CN109777406A - A method of preparing carbon quantum dot - Google Patents
A method of preparing carbon quantum dot Download PDFInfo
- Publication number
- CN109777406A CN109777406A CN201910121082.8A CN201910121082A CN109777406A CN 109777406 A CN109777406 A CN 109777406A CN 201910121082 A CN201910121082 A CN 201910121082A CN 109777406 A CN109777406 A CN 109777406A
- Authority
- CN
- China
- Prior art keywords
- carbon quantum
- quantum dot
- raw material
- paper pulp
- pulp fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention relates to a kind of methods for preparing carbon quantum dot, the method includes the preparations of the pretreatment of raw material and carbon quantum dot, the specific steps are as follows: (1) paper pulp fiber raw material is discongested；(2) High-temperature water heat treatment；(3) classification dialysis；(4) freeze-drying process: the filtrate being collected into is passed through into freeze-drying process, collects and retains, obtain the carbon quantum dot solid with different molecular weight cut off.This method is the carbon quantum dot for having different function and different molecular weight with paper pulp fiber raw material preparation, the raw material sources of carbon quantum dot have been widened to a certain extent, the characteristic and function for exploring the carbon quantum dot of different molecular weight are conducive to the research and development for accelerating carbon quantum dot.
Description
Technical field
It is especially a kind of to prepare carbon quantum the invention belongs to biomass resource utilization and environmental protection combined technology field
The method of point.
Background technique
Higher value application is carried out using biomass to be of great significance, and can satisfy market to the length of bio-based materials
Phase demand meets the values of sustainable development, has important practical value and application prospect.
Nearly ten years, the advantages that carbon quantum dot is because of its excellent optical property, nontoxic, highly-water-soluble, biocompatibility, at
For the carbon-based fluorescent nano material of a new generation.Currently, synthesis carbon quantum dot has two approach, one is top-down route, packets
Include electrochemical oxidation, acidic oxidation, arc discharge, laser ablation；Another kind is bottom-up route, such as hydrothermal method, microwave
Method.The fluorescence intensity of carbon quantum can be improved in addition, introducing suitable functional group and carrying out surface passivation.In recent years, discovery doping
Nitrogen and phosphorus element carbon quantum dot can be improved the structure of graphene and reduce forbidden bandwidth, so that fluorescence quantum yield is improved, optics
Property and catalytic performance.In general, carrying out element respectively as carbon source, nitrogen source and phosphorus source using citrate, ammonium hydroxide and phosphate
Doping, however, this technique prices of raw materials are high, preparation process is complicated, has a certain impact to environment to prepare carbon quantum dot,
Limit its fast development.If will further facilitate carbon quantum as raw material using the biomass rich in carbon to prepare carbon quantum
The application of point in all respects.Paper pulp fiber is prepared from plant fiber biomass, and it is one that main component, which is cellulose,
The typical commodity of kind, are the primary raw materials of paper industry, this material rich in carbon is expected to as carbon quantum dot raw material.Currently,
Using paper pulp raw material prepare carbon quantum dot, and develop its application document there is not been reported, in particular by the preparation of one kettle way
Technique realizes element doping, and preparing, there is the carbon quantum dot of different function and different molecular weight also to have not been reported.
Summary of the invention
It is an object of the invention in place of overcome the deficiencies in the prior art, provide a kind of to prepare nitrogen, phosphorus doping wood fibre
The method of biomass-based carbon quantum dot, this method are the carbon for having different function and different molecular weight with paper pulp fiber raw material preparation
Quantum dot has widened the raw material sources of carbon quantum dot to a certain extent, explore the carbon quantum dot of different molecular weight characteristic and
Function is conducive to the research and development for accelerating carbon quantum dot.
The present invention solves its technical problem and adopts the following technical solutions to achieve:
A method of carbon quantum dot being prepared, the method includes the preparations of the pretreatment of raw material and carbon quantum dot, specifically
Steps are as follows:
(1) paper pulp fiber raw material is discongested: paper pulp fiber raw material being impregnated 20~60min in water, in fluffer sufficiently
It stirs 5000-15000 to turn, disperses it fully, be washed with deionized, be placed in equilibrium water conten in sealing device, store standby
With；
(2) High-temperature water heat treatment: using the paper pulp fiber after discongesting as raw material, deionized water mixing is added, after control is discongested
The oven dry weight of paper pulp fiber: the mass ratio of deionized water is 1:5~1:20；It is added in paper pulp fiber raw material suspension system
Diammonium hydrogen phosphate, the oven dry weight of the paper pulp fiber after discongesting: the mass ratio of diammonium hydrogen phosphate is 1:0.2~1:10, is sufficiently stirred
20~30min is mixed, it is made to be uniformly dispersed, is then transferred in high-temperature high-pressure reaction kettle, high-temperature high-pressure reaction kettle condition setting are as follows:
120 DEG C~300 DEG C, heating 2~10h of reaction, mixing speed is 50~500 revs/min, stops heating after reaction terminating, to anti-
Answer kettle cooled to room temperature；
(3) classification dialysis: by above-mentioned steps (2) obtained in liquid and solid taken out from high-temperature high-pressure reaction kettle, use
The aggregation of 0.22~0.45 μm of filter membrane removal bulky grain, and collect the resulting filtrate of filtering；By gained filtrate using not
Dialysis apparatus with molecular cut off carries out dialysis treatment, and collects resulting filtrate respectively；
(4) freeze-drying process: passing through freeze-drying process for the filtrate being collected into, collect and retain, and obtaining has different cut
Stay the carbon quantum dot solid of molecular weight.
Moreover, (3) middle different molecular weight cut off is 100~10000 dalton to the step.
Moreover, (1) middle paper pulp fiber raw material is chemical pulp, mechanical pulp, chemi-mechanical pulp or semi-chemical pulp to the step.
The advantages of present invention obtains and good effect are:
1, the raw material that the method for the present invention uses is biomass material, have resourceful, green cleaning, it is renewable, can give birth to
The advantage of object degradation, has widened the raw material sources of carbon quantum dot to a certain extent.
2, the present invention is using paper pulp fiber raw material as precursor, the process route of simple and environmentally-friendly, the efficient one pot of hydro-thermal method of use
Carbon quantum dot is prepared, there is significant advantage in price and secure context, provides beneficial reference for the efficient preparation of carbon quantum dot.
3, the method for the present invention is prepared for the carbon quantum dot with different molecular weight cut off for the first time, and take the lead in disclosing its
Difference in terms of Wuli-Shili-Renli system approach.
Specific embodiment
Below with reference to the invention will be further described by specific embodiment, following embodiment be it is descriptive, no
It is restrictive, this does not limit the scope of protection of the present invention.
Raw material used in the present invention is unless otherwise specified conventional commercial product；Used in the present invention
Method is unless otherwise specified the conventional method of this field.
The paper pulp fiber raw material arrived used in the present invention more preferably can for chemical pulp, mechanical pulp, chemi-mechanical pulp or
Semi-chemical pulp.
Embodiment 1
A method of carbon quantum dot being prepared, the method includes the preparations of the pretreatment of raw material and carbon quantum dot, specifically
Steps are as follows:
(1) paper pulp fiber raw material is discongested: the pulp board 50g of purchase being torn up, and impregnates 30min in water, is discongesting
After discongesting 10000 turns in machine, distillation water washing three times, it is spare to be put into hermetic bag.
(2) High-temperature water heat treatment: using the paper pulp fiber after discongesting as raw material, deionized water mixing is added, after control is discongested
Paper pulp fiber oven dry weight: the mass ratio of deionized water be 1:7；Phosphoric acid is added in paper pulp fiber raw material suspension system
Hydrogen diammonium, the oven dry weight of the paper pulp fiber after discongesting: the mass ratio of diammonium hydrogen phosphate is 1:2, and 30min, which is sufficiently stirred, makes its point
It dissipates uniformly, is then transferred in high-temperature high-pressure reaction kettle.High-temperature high-pressure reaction kettle condition setting are as follows: 200 DEG C, heating reaction 5h,
Mixing speed is 200 revs/min, by reaction kettle cooled to room temperature after reaction.
(3) classification dialysis and freeze-drying process: by carbon quantum dot obtained in above-mentioned steps from high-temperature high-pressure reaction kettle
It takes out, remove the aggregation of bulky grain with 0.22 μm of ultrafiltration membrane and obtains filtrate.Gained filtrate is using 3500D bag filter dialysis 2d
(6h changes a deionized water).After dialysis, the carbon quantum dot that molecular cut off is 3500 or more is collected.Use freeze-drying
Handle carbon quantum dot solid.
Testing result:
Under these experimental conditions: the carbon quantum dot that molecular cut off is 3500 or more finds best excitation in fluorescence detection
Wavelength is 371nm, launch wavelength 438nm.The carbon of carbon quantum dot is 39.82%, oxygen element 35.15%, nitrogen
It is 17.19%, phosphorus content 7.38%, sulfur content 0.47%.Fluorescence intensity is maximum under the environmental condition of pH=4.
Embodiment 2
A method of carbon quantum dot being prepared, the method includes the preparations of the pretreatment of raw material and carbon quantum dot, specifically
Steps are as follows:
(1) paper pulp fiber raw material is discongested: being taken 50g to tear up the pulp board of purchase, and is impregnated 30min in water, is dredging
After discongesting 10000 turns in solution machine, distillation water washing three times, it is spare to be put into hermetic bag.
(2) High-temperature water heat treatment: using the paper pulp fiber after discongesting as raw material, deionized water mixing is added, after control is discongested
Paper pulp fiber oven dry weight: the mass ratio of deionized water be 1:10；Phosphorus is added in paper pulp fiber raw material suspension system
Sour hydrogen diammonium, the oven dry weight of the paper pulp fiber after discongesting: the mass ratio of diammonium hydrogen phosphate is 1:5, and 30min, which is sufficiently stirred, makes it
It is uniformly dispersed, is then transferred in high-temperature high-pressure reaction kettle.High-temperature high-pressure reaction kettle condition setting are as follows: 200 DEG C, heating reaction
8h, mixing speed is 200 revs/min, by reaction kettle cooled to room temperature after reaction.
(3) classification dialysis and freeze-drying process: by carbon quantum dot obtained in above-mentioned steps from high-temperature high-pressure reaction kettle
It takes out, remove the aggregation of bulky grain with 0.22 μm of ultrafiltration and obtains filtrate.Gained filtrate is using 3500D bag filter dialysis 2d
(6h changes a deionized water).Liquid outside bag filter selects the bag filter of 1000D to continue to dialyse, and dialysis procedure is same as above, thoroughly
After analysis, the liquid in bag filter is collected to obtain the carbon quantum dot that molecular cut off is 3500~1000.With freeze-drying
The solution that method is handled obtains the carbon quantum dot solid of different molecular weight cut off respectively.
Testing result:
Under these experimental conditions, the carbon quantum dot that molecular cut off is 3500~1000 is best sharp in fluorescence detection discovery
Hair wavelength is 340nm, launch wavelength 417nm.The carbon of carbon quantum dot is 41.49%, oxygen element 17.52%, nitrogen member
Element is 12.78%, phosphorus content 25.05%, sulfur content 2.16%.Fluorescence intensity is maximum under the environmental condition of pH=6.
Embodiment 3
A method of carbon quantum dot being prepared, the method includes the preparations of the pretreatment of raw material and carbon quantum dot, specifically
Steps are as follows:
(1) paper pulp fiber raw material is discongested: being taken 50g to tear up the pulp board of purchase, and is impregnated 30min in water, is dredging
After discongesting 10000 turns in solution machine, distillation water washing three times, it is spare to be put into hermetic bag.
(2) High-temperature water heat treatment: using the paper pulp fiber after discongesting as raw material, deionized water mixing is added, control control is dredged
The oven dry weight of paper pulp fiber after solution: the mass ratio of deionized water is 1:7；It is added in paper pulp fiber raw material suspension system
Diammonium hydrogen phosphate, the oven dry weight of the paper pulp fiber after discongesting: the mass ratio of diammonium hydrogen phosphate is 1:2, and 30min, which is sufficiently stirred, to be made
It is uniformly dispersed, and is then transferred in high-temperature high-pressure reaction kettle.High-temperature high-pressure reaction kettle condition setting are as follows: 220 DEG C, heating reaction
5h, mixing speed is 200 revs/min, by reaction kettle cooled to room temperature after reaction.
(3) classification dialysis and freeze-drying process: by carbon quantum dot obtained in above-mentioned steps from high-temperature high-pressure reaction kettle
It takes out, remove the aggregation of bulky grain with 0.22 μm of ultrafiltration membrane and obtains filtrate.Gained filtrate is using 3500D bag filter dialysis 2
~6 days (6h changes a deionized water).After dialysis, the liquid in bag filter is collected, obtaining molecular cut off is 3500
Above carbon quantum dot；Liquid outside bag filter selects the bag filter of 1000 molecular weight to continue to dialyse, and dialysis procedure is same as above, thoroughly
After analysis, the liquid in bag filter is collected to obtain the carbon quantum dot that molecular cut off is 3500~1000；Outside bag filter
Liquid select 500~100 molecular weight bag filter continue to dialyse, dialysis procedure is same as above, by bag filter liquid collect, obtain
The carbon quantum dot for being 1000~100 to molecular cut off.The solution handled with freeze-drying obtains different retentions respectively
The carbon quantum dot solid of molecular weight.
Testing result:
Under these experimental conditions: the carbon quantum dot that molecular cut off is 1000~100 is best sharp in fluorescence detection discovery
Hair wavelength is 330nm, launch wavelength 420nm.The carbon of carbon quantum dot is 13.32%, oxygen element 51.97%, nitrogen member
Element is 12.49%, phosphorus content 21.01%, sulfur content 1.21%.Fluorescence intensity is maximum under pH=3 environmental condition.
Although disclosing the embodiment of the present invention for the purpose of illustration, it will be appreciated by those skilled in the art that: not
Be detached from the present invention and spirit and scope of the appended claims in, various substitutions, changes and modifications be all it is possible, therefore, this
The range of invention is not limited to the embodiment disclosure of that.
Claims (3)
1. a kind of method for preparing carbon quantum dot, it is characterised in that: the method includes the pretreatment of raw material and carbon quantum dots
Preparation, the specific steps are as follows:
(1) paper pulp fiber raw material is discongested: paper pulp fiber raw material being impregnated 20~60min in water, is sufficiently stirred in fluffer
5000-15000 turns, and disperses it fully, is washed with deionized, is placed in equilibrium water conten in sealing device, stores for future use；
(2) High-temperature water heat treatment: using the paper pulp fiber after discongesting as raw material, being added deionized water mixing, control discongest after paper pulp
The oven dry weight of fiber: the mass ratio of deionized water is 1:5~1:20；Phosphoric acid is added in paper pulp fiber raw material suspension system
Hydrogen diammonium, the oven dry weight of the paper pulp fiber after discongesting: the mass ratio of diammonium hydrogen phosphate is 1:0.2~1:10, is sufficiently stirred 20
~30min, makes it be uniformly dispersed, and is then transferred in high-temperature high-pressure reaction kettle, high-temperature high-pressure reaction kettle condition setting are as follows: 120
DEG C~300 DEG C, heating 2~10h of reaction, mixing speed is 50~500 revs/min, stops heating after reaction terminating, to reaction kettle
Cooled to room temperature；
(3) classification dialysis: by above-mentioned steps (2) obtained in liquid and solid taken out from high-temperature high-pressure reaction kettle, with 0.22~
The aggregation of 0.45 μm of filter membrane removal bulky grain, and collect the resulting filtrate of filtering；Gained filtrate is used into different retentions
The dialysis apparatus of molecular weight carries out dialysis treatment, and collects resulting filtrate respectively；
(4) freeze-drying process: passing through freeze-drying process for the filtrate being collected into, collect and retain, and obtains with different retentions point
The carbon quantum dot solid of son amount.
2. the method for preparation carbon quantum dot according to claim 1, it is characterised in that: the step (3) middle different retentions point
Son amount is 100~10000 dalton.
3. the method for preparation carbon quantum dot according to claim 1, it is characterised in that: (1) middle paper pulp fiber is former for the step
Material is chemical pulp, mechanical pulp, chemi-mechanical pulp or semi-chemical pulp.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910121082.8A CN109777406A (en) | 2019-02-19 | 2019-02-19 | A method of preparing carbon quantum dot |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910121082.8A CN109777406A (en) | 2019-02-19 | 2019-02-19 | A method of preparing carbon quantum dot |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109777406A true CN109777406A (en) | 2019-05-21 |
Family
ID=66504408
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910121082.8A Pending CN109777406A (en) | 2019-02-19 | 2019-02-19 | A method of preparing carbon quantum dot |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109777406A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110791289A (en) * | 2019-10-21 | 2020-02-14 | 天津科技大学 | Nitrogen-phosphorus-doped biomass-based carbon quantum dot, application and method for cell imaging detection by using nitrogen-phosphorus-doped biomass-based carbon quantum dot |
| CN113913830A (en) * | 2021-10-26 | 2022-01-11 | 中北大学 | Environment-friendly biomass carbon quantum dot corrosion inhibitor, and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103922314A (en) * | 2014-04-24 | 2014-07-16 | 华南师范大学 | Fluorescent carbon nanoparticles as well as preparation method and application thereof |
| CN105256626A (en) * | 2015-10-27 | 2016-01-20 | 北京印刷学院 | Mulberry bark chemi-mechanical pulp as well as preparation method and application thereof |
| WO2016125189A1 (en) * | 2015-02-03 | 2016-08-11 | Council Of Scientific & Industrial Research | Novel composite of silica and graphene quantum dots and preparation thereof |
| CN106241772A (en) * | 2016-07-26 | 2016-12-21 | 中国科学院兰州化学物理研究所 | A kind of method utilizing biomass flue dust efficiently to prepare carbon quantum dot |
| CN106497562A (en) * | 2016-10-20 | 2017-03-15 | 广西壮族自治区林业科学研究院 | A kind of preparation method of carbon quantum dot |
| CN107955601A (en) * | 2017-11-13 | 2018-04-24 | 东华大学 | Iron ion detection nitrogen sulphur codope carbon quantum dot and preparation method thereof |
| CN108485660A (en) * | 2018-03-12 | 2018-09-04 | 大连工业大学 | A kind of preparation method and application of cellulose base N doping fluorescent carbon quantum dot |
| CN109207148A (en) * | 2017-07-08 | 2019-01-15 | 张宏伟 | A kind of magnanimity preparation method of high yield carbon quantum dot |
-
2019
- 2019-02-19 CN CN201910121082.8A patent/CN109777406A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103922314A (en) * | 2014-04-24 | 2014-07-16 | 华南师范大学 | Fluorescent carbon nanoparticles as well as preparation method and application thereof |
| WO2016125189A1 (en) * | 2015-02-03 | 2016-08-11 | Council Of Scientific & Industrial Research | Novel composite of silica and graphene quantum dots and preparation thereof |
| CN105256626A (en) * | 2015-10-27 | 2016-01-20 | 北京印刷学院 | Mulberry bark chemi-mechanical pulp as well as preparation method and application thereof |
| CN106241772A (en) * | 2016-07-26 | 2016-12-21 | 中国科学院兰州化学物理研究所 | A kind of method utilizing biomass flue dust efficiently to prepare carbon quantum dot |
| CN106497562A (en) * | 2016-10-20 | 2017-03-15 | 广西壮族自治区林业科学研究院 | A kind of preparation method of carbon quantum dot |
| CN109207148A (en) * | 2017-07-08 | 2019-01-15 | 张宏伟 | A kind of magnanimity preparation method of high yield carbon quantum dot |
| CN107955601A (en) * | 2017-11-13 | 2018-04-24 | 东华大学 | Iron ion detection nitrogen sulphur codope carbon quantum dot and preparation method thereof |
| CN108485660A (en) * | 2018-03-12 | 2018-09-04 | 大连工业大学 | A kind of preparation method and application of cellulose base N doping fluorescent carbon quantum dot |
Non-Patent Citations (6)
| Title |
|---|
| DÉBORA ROSA DA SILVA SOZA ET AL.,: "Cellulose nanocrystals: A versatile precursor for the preparation of different carbon structures and luminescent carbon dots", 《INDUSTRIAL CROPS AND PRODUCTS》 * |
| 关清卿等: "《亚/超临界水技术与原理》", 31 December 2014, 冶金工业出版社 * |
| 唐元洪主编: "《制浆造纸机械与设备 下 第3版》", 30 June 2011, 中国轻工业出版社 * |
| 朱安伟等: "《基于无机 有机功能纳米材料检察金属离子及其生物成像》", 31 August 2017, 同济大学出版社 * |
| 石淑兰等: "《制浆造纸分析与检测》", 28 February 2017, 中国轻工业出版社 * |
| 胡超凡著: "《光学功能化石墨烯基纳米材料的制备及其生物医学中的应用》", 30 June 2016, 山西科学技术出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110791289A (en) * | 2019-10-21 | 2020-02-14 | 天津科技大学 | Nitrogen-phosphorus-doped biomass-based carbon quantum dot, application and method for cell imaging detection by using nitrogen-phosphorus-doped biomass-based carbon quantum dot |
| CN113913830A (en) * | 2021-10-26 | 2022-01-11 | 中北大学 | Environment-friendly biomass carbon quantum dot corrosion inhibitor, and preparation method and application thereof |
| CN113913830B (en) * | 2021-10-26 | 2024-05-03 | 中北大学 | Environment-friendly biomass carbon quantum dot corrosion inhibitor, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105463606A (en) | Nano-crystalline cellulose fiber high in carboxyl group content and preparation and application thereof | |
| CN105777913B (en) | A kind of efficient Cellulose nanocrystal preparation method | |
| CN101949103B (en) | Preparation method of straw micro-nano cellulose | |
| CN105480973A (en) | Method for efficiently preparing cotton based mesoporous activated carbon fiber | |
| CN105568744B (en) | A kind of cornstalk nano-cellulose whisker and preparation method and application | |
| CN102995475B (en) | Extraction method of bagasse cellulose | |
| CN103832993A (en) | Method for preparing luminescent carbon dots from carbohydrate | |
| CN109777406A (en) | A method of preparing carbon quantum dot | |
| CN103084187A (en) | Carbon-based solid acid and preparation method thereof | |
| CN104340965A (en) | Macroscopic preparation method of fluorescent carbon quantum dots | |
| CN102093484B (en) | Method for preparing nano crystal cellulose by dissociating ZnCl2 | |
| CN109879973A (en) | A method of Cellulose nanocrystal body is prepared with mixed-acid hydrolysis | |
| CN114558575B (en) | Method for preparing biochar bimetallic catalyst and lignin fluorescent carbon dots by straw classification and water treatment application thereof | |
| CN103908979A (en) | Supported nano TiO2 catalyst and preparation method thereof | |
| CN110437826A (en) | A kind of lignin-base carbon dots of high-fluorescence quantum yield and preparation method thereof | |
| CN104558210A (en) | Method for preparing nano-cellulose | |
| CN108221438A (en) | A kind of preparation method of bleached eucalyptus pulp nano-cellulose | |
| CN109749738A (en) | Sulfonation carbon quantum dot, preparation method and the application in 5 hydroxymethyl furfural is being prepared as catalyst | |
| CN105502346A (en) | Carbon aerogel prepared from chitin aerogel and preparation method thereof | |
| CN106149433B (en) | Nano-cellulose and preparation method thereof | |
| CN109054825A (en) | A kind of fluorescent carbon quantum dot and its high efficiency preparation method | |
| CN109468871A (en) | The wooden nano-cellulose and its method of a kind of preparation of straw and application | |
| CN114032254A (en) | Method for promoting anaerobic methane production by treating straws with ultrasonic-assisted ternary DES (data encryption standard) | |
| CN112852147A (en) | High-conversion-efficiency light absorber film, preparation method thereof and seawater desalination device comprising film | |
| CN109944060A (en) | A kind of nonwoven cloth material and preparation method thereof of supported porous manganese dioxide rod-like nano enzyme |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190521 |