CN108821261A - A kind of nitrogen-doped carbon nano-rings and the preparation method and application thereof - Google Patents
A kind of nitrogen-doped carbon nano-rings and the preparation method and application thereof Download PDFInfo
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- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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Abstract
The present invention provides a kind of nitrogen-doped carbon nano-rings and the preparation method and application thereof, and the preparation method includes：Carbon source is mixed into obtain precursor mixture with nitrogen source；And the precursor mixture is directly heated, can make nitrogen source therein fusing at a temperature of react to obtain the nitrogen-doped carbon nano-rings；The nitrogen source is urea, and the carbon source is sodium citrate.The high photoluminescence carbon nano ring of N doping is prepared using method of the invention, only need single step reaction, without high pressure, reaction speed is ultrafast, and by-product and intermediate product are few, and raw material dosage is few, it is arbitrary proportion, at low cost, fluorescence quantum yield is high, and resulting carbon nano ring luminous intensity is high, and is successfully applied to Fe3+Detection, furthermore, it is possible to identify the pH value in solution, has broad application prospects to water process.
Description
Technical field
The present invention relates to a kind of nitrogen-doped carbon nano-rings and its preparation method and applications, belong to field of nanometer material technology.
Background technique
Carbon is the basis of all known life on the earth, and very important effect is possessed in modern development in science and technology.
The countless compounds of carbon are indispensable substances in daily life, and product is from nylon and gasoline, perfume and plastics to shoe polish, drop
DDT and explosive etc., it is in extensive range many kinds of.Carbon has electron orbit characteristic (sp, sp of multiplicity2And sp3), so can
To form many structures and the peculiar substance of property, such as carbon nanotube, fullerene, Nano diamond, graphene and graphite oxide
Alkene etc..
In recent years just in progress like a raging fire, fluorescence carbon nano ring is received as a kind of novel carbon for the research of nano-carbon material
Rice material, outstanding optical property and low toxicity characteristic make carbon nano ring as the environmentally friendly nanometer material of most application prospect
Material with superior luminescent properties and stable luminescence, is easy to functionalization and industrialization, has low toxicity, easily preparing, biofacies
The fabulous characteristic of capacitive, can be widely applied to environmental monitoring, bio-imaging, cell detection, in the fields such as photoelectrocatalysis, gather around
There is important application value.
In recent years, researcher has done a large amount of research in the preparation of high fluorescence property carbon nanomaterial and its application aspect,
The synthetic method of carbon nanomaterial is broadly divided into method " from top to bottom " and " from bottom to top ".The carbon source for preparing carbon nanomaterial is non-
Often extensively, either carbon simple substance is also possible to carbon compound.But prepare carbon nanomaterial at present and usually require pressurizeing,
It is carried out under the harsh conditions such as microwave, these conditions limit the popularization and application of carbon nanomaterial.In addition, being made using different raw materials
The carbon nanomaterial fluorescent effect that carbon source and different synthetic methods obtain differs widely, and some is even without fluorescence.In order to obtain
The high carbon nanomaterial of luminous intensity is obtained, widens it in the application in the fields such as biomedicine, good water solubility is simply prepared and shines
The high fluorescence carbon nanomaterial of intensity still has very big exploration space.
Summary of the invention
It is needed in view of reality, the main purpose of the present invention is to provide a kind of preparation method of nitrogen-doped carbon nano-rings,
To can conveniently obtain the high carbon nano ring of luminous intensity.
Another object of the present invention is to provide the nitrogen-doped carbon nano-rings obtained by above-mentioned preparation method.
A further object of the present invention is to provide the applications of the nitrogen-doped carbon nano-rings.
To achieve the above object, on the one hand, the preparation method of present invention offer nitrogen-doped carbon nano-rings comprising：By carbon
Source mixes to obtain precursor mixture with nitrogen source；And the precursor mixture is directly heated, nitrogen source fusing therein can be made
At a temperature of react to obtain the nitrogen-doped carbon nano-rings；The nitrogen source is urea, and the carbon source is sodium citrate.
Above-mentioned preparation method is snead process, very easy, is avoided used when existing synthesis carbon nanomaterial
The harsh conditions such as pressurization, microwave, energy one-step synthesis obtain the high nitrogen-doped carbon nano-rings of fluorescence intensity.
About the dosage of sodium citrate and urea, the present invention can be had regardless of being reacted with any mass ratio
The nitrogen-doped carbon nano-rings product of fluorescent effect.
It is further preferred that the mass ratio of the sodium citrate and the urea is 1:0.1 to 1:16, such as 1:0.1,1:
0.25,1:0.3,1:0.4,1:0.5,1:0.6,1:0.7,1:0.8,1:0.9,1:1,1:2,1:3,1:4,1:5,1:6,1:7,1:
8,1:9,1:10,1:11,1:12,1:13,1:14,1:15,1:16 etc..It is preferred that 1:4, experiments indicate that working as the citric acid
The mass ratio of sodium and urea is 1:When 4, fluorescence intensity and quantum yield will appear a peak value, when 1:4 hereinafter, its fluorescence is strong
Degree does not have apparent increase；When greater than 1:After 4, fluorescence intensity does not also significantly decrease, i.e., pico- decline, but less aobvious
It writes.
Preferably, the quality of sodium citrate is 0.25g in the precursor solution, and the quality of urea is 0.25~4g, excellent
Select 1g.The mass ratio of the i.e. described sodium citrate and urea is 1:1~1:16, for example, 1:1,1:2.5,1:4 or 1:8 etc., preferably
It is 1:4.If the mass ratio of the preferably described sodium citrate of the present invention and urea is 1:4, fluorescence quantum yield can achieve
20.9%.
About reaction temperature, as long as described above, the present invention can be such that the urea in solid precursor mixture melts
At a temperature of react, at such a temperature reaction can synthesize have fluorescence property nitrogen-doped carbon nano-rings.Preferably, described
Reaction temperature be 140~240 DEG C (for example, 140 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 195 DEG C, 200 DEG C,
210 DEG C, 220 DEG C, 230 DEG C, 240 DEG C etc.), the nitrogen-doped carbon nanometer with fluorescence property can be synthesized within this temperature range
Ring.
About the reaction time, the present invention is not construed as limiting, and can be generated the nitrogen with fluorescence property as long as reaction has occurred and be mixed
Miscellaneous carbon nano ring, it is preferable that the time of the reaction is 1min or more, for example, 1min, 5min, 30min, 1h or 2h etc., excellent
It is selected as 1h or more.
The above-mentioned mode that directly heats of the present invention can operate in the usual way, such as carbon source, nitrogen source are placed in crucible and are mixed
Precursor mixture is obtained, the crucible of precursor mixture is then filled with cap covers, and is placed it in straight in heating equipment
Heating is connect, the heating equipment is equipment commonly used in the art, as long as heating can be heated up, the present invention is not particularly limited,
Such as a conventional oven or Muffle furnace etc..
In above-mentioned preparation method, it is preferable that can be ground before being directly heated to the precursor mixture.So that object
Material is completed to be uniformly mixed.
In above-mentioned preparation method, it is preferable that it further includes separating step, it is highly preferred that the separating step includes：
By the material natural cooling (being preferably cooled to room temperature) after reaction, and water is added in material after the cooling period, then
It is filtered to get filtrate using mwco membrane, and filtrate is freeze-dried to obtain the nitrogen-doped carbon nano-rings.
Room temperature of the present invention refers to 20~30 DEG C.
The molecular cut off of mwco membrane of the present invention be 3kDa, 5kDa, 10kDa or 30kDa in any one or
At least two combination.
The present invention is not particularly limited the form of filtering, can be used in the lab cylindrical membrane separator-filter into
Row, but this is not precluded the present invention and is filtered operation using other modes.
In the above preparation method, the freeze-drying is carried out under the conditions of vacuum and -50 DEG C to -45 DEG C, preferably dry
It is dry for 24 hours.
The preparation method of nitrogen-doped carbon nano-rings of the present invention is snead process, and preferably it includes the following steps：
(1) weigh carbon source, nitrogen source and placing it in crucible mixes, obtain precursor mixture；
(2) obtained precursor mixture is placed on reaction synthesis nitrogen-doped carbon nano-rings in heating equipment, then certainly
So it is cooled to room temperature to obtain solid product；
(3) deionized water is added in gained solid product and carries out separated and dissolved product, obtain clear solution；
(4) gained clear solution is condensed and is lyophilized, obtain the nitrogen-doped carbon nano-rings；
Carbon source described in step (1) is sodium citrate, and the nitrogen source is urea, and the sodium citrate and the nitrogen source
Mass ratio is 1:4 (such as the quality of sodium citrate is 0.25g, and the quality of the urea is 1g).It is in this way, it can be achieved that big
In 20% relative fluorescence quantum yield.
The above-mentioned preparation method of the present invention has preparation method simple, and raw material can (present invention be closed with others with arbitrary proportion
It is exactly that raw material can be arbitrary proportion at the different particularly pertinent place of nano material), the required reaction time is very short (as long as urine
The fusing point of element, which has reached, can be obtained by product for sodium citrate addition), it can react 1 in the case where reaction temperature reaches~
5min can be obtained by initial stage product, and nitrogen-doped carbon nano-rings fluorescence intensity obtained is high (dilute molten under ultraviolet light irradiation
Very strong yellow-green fluorescence is presented in liquid), fluorescent stabilization (can keep good fluorescent effect in placement 1 month or more).
On the other hand, the present invention provides nitrogen-doped carbon nano-rings prepared by the preparation method.Preferably, the nitrogen
Carbon nano ring is adulterated through XPS analysis, constituent content be C be 50~60%, N is 15~20%, O is 20~30%, such as C is
55.35%, N 18.20%, O 26.45%.
As described above, present invention gained nitrogen-doped carbon nano-rings fluorescence intensity is high, fluorescent stabilization.
On the other hand, the present invention provides the nitrogen-doped carbon nano-rings as soda acid identifier aqueous solution pH for identification
Using.Present invention discover that after the nitrogen-doped carbon nano-rings are added in the aqueous solution to pH less than 11, in hand-held ultraviolet lamp
Yellow green is presented under 365nm irradiation condition, after the nitrogen-doped carbon nano-rings are added in aqueous solution of the pH greater than 11, ultraviolet
Blue is presented under lamp 365nm irradiation condition.It accordingly, can be using nitrogen-doped carbon nano-rings of the present invention as soda acid according to the property
Aqueous solution pH is greater than 11 and is also less than 11 identifier for identification.
On the other hand, the present invention provides the nitrogen-doped carbon nano-rings as detection reagent for detecting Fe3+Ion it is dense
The application of degree.Specifically, aqueous solution is in purple when being free of ferric ion in the aqueous solution containing the nitrogen-doped carbon nano-rings
Outer lamp 365nm irradiation is lower to be presented green-yellow light, and has very high fluorescence intensity, once but be added in aqueous solution ferric iron from
Son, and with the increase of concentration, the color which is presented under ultraviolet lamp 365nm irradiation is more and more lighter until disappearing, originally
Invention experiment shows that the nitrogen-doped carbon nano-rings of synthesis can detecte the Fe in aqueous solution3+Ion.
On the other hand, the present invention provides the nitrogen-doped carbon nano-rings and is used to absorb the PM particle in air as adsorbent
Application.Experiments indicate that the adsorption effect of the nitrogen-doped carbon nano-rings be much higher than active carbon, can achieve 2 times with
On.
In summary, nitrogen is prepared invention broadly provides a kind of preparation method of nitrogen-doped carbon nano-rings and by it
Carbon nano ring and its application are adulterated, the high photoluminescence carbon nano ring of N doping is prepared using method of the invention, only needs single step reaction,
Without high pressure, reaction speed is very fast, and seldom (product separated after reaction is not in addition to for by-product and intermediate product
Except reacted insoluble solid, remaining product separated belongs to nitrogen-doped carbon nano-rings), raw material dosage is few,
Arbitrary proportion, at low cost, fluorescence quantum yield height, resulting carbon nano ring luminous intensity height, and it is successfully applied to Fe3+Detection,
Furthermore, it is possible to identify the pH value in solution, have broad application prospects to water process.
Detailed description of the invention
The transmission electron microscope picture of nitrogen-doped carbon nano-rings prepared by Fig. 1 embodiment of the present invention 1.
Nitrogen-doped carbon nano-rings fluorescence spectra prepared by Fig. 2 embodiment of the present invention 1.
The excitation of nitrogen-doped carbon nano-rings prepared by Fig. 3 embodiment of the present invention 1 and transmitting figure.
The ultravioletvisible absorption figure of nitrogen-doped carbon nano-rings prepared by Fig. 4 embodiment of the present invention 1.
The XPS analysis figure of nitrogen-doped carbon nano-rings prepared by Fig. 5 embodiment of the present invention 1.
Fig. 6 is nitrogen-doped carbon nano-rings figure fluorescence intensity change and Fe prepared by the embodiment of the present invention 13+Pair of solution concentration
Answer linear relationship chart.
The adsorption effect comparison diagram of nitrogen-doped carbon nano-rings and active carbon prepared by Fig. 7 embodiment of the present invention 1.
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now in conjunction with specific implementation
Example and technical solution of the present invention is carried out described further below, it should be understood that these examples be merely to illustrate the present invention rather than
It limits the scope of the invention.In embodiment, each Starting reagents material is commercially available, test method without specific conditions
For conventional method known to fields and normal condition, or according to condition proposed by apparatus manufacturer.
Embodiment 1
(a) urea of the sodium citrate and different quality that take 0.25g, which is placed in, to carry out grinding to obtain precursor mixture in mortar；
(b) precursor mixture after grinding is transferred in crucible, and is covered with lid；Crucible is placed baking oven to carry out
It is heated to 200 DEG C and carries out reaction 30min；
(c) several groups of samples for making addition different quality urea compare and analyze, i.e., urea quality is 0.25g；0.50g；
1.0g；1.25g；1.5g；
(d) by reacted mixture cooled to room temperature i.e. 20~30 DEG C, initial reaction product is obtained；
(e) add 20g pure water to dissolve initial reaction product, obtain suspension；
(f) suspension is filtered with molecular cut off 3kDa cylindrical membrane separator-filter, collects filtered solution, measurement
The fluorescence quantum yield of different quality urea is added, different quality urea is added it can be concluded that being most when additional amount is 1.0g in optimization
It is good；Freeze-drying obtains the nitrogen-doped carbon nano-rings of the present embodiment high fluorescent yield.
Fig. 1 is the transmission electron microscope picture of nitrogen-doped carbon nano-rings manufactured in the present embodiment, tests to obtain its spacing of lattice from Fig. 1
About 0.36nm has apparent ring structure.
Embodiment 2
(a) sodium citrate of the urea and different quality that take 1.0g, which is placed in, to carry out grinding to obtain precursor mixture in mortar；
(b) precursor mixture after grinding is transferred in crucible, and is covered with lid；Crucible is placed baking oven to carry out
It is heated to 200 degrees Celsius and carries out reaction 30min；
(c) several groups of samples for doing addition different quality sodium citrate compare and analyze, i.e. sodium citrate quality is
0.05g；0.10g；0.25g；0.50g；1.0g waiting；
(d) by reacted mixture cooled to room temperature i.e. 20~30 DEG C, initial reaction product is obtained；
(e) add 20g pure water to dissolve initial reaction product, obtain suspension；
(f) suspension is filtered with molecular cut off 3kDa cylindrical membrane separator-filter, collects filtered solution, measurement
The fluorescence quantum yield of different quality sodium citrate is added, different quality sodium citrate is added it can be concluded that when additional amount is in optimization
0.25g is best；Freeze-drying obtains the nitrogen-doped carbon nano-rings of the present embodiment high fluorescent yield.
Fig. 2 is the fluorescence spectra of nitrogen-doped carbon nano-rings manufactured in the present embodiment, as can be seen from Figure 2 gained fluorescence
Spectrogram has excitation dependency characteristic.
Embodiment 3
(a) it takes the sodium citrate of 0.25g and 1.0g urea to be placed in carry out grinding to obtain precursor mixture in mortar；
(b) precursor mixture after grinding is transferred in crucible, and is covered with lid；Crucible is placed baking oven to carry out
It is heated to 200 degrees Celsius；
(c) several groups of samples for doing the differential responses time compare and analyze, i.e. the reaction time is 1min；5min；15min；
30min；1h；2h etc..
(d) by reacted mixture cooled to room temperature i.e. 20~30 DEG C, initial reaction product is obtained；
(e) add 20g pure water to dissolve initial reaction product, obtain suspension；
(f) suspension is filtered with molecular cut off 3kDa cylindrical membrane separator-filter, collects filtered solution, measurement
The fluorescence quantum yield of differential responses time, the also available production with fluorescent effect in extremely short reaction time 1min
Object；Optimizing reaction time is it can be concluded that be 1h in the reaction time be best；Freeze-drying obtains the present embodiment high fluorescent yield
Nitrogen-doped carbon nano-rings.
Fig. 3 is excitation and the transmitting figure that the present embodiment prepares nitrogen-doped carbon nano-rings, and excitation wavelength is as can be seen from Figure 3
Available strongest fluorescence intensity, fluorescence emission spectrum peak position are set to 535nm when 410nm.
Embodiment 4
(a) it takes the sodium citrate of 0.25g and 1.0g urea to be placed in carry out grinding to obtain precursor mixture in mortar；
(b) precursor mixture after grinding is transferred in crucible, and is covered with lid；Crucible is placed baking oven to carry out
Reaction 1 hour；
(c) several groups of samples for doing differential responses temperature compare and analyze, i.e., reaction temperature is 145 DEG C；165℃；185
℃；205℃；225 DEG C etc..
(d) by reacted mixture cooled to room temperature i.e. 20~30 DEG C, initial reaction product is obtained；
(e) add 20g pure water to dissolve initial reaction product, obtain suspension；
(f) suspension is filtered with molecular cut off 3kDa cylindrical membrane separator-filter, collects filtered solution, measurement
The fluorescence quantum yield of differential responses temperature；Optimize reaction temperature it can be concluded that be 185 DEG C in reaction temperature being best；Freezing is dry
The dry nitrogen-doped carbon nano-rings for obtaining the present embodiment high fluorescent yield.
Fig. 4 is the ultravioletvisible absorption figure of nitrogen-doped carbon nano-rings manufactured in the present embodiment, is as can be seen from Figure 4 existed
410nm nearby has preferable absorbent properties.
Fig. 5 is that the XPS element of nitrogen-doped carbon nano-rings manufactured in the present embodiment is constituted and content analysis is as a result, from Fig. 5
It can be seen that the nitrogen-doped carbon nano-rings that the present embodiment obtains are mainly by C (55.35%), N (18.20%), O (26.45%) three
Kind element composition.
Embodiment 5
(a) it takes the sodium citrate of 0.25g and 1.0g urea to be placed in carry out grinding to obtain precursor mixture in mortar；
(b) precursor mixture after grinding is transferred in crucible, and is covered with lid；Crucible is placed into baking oven heating
Reaction 1 hour is carried out to 185 DEG C；
(c) by reacted mixture cooled to room temperature i.e. 20~30 DEG C, initial reaction product is obtained；
(d) add 20g pure water to dissolve initial reaction product, obtain suspension；
(e) suspension is filtered with molecular cut off 3kDa cylindrical membrane separator-filter, collects filtered solution；
(f) filtered fluid is placed on vial, it is normal at room temperature to place, it places different time (i.e. 1 day；5 days；10 days；
15 days；25 days；30 days) fluorescence quantum yield is measured afterwards, it can be deduced that it can also keep original after 30 days in standing time
Fluorescence quantum yield, show that filtered fluid i.e. nitrogen-doped carbon nano-rings optical property is particularly stable.
In the range of pH is 1-11, nitrogen-doped carbon nano-rings luminescent color variation prepared by the present embodiment is unobvious i.e.
It shows yellow green, but the linkage of original element of nitrogen-doped carbon nano-rings can be destroyed when alkalinity is too strong, the destruction of key leads to Huang
Green obviously die down becomes blue color led until disappearing, and the variation of luminescent color can be used as the strong basicity environment in identification solution
That is pH is greater than 11.
Detection part
Embodiment 6
Nitrogen-doped carbon nano-rings in the present invention are used successfully to Fe3+Detection.2.5 μ L carbon nano ring deionized waters are dilute
It is interpreted as 1mL, after the light excitation of wavelength 410nm, the luminous intensity at 530nm is denoted as initial strength F0.Add into the solution
Enter containing Fe3+Solution, survey luminous intensity after 5min, be denoted as F1.Δ F is Fe3+Detection signal, expression formula be Δ F=F0-
F1.It excites crack width and transmite slit width is respectively 5nm and 5nm.Fig. 6 is the carbon nano ring to Fe3+Sensibility reality
Test result.Different Fe3+The luminous intensity of carbon nano ring under concentration (0,1,25,50,100,150,200 μM).Luminous intensity is with Fe3 +The increase of concentration is decreased obviously.Fig. 7 is the pad value and Fe of luminous intensity3+The relationship of concentration.Work as Fe3+Concentration is at 1~200 μM)
In range, the two is in strong linear relationship, related coefficient 0.9984.It is then calculated according to triple standard difference method, detection is limited to 10nmol/
L。
Granular absorption application
Embodiment 7
Nitrogen-doped carbon nano-rings in the present invention are used successfully to the absorption of PM particle.Using small-sized adsorbent equipment, by equipment
After intermediate glass tube weighs, be passed through smog from the one end for being inverted round-bottomed flask until being full of flask, round-bottomed flask it is another
One end connects air pump, opens the adsorption test operation that circulating pump carries out smog after ready again.
Fig. 7 is the adsorption plant that nitrogen-doped carbon nano-rings solid powder prepared by the embodiment of the present invention 1 is applied to PM particle
In, the absorption property of nitrogen-doped carbon nano-rings and active carbon is compared and analyzed, it can be seen that adulterate the absorption of carbon nano ring
Effect is much higher than active carbon, can achieve 2 times or more.
Finally, it is stated that：Above embodiments are merely to illustrate implementation process and feature of the invention, rather than limit this hair
Bright technical solution, although the present invention has been described in detail with reference to the above embodiments, those skilled in the art answer
Work as understanding：It is still possible to modify or equivalently replace the present invention, without departing from the spirit and scope of the present invention any
Modification or part replacement, should all cover in protection scope of the present invention.
Claims (10)
1. a kind of preparation method of nitrogen-doped carbon nano-rings comprising：Carbon source is mixed into obtain precursor mixture with nitrogen source；And it is right
The precursor mixture directly heats, can make nitrogen source therein fusing at a temperature of react to obtain the nitrogen-doped carbon nano-rings；
The nitrogen source is urea, and the carbon source is sodium citrate；
Preferably, it is ground before being directly heated to the precursor mixture.
2. preparation method according to claim 1, wherein the mass ratio of the sodium citrate and the urea is 1:0.1
To 1:16.
3. preparation method according to claim 2, wherein the mass ratio of the sodium citrate and the urea is 1:4.
4. preparation method described in any one of claim 1 to 3, wherein the temperature of the reaction is 140~240 DEG C.
5. preparation method according to any one of claims 1 to 4, wherein the time of the reaction is 1min or more, excellent
Select 1h or more.
6. preparation method according to any one of claims 1 to 5, wherein the preparation method further includes separating step,
Preferably, the separating step includes：
Water is added by the material natural cooling after reaction, and in material after the cooling period, is then filtered to get filtrate using mwco membrane,
And filtrate is freeze-dried to obtain the nitrogen-doped carbon nano-rings；
Preferably, the molecular cut off of the mwco membrane be 3kDa, 5kDa, 10kDa or 30kDa in any one or at least
Two kinds of combination；
Preferably, the freeze-drying is carried out under the conditions of vacuum and -50 DEG C to -45 DEG C.
7. a kind of nitrogen-doped carbon nano-rings are prepared by preparation method according to any one of claims 1 to 6；
Preferably, the nitrogen-doped carbon nano-rings are through XPS analysis, constituent content be C be 50~60%, N is 15~20%, O be 20~
30%.
8. application of the nitrogen-doped carbon nano-rings as claimed in claim 7 as soda acid identifier aqueous solution pH for identification.
9. nitrogen-doped carbon nano-rings as claimed in claim 7 are as detection reagent for detecting Fe3+The application of ion concentration.
10. the application that nitrogen-doped carbon nano-rings described in claim 7 are used to absorb the PM particle in air as adsorbent.
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|---|---|---|---|---|
| CN110429290A (en) * | 2019-08-06 | 2019-11-08 | 四川轻化工大学 | A method of preparing nitrogen-doped carbon material load transition metal compound catalyst |
| CN113735098A (en) * | 2020-05-29 | 2021-12-03 | 中国石油天然气股份有限公司 | Nitrogen-doped carbon nanoring, and preparation method and application thereof |
| CN115812699A (en) * | 2022-11-29 | 2023-03-21 | 贵州大学 | Carbon-based nano material for delivering dsRNA (double-stranded ribonucleic acid) as nucleic acid carrier as well as preparation method and application of carbon-based nano material |
-
2018
- 2018-03-23 CN CN201810243998.6A patent/CN108821261B/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110429290A (en) * | 2019-08-06 | 2019-11-08 | 四川轻化工大学 | A method of preparing nitrogen-doped carbon material load transition metal compound catalyst |
| CN113735098A (en) * | 2020-05-29 | 2021-12-03 | 中国石油天然气股份有限公司 | Nitrogen-doped carbon nanoring, and preparation method and application thereof |
| CN113735098B (en) * | 2020-05-29 | 2023-08-22 | 中国石油天然气股份有限公司 | Nitrogen-doped carbon nano ring, and preparation method and application thereof |
| CN115812699A (en) * | 2022-11-29 | 2023-03-21 | 贵州大学 | Carbon-based nano material for delivering dsRNA (double-stranded ribonucleic acid) as nucleic acid carrier as well as preparation method and application of carbon-based nano material |
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| CN108821261B (en) | 2020-08-28 |
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