample is taken out, removes through acid treatment
Remove catalyst copper simple substance milli-Q water several times, after vacuum drying, the controlled Graphene of the number of plies.
Scanning electron microscope, Raman spectrum and X-ray diffractometer same as in Example 1 is used to measure product pattern, carbonization journey
Degree and degree of crystallinity, result is essentially identical with Fig. 1, Fig. 2 and Fig. 3.
Embodiment 4
(1) SL is made into the aqueous solution of 6g/L；Claim 41.71g FeSO4·7H2O solid, is dissolved in water and is made into 0.3mol/L's
Solution.
(2) iron plate good for pretreatment is first sufficiently impregnated with 10min in SL solution, soaks in ultra-pure water after taking-up
5min, then with ultrapure water for several times, and dries up with cold wind；Place into dipping 10min in copperas solution, after taking-up,
First soak 5min with ultra-pure water, then rinse for several times, and dry up with cold wind；I.e. can get one layer of SL/Fe2+Electrostatic self-assembled film；Weight
Multiple above operation, prepares 10 layers of SL/Fe2+Electrostatic self-assembled film.
(3) sample that step (2) obtains is placed in double temperature-area tubular furnace, is passed through H with the speed of 50mL/min2/Ar(5:
95, V/V) mixed gas is as protection gas and reducing gases, carries out temperature programming with the speed of 8 DEG C/min simultaneously, is heated to target
After temperature 600 DEG C, constant temperature 4h, then cool the temperature to room temperature with the speed of 8 DEG C/min；The controlled Graphene of the number of plies.
Scanning electron microscope, Raman spectrum and X-ray diffractometer same as in Example 1 is used to measure product pattern, carbonization journey
Degree and degree of crystallinity, result is essentially identical with Fig. 1, Fig. 2 and Fig. 3.
Embodiment 5
(1) SL is made into the aqueous solution of 2g/L, claims 13.90gFeSO4·7H2O solid, is dissolved in water and is made into the molten of 0.1mol/L
Liquid.
(2) weigh 6g graphite powder to join in 25mL SL solution, be sufficiently stirred for 10min, pour in centrifuge tube, with
The speed of 5000r/min is centrifuged 10min；Outwell supernatant, after adding ultra-pure water, be centrifuged 10min with the speed of 5000r/min,
Outwell supernatant after taking-up, be vacuum dried at 25 DEG C；In dried sample, add 25mL copperas solution, be sufficiently stirred for
10min, is then centrifuged 10min with the speed of 5000r/min；Outwell supernatant, after adding ultra-pure water, with the speed of 5000r/min
Rate is centrifuged 10min, outwells supernatant after taking-up, is vacuum dried, i.e. can get one layer of SL/ with graphite powder as base material at 25 DEG C
Fe2+Electrostatic self-assembled film；Repeat above operation, prepare 10 layers of SL/Fe2+Electrostatic self-assembled film.
(3) sample that step (2) obtains is placed in double temperature-area tubular furnace, is passed through H with the speed of 50mL/min2/Ar(5:
95, V/V) mixed gas is as protection gas and reducing gases, carries out temperature programming with the speed of 4 DEG C/min simultaneously, is heated to target
After temperature 750 DEG C, constant temperature 5h, then cool the temperature to room temperature with the speed of 5 DEG C/min；Sample is taken out, soaks through dilute hydrochloric acid
Remove catalyst ferrum simple substance, with milli-Q water several times, treat sample F eCl2After removing, at 25 DEG C be vacuum dried, layer
The Graphene that number is controlled.
Scanning electron microscope, Raman spectrum and X-ray diffractometer same as in Example 1 is used to measure product pattern, carbonization journey
Degree and degree of crystallinity, result is essentially identical with Fig. 1, Fig. 2 and Fig. 3.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-described embodiment
Limit, the change made under other any spirit without departing from the present invention and principle, modify, substitute, combine, simplify,
All should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (7)
1. the method preparing Graphene for raw material with lignin, it is characterised in that comprise the following steps:
(1) lignin is made into certain density aqueous solution, claims a certain amount of catalyst precursor to be made into aqueous solution；Described catalysis
Agent presoma is FeCl3、FeSO4·7H2O、Fe(NO3)3·9H2O、CuSO4·5H2O、Co(NO3)2And NiSO4·6H2In O
A kind of；
(2) pretreated base material is first sufficiently impregnated with a period of time in lignin liquor, soaks in ultra-pure water after taking-up
A period of time, then with ultrapure water for several times, and cold drying in the range of 10～25 DEG C；Place into catalyst precursor molten
Time of infusion in liquid, first soaks with ultra-pure water after taking-up and rinses for several times, and cold drying in the range of 10～25 DEG C, i.e.
Obtain one layer of lignin polyelectrolyte and the self-assembled film of catalyst precursor；Repetition lignin liquor impregnates, ultra-pure water soaks,
Milli-Q water, Catalyst precursor solutions dipping, ultra-pure water soak, the operation of milli-Q water, i.e. can get the number of plies controlled
Self-assembled film；
(3) sample that step (2) obtains is placed in vacuum tube furnace, is passed through H with given pace2/ Ar mixed gas, simultaneously with
Certain speed heats up, and after being heated to target temperature, constant temperature certain time, treats that double temperature-area tubular furnace temperature is down to room temperature,
Sample is taken out, removes catalyst through acid soak, washing several times, after vacuum drying, the controlled Graphene of the number of plies.
The method preparing Graphene for raw material with lignin the most according to claim 1, it is characterised in that step (1) institute
Stating lignin liquor concentration range is 0.05～10g/L, and Catalyst precursor solutions concentration range is 0.01～0.5mol/L, wood
In quality, carbon controls 10～400 with the mol ratio of catalyst precursor.
The method preparing Graphene for raw material with lignin the most according to claim 1, it is characterised in that step (1) institute
Stating lignin is the one in alkali lignin, sodium lignin sulfonate, Milled wood lignin and organosolv lignin.
The method preparing Graphene for raw material with lignin the most according to claim 1, it is characterised in that step (2) institute
Stating base material is the one in quartz slide, copper sheet, iron plate, graphite powder, NaCl and LiFePO4.
The method preparing Graphene for raw material with lignin the most according to claim 4, it is characterised in that described base material is
Preprocess method during quartz slide is: quartz slide is used dense H2SO4With H2O2Mixed liquid dipping 1h, with ultrapure after taking-up
Water soaking 10min, then with ultra-pure water drip washing quartz slide 3～4 times, then with ammonia, H2O2With H2The mixed solution of O soaks 1h,
With ultra-pure water drip washing 3～4 times, it is soaked in ultra-pure water standby.
The method preparing Graphene for raw material with lignin the most according to claim 1, it is characterised in that step (3) is led to
The speed range entering gaseous mixture is 20～100mL/min.
The method preparing Graphene for raw material with lignin the most according to claim 1, it is characterised in that step (3) institute
Stating heating rate is 2～8 DEG C/min, and target temperature is 600～800 DEG C, and the retention time is 1～6h.
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| CN107235484A (en) * | 2017-08-03 | 2017-10-10 | 中南林业科技大学 | A kind of method that utilization black liquor rugose wood element prepares graphene |
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| CN109485029A (en) * | 2018-11-19 | 2019-03-19 | 华南理工大学 | A kind of porous carbon nanosheet of lignin and preparation method thereof and the application in electrode material for super capacitor |
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| CN112062121A (en) * | 2020-08-26 | 2020-12-11 | 广西大学 | Method for preparing thermal reduction graphene oxide film by blending sodium lignosulfonate and graphene oxide |
| CN112607731A (en) * | 2020-12-24 | 2021-04-06 | 广东工业大学 | Device and method for preparing graphene powder |
| CN112875685A (en) * | 2021-02-03 | 2021-06-01 | 陕西科技大学 | Graphene generated in situ based on lignin and preparation method thereof |
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