CN111592883B - Magnesium ion doped carbon quantum dot and preparation and application methods thereof - Google Patents
Magnesium ion doped carbon quantum dot and preparation and application methods thereof Download PDFInfo
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
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- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
Abstract
The invention relates to a magnesium ion doped carbon quantum dot and a preparation and application method thereof, which are characterized in that: 1) Under the condition of oil bath, carrying out melt mixing on magnesium gluconate and 1-aminopropyl-3-methylimidazolium bromide according to the molar ratio of 1 to 4, and stirring and uniformly mixing to form gel; 2) Under the protection of nitrogen and magnetic stirring, pyrolyzing the gel at 180-240 ℃ for 1-6 h, and cooling the product; 3) Dissolving the product in ultrapure water to obtain a brownish black dispersion liquid, wherein the volume ratio of the mass of the product to the volume of water is 1 to 10-50, and centrifuging the dispersion liquid to obtain an upper-layer dispersion liquid containing carbon quantum dots; 4) Transferring the upper layer dispersion liquid into a dialysis bag, and dialyzing in ultrapure water for 3~5 days; 5) Freeze drying the dispersion, and air drying. The invention has the advantages that: the magnesium ion doped carbon quantum dots have small particle size, uniform size distribution, simple preparation process and easy operation, and are suitable for industrial production; the magnesium ion doped carbon quantum dots are added into the water-based lubricating base liquid, and the average friction coefficient is reduced by 60.6%; the abrasion volume decreased by 81.8%.
Description
Technical Field
The invention belongs to the technical field of novel functional nano material preparation, and relates to a magnesium ion doped carbon quantum dot and preparation and application methods thereof.
Technical Field
It is reported that one third of the total energy of the earth is consumed in the form of friction, wear causes about 60% of the mechanical component damage, and more than 50% of mechanical failure is attributable to lubrication failure and excessive wear. The economic loss of China caused by friction and abrasion is only about 600 million yuan every year. As a natural enemy of friction and abrasion, lubrication is generated at the same time and is ubiquitous in life, production and aerospace. Lubrication is one of the key technologies for improving the energy utilization efficiency and the service life of mechanical equipment. The friction generated by the running of the engine and the transmission of the common car consumes about 16.5 percent of the total energy of the fuel, if advanced lubrication technology is adopted to avoid the part of energy consumption, about 170 liters of fuel is saved per car every year, and 1040 hundred million liters of fuel can be saved in the whole world every year. It is further reported that the cost saved by increasing lubrication technology in a country can account for 1.0-1.4% of the total domestic production. The most straightforward and effective way to advance lubrication technology is to develop high performance lubricants with long service lives.
Before the appearance of vegetable oil and animal fat, water is always the most commonly used lubricant for human beings, but the water as the lubricant has a plurality of defects, such as poor film forming capability, low shearing stress, small viscosity-temperature coefficient, poor friction-reducing and wear-resisting properties and the like, particularly poor friction-reducing and wear-resisting capabilities, and the development and application of the water-based lubricant are greatly limited. The development of water-based lubricants has become more retarded, particularly after the birth of mineral oils. As is well known, the fact that petroleum resources are increasingly depleted is a non-competitive fact, energy shortage and environmental pollution become important problems which plague countries in the world, and water-based lubricants are gradually paid attention to the fields of fire-resistant hydraulic fluids, metal working fluids and the like by virtue of the advantages of excellent cooling performance, non-combustibility, low pollution and the like, but the problem of poor wear resistance and friction reduction performance of the water-based lubricants is still not solved, and further development of the water-based lubricants is restricted to a great extent.
Researches show that the tribological performance of the water-based lubricant can be effectively improved by adding the additional additive, the friction-reducing and wear-resisting performance of the water-based lubricant is greatly improved, and the application range of the water-based lubricant is further widened. The green and environment-friendly carbon-based nano material can effectively improve the tribological property of the base liquid by virtue of excellent lubricating property and mechanical property of the carbon-based nano material as a water-based nano lubricating additive, but when the traditional carbon-based nano material (such as fullerene, carbon nano tube, nano diamond and the like) is used as the water-based additive, the defects of complex preparation process, poor dispersion stability, easy agglomeration and the like exist, and the application of the carbon-based nano material is limited to a certain extent.
Disclosure of Invention
In order to solve the problems of uneven size distribution, poor dispersion stability, easy agglomeration and single function of the nano particle additive in the prior art, the invention provides a magnesium ion doped carbon quantum dot and a preparation and application method thereof; the magnesium ion doped carbon quantum dot as a lubricating oil additive has the characteristics of good water dispersibility, high uniformity, strong self-repairing capability and high reaction activity, can respectively reduce the friction coefficient and the wear volume of a water-based lubricating base liquid by 60.6 percent and 81.8 percent, shows excellent antifriction and antiwear properties, and has a great application prospect in a water lubricating system.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a magnesium ion doped carbon quantum dot is characterized in that: the average particle diameter of the magnesium ion doped carbon quantum dot is 3-10 nm, the surface of the magnesium ion doped carbon quantum dot contains a large number of oxygen-containing groups (such as carboxyl, hydroxyl, epoxy group and carbonyl) and 1-aminopropyl-3-methylimidazolium bromide, and the oxygen-containing groups and the 1-aminopropyl-3-methylimidazolium bromide are modified on the surface of the carbon quantum dot through covalent bonds; meanwhile, the surface of the carbon quantum dots and the inside of the carbon core contain a large amount of magnesium ions.
Further, the oxygen-containing group is a carboxyl group, a hydroxyl group, an epoxy group, a carbonyl group, or the like (as shown in fig. 3).
A preparation method of magnesium ion doped carbon quantum dots is characterized by comprising the following steps:
1) Magnesium gluconate (C) is prepared under the condition of oil bath (95-105 deg.C)12H22MgO14) And 1-aminopropyl-3-methylimidazolium bromide are subjected to melt mixing according to a molar ratio of 1 to 4, and are stirred to be uniformly mixed to form a gel;
2) Under the protection of nitrogen and magnetic stirring (100 to 600 rpm/min), pyrolyzing the gel prepared in the step 1) at 180 to 240 ℃, wherein the reaction time is 1 to 6 hours, and after the reaction is finished, cooling the product to room temperature;
3) Dissolving the product obtained in the step 2) in ultrapure water, controlling the ratio of the mass (g) of the product to the volume (mL) of water to be 1 to 10 to 50, completely dissolving the product under mechanical stirring to obtain a brownish black dispersion, then transferring the dispersion into a centrifuge tube, separating at a centrifugal speed of 6000 to 12000 rpm/min for 5 to 30min, and keeping an upper-layer dispersion containing carbon quantum dots;
4) Transferring the upper-layer dispersion liquid obtained in the step 3) into a dialysis bag (with the molecular weight cutoff of 1000 to 4000), dialyzing in ultrapure water for 3~5 days, and changing water for 5-8 times to remove unreacted precursors;
5) After dialysis, transferring the dispersion liquid into a freeze dryer (minus 15 to minus 25 ℃) to dry for 24 to 48h; and then transferring the product after freeze drying into an air drying oven, and continuously drying for 12 to 48h at the temperature of 60 to 80 ℃ to obtain the magnesium ion doped carbon quantum dot.
Further, the oil used in the oil bath in the step 1) of the invention is one of dimethyl silicone oil, methyl phenyl silicone oil and methyl chlorophenyl silicone oil.
The magnesium ion doped carbon quantum dot water-based lubricating oil is characterized by being prepared from the following raw materials in percentage by weight:
0.01-5% of magnesium ion doped carbon quantum dots, 1-5% of triethanolamine and 90-100% of water.
The method adopts doping and in-situ surface modification technology, takes magnesium gluconate as a precursor (the magnesium gluconate is taken as a carbon source and a magnesium doping agent), takes 1-aminopropyl-3-methylimidazolium bromide ionic liquid as a modifier and a reaction medium, and prepares the magnesium ion-doped carbon quantum dot by uniformly heating in the processes of magnesium gluconate carbonization and dehydration through one-step pyrolysis; other carbon sources and metal dopants are not involved in the preparation process, and the preparation process is simple; the whole reaction is finished in one step, and complex pretreatment and post-treatment processes are not involved in the reaction process; the prepared carbon quantum dots have good water dispersibility, high uniformity, strong self-repairing capability and high reaction activity; the prepared magnesium ion doped carbon quantum dots are spherical-like, the particle size of the magnesium ion doped carbon quantum dots is mainly concentrated between 3.0 and 10.0 to nm, the average particle size is 8.2 to nm, and the magnesium ion doped carbon quantum dots are mainly composed of amorphous carbon.
In the process of preparing the magnesium ion doped carbon quantum dot, 1-aminopropyl-3-methylimidazole bromine salt is used as a functional reagent, the surface of the carbon quantum dot can be effectively modified through a covalent bond, and further growth of a carbon core of the magnesium ion doped carbon quantum dot can be effectively inhibited by virtue of the steric hindrance effect and the electrostatic repulsion effect of the carbon quantum dot, so that the size distribution of the prepared carbon quantum dot is more uniform, and the carbon quantum dot can be effectively prevented from agglomerating in a dispersion medium; in addition, the 1-aminopropyl-3-methylimidazolium bromide shows stronger hydrophilicity, and the modification of the surface of the carbon quantum dot can provide good water dispersibility for the carbon quantum dot, so that the carbon quantum dot can be stably dispersed in a water-based lubricating system for a long time; the ionic liquid is also a lubricating additive with excellent performance, and can further improve the tribological performance of the carbon quantum dots when being used as a functional reagent; magnesium is used as a soft metal, can effectively repair a metal wear surface, has good reaction activity with a friction surface, can remarkably improve the film forming speed of a carbon quantum dot and the metal friction surface, and greatly improves the tribology performance of the carbon quantum dot and the metal friction surface;
it is well known that during rubbing, a large number of low energy electrons are ejected from the asperities on the metal rubbing surface and a positive charge is concentrated around the asperities, resulting in a positively charged rubbing surface. The surface of the magnesium ion-doped carbon quantum dot contains a large amount of bromide ions and is negatively charged, so that the magnesium ion-doped carbon quantum dot can quickly form a firm interface lubricating film on a friction surface through electrostatic adsorption. The ionic liquid group can greatly improve the embedding stability of the magnesium ion doped carbon quantum dots on the friction surface, so that the magnesium ion doped carbon quantum dots can be stably adsorbed on the friction surface in the friction test process, an interface lubricating film formed by the magnesium ion doped carbon quantum dots on the friction surface cannot be damaged, the interface lubricating film can effectively prevent the friction interface from directly contacting, the friction and the abrasion of a friction pair are greatly reduced, and the lubricating performance of the base liquid is improved. Therefore, the magnesium ion doped carbon quantum dot as the water-based nano lubricating additive can respectively reduce the average friction coefficient and the average wear volume of the water-based lubricating base fluid by 60.6 percent and 81.8 percent by virtue of the excellent film forming capability of the magnesium ion doped carbon quantum dot, and has a good application prospect in a water lubricating system.
Compared with the prior art, the invention has the following advantages:
1. the magnesium ion doped carbon quantum dots prepared by the method have small particle size and uniform size distribution, and the preparation process is simple and easy to operate, and is beneficial to large-scale and even industrial production;
2. the magnesium ion doped carbon quantum dot prepared by the invention is added into a water-based lubricating base solution (triethanolamine aqueous solution with the mass fraction of 2%), and the average friction coefficient is reduced from 0.4266 to 0.1681 by 60.6%; wear volume from 1.43X 10-3 mm-3Down to 2.6X 10-4 mm-3The reduction is 81.8%; the magnesium ion doped carbon quantum dot has wide application prospect in the field of water-based lubricating additives.
Drawings
FIG. 1 is a schematic diagram of a process for preparing magnesium ion-doped carbon quantum dots according to the present invention;
FIG. 2 is a TEM image of magnesium ion-doped carbon quantum dots prepared in example 1
FIG. 3 is an FTIR chart of magnesium ion doped carbon quantum dots prepared in example 1;
FIG. 4 is an XRD pattern of the magnesium ion doped carbon quantum dot prepared in example 1;
fig. 5 is a graph showing the relationship between the friction coefficient and the wear volume of the magnesium ion-doped carbon quantum dot prepared in example 1 as a function of concentration.
Detailed Description
With reference to fig. 1, a preparation method of a magnesium metal doped carbon quantum dot includes the following specific implementation steps:
example 1
(1) Mixing 2g C12H22MgO14And 3.18g 1-aminopropyl-3-methylimidazolium bromide (molar ratio 1:3) into a round bottom flask, the flask was immersed in a 100 ℃ oil (dimethylsilicone oil) bath and stirred with magnetic stirring (200 rpm/min) for 20 min to mix well to form a gel;
(2) Immersing the round-bottom flask obtained in the step (1) into an oil bath kettle at the temperature of 200 ℃, introducing nitrogen for protection, and continuously reacting for 2 h under magnetic stirring (500 rpm/min);
(3) After the reaction is finished, cooling the reaction product in the step (2) to room temperature, adding 20 mL ultrapure water, and completely dissolving the reaction product under mechanical stirring to obtain a brownish black dispersion liquid; transferring the dispersion liquid into a centrifugal tube, centrifuging for 10 min at the rotating speed of 12000 rpm/min, removing precipitates at the bottom of the centrifugal tube, and reserving the upper-layer dispersion liquid containing the carbon quantum dots;
(4) Transferring the upper layer dispersion liquid obtained in the step 3) into a dialysis bag (4000 Da), dialyzing in ultrapure water for 5 days, and changing water for 8 times to remove unreacted precursors;
(5) After the dialysis is finished, the dispersion is transferred to a freeze dryer (-20 ℃) and dried for 24 hours; and then transferring the freeze-dried product to a forced air drying oven, and continuously drying for 24 hours at the temperature of 60 ℃ to obtain the magnesium ion doped carbon quantum dot.
Preparing magnesium ion doped carbon quantum dot water-based lubricating oil according to the following weight percentage: 0.1% of magnesium ion doped carbon quantum dots, 2% of triethanolamine and 97.9% of water.
Example 2
(1) Mixing 2g C12H22MgO14And 1g of 1-aminopropyl-3-methylimidazolium bromide (molar ratio 1:1) were added to a round bottom flask, the flask was immersed in an oil (methylphenyl silicone oil) bath at 102 ℃ and stirred with magnetic stirring (300 rpm/min) for 25min to mix well to form a gel;
(2) Immersing the round-bottom flask obtained in the step (1) into an oil bath kettle at 180 ℃, introducing nitrogen for protection, and continuously reacting for 2.5 h under magnetic stirring (300 rpm/min);
(3) After the reaction is finished, cooling the reaction product in the step (2) to room temperature, adding 20 mL ultrapure water, and completely dissolving the reaction product under mechanical stirring to obtain a brownish black dispersion liquid; transferring the dispersion liquid into a centrifugal tube, centrifuging for 15 min at the rotating speed of 10000 rpm/min, removing sediment at the bottom of the centrifugal tube, and reserving the upper-layer dispersion liquid containing carbon quantum dots;
(4) Transferring the upper dispersion liquid obtained in the step 3) into a dialysis bag (1000 Da), dialyzing in ultrapure water for 4 days, and changing water for 7 times to remove unreacted precursors;
(5) After the dialysis is finished, the dispersion is transferred to a freeze dryer (-22 ℃) to be dried for 30h; and then transferring the freeze-dried product to a forced air drying oven, and continuously drying for 30h at 65 ℃ to obtain the magnesium ion doped carbon quantum dot.
Preparing magnesium ion doped carbon quantum dot water-based lubricating oil according to the following weight percentage: 3% of magnesium ion doped carbon quantum dots, 2% of triethanolamine and 95% of water.
Example 3
(1) Will 2g C12H22MgO14And 2.12g1-aminopropyl-3-methylimidazolium bromide (molar ratio 1:2) was added to a round bottom flask, the flask was immersed in a 105 deg.C oil (methyl chlorophenyl silicone oil) bath and stirred with magnetic stirring (400 rpm/min) 15 min, mixing the components uniformly to form gel;
(2) Immersing the round-bottom flask obtained in the step (1) into an oil bath kettle at 240 ℃, introducing nitrogen for protection, and continuously reacting for 4h under magnetic stirring (400 rpm/min);
(3) After the reaction is finished, cooling the reaction product in the step (2) to room temperature, adding 30 mL ultrapure water, and completely dissolving the reaction product under mechanical stirring to obtain a brownish black dispersion liquid; transferring the dispersion liquid into a centrifugal tube, centrifuging for 25min at the rotating speed of 8000 rpm/min, removing sediment at the bottom of the centrifugal tube, and reserving the upper-layer dispersion liquid containing carbon quantum dots;
(4) Transferring the upper layer dispersion liquid obtained in the step 3) into a dialysis bag (2000 Da), dialyzing in ultrapure water for 3 days, and changing water for 5 times to remove unreacted precursors;
(5) After the dialysis is finished, the dispersion is transferred to a freeze dryer (-18 ℃) and dried for 26 hours; and then transferring the freeze-dried product to a forced air drying oven, and continuously drying for 35 hours at 70 ℃ to obtain the magnesium ion doped carbon quantum dot.
Preparing magnesium ion doped carbon quantum dot water-based lubricating oil according to the following weight percentage: 5% of magnesium ion doped carbon quantum dots, 5% of triethanolamine and 90% of water.
Example 4
(1) Mixing 2g C12H22MgO14And 2.12g 1-aminopropyl-3-methylimidazolium bromide (molar ratio 1:2) were added to a round bottom flask, the flask was immersed in a 105 ℃ oil (dimethicone) bath and stirred with magnetic stirring (400 rpm/min) for 15 min to mix well to form a gel;
(2) Immersing the round-bottom flask obtained in the step (1) into an oil bath kettle at 240 ℃, introducing nitrogen for protection, and continuously reacting for 3.5 h under magnetic stirring (350 rpm/min);
(3) After the reaction is finished, cooling the reaction product obtained in the step (2) to room temperature, adding 40 mL ultrapure water, and completely dissolving the reaction product under mechanical stirring to obtain a brownish black dispersion liquid; transferring the dispersion liquid into a centrifugal tube, centrifuging for 30min at the rotating speed of 6000 rpm/min, removing sediment at the bottom of the centrifugal tube, and reserving the upper-layer dispersion liquid containing carbon quantum dots;
(4) Transferring the upper layer dispersion liquid obtained in the step 3) into a dialysis bag (3000 Da), dialyzing in ultrapure water for 3 days, and changing water for 8 times to remove unreacted precursors;
(5) After the dialysis is finished, the dispersion is transferred to a freeze dryer (-15 ℃) and dried for 24 hours; and then transferring the freeze-dried product to a forced air drying oven, and continuously drying for 18 hours at the temperature of 75 ℃ to obtain the magnesium ion doped carbon quantum dots.
Preparing magnesium ion doped carbon quantum dot water-based lubricating oil according to the following weight percentage: 0.5% of magnesium ion doped carbon quantum dots, 1.5% of triethanolamine and 98% of water.
Example 5
(1) Mixing 2g C12H22MgO14And 3.18gAdding 1-aminopropyl-3-methylimidazolium bromide (molar ratio is 1:3) into a round-bottom flask, immersing the flask into an oil (methyl chlorophenyl silicone oil) bath kettle at 95 ℃, and stirring by using magnetic stirring (300 rpm/min) for 20 min to uniformly mix to form gel;
(2) Immersing the round-bottom flask obtained in the step (1) into an oil bath kettle at 220 ℃, introducing nitrogen for protection, and continuously reacting for 4h under magnetic stirring (200 rpm/min);
(3) After the reaction is finished, cooling the reaction product obtained in the step (2) to room temperature, adding 35 mL ultrapure water, and completely dissolving the reaction product under mechanical stirring to obtain a brownish black dispersion liquid; transferring the dispersion liquid into a centrifugal tube, centrifuging for 25min at the rotating speed of 7000 rpm/min, removing precipitates at the bottom of the centrifugal tube, and reserving the upper-layer dispersion liquid containing the carbon quantum dots;
(4) Transferring the upper layer dispersion liquid obtained in the step 3) into a dialysis bag (2000 Da), dialyzing in ultrapure water for 4 days, and changing water for 8 times to remove unreacted precursors;
(5) After the dialysis is finished, the dispersion is transferred to a freeze dryer (-18 ℃) and dried for 25 hours; and then transferring the freeze-dried product to a forced air drying oven, and continuously drying for 20 hours at the temperature of 80 ℃ to obtain the magnesium ion doped carbon quantum dot.
Preparing the magnesium ion doped carbon quantum dot water-based lubricating oil according to the following weight percentage: 4% of magnesium ion doped carbon quantum dots, 2% of triethanolamine and 94% of water.
Example 6
(1) Mixing 2g C12H22MgO14And 3.18g 1-aminopropyl-3-methylimidazolium bromide (molar ratio 1:3) into a round bottom flask, the flask was immersed in a 105 ℃ oil (methyl chlorophenyl silicone oil) bath and stirred with magnetic stirring (600 rpm/min) for 15 min to mix well to form a gel;
(2) Immersing the round-bottom flask obtained in the step (1) into an oil bath kettle at 180 ℃, introducing nitrogen for protection, and continuously reacting for 2 h under magnetic stirring (500 rpm/min);
(3) After the reaction is finished, cooling the reaction product in the step (2) to room temperature, adding 50 mL ultrapure water, and completely dissolving the reaction product under mechanical stirring to obtain a brownish black dispersion liquid; transferring the dispersion liquid into a centrifugal tube, centrifuging for 20 min at the rotating speed of 8000 rpm/min, removing sediment at the bottom of the centrifugal tube, and reserving the upper-layer dispersion liquid containing carbon quantum dots;
(4) Transferring the upper layer dispersion liquid obtained in the step 3) into a dialysis bag (4000 Da), dialyzing in ultrapure water for 5 days, and changing water for 8 times to remove unreacted precursors;
(5) After the dialysis is finished, the dispersion is transferred to a freeze dryer (-20 ℃) and dried for 30h; and then transferring the freeze-dried product to a forced air drying oven, and continuously drying for 40 hours at the temperature of 75 ℃ to obtain the magnesium ion doped carbon quantum dots.
Preparing magnesium ion doped carbon quantum dot water-based lubricating oil according to the following weight percentage: 2% of magnesium ion doped carbon quantum dots, 3% of triethanolamine and 95% of water.
Example 7
(1) Mixing 2g C12H22MgO14And 3.18g 1-aminopropyl-3-methylimidazolium bromide (molar ratio 1:3) into a round bottom flask, the flask was immersed in a 100 ℃ oil (dimethylsilicone oil) bath and stirred with magnetic stirring (400 rpm/min) for 20 min to mix well and form a gel;
(2) Immersing the round-bottom flask obtained in the step (1) into an oil bath kettle at the temperature of 200 ℃, introducing nitrogen for protection, and continuously reacting for 3 h under magnetic stirring (500 rpm/min);
(3) After the reaction is finished, cooling the reaction product in the step (2) to room temperature, adding 25 mL ultrapure water, and completely dissolving the reaction product under mechanical stirring to obtain a brownish black dispersion liquid; transferring the dispersion liquid into a centrifugal tube, centrifuging for 25min at the rotating speed of 10000 rpm/min, removing sediment at the bottom of the centrifugal tube, and reserving the upper-layer dispersion liquid containing carbon quantum dots;
(4) Transferring the upper layer dispersion liquid obtained in the step 3) into a dialysis bag (4000 Da), dialyzing in ultrapure water for 5 days, and changing water for 6 times to remove unreacted precursors;
(5) After dialysis, the dispersion was transferred to a freeze dryer (-20 ℃) and dried for 35h; and then transferring the freeze-dried product to a forced air drying oven, and continuously drying for 30h at 65 ℃ to obtain the magnesium ion doped carbon quantum dot.
Preparing magnesium ion doped carbon quantum dot water-based lubricating oil according to the following weight percentage: 3.5% of magnesium ion doped carbon quantum dots, 1.5% of triethanolamine and 95% of water.
The tribological performance of magnesium ion doped carbon quantum dots as water-based lubricant additives was evaluated using a common UMT-Lab multifunctional friction wear tester (bruker instruments ltd., usa): a linear reciprocating ball-disc mode (steel/steel contact) is selected, a commercial AISI-52100 steel ball (the diameter is 12.7 mm, the hardness is 59-61 HRC, the average roughness is 16.2 nm) is fixed on an upper support, and an AISI-52100 steel block (50 mm X35 mm X4 mm, the hardness is 59-61 HRC, the average roughness is 25.1 nm) at the lower part is fixed on a reciprocating module; before testing, the prepared lubricant is dripped into a steel ball-disc contact area, and the dripping volume of the lubricant is 0.5 mL; friction test conditions: the load is 40-300N, the duration is 20 min, the frequency is 5 Hz, the amplitude is 5 mm, the ambient temperature is adopted, each group of samples is tested at least three times, and the steel ball and the steel block need to be subjected to ultrasonic cleaning in petroleum ether (60-90%) before and after the friction test; in the test process, the friction coefficient is automatically recorded by a computer connected with the UMT-Lab friction wear testing machine system, and the wear volume and the profile of a grinding crack are measured by a white light interferometer; meanwhile, a scanning electron microscope and an X-ray photoelectron spectrometer are respectively adopted to analyze the appearance of the grinding crack and the element composition of the surface of the grinding crack.
The carbon quantum dots doped with magnesium ions prepared in the above examples 2 to 7 were detected by TEM, XPS and XRD, and found that: the obtained products are magnesium ion doped carbon quantum dots, have uniform size distribution and smaller particle size, and have good dispersibility and lubricating property when added into a water-based lubricating base solution.
A TEM image of the magnesium ion-doped carbon quantum dot prepared above (example 1) is shown in fig. 2; as can be seen from FIG. 2, the prepared magnesium ion doped carbon quantum dots have uniform size distribution and small particle size, the average particle size is about 8.2 nm, and no obvious agglomeration phenomenon occurs.
An FTIR diagram of the magnesium metal-doped carbon quantum dots prepared above (example 1) is shown in fig. 3; as can be seen from fig. 3, a large number of characteristic peaks of oxygen-containing groups appear on the surface of the magnesium ion-doped carbon quantum dot, which indicates that the surface thereof is rich in oxygen-containing groups; meanwhile, an FTIR spectrogram of the carbon quantum dot also shows a characteristic absorption peak of an amido bond, which shows that the ionic liquid is covalently modified on the surface of the carbon quantum dot, so that the prepared magnesium ion doped carbon quantum dot shows excellent dispersibility and dispersion stability in the water-based lubricating base liquid.
The XRD pattern of the magnesium ion doped carbon quantum dot prepared in the above (example 1) is shown in figure 4; as can be seen from fig. 4, the magnesium ion doped carbon quantum dots have a mainly amorphous structure.
The graph of the relationship between the friction coefficient and the wear volume of the magnesium ion doped carbon quantum dot prepared in the above (example 1) along with the change of the concentration is shown in FIG. 5; as can be seen from fig. 5, the average friction coefficient and the average wear volume of the water-based lubricating base fluid are significantly reduced after a small amount of magnesium ion doped carbon quantum dots are added. When 1.0 wt% of magnesium ion doped carbon quantum dots are added into the water-based lubricating base liquid, the average friction coefficient and the average wear volume are respectively reduced by 60.6% and 81.8%, and the optimal antifriction and wear-resistant performances are shown, so that the magnesium ion doped carbon quantum dots serving as the nano lubricating additive can remarkably improve the tribological performance of the water-based lubricating base liquid.
In conclusion, it can be found that: the magnesium ion doped carbon quantum dot has excellent tribological performance, and can be widely applied as a water-based nano lubricating additive.
Claims (8)
1. A magnesium ion doped carbon quantum dot is characterized in that: the average particle size of the magnesium ion doped carbon quantum dot is 3-10 nm, the surface of the carbon quantum dot contains oxygen-containing groups and 1-aminopropyl-3-methylimidazolium bromide, and the oxygen-containing groups and the 1-aminopropyl-3-methylimidazolium bromide are modified on the surface of the carbon quantum dot through covalent bonds; meanwhile, the surface of the carbon quantum dot and the inside of the carbon core contain magnesium ions.
2. The magnesium ion doped carbon quantum dot of claim 1, wherein: the oxygen-containing group is any one or more of carboxyl, hydroxyl, epoxy and carbonyl.
3. A preparation method of magnesium ion doped carbon quantum dots is characterized by comprising the following steps:
1) Under the condition of oil bath, carrying out melt mixing on magnesium gluconate and 1-aminopropyl-3-methylimidazolium bromide according to the molar ratio of 1 to 4, and stirring to uniformly mix the magnesium gluconate and the 1-aminopropyl-3-methylimidazolium bromide so as to form gel;
2) Under the protection of nitrogen and magnetic stirring, pyrolyzing the gel prepared in the step 1) at 180 to 240 ℃, wherein the reaction time is 1 to 6 hours, and after the reaction is finished, cooling the product to room temperature;
3) Dissolving the product obtained in the step 2) in ultrapure water, controlling the volume ratio of the mass of the product to the water to be 1 to 10-50, completely dissolving the product under mechanical stirring to obtain a brownish black dispersion liquid, then transferring the dispersion liquid into a centrifuge tube, separating the dispersion liquid for 5 to 30min at the centrifugal speed of 6000 to 12000 rpm/min, and reserving the upper-layer dispersion liquid containing carbon quantum dots;
4) Transferring the upper layer dispersion liquid obtained in the step 3) into a dialysis bag, dialyzing in ultrapure water for 3~5 days, and changing water for 5-8 times to remove unreacted precursors;
5) After dialysis is finished, transferring the dispersion liquid into a freeze dryer for drying for 24 to 48h; and then transferring the product after freeze drying into an air-blast drying oven, and continuously drying for 12 to 48h at the temperature of 60 to 80 ℃ to obtain the magnesium ion doped carbon quantum dot.
4. The preparation method of the magnesium ion doped carbon quantum dot according to claim 3, characterized in that: the oil used in the oil bath in the step 1) is one of dimethyl silicone oil, methyl phenyl silicone oil and methyl chlorphenyl silicone oil.
5. The preparation method of the magnesium ion doped carbon quantum dot according to claim 3, characterized in that: the temperature of the oil bath in the step 1) is 95-105 ℃.
6. The method for preparing the magnesium ion doped carbon quantum dot according to the claim 3, 4 or 5, wherein the method comprises the following steps: the molecular weight cutoff of the dialysis bag in the step 4) is 1000 to 4000.
7. The method for preparing the magnesium ion doped carbon quantum dot according to the claim 3, 4 or 5, wherein the method comprises the following steps: the freeze-drying temperature in the step 5) is-15 to-25 ℃.
8. The water-based lubricating oil prepared by doping the carbon quantum dots with the magnesium ions is characterized by being prepared from the following raw materials in percentage by weight: 0.01-5% of magnesium ion doped carbon quantum dots, 1-5% of triethanolamine and 90-100% of water.
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