CN105854936B - A kind of lignin electrostatic nanoparticle copper-loading catalyst and preparation and application - Google Patents
A kind of lignin electrostatic nanoparticle copper-loading catalyst and preparation and application Download PDFInfo
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- CN105854936B CN105854936B CN201610209408.9A CN201610209408A CN105854936B CN 105854936 B CN105854936 B CN 105854936B CN 201610209408 A CN201610209408 A CN 201610209408A CN 105854936 B CN105854936 B CN 105854936B
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- 229920005610 lignin Polymers 0.000 title claims abstract description 87
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 56
- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 8
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 7
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007921 spray Substances 0.000 claims abstract description 7
- 229960000583 acetic acid Drugs 0.000 claims abstract description 4
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 4
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 238000007590 electrostatic spraying Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- TZRXHJWUDPFEEY-UHFFFAOYSA-N Pentaerythritol Tetranitrate Chemical compound [O-][N+](=O)OCC(CO[N+]([O-])=O)(CO[N+]([O-])=O)CO[N+]([O-])=O TZRXHJWUDPFEEY-UHFFFAOYSA-N 0.000 claims description 4
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
- 238000007259 addition reaction Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract 1
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- UDLLFLQFQMACJB-UHFFFAOYSA-N azidomethylbenzene Chemical compound [N-]=[N+]=NCC1=CC=CC=C1 UDLLFLQFQMACJB-UHFFFAOYSA-N 0.000 description 6
- 238000006352 cycloaddition reaction Methods 0.000 description 6
- 238000000643 oven drying Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 239000011805 ball Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B01J35/51—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/04—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles
- C07D249/06—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles with aryl radicals directly attached to ring atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/324—Cyclisations via conversion of C-C multiple to single or less multiple bonds, e.g. cycloadditions
Abstract
The invention belongs to catalysis material technical field, a kind of lignin electrostatic nanoparticle copper-loading catalyst and preparation and application are disclosed.The preparation method is that：Alkali lignin is weighed, using acetone, N, N dimethylformamides or glacial acetic acid are solvent, are configured to the lignin electrostatic solution that mass fraction is 25%~50%；Then lignin electrostatic solution is obtained into lignin nanoparticle by electrostatic spray；Lignin nanoparticle is placed in container, CuSO is added4Solution, it is reducing agent to add hydrazine hydrate or sodium borohydride, is stirred reaction under room temperature, reaction product is washed, dry, obtains lignin electrostatic nanoparticle copper-loading catalyst.The catalyst of the present invention has raw material cheap and easy to get using renewable, degradable alkali lignin as carrier, and the advantage that catalytic activity is high, easy to use and recycling is simple has good actual application value.
Description
Technical field
The invention belongs to catalysis material technical fields, and in particular to a kind of lignin electrostatic nanoparticle load copper catalysis
Agent and preparation and application.
Background technology
It is how more efficient and green resource such as biomass is made full use of to provide with increasingly sharpening for energy and environment problem
Source has obtained the extensive concern of society.
One of the resource that lignin is most widely present as nature is that plant kingdom's content is only second to the second largest of cellulose
The polyphenol polymer of unformed shape.It is a kind of renewable, green, environmentally friendly natural macromolecular material.Commercial wood element conduct
The byproduct of paper industry, is present in black liquid, is seldom further processed and is utilized, and the waste of resource is caused,
Even bring environmental problem.Lignin contains abundant phenolic hydroxyl group, thus has certain reducing property, and lignin is as carrier
Different-phase catalyst caused the attention of researcher.2001, the synthesis that chemist's Barry summer Price introduces was general
Thought-click chemistry, people are also referred to as Click chemistry, wherein the nitrine and alkynyl of the reaction that represents the most as copper catalysis
Husigen cycloaddition reactions.Currently, catalyst used in Click chemistry is generally the homogeneous catalyst of copper, homogeneous catalyst
Have the characteristics that reaction process mass transfer velocity is fast, catalytic performance is high, but it is detached in the presence of more difficult with substrate, cycle profit cannot be carried out
With the problems such as, meanwhile, be easy to remain among reaction system, difficulty brought to the separation of product.Currently, in Click chemistry
Rarely have the research to lignin nanoparticle copper-loading catalyst, the present invention homogeneous used in Click chemistry to solve
Catalyst is not recyclable and the problem that recycles, accelerates its related industry development process.
Invention content
In order to solve the disadvantage that the prior art and shortcoming, the primary purpose of the present invention is that it is quiet to provide a kind of lignin
The preparation method of EFI nanoparticle copper-loading catalyst.
Another object of the present invention is to provide a kind of lignin electrostatic nanometer being prepared by the above method is micro-
Ball copper-loading catalyst.
It is still another object of the present invention to provide above-mentioned lignin electrostatic nanoparticle copper-loading catalyst nitrine with
Application in the Husigen cycloaddition reactions of alkynyl.
The object of the invention is achieved through the following technical solutions：
A kind of preparation method of lignin electrostatic nanoparticle copper-loading catalyst, including following preparation process：
(1) alkali lignin is weighed, the use of acetone, n,N-Dimethylformamide or glacial acetic acid is solvent, is configured to quality point
The lignin electrostatic solution that number is 25%~50%；
(2) lignin electrostatic solution is transferred in electrostatic spraying equipment, it is micro- to obtain lignin nanometer by electrostatic spray
Ball；
(3) lignin nanoparticle is placed in container, CuSO is added4Solution, adds hydrazine hydrate or sodium borohydride is
Reducing agent is stirred reaction under room temperature, and reaction product is washed, dry, and it is negative to obtain lignin electrostatic nanoparticle
Copper-loaded catalyst.
The preferred electrostatic pressure of electrostatic described in step (2) is 15~25kV, and it is 10~20cm to receive distance, and electrostatic is molten
The fltting speed of liquid is the electrostatic under the conditions of 1~3mL/h.
Lignin nanoparticle and CuSO described in step (3)4CuSO contained by solution4Mass ratio be preferably 1:(0.2~
0.5)。
CuSO described in step (3)4Solution concentration is 2~5%g/mL, preferred concentration 2%g/mL.
The time being stirred to react described in step (3) is preferably 2h.
Washing described in step (3) refers to being washed with deionized, and the temperature of the drying is 40~80 DEG C.
A kind of lignin electrostatic nanoparticle copper-loading catalyst, is prepared by above method.
Husigen ring of the above-mentioned lignin electrostatic nanoparticle copper-loading catalyst in Click chemistry nitrine and alkynyl
Application in addition reaction has good effect.
The present invention preparation method and obtained product has the following advantages that and advantageous effect：
(1) lignin electrostatic nanoparticle copper-loading catalyst of the invention is with renewable, degradable alkali lignin
As carrier, compared with previous simple copper homogeneous catalyst, have raw material cheap and easy to get, catalytic activity is high, it is easy to use and
Recycle simple advantage, catalyst can by filter and etc. recycled, there is good actual application value；
(2) support and peptizaiton of catalyst of the invention due to lignin electrostatic nanoparticle, makes catalyst have
There is higher load capacity, improves the catalytic efficiency of catalyst；
(3) the obtained lignin electrostatic nanoparticle copper-loading catalyst of the present invention is made at room temperature, catalysis it is anti-
It should also carry out at ambient temperature, solvent can not be used in reaction process or using green solvents such as water, ethyl alcohol, whole process is all
Green chemistry principles are fully considered, this has great importance for the sustainable development of resource and environment.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the lignin electrostatic nanoparticle prepared by the embodiment of the present invention 1；
Fig. 2 is the scanning electron microscope (SEM) photograph for the copper-loaded catalyst of lignin electrostatic nanoparticle that the embodiment of the present invention 1 obtains；
Fig. 3 is that the embodiment of the present invention 1 is catalyzed benzyl azide and benzene second using lignin electrostatic nanoparticle copper catalyst
Alkynes Husigen cycloaddition reaction products1H spectrograms.
Specific implementation mode
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
Embodiment 1
(1) weigh alkali lignin, using n,N-Dimethylformamide be solvent, be configured to mass fraction be 45% it is wooden
Plain electrostatic solution；
(2) the lignin electrostatic solution of step (1) is transferred in electrostatic spraying equipment, is 15kv in electrostatic pressure, receives
Distance is 10cm, and the fltting speed of electrostatic solution obtains lignin electrostatic and receive to carry out Static Spinning spray under conditions of 1mL/h
Meter Wei Qiu；
(3) among 0.5g lignin electrostatic nanoparticles being placed on the test tube of 50mL, it is injected separately into 2%g/mL's
CuSO45% (w/w) hydrazine hydrate of solution 5mL, 10mL, are stirred to react 2h, reaction product is successively through deionized water under room temperature
Washing, 40~80 DEG C of baking oven drying, obtain lignin electrostatic nanoparticle loaded Cu catalyst.
The lignin electrostatic nanoparticle and lignin electrostatic nanoparticle loaded Cu catalyst that the present embodiment obtains
Scanning electron microscope (SEM) photograph difference it is as depicted in figs. 1 and 2, can be seen that by Fig. 1 and Fig. 2：Lignin electrostatic nanoparticle catalyst
It is close with lignin electrostatic nanoparticle size, but pattern is slightly different.
Using benzyl azide in lignin electrostatic nanoparticle catalyst Click chemistry and phenylacetylene Husigen
Cycloaddition reaction reacts 3h under the conditions of room temperature solvent-free, and yield is up to 99%.Reaction product1H spectrograms are as shown in Figure 3.
Embodiment 2
(1) weigh alkali lignin, using n,N-Dimethylformamide be solvent, be configured to mass fraction be 35% it is wooden
Plain electrostatic solution；
(2) the lignin electrostatic solution of step (1) is transferred in electrostatic spraying equipment, is 25kv in electrostatic pressure, receives
Distance is 15cm, and the fltting speed of electrostatic solution to carry out electrostatic under conditions of 3mL/h, receive by the electrostatic for obtaining lignin
Meter Wei Qiu；
(3) among 0.5g lignin electrostatic nanoparticles being placed on the test tube of 50mL, to Zhu Ru not 5%g/mL
CuSO4Solution 5mL, 5% sodium borohydride (w/w) that 20mL is added are used as reducing agent, are stirred to react 2h, reaction production under room temperature
Object through deionized water washing, 40~80 DEG C of baking oven drying, obtains lignin electrostatic nanoparticle loaded Cu catalyst successively.
Scanned Electronic Speculum detection, the copper-loaded catalyst of lignin electrostatic nanoparticle, pattern are spherical shape, and grain size is 0.2~1
μm.Using benzyl azide in lignin electrostatic nanoparticle catalyst Click chemistry and phenylacetylene Husigen cycloaddition
It reacts, reacts 3h under the conditions of room temperature solvent-free, yield is up to 99%.
Embodiment 3
(1) alkali lignin microballoon is weighed, the use of glacial acetic acid is solvent, is configured to the lignin electrostatic that mass fraction is 45%
Spray solution；
(2) the lignin electrostatic spinning solution of step (1) is transferred in electrostatic spraying equipment, is 15kv in electrostatic pressure, connects
It is 10cm to receive distance, and the fltting speed of electrostatic solution obtains the electrostatic of lignin to carry out Static Spinning spray under conditions of 1mL/h
Spray nanoparticle；
(3) among 0.5g lignin electrostatic nanoparticles being placed on the test tube of 50mL, sequentially add 2%g/mL's
CuSO4Solution 5mL is stirred to react 2h, reaction product is successively through going under room temperature using 5% (w/w) hydrazine hydrate as reducing agent
Ion water washing, 40~80 DEG C of baking oven drying, obtain lignin electrostatic nanoparticle loaded Cu catalyst.
Scanned Electronic Speculum detection, the copper-loaded catalyst of lignin electrostatic nanoparticle, pattern are spherical shape, grain size 0.2
~1 μm.Using benzyl azide in lignin electrostatic nanoparticle catalyst Click chemistry and phenylacetylene Husigen rings
Addition reaction reacts 3h under room temperature, and yield is up to 99%.
Embodiment 4
(1) weigh alkali lignin, using n,N-Dimethylformamide be solvent, be configured to mass fraction be 35% it is wooden
Plain electrostatic solution；
(2) the electrostatic solution of the lignin of step (1) is transferred in electrostatic spraying equipment, is 10kv in electrostatic pressure, connects
It is 20cm to receive distance, and the fltting speed of electrostatic solution obtains lignin electrostatic and receive to carry out electrostatic under conditions of 2mL/h
Meter Wei Qiu；
(3) among 0.5g lignin electrostatic nanoparticles being placed on the test tube of 50mL, to Zhu Ru not 2%g/mL
CuSO4Solution 5mL adds 5% (w/w) hydrazine hydrate of 10mL, is stirred to react 2h under room temperature, products therefrom is successively through going
Ion water washing, 40~80 DEG C of baking oven drying, obtain lignin electrostatic nanoparticle loaded Cu catalyst.
Scanned Electronic Speculum detection, the copper-loaded catalyst of lignin electrostatic nanoparticle, pattern is spherical shape, and grain size is about
0.2-1μm.Using benzyl azide in lignin electrostatic nanoparticle catalyst Click chemistry and phenylacetylene Husigen
Cycloaddition reaction reacts 3h using ethyl alcohol as reaction dissolvent under room temperature, and yield is up to 99%.
Embodiment 5
(1) weigh alkali lignin, using n,N-Dimethylformamide be solvent, be configured to mass fraction be 35% it is wooden
Plain electrostatic solution；
(2) the electrostatic solution of the lignin of step (1) is transferred in electrostatic spraying equipment, is 10kv in electrostatic pressure, connects
It is 20cm to receive distance, and the fltting speed of electrostatic solution obtains lignin electrostatic and receive to carry out electrostatic under conditions of 2mL/h
Meter Wei Qiu；
(3) among 0.5g lignin electrostatic nanoparticles being placed on the test tube of 50mL, to Zhu Ru not 2%g/mL
CuSO4Solution 5mL adds 5% (w/w) hydrazine hydrate of 10mL as reducing agent, is stirred to react 2h, reaction production under room temperature
Object through deionized water washing, 40~80 DEG C of baking oven drying, obtains lignin electrostatic nanoparticle loaded Cu catalyst successively.
Scanned Electronic Speculum detection, the copper-loaded catalyst of lignin electrostatic nanoparticle, pattern are spherical shape, grain size 0.2-
1μm.Add with phenylacetylene Husigen rings using benzyl azide in lignin electrostatic nanoparticle catalyst Click chemistry
At reaction, under room temperature, 3h is reacted using water as reaction dissolvent, yield is up to 87%.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (6)
1. a kind of preparation method of lignin electrostatic nanoparticle copper-loading catalyst, it is characterised in that walked including following preparation
Suddenly：
(1) alkali lignin is weighed, the use of acetone, n,N-Dimethylformamide or glacial acetic acid is solvent, being configured to mass fraction is
25%~50% lignin electrostatic solution；
(2) lignin electrostatic solution is transferred in electrostatic spraying equipment, lignin nanoparticle is obtained by electrostatic spray；
(3) lignin nanoparticle is placed in container, CuSO is added4Solution, it is reduction to add hydrazine hydrate or sodium borohydride
Agent is stirred reaction under room temperature, and reaction product is washed, dry, obtains lignin electrostatic nanoparticle supported copper
Catalyst；
Lignin nanoparticle and CuSO described in step (3)4CuSO contained by solution4Mass ratio be 1:(0.2~0.5)；It is described
CuSO4Solution concentration is 2~5%g/mL.
2. a kind of preparation method of lignin electrostatic nanoparticle copper-loading catalyst according to claim 1, special
Sign is：It is 15~25kV that electrostatic described in step (2), which refers in electrostatic pressure, and it is 10~20cm, electrostatic to receive distance
The fltting speed of solution is the electrostatic under the conditions of 1~3mL/h.
3. a kind of preparation method of lignin electrostatic nanoparticle copper-loading catalyst according to claim 1, special
Sign is：The time being stirred to react described in step (3) is 2h.
4. a kind of preparation method of lignin electrostatic nanoparticle copper-loading catalyst according to claim 1, special
Sign is：Washing described in step (3) refers to being washed with deionized, and the temperature of the drying is 40~80 DEG C.
5. a kind of lignin electrostatic nanoparticle copper-loading catalyst, it is characterised in that：Pass through any one of Claims 1 to 4
The method is prepared.
6. lignin electrostatic nanoparticle copper-loading catalyst described in claim 5 is in the Husigen rings of nitrine and alkynyl
Application in addition reaction.
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| CN107837606B (en) * | 2017-11-21 | 2020-05-08 | 福州大学 | Lignin modified composite filter material loaded with ternary denitration sulfur-resistant catalyst and preparation method thereof |
| CN108722413B (en) * | 2018-05-15 | 2020-10-30 | 江苏理工学院 | Preparation method and application of yolk-eggshell structure graphitized carbon-coated transition metal material |
| CN109225113A (en) * | 2018-10-18 | 2019-01-18 | 东华大学 | A kind of nano-cellulose porous material reactor and the preparation method and application thereof |
| CN109926089A (en) * | 2019-03-22 | 2019-06-25 | 三峡大学 | The preparation method and application of the stable copper nanocatalyst of porphyrin |
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| CN101768799A (en) * | 2010-01-29 | 2010-07-07 | 华南理工大学 | Lignin carbon nanofiber and preparation method thereof |
| CN101921410A (en) * | 2010-09-16 | 2010-12-22 | 武汉工程大学 | Method for preparing cellulose microspheres |
| CN104277468A (en) * | 2013-07-10 | 2015-01-14 | 石家庄铁道大学 | Composite material of lignin/metal nanoparticles and preparation method of composite material |
| CN105153051A (en) * | 2015-08-31 | 2015-12-16 | 河南师范大学 | Method for catalytically synthesizing 1, 2, 3-triazole compounds by aid of carboxymethyl cellulose/nanometer copper |
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| US8871940B2 (en) * | 2012-07-16 | 2014-10-28 | The Florida State University Research Foundation, Inc. | Unsymmetrical bisazides for chemoselective sequential ligation |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768799A (en) * | 2010-01-29 | 2010-07-07 | 华南理工大学 | Lignin carbon nanofiber and preparation method thereof |
| CN101921410A (en) * | 2010-09-16 | 2010-12-22 | 武汉工程大学 | Method for preparing cellulose microspheres |
| CN104277468A (en) * | 2013-07-10 | 2015-01-14 | 石家庄铁道大学 | Composite material of lignin/metal nanoparticles and preparation method of composite material |
| CN105153051A (en) * | 2015-08-31 | 2015-12-16 | 河南师范大学 | Method for catalytically synthesizing 1, 2, 3-triazole compounds by aid of carboxymethyl cellulose/nanometer copper |
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