CN104071782B - A kind of preparation method of Graphene - Google Patents
A kind of preparation method of Graphene Download PDFInfo
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- CN104071782B CN104071782B CN201410299588.5A CN201410299588A CN104071782B CN 104071782 B CN104071782 B CN 104071782B CN 201410299588 A CN201410299588 A CN 201410299588A CN 104071782 B CN104071782 B CN 104071782B
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Abstract
The invention discloses a kind of preparation method of Graphene, comprise the following steps: 1) at-5 ~ 0 DEG C, Graphite Powder 99, SODIUMNITRATE, vitriol oil three are reacted; 2) add potassium permanganate, reaction, prepares graphite suspension, 3) add dilute sulphuric acid, ultrasonic; 4) deionized water is added; 5) add superoxol, entirely overflow to gas; 6) add hydrochloric acid, fully react, product deionized water wash; 7) precipitation is placed in deionized water, fully disperses; 8) add oxalic acid powder, reaction, removes excessive oxalic acid.The present invention, by conjunction with physics and chemical process, improves intercalation and the extent of exfoliation of graphite oxide, improves the preparation efficiency of Graphene, improves 25% ~ 30% than the productive rate of oxidation-reduction method of the prior art.In addition, present invention achieves high yield and prepare high-quality Graphene, there is the features such as technique is simple, product performance are excellent simultaneously, be applicable to the scale operation of multi-layer graphene.
Description
Technical field
The present invention relates to a kind of preparation method of Graphene.
Background technology
Except three-layer laminated graphite, scientists finds that Tan Xi family also has the soccerballene of zero dimension, the carbon nanotube of one dimension, and can the carbon material of two dimension stable existence be at room temperature a mystery always.As far back as many years ago, famous physicist Peierls and Landau proposes strict two dimensional crystal in theory due to its thermodynamic instability, can not exist.1966, the Mermin-Wagner theory of Mermin and Wagner pointed out that long wavelength fluctuations also can make the two dimensional crystal of long-range order be damaged.Now, Two-dimensional Carbon material be it is believed that a just theoretical model, but this does not hinder people to the exploration of Two-dimensional Carbon materials theory and experiment, and scientists attempts obtaining stable mono-layer graphite sheet.Until 2004, scientist A.K.Geim and K.S.Novoselov of University of Manchester successfully isolates Graphene (also referred to as mono-layer graphite) by mechanically peel method first from graphite, this discovery has shocked scientific circles, not only overthrown original perfect two dimensional crystal material can not under non-zero absolute temperature the theory of stable existence, and excite the research interest of scientists to other two-dimensional material, enriched carbon system family member simultaneously.
Graphene, can regard the mono-layer graphite sheet be stripped as, the two-dimensional crystal lattice be made up of the carbon atom of monoatomic layer thickness, wherein carbon atom with six-ring form periodic arrangement in graphene planes.It is the thinnest material found at present, and thickness only has 0.35nm, and carbon atom is with the mutual bonding of the mode of sp2 hydridization, and the bond distance of C-C is 0.142nm, bond angle 120 °.It is the elementary cell building other dimension carbon material, it can the bent richness forming zero dimension (0D) of wing be strangled rare (fullerene), the carbon nanotube (carbonnano-tube, CNT) being rolled into one dimension (1D) can also pile the graphite (graphite) of three-dimensional (3D).
Just because of the two-dirnentional structure of Graphene uniqueness, make it have the special propertys such as the many electricity of excellence, mechanics, optics and calorifics of being different from other dimension materials, thus within several years, receive much concern at this.Research for it is not only confined to theoretical aspect at present.Graphene has been applied to the preparation of various device, comprises low-yield highdensity electron device, senser element etc.The same with the novel material that other prepare large-scale application, the preparation of material and process are the prerequisites that Graphene is able to practical application.After first passage micromechanics stripping method obtains Graphene, people in succession propose the methods such as epitaxy method, chemical Vapor deposition process, solvent-thermal method, electrochemical process, chemical reduction method and prepare Graphene.Wherein, the softening method of chemical reduction method to be a kind of with graphite be raw material, namely carries out stripping by microwave or ultrasonic wave to graphite oxide and obtains graphene oxide solution, and then carries out chemical reduction to GO and obtain Graphene.This method for raw material with the graphite of cheapness, through peroxidation, stripping, reduction, easily realizes the mass production of Graphene, can meet large-scale application demand.
At present, oxidation reduction process becomes industry prepare one of the most attractive approach of Graphene so that its technique is simple, with low cost.Prepare in the method for graphite oxide numerous, the technical process of Hmnmers method be simple, green, safety, thus become and prepare one of the most frequently used method of graphite oxide at present.The method mainly contains low temperature, middle temperature, high temperature three step of reaction.Research shows M:(Fu Ling, Liu Hongbo, Zou Yanhong, Li Bo .Hummers legal system is for technological factor research [J] affecting degree of oxidation during graphite oxide. carbon element, 2005 (4): 10-14) and mainly there is sulfuric acid molecule at graphite layers intercalation in low-temp reaction; The main deep oxidation that graphite occurs of middle temperature reaction; Then mainly there is the hydrolysis reaction of compound in high-temperature reaction process.Low-temp reaction intercalation is abundant, and completely, pyroreaction hydrolysis thoroughly, will be one of approach obtaining the larger graphite oxide of interlamellar spacing in middle temperature reaction depth oxidation.The pyroreaction stage of Hummers method, deionized water is added in higher the containing in the mixed solution of the vitriol oil of temperature, mixed solution can be made to produce the high temperature of local, temperature of reaction is caused to be difficult to control, the local temperature of mixed solution is too high simultaneously, make the decomposes of sulfuric acid-compound between graphite layers, the insets such as sulfuric acid are deviate from rapidly from graphite layers, thus greatly have impact on the quality of graphite oxide.
In prior art, the method usually preparing Graphene is: 1, micromechanics stripping method; 2, chemical Vapor deposition process; 3, oxidation-reduction method; 4, solvent stripping method; 5, solvent-thermal method, 6, additive method.Wherein for the 3rd kind of method, before also carried out discussion, mainly through the Hummers legal system of Hummers method or improvement for GO, then obtain graphene oxide with reduction GO such as sodium borohydrides, the productive rate that this method obtains Graphene is on the low side.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of Graphene.
The technical solution used in the present invention is:
A preparation method for Graphene, comprises the following steps:
The first step, under-5 ~ 0 DEG C of condition, adds Graphite Powder 99, SODIUMNITRATE in reaction vessel, then adds the vitriol oil, and keep temperature of reaction system at-5 ~ 0 DEG C, supersound process, then fully stirs;
Second step, adds potassium permanganate in the first step gained solution, keeps temperature of reaction system not higher than 10 DEG C, stirs 16 ~ 24h, prepare graphite suspension;
3rd step, adds dilute sulphuric acid, supersound process in graphite suspension, then under the condition stirred, fully reacts 2 ~ 6h;
4th step, then add deionized water, keep temperature of reaction system not higher than 10 DEG C, fully react 6 ~ 12h;
5th step, keeps temperature of reaction system not higher than under the condition of 10 DEG C, dropwise adds superoxol, until gas is overflowed completely;
6th step, adds hydrochloric acid, fully reacts, and then reaction product is used deionized water centrifuge washing, and the pH to finally centrifugal supernatant liquid is 6.5 ~ 7.5;
7th step, the precipitation of the 6th step gained is placed in deionized water for ultrasonic dispersion, and after centrifugal treating, gained upper solution is graphene oxide dispersion;
8th step, adds oxalic acid powder in graphene oxide dispersion, and then heating also isothermal reaction under the condition stirred, reheats to remove excessive oxalic acid, obtain the graphene solution of homogeneous dispersion.
In the first step, described Graphite Powder 99 is 400-600 object natural graphite powder; The mass concentration of the described vitriol oil is 68% ~ 98%.
In the first step, described supersound process refers to that operating frequency is 20 ~ 40kHz, the ultrasonic cleaning instrument of ultrasonic power 120 ~ 400w and operating frequency are 20 ~ 40kHz, and the alternately supersound process of the ultrasonic cell disrupte machine of ultrasonic power 800 ~ 1200w, the total time of alternate treatment is 1 ~ 2h.
In 3rd step, the mass concentration of described dilute sulphuric acid is 5% ~ 10%.
In 3rd step, supersound process refers to that operating frequency is 20 ~ 40kHz, the ultrasonic cleaning instrument supersound process of ultrasonic power 120 ~ 400w, and the time of process is 0.5-1h.
In 5th step, the mass concentration of described superoxol is 1 ~ 3%.
In 6th step, the mass concentration of described hydrochloric acid is 5% ~ 10%.
In 6th step, the temperature of deionized water is lower than 10 DEG C, and the condition of centrifuge washing is: centrifuge speed: 8000 ~ 10000r/min; Centrifugation time 15 ~ 30min.
In 7th step, described ultrasonic disperse refers to that by operating frequency be 20 ~ 40kHz, and the ultrasonic disintegrator of ultrasonic power 800 ~ 1200w carries out supersound process; The time of supersound process is 0.5 ~ 2h.
The amount ratio of the deionized water in Graphite Powder 99, SODIUMNITRATE, the vitriol oil, potassium permanganate, dilute sulphuric acid, the 4th step, superoxol, hydrochloric acid is: 1g:(0.45-0.55) g:(23-25) ml:(2.5-3.5) g:(18-22) ml:(55-65) ml:(18-22) ml:(38-42) ml; Graphene dispersing solution in 8th step, the amount ratio of oxalic acid are 20ml:(2.5-3.5) g.
The invention has the beneficial effects as follows:
The present invention, by conjunction with physics and chemical process, improves intercalation and the extent of exfoliation of graphite oxide, improves the preparation efficiency of Graphene, improves 25% ~ 30% than the productive rate of oxidation-reduction method of the prior art.In addition, present invention achieves high yield and prepare high-quality Graphene, there is the features such as technique is simple, product performance are excellent simultaneously, be applicable to the scale operation of multi-layer graphene.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope diagram sheet of Graphene in the embodiment of the present invention 1;
Fig. 2 is the scanning electron microscope diagram sheet of Graphene in the embodiment of the present invention 1;
Fig. 3 is the transmission electron micrograph of Graphene in the embodiment of the present invention 1.
Embodiment
The first step, under-5 ~ 0 DEG C of condition, adds Graphite Powder 99, SODIUMNITRATE in reaction vessel, then adds the vitriol oil, and keep temperature of reaction system at-5 ~ 0 DEG C, supersound process, then fully stirs;
Second step, adds potassium permanganate in the first step gained solution, keeps temperature of reaction system not higher than 10 DEG C, stirs 16 ~ 24h, prepare graphite suspension;
3rd step, adds dilute sulphuric acid, supersound process in graphite suspension, then under the condition stirred, fully reacts 2 ~ 6h;
4th step, then add deionized water, keep temperature of reaction system not higher than 10 DEG C, fully react 6 ~ 12h;
5th step, keeps temperature of reaction system not higher than under the condition of 10 DEG C, dropwise adds superoxol, until gas is overflowed completely;
6th step, adds hydrochloric acid, fully reacts, and then reaction product is used deionized water centrifuge washing, and the pH to finally centrifugal supernatant liquid is 6.5 ~ 7.5;
7th step, the precipitation of the 6th step gained is placed in deionized water for ultrasonic dispersion, and after centrifugal treating, gained upper solution is graphene oxide dispersion;
8th step, adds oxalic acid powder in graphene oxide dispersion, and then heating also isothermal reaction under the condition stirred, reheats to remove excessive oxalic acid, obtain the graphene solution of homogeneous dispersion.
In the first step, described Graphite Powder 99 is 400-600 object natural graphite powder; The mass concentration of the described vitriol oil is 68% ~ 98%; Preferably, the mass concentration of the vitriol oil is 98%.
In the first step, described supersound process refers to that operating frequency is 20 ~ 40kHz, the ultrasonic cleaning instrument of ultrasonic power 120 ~ 400w and operating frequency are 20 ~ 40kHz, and the alternately supersound process of the ultrasonic cell disrupte machine of ultrasonic power 800 ~ 1200w, the total time of alternate treatment is 1 ~ 2h.
In 3rd step, the mass concentration of described dilute sulphuric acid is 5% ~ 10%; Preferably, be 10%.
In 3rd step, supersound process refers to that operating frequency is 20 ~ 40kHz, the ultrasonic cleaning instrument supersound process of ultrasonic power 120 ~ 400w, and the time of process is 0.5-1h.
In 5th step, the mass concentration of described superoxol is 1 ~ 3%; Preferably, be 3%.
In 6th step, the mass concentration of described hydrochloric acid is 5% ~ 10%; Preferably, be 10%.
In 6th step, the temperature of deionized water is lower than 10 DEG C, and the condition of centrifuge washing is: centrifuge speed: 8000 ~ 10000r/min; Centrifugation time 15 ~ 30min.
In 7th step, described ultrasonic disperse refers to that by operating frequency be 20 ~ 40kHz, and the ultrasonic disintegrator of ultrasonic power 800 ~ 1200w carries out supersound process; The time of supersound process is 0.5 ~ 2h.
The amount ratio of the deionized water in Graphite Powder 99, SODIUMNITRATE, the vitriol oil, potassium permanganate, dilute sulphuric acid, the 4th step, superoxol, hydrochloric acid is: 1g:(0.45-0.55) g:(23-25) ml:(2.5-3.5) g:(18-22) ml:(55-65) ml:(18-22) ml:(38-42) ml; Graphene dispersing solution in 8th step, the amount ratio of oxalic acid are 20ml:(2.5-3.5) g.
Preferably, after the 8th step obtains graphene solution, then through except desolventizing, obtain graphene powder.
The present invention, by conjunction with physics and chemical process, improves intercalation and the extent of exfoliation of graphite oxide, improves the preparation efficiency of Graphene, improve 25% ~ 30% than traditional method productive rate.
Below in conjunction with specific embodiment, the present invention is described further:
embodiment 1:
1, under ice-water bath condition, by 500 object particulate state natural graphite 1g, SODIUMNITRATE 0.5g adds in 250mL there-necked flask.Then the 24mL vitriol oil (mass concentration is 98%) is slowly added in there-necked flask and fully stirs, maintenance system temperature of reaction is about 0 DEG C, be first 20kHz by operating frequency, the ultrasonic cell disrupte machine supersound process 15min of ultrasonic power 800w, then be 20kHz by operating frequency, the ultrasonic cleaning instrument supersound process 30min of ultrasonic power 120w, last is 20kHz by operating frequency again, the ultrasonic cell disrupte machine supersound process 15min of ultrasonic power 800w, system temperature must be kept to be about 0 DEG C with ice bath in ultrasonication, after supersound process, fully stir 2 ~ 3h.
2,3.0g potassium permanganate is added in there-necked flask, keeps temperature of reaction system lower than 10 DEG C, insulated and stirred 16h, preparation feedback suspension.
3, slowly add 20ml to reaction suspension, mass concentration is the dilute sulphuric acid of 10%, is 20kHz by operating frequency, the ultrasonic cleaning instrument supersound process 0.5h of ultrasonic power 120w, then under the condition stirred, fully reacts 2h.
4, add 60ml deionized water, keep system temperature of reaction lower than 10 DEG C, fully react 6h.
5, keep temperature of reaction system not higher than under the condition of 10 DEG C, dropwise add 20ml, mass concentration is the superoxol of 3%, until gas is overflowed completely.
6, add 40ml, mass concentration is the hydrochloric acid of 10%, fully reacts, with not higher than the deionized water repeated centrifugation process of 10 DEG C, until the pH of supernatant liquor is neutral.
7, be 20kHz the precipitation operating frequency of gained, the ultrasonic disintegrator supersound process 0.5h of ultrasonic power 800w, ultrasonic disperse is in deionized water, and after centrifugal treating, upper solution is graphene oxide dispersion.
8, by the graphene oxide solution of homogeneous for 20mL dispersion, add 2.5g oxalic acid powder, then under the condition stirred, be added to 75 DEG C and isothermal reaction 24h, to reheat to 150 DEG C to remove excessive oxalic acid, obtain the graphene solution of homogeneous dispersion.
9, remove the solvent in solution, obtain graphene powder.
Fig. 1-2 is the scanning electron microscope diagram sheet of Graphene in the embodiment of the present invention 1; Fig. 3 is the transmission electron micrograph of Graphene in the embodiment of the present invention 1.
embodiment 2:
1, under ice-water bath condition, by 500 object particulate state natural graphite 1g, SODIUMNITRATE 0.5g adds in 250mL there-necked flask.Then the 24mL vitriol oil (mass concentration is 98%) is slowly added in there-necked flask and fully stirs, maintenance system temperature of reaction is about 0 DEG C, be first 20kHz by operating frequency, the ultrasonic cleaning instrument supersound process 15min of ultrasonic power 120w, then be 20kHz by operating frequency, the ultrasonic cell disrupte machine supersound process 30min of ultrasonic power 800w, last is 20kHz by operating frequency again, the ultrasonic cleaning instrument supersound process 15min of ultrasonic power 120w, system temperature must be kept to be about 0 DEG C with ice bath in ultrasonication, after supersound process, fully stir 2 ~ 3h.
2,3.0g potassium permanganate is added in there-necked flask, keeps temperature of reaction system lower than 10 DEG C, insulated and stirred 16h, preparation feedback suspension.
3, slowly add 20ml to reaction suspension, mass concentration is 10% dilute sulphuric acid, is 20kHz by operating frequency, the ultrasonic cleaning instrument supersound process 0.5h of ultrasonic power 120w, then under the condition stirred, fully reacts 2h.
4, add 60ml deionized water, keep system temperature of reaction lower than 10 DEG C, fully react 6h.
5, keep temperature of reaction system not higher than under the condition of 10 DEG C, dropwise add 20ml, mass concentration is 3% superoxol, until gas is overflowed completely.
6, add 40ml, mass concentration is 10% hydrochloric acid, fully reacts, with not higher than the deionized water repeated centrifugation process of 10 DEG C, until the pH of supernatant liquor is neutral.
7, be 20kHz the precipitation operating frequency of gained, the ultrasonic disintegrator supersound process 0.5h of ultrasonic power 800w, ultrasonic disperse is in deionized water, and after centrifugal treating, upper solution is graphene oxide dispersion.
8, by the graphene oxide solution of homogeneous for 20mL dispersion, add 2.5g oxalic acid powder, then under the condition stirred, be added to 75 DEG C and isothermal reaction 24h, to reheat to 150 DEG C to remove excessive oxalic acid, obtain the graphene solution of homogeneous dispersion.
9, remove the solvent in solution, obtain graphene powder.
embodiment 3:
1, under ice-water bath condition, by 500 object particulate state natural graphite 1g, SODIUMNITRATE 0.5g adds in 250mL there-necked flask.Then the 24mL vitriol oil (mass concentration is 98%) is slowly added in there-necked flask and fully stirs, keep system temperature of reaction not higher than 5 DEG C, fully react 3h.
2,3.0g potassium permanganate is added in there-necked flask, keeps temperature of reaction system in 20 ~ 30 DEG C, insulated and stirred 3h.
3, add 500ml rubble ice, dropwise add 20ml, mass concentration is the superoxol of 3%, until gas is overflowed completely.
4, add 20ml, mass concentration is the hydrochloric acid of 10%, fully reacts, with not higher than the deionized water repeated centrifugation process of 10 DEG C, until the pH of supernatant liquor is neutral.
5, be 20kHz the precipitation operating frequency of gained, the ultrasonic disintegrator supersound process 0.5h of ultrasonic power 800w, ultrasonic disperse is in deionized water, and after centrifugal treating, upper solution is graphene oxide dispersion.
6, by the graphene oxide solution of homogeneous for 20mL dispersion, add 2.5g oxalic acid powder, then under the condition stirred, be added to 75 DEG C and isothermal reaction 24h, to reheat to 150 DEG C to remove excessive oxalic acid, obtain the graphene solution of homogeneous dispersion.
9, remove the solvent in solution, obtain graphene powder.
In embodiment 1-3, productive rate is respectively: embodiment 1 productive rate: 11.6%; Embodiment 2 productive rate: 10.7%; Embodiment 3 productive rate: 9.1%.
As a comparison, the present invention adopts, and " power technology, 02 phase in 2010, the method reported in p177-180 carries out the synthesis of Graphene, and the productive rate obtaining Graphene is 8.3% for the preparation of Graphene and chemical property thereof, Yang Changling etc.
Claims (7)
1. a preparation method for Graphene, is characterized in that: comprise the following steps:
The first step, under-5 ~ 0 DEG C of condition, adds Graphite Powder 99, SODIUMNITRATE in reaction vessel, then adds the vitriol oil, and keep temperature of reaction system at-5 ~ 0 DEG C, supersound process, then fully stirs;
Second step, adds potassium permanganate in the first step gained solution, keeps temperature of reaction system not higher than 10 DEG C, stirs 16 ~ 24h, prepare graphite suspension;
3rd step, adds dilute sulphuric acid, supersound process in graphite suspension, then under the condition stirred, fully reacts 2 ~ 6h;
4th step, then add deionized water, keep temperature of reaction system not higher than 10 DEG C, fully react 6 ~ 12h;
5th step, keeps temperature of reaction system not higher than under the condition of 10 DEG C, dropwise adds superoxol, until gas is overflowed completely;
6th step, adds hydrochloric acid, fully reacts, and then reaction product is used deionized water centrifuge washing, and the pH to finally centrifugal supernatant liquid is 6.5 ~ 7.5;
7th step, the precipitation of the 6th step gained is placed in deionized water for ultrasonic dispersion, and after centrifugal treating, gained upper solution is graphene oxide dispersion;
8th step, adds oxalic acid powder in graphene oxide dispersion, and then heating also isothermal reaction under the condition stirred, reheats to remove excessive oxalic acid, obtain the graphene solution of homogeneous dispersion;
In the first step, described supersound process refers to that operating frequency is 20 ~ 40kHz, the ultrasonic cleaning instrument of ultrasonic power 120 ~ 400w and operating frequency are 20 ~ 40kHz, the alternately supersound process of the ultrasonic cell disrupte machine of ultrasonic power 800 ~ 1200w, and the total time of alternate treatment is 1 ~ 2h;
In 3rd step, supersound process refers to that operating frequency is 20 ~ 40kHz, the ultrasonic cleaning instrument supersound process of ultrasonic power 120 ~ 400w, and the time of process is 0.5-1h;
In 7th step, described ultrasonic disperse refers to that by operating frequency be 20 ~ 40kHz, and the ultrasonic disintegrator of ultrasonic power 800 ~ 1200w carries out supersound process; The time of supersound process is 0.5 ~ 2h.
2. the preparation method of a kind of Graphene according to claim 1, is characterized in that: in the first step, and described Graphite Powder 99 is 400-600 object natural graphite powder; The mass concentration of the described vitriol oil is 68% ~ 98%.
3. the preparation method of a kind of Graphene according to claim 1, is characterized in that: in the 3rd step, and the mass concentration of described dilute sulphuric acid is 5% ~ 10%.
4. the preparation method of a kind of Graphene according to claim 1, is characterized in that: in the 5th step, and the mass concentration of described superoxol is 1 ~ 3%.
5. the preparation method of a kind of Graphene according to claim 1, is characterized in that: in the 6th step, and the mass concentration of described hydrochloric acid is 5% ~ 10%.
6. the preparation method of a kind of Graphene according to claim 1, is characterized in that: in the 6th step, and the temperature of deionized water is lower than 10 DEG C, and the condition of centrifuge washing is: centrifuge speed: 8000 ~ 10000r/min; Centrifugation time 15 ~ 30min.
7. the preparation method of a kind of Graphene according to claim 1, is characterized in that: the amount ratio of the deionized water in Graphite Powder 99, SODIUMNITRATE, the vitriol oil, potassium permanganate, dilute sulphuric acid, the 4th step, superoxol, hydrochloric acid is: 1g:(0.45-0.55) g:(23-25) ml:(2.5-3.5) g:(18-22) ml:(55-65) ml:(18-22) ml:(38-42) ml; Graphene dispersing solution in 8th step, the amount ratio of oxalic acid are 20ml:(2.5-3.5) g.
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| CN113247889A (en) * | 2021-06-16 | 2021-08-13 | 河南师范大学 | Method for preparing double-layer graphene |
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Denomination of invention: Graphene preparation method Effective date of registration: 20200320 Granted publication date: 20160127 Pledgee: China Co truction Bank Corp Guangzhou green finance reform and innovation pilot area Huadu Branch Pledgor: UV TECH MATERIAL Ltd. Registration number: Y2020980000908 |
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