CN114656960B - Lysine-based carbon quantum dot corrosion inhibitor and preparation method and application thereof - Google Patents

Lysine-based carbon quantum dot corrosion inhibitor and preparation method and application thereof Download PDF

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CN114656960B
CN114656960B CN202210320617.6A CN202210320617A CN114656960B CN 114656960 B CN114656960 B CN 114656960B CN 202210320617 A CN202210320617 A CN 202210320617A CN 114656960 B CN114656960 B CN 114656960B
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叶育伟
程雄
谢浩琳
曾申有
陈颢
陈昊
刘跃华
汪枞
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Jiangxi University of Science and Technology
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Abstract

The invention discloses a lysine-based carbon quantum dot corrosion inhibitor and a preparation method and application thereof. The lysine-based carbon quantum dot corrosion inhibitor is obtained through high-temperature pyrolysis of lysine and/or lysine derivatives, the lysine-based carbon quantum dot corrosion inhibitor comprises an aromatic heterocyclic structure formed by C, H, O, N, wherein N exists in the form of pyridine nitrogen, pyrrole nitrogen or graphite nitrogen, and the size of the lysine-based carbon quantum dot corrosion inhibitor is 5-20 nm. The lysine-based carbon quantum dot corrosion inhibitor provided by the invention has excellent water solubility and corrosion resistance, and the preparation method has the advantages of convenience in operation, low cost and environment friendliness, and can be applied to industries such as steel, chemical industry, petroleum, electric power, papermaking, oil refining, ships, storage, traffic and the like.

Description

Lysine-based carbon quantum dot corrosion inhibitor and preparation method and application thereof
Technical Field
The invention belongs to the technical field of corrosion inhibitors, and particularly relates to a lysine-based carbon quantum dot corrosion inhibitor, and a preparation method and application thereof.
Background
Metal materials such as steel, copper, etc. are widely used in various industries concerning national folk life, such as machinery manufacturing industry, marine industry, defense industry, construction industry, transportation industry, etc., and have a very important role. However, metallic materials are extremely susceptible to corrosion by corrosive media (e.g., acids, bases, salts, etc.) in the environment during use. The corrosion of metal is closely related to the safety of mechanical devices, instruments and equipment, production buildings, working platforms, metal pipelines and the like which are prepared based on the corrosion.
In order to reduce the loss caused by corrosion, the addition of the corrosion inhibitor is one of the most widely used means, and the method has the advantages of small dosage, simple operation, low cost, obvious effect, strong universality and the like, so that the corrosion inhibitor occupies an important position in various anti-corrosion methods. The earliest options were inorganic corrosion inhibitors such as chromates, phosphates and molybdates. Although these corrosion inhibitors are effective in inhibiting corrosion of metals or alloys, some harmful components are still detected in these conventional corrosion inhibitors, which may be harmful to human health or cause serious ecological pollution. In particular, in recent years, the awareness of environmental protection has been gradually improved, and the development and application requirements of corrosion inhibitors have been increased. The research and development of efficient, environment-friendly and low-cost green inhibitors have gradually become the direction of future development. The development of a new corrosion inhibitor for metals is therefore a highly desirable problem.
Disclosure of Invention
The invention mainly aims to provide a lysine-based carbon quantum dot corrosion inhibitor, and a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a lysine-based carbon quantum dot corrosion inhibitor, which is obtained by high-temperature pyrolysis of lysine and/or lysine derivatives, and comprises an aromatic heterocyclic structure formed by C, H, O, N, wherein N exists in the form of pyridine-like nitrogen, pyrrole-like nitrogen or graphite-like nitrogen, and the size of the lysine-based carbon quantum dot corrosion inhibitor is 5-20 nm.
The embodiment of the invention also provides a preparation method of the lysine-based carbon quantum dot corrosion inhibitor, which comprises the following steps: and (3) cracking the lysine and/or the lysine derivative at the high temperature of 150-250 ℃ for 1-3 hours to prepare the lysine-based carbon quantum dot corrosion inhibitor.
The embodiment of the invention also provides application of the lysine-based carbon quantum dot corrosion inhibitor in the field of corrosion prevention of the surface of the metal substrate.
The embodiment of the invention also provides a surface protection method of the metal substrate, which comprises the following steps: and applying the lysine-based carbon quantum dot corrosion inhibitor to the surface of the metal substrate, thereby realizing the protection of the metal substrate.
Compared with the prior art, the invention has the beneficial effects that:
(1) The method for preparing the lysine-based carbon quantum dot corrosion inhibitor by high-temperature pyrolysis has the advantages of convenience in operation, low cost and environmental protection;
(2) The lysine-based carbon quantum dot corrosion inhibitor provided by the invention has excellent water solubility and corrosion resistance, and has more active sites, so that the chemical bonding with the metal surface is improved, and the corrosion rate of the metal is reduced; meanwhile, the good water solubility can effectively improve the dispersibility of the corrosion inhibitor in water environment;
(3) The prepared corrosion inhibitor has good water solubility and excellent corrosion resistance through high-temperature pyrolysis of lysine and/or lysine derivatives, can be applied to industries such as steel, chemical industry, petroleum, electric power, papermaking, oil refining, ships, storage, transportation and the like, is particularly expected to be applied to large-scale equipment such as chemical equipment, steel, petroleum, offshore platforms and the like, and can be used for the surface of a metal substrate and further prolong the service life of the substrate.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present invention, and other drawings may be obtained according to the drawings without inventive effort to those skilled in the art.
FIG. 1 is a schematic illustration of a preparation flow of a lysine-based carbon quantum dot corrosion inhibitor in accordance with an exemplary embodiment of the present invention;
FIGS. 2 a-2 b are electrochemical impedance spectra of carbon steel in comparative example 1 of the present invention in a 1M HCl environment;
FIG. 3 is a graph showing the polarization of carbon steel in comparative example 1 of the present invention in a 1M HCl environment;
FIGS. 4 a-4 b are electrochemical impedance spectra of carbon steel in comparative example 2 of the present invention in a 3.5% NaCl environment;
FIG. 5 is a graph showing the polarization of carbon steel in comparative example 2 of the present invention in a 3.5% NaCl environment;
FIGS. 6 a-6 b are electrochemical impedance spectra of carbon steel in comparative example 3 of the present invention in environments containing different corrosion inhibitors;
FIG. 7 is an infrared spectrum of lysine-based carbon quantum dots in example 1 of the present invention;
FIGS. 8 a-8 b are electrochemical impedance spectra of the electrode of example 1 of the present invention;
FIGS. 9 a-9 b are graphs of polarization curves and corrosion current densities for electrodes in example 2 of the present invention;
FIG. 10 is a graph showing the corrosion rate of the electrode in example 2 of the present invention;
FIGS. 11 a-11 b are electrochemical impedance spectra of the electrode of example 3 of the present invention;
FIGS. 12 a-12 b are graphs of polarization curves and corrosion current densities for electrodes in example 4 of the present invention;
FIG. 13 is a graph showing the corrosion rate of the electrode in example 4 of the present invention;
FIGS. 14 a-14 b are electrochemical impedance spectra of electrodes in example 5 of the present invention;
FIGS. 15 a-15 b are electrochemical impedance spectra of the electrode of example 6 of the present invention;
FIGS. 16 a-16 b are electrochemical impedance spectra in an electrode of example 7 of the present invention;
fig. 17 a-17 b are electrochemical impedance spectra in the electrode of example 8 of the present invention.
Detailed Description
In view of the shortcomings of the prior art, the inventor of the present application has long studied and put forward a great deal of practice, and the technical solution of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Specifically, as one aspect of the technical scheme of the invention, the lysine-based carbon quantum dot corrosion inhibitor is obtained by high-temperature cracking of lysine and/or lysine derivatives, the lysine-based carbon quantum dot corrosion inhibitor comprises an aromatic heterocyclic structure formed by C, H, O, N, N element in the lysine-based carbon quantum dot corrosion inhibitor exists in the form of pyridine nitrogen, pyrrole nitrogen or graphite nitrogen, and the size of the lysine-based carbon quantum dot corrosion inhibitor is 5-20 nm.
Wherein, the structural formulas of pyridine nitrogen, pyrrole nitrogen and graphite nitrogen are respectively shown as the following formulas:
Figure BDA0003571488410000031
in some preferred embodiments, the lysine-based carbon quantum dot corrosion inhibitor has a solubility in water of 5 to 500mg/1mL of water, i.e., the lysine-based carbon quantum dot corrosion inhibitor has excellent water solubility.
In some preferred embodiments, the lysine derivative includes any one or a combination of two or more of D-lysine hydrochloride, L-lysine hydrate, and is not limited thereto.
In some preferred embodiments, the metal still has a resistance of 10 after soaking in HCl and NaCl solutions of the lysine-based carbon quantum dot corrosion inhibitor for 24 hours 2 ～10 3 The corrosion current density is as low as 10 -5 ～10 -6 A/cm 2 Exhibits excellent corrosion resistance.
Further, after the metal is soaked in HCl and NaCl solutions of the lysine-based carbon quantum dot corrosion inhibitor for 24 hours, the low-frequency impedance modulus is improved by 1-2 orders of magnitude compared with the metal placed in the solution without the corrosion inhibitor.
Further, after the metal is soaked in HCl and NaCl solutions of the lysine-based carbon quantum dot corrosion inhibitor for 24 hours, the corrosion current density is reduced by 1-2 orders of magnitude compared with the corrosion current density in the solution without the corrosion inhibitor.
The invention also provides a preparation method of the lysine-based carbon quantum dot corrosion inhibitor, which comprises the following steps: and (3) cracking the lysine and/or the lysine derivative at the high temperature of 150-250 ℃ for 1-3 hours to prepare the lysine-based carbon quantum dot corrosion inhibitor.
In some more specific embodiments, the preparation scheme of the lysine-based carbon quantum dot corrosion inhibitor is schematically shown in fig. 1.
In some preferred embodiments, the method of making further comprises: after lysine is placed in a beaker, the beaker is sealed by tinfoil paper, then small holes are punched on the surface of the lysine for exhausting, and finally the lysine is placed in a constant temperature drying oven for high-temperature cracking treatment.
In some preferred embodiments, the method of making further comprises: and (3) dissolving, centrifuging, filtering, dialyzing and drying the lysine-based carbon quantum dot corrosion inhibitor.
Further, the preparation method comprises the following steps: mixing the lysine-based carbon quantum dot corrosion inhibitor with water for stirring and carrying out ultrasonic treatment, wherein the stirring treatment time is 10-20 min, and the ultrasonic treatment time is 10-25 min.
Further, the rotational speed of the centrifugal treatment is 8000-15000 r/min.
Further, the filtering step is repeated 3 to 5 times.
Further, the molecular weight of a dialysis bag adopted in the dialysis treatment is 1 KD-3 KD.
Further, the temperature of the drying treatment is 60-90 ℃ and the time is 24-48 h.
The embodiment of the invention also provides the application of the lysine-based carbon quantum dot corrosion inhibitor in the field of corrosion prevention of the surface of the metal substrate.
Further, the metal substrate includes any one of carbon steel, copper, iron, and alloy, and is not limited thereto.
Further, the metal substrate may be used in petroleum industry, marine industry, national defense industry, machinery industry, paper industry, transportation platform, etc., but is not limited thereto.
The lysine-based carbon quantum dot corrosion inhibitor can be used in the fields of steel, chemical industry, petroleum, electric power, papermaking, oil refining, ships, storage, traffic and the like.
Another aspect of the embodiments of the present invention also provides a surface protection method for a metal substrate, including: and immersing the surface of the metal substrate in the lysine-based carbon quantum dot corrosion inhibitor solution, so that the protection of the metal substrate is realized.
By means of the technical scheme, the lysine-based carbon quantum dot corrosion inhibitor provided by the invention has the advantages that more active sites are added on the basis of lysine, and the probability of chemical bonding with the surface of metal is improved, so that the corrosion rate of the metal is reduced; meanwhile, the good water solubility of the lysine-based carbon quantum dots effectively improves the dispersibility of the corrosion inhibitor in water environment.
In conclusion, the corrosion inhibitor prepared by the high-temperature cracking method has good water solubility and excellent corrosion resistance, can be applied to industries such as steel, chemical industry, petroleum, electric power, papermaking, oil refining, ships, storage, traffic and the like, is particularly expected to be applied to large-scale equipment such as chemical equipment, steel, petroleum, offshore platforms and the like, and can be used for the surface of a metal substrate to prolong the service life of the substrate.
The technical scheme of the present invention is further described in detail below with reference to several preferred embodiments and the accompanying drawings, and the embodiments are implemented on the premise of the technical scheme of the present invention, and detailed implementation manners and specific operation processes are given, but the protection scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples described below, unless otherwise specified, were all commercially available from conventional biochemicals.
Comparative example 1
Firstly, deoiling a Q235 carbon steel substrate, welding a copper wire on the surface of the carbon steel by soldering tin, sealing in AB glue (3:1) to expose only a test surface of 1cm multiplied by 1cm, polishing the working surface for 20min by using 400# abrasive paper, 800# abrasive paper and 1500# abrasive paper respectively, and finally flushing with ethanol and drying. After the treatment, the carbon steel substrate is used as a working electrode, the saturated calomel electrode is used as a reference electrode, and the platinum sheet is used as a counter electrode for electrochemical test, and the electrochemical impedance spectrum and the polarization curve of the platinum sheet in 1M HCl solution can be seen in figures 2 a-2 b and 3.
Comparative example 2
Firstly, deoiling a Q235 carbon steel substrate, welding a copper wire on the surface of the carbon steel by soldering tin, sealing in AB glue (3:1), exposing only a test surface of 1cm multiplied by 1cm, polishing the working surface for 20min by using 400# abrasive paper, 800# abrasive paper and 1500# abrasive paper respectively, and finally washing by using ethanol and drying. After the treatment, the carbon steel substrate is used as a working electrode, the saturated calomel electrode is used as a reference electrode, and the platinum sheet is used as a counter electrode for electrochemical test, and the electrochemical impedance spectrum and the polarization curve of the platinum sheet in 3.5% NaCl solution can be seen in figures 4 a-4 b and 5.
Comparative example 3
2g each of citric acid, threonine, leucine and aspartic acid was placed in a beaker, and then transferred to a drying oven, and the heating temperature was set at 210℃for 2 hours. After the reaction is finished, adding 30mL of deionized water into a beaker, stirring for 10min, performing ultrasonic treatment for 10min, filtering and centrifuging the obtained aqueous solution, wherein the rotating speed in the centrifuging process is 10000r/min, and then performing dialysis treatment, wherein the molecular weight of a dialysis bag is 2KD. And finally, placing the dialyzate into a vacuum drying oven for drying treatment at the temperature of 60 ℃ to obtain the carbon quantum dot corrosion inhibitor. Then, a certain amount of carbon quantum dots was added to a 1M HCl solution to prepare a corrosion inhibitor solution with a concentration of 200 mg/L. The electrodes prepared in the comparative example were placed in the above solution for electrochemical measurement, and the electrochemical impedance spectra obtained finally are shown in fig. 6a to 6 b. In terms of antibacterial performance, escherichia coli and staphylococcus aureus are selected as research objects. Through tests, the antibacterial rate of the citric acid, threonine, leucine and aspartic acid carbon quantum dots on escherichia coli and staphylococcus aureus is about 8-15% and 12-20%.
Example 1
2g of lysine was placed in a beaker and subsequently transferred to a drying oven, the heating temperature was set at 210℃and the heating time was 2h. After the reaction is finished, adding 30mL of deionized water into a beaker, stirring for 10min, performing ultrasonic treatment for 10min, filtering and centrifuging the obtained aqueous solution, wherein the rotating speed in the centrifuging process is 10000r/min, and then performing dialysis treatment, wherein the molecular weight of a dialysis bag is 2KD. Finally, the dialyzate is placed into a vacuum drying oven for drying treatment, the temperature is 60 ℃, and the lysine-based carbon quantum dot corrosion inhibitor is obtained, and the infrared characterization of the corrosion inhibitor is shown in figure 7. Subsequently, a certain amount of lysine-based carbon quantum dots was added to 1M HCl solution to prepare a corrosion inhibitor solution having a concentration of 25, 50, 100, 200 mg/L. The electrode prepared in comparative example 1 was placed in the above solution for electrochemical measurement, and the electrochemical impedance spectra obtained finally are shown in fig. 8a to 8 b. The antibacterial experiment shows that the antibacterial rate of the lysine-based carbon quantum dot to escherichia coli and staphylococcus aureus is about 81% and 90%.
Example 2
2g of lysine was placed in a beaker and subsequently transferred to a drying oven, the heating temperature was set at 200℃and the heating time was 2h. After the reaction is finished, adding 30mL of deionized water into a beaker, stirring for 10min, performing ultrasonic treatment for 10min, filtering and centrifuging the obtained aqueous solution, wherein the rotating speed in the centrifuging process is 10000r/min, and then performing dialysis treatment, wherein the molecular weight of a dialysis bag is 2KD. And finally, placing the dialyzate into a vacuum drying oven for drying treatment at the temperature of 60 ℃ to obtain the lysine-based carbon quantum dot corrosion inhibitor. Subsequently, a certain amount of lysine-based carbon quantum dots was added to 1M HCl solution to prepare a corrosion inhibitor solution having a concentration of 25, 50, 100, 200 mg/L. The electrode prepared in comparative example 1 was placed in the above solution for electrochemical measurement, and the resulting polarization curve and corrosion current density are shown in fig. 9a to 9 b. Meanwhile, the corrosion rate of the matrix after soaking was calculated and analyzed by a weightlessness method, and the result is shown in fig. 10. The antibacterial experiments show that the antibacterial rate of the lysine-based carbon quantum dots to escherichia coli and staphylococcus aureus is about 78% and 86%.
Example 3
2g of lysine was placed in a beaker and subsequently transferred to a drying oven, the heating temperature was set at 210℃and the heating time was 2h. After the reaction is finished, adding 30mL of deionized water into a beaker, stirring for 10min, performing ultrasonic treatment for 10min, filtering and centrifuging the obtained aqueous solution, wherein the rotating speed in the centrifuging process is 10000r/min, and then performing dialysis treatment, wherein the molecular weight of a dialysis bag is 2KD. And finally, placing the dialyzate into a vacuum drying oven for drying treatment at the temperature of 60 ℃ to obtain the lysine-based carbon quantum dot corrosion inhibitor. Subsequently, a certain amount of lysine-based carbon quantum dots was added to a 3.5% NaCl solution to prepare a corrosion inhibitor solution having a concentration of 25, 50, 100, 200 mg/L. The electrode prepared in comparative example 1 was placed in the above solution to perform electrochemical measurement, and the electrochemical impedance spectra finally obtained are shown in fig. 11a to 11 b. The antibacterial experiment shows that the antibacterial rate of the lysine-based carbon quantum dot to escherichia coli and staphylococcus aureus is about 80% and 89%.
Example 4
2g of lysine was placed in a beaker and subsequently transferred to a drying oven, the heating temperature was set at 200℃and the heating time was 2h. After the reaction is finished, adding 30mL of deionized water into a beaker, stirring for 10min, performing ultrasonic treatment for 10min, filtering and centrifuging the obtained aqueous solution, wherein the rotating speed in the centrifuging process is 10000r/min, and then performing dialysis treatment, wherein the molecular weight of a dialysis bag is 2KD. And finally, placing the dialyzate into a vacuum drying oven for drying treatment at the temperature of 60 ℃ to obtain the lysine-based carbon quantum dot corrosion inhibitor. Subsequently, a certain amount of lysine-based carbon quantum dots was added to a 3.5% NaCl solution to prepare a corrosion inhibitor solution having a concentration of 25, 50, 100, 200 mg/L. The electrode prepared in comparative example 1 was placed in the above solution for electrochemical measurement, and the resulting polarization curve and corrosion current density are shown in fig. 12a to 12 b. Meanwhile, the corrosion rate of the matrix after soaking was calculated and analyzed by a weightlessness method, and the result is shown in fig. 13. The antibacterial experiment shows that the antibacterial rate of the lysine-based carbon quantum dot to escherichia coli and staphylococcus aureus is about 81% and 90%.
Example 5
2g of lysine were placed in a beaker and subsequently transferred to a drying oven, the heating temperature being set at 210℃and the heating time being 2.5h. After the reaction is finished, adding 30mL of deionized water into a beaker, stirring for 10min, performing ultrasonic treatment for 10min, filtering and centrifuging the obtained aqueous solution, wherein the rotating speed in the centrifuging process is 10000r/min, and then performing dialysis treatment, wherein the molecular weight of a dialysis bag is 2KD. And finally, placing the dialyzate into a vacuum drying oven for drying treatment at the temperature of 60 ℃ to obtain the lysine-based carbon quantum dot corrosion inhibitor. Subsequently, a certain amount of lysine-based carbon quantum dots was added to 1M HCl solution to prepare a corrosion inhibitor solution having a concentration of 25, 50, 100 mg/L. The electrode prepared in comparative example 1 was placed in the above solution for electrochemical measurement, and the electrochemical impedance spectra obtained finally are shown in fig. 14a to 14 b. The antibacterial experiments show that the antibacterial rate of the lysine-based carbon quantum dots to escherichia coli and staphylococcus aureus is about 75% and 87%.
Example 6
2g of lysine was placed in a beaker and subsequently transferred to a drying oven, the heating temperature was set at 180℃and the heating time was 2h. After the reaction is finished, adding 30mL of deionized water into a beaker, stirring for 10min, performing ultrasonic treatment for 10min, filtering and centrifuging the obtained aqueous solution, wherein the rotating speed in the centrifuging process is 10000r/min, and then performing dialysis treatment, wherein the molecular weight of a dialysis bag is 2KD. And finally, placing the dialyzate into a vacuum drying oven for drying treatment at the temperature of 60 ℃ to obtain the lysine-based carbon quantum dot corrosion inhibitor. Subsequently, a certain amount of lysine-based carbon quantum dots was added to a 3.5% NaCl solution to prepare a corrosion inhibitor solution having a concentration of 25, 50, 100 mg/L. The electrode prepared in comparative example 1 was placed in the above solution for electrochemical measurement, and the electrochemical impedance spectra obtained finally are shown in fig. 15a to 15 b. The antibacterial experiments show that the antibacterial rate of the lysine-based carbon quantum dots to escherichia coli and staphylococcus aureus is about 77% and 86%.
Example 7
2g of lysine was placed in a beaker and subsequently transferred to a drying oven, the heating temperature was set at 150℃and the heating time was 3h. After the reaction is finished, adding 30mL of deionized water into a beaker, stirring for 20min, performing ultrasonic treatment for 15min, filtering and centrifuging the obtained aqueous solution, wherein the rotating speed in the centrifuging process is 8000r/min, and then performing dialysis treatment, wherein the molecular weight of a dialysis bag is 1KD. And finally, placing the dialyzate into a vacuum drying oven for drying treatment at the temperature of 80 ℃ to obtain the lysine-based carbon quantum dot corrosion inhibitor. Subsequently, a certain amount of lysine-based carbon quantum dots was added to 1M HCl solution to prepare a corrosion inhibitor solution having a concentration of 25, 50, 100 mg/L. The electrode prepared in comparative example 1 was placed in the above solution for electrochemical measurement, and the resulting electrochemical impedance spectra are shown in fig. 16a to 16 b. The antibacterial experiments show that the antibacterial rate of the lysine-based carbon quantum dots to escherichia coli and staphylococcus aureus is about 79% and 85%.
Example 8
2g of lysine was placed in a beaker and subsequently transferred to a drying oven, the heating temperature was set at 250℃and the heating time was 1h. After the reaction is finished, adding 30mL of deionized water into a beaker, stirring for 15min, performing ultrasonic treatment for 20min, filtering and centrifuging the obtained aqueous solution, wherein the rotating speed in the centrifuging process is 10000r/min, and then performing dialysis treatment, wherein the molecular weight of a dialysis bag is 3KD. And finally, placing the dialyzate into a vacuum drying oven for drying treatment at the temperature of 90 ℃ to obtain the lysine-based carbon quantum dot corrosion inhibitor. Subsequently, a certain amount of lysine-based carbon quantum dots was added to 1M HCl solution to prepare a corrosion inhibitor solution having a concentration of 25, 50, 100 mg/L. The electrode prepared in comparative example 1 was placed in the above solution to perform electrochemical measurement, and the electrochemical impedance spectra finally obtained are shown in fig. 17a to 17 b. The antibacterial experiments show that the antibacterial rate of the lysine-based carbon quantum dots to escherichia coli and staphylococcus aureus is about 80% and 84%.
The lysine-based carbon quantum dot corrosion inhibitors prepared in comparative example 1, example 2 and example 5 are used for characterizing the electrochemical behavior of carbon steel in an HCl environment, carbon steel is soaked in 1M HCl solutions with different corrosion inhibitor concentrations, and after soaking for 24 hours, an AC impedance spectrum and a polarization curve are monitored by using a Shanghai Chenhua CHI660E electrochemical workstation. As shown in FIGS. 2 a-2 b, the resistance of carbon steel after 24h of soaking in 1M HCl solution was 70 Ω cm 2 . As shown in FIGS. 8 a-8 b, after adding 25, 50, 100 and 200mg/L carbon quantum dot corrosion inhibitor, the impedance of the carbon steel is 160, 580, 750 and 1200 Ω cm in sequence 2 Compared with the low-frequency impedance modulus of the carbon steel before the corrosion inhibitor is added, the low-frequency impedance modulus of the carbon steel is sequentially improved by 2.3 times, 8.3 times, 10.7 times and 17.1 times. As shown in FIGS. 14 a-14 b, after adding 25, 50 and 100mg/L carbon quantum dot corrosion inhibitor, the impedance of the carbon steel is 380, 760 and 1000 Ω cm in sequence along with the extension of the heating time 2 To a certain degree as compared to example 1. As shown in FIG. 3, the corrosion current density of carbon steel after 24 hours of soaking in 1M HCl solution is 3.1X10 -4 A cm 2 . As shown in fig. 9 a-9 b, compared with the corrosion inhibitor without the corrosion inhibitor, after the addition of 25, 50, 100 and 200mg/L carbon quantum dot corrosion inhibitor, the corrosion current density of the carbon steel is reduced by 6.6, 8.7, 14.5 and 21.1 times in turn, and the corresponding corrosion inhibition efficiency is 86.8%, 89.7%, 93.5 and 95.5%, which indicates that the corrosion inhibitor has excellent protection effect on the carbon steel in a 1M HCl environment. As shown in fig. 10, the corrosion rate of carbon steel after 24h immersion in 1M HCl solution was highest. As the corrosion inhibitor concentration increases, the corrosion rate of carbon steel drops dramatically, mainly because an effective adsorption film is formed on the surface of carbon steel, the nature of which is chemical and physical adsorption between lysine-based carbon quantum dots and the steel surface. Among them, chemisorption is mainly due to pyridine-like N and pyrrole-like N atoms. Due to the presence of lone pair electrons, they can easily fill unoccupied 3D orbitals outside the iron atomThen, chemical coordination bonds are formed between the hetero atoms and the steel matrix, and the metal active sites on the surface of the carbon steel are reduced. Meanwhile, the remaining graphite-like N atoms in the lysine-based carbon quantum dots can be gathered on the surface of the steel, so that an agglomeration effect is induced, and the exposure area (physical adsorption) of the carbon steel in a corrosive environment is reduced. The synergistic effect of the two behaviors enables the lysine-based carbon quantum dot to show excellent protective performance in corrosive media.
The lysine-based carbon quantum dot corrosion inhibitors prepared in comparative example 2, examples 3, 4 and 6 are used for characterizing the electrochemical behavior of carbon steel in a NaCl environment, the carbon steel is soaked in 3.5% NaCl solution with different corrosion inhibitor concentrations for 24 hours, and an AC impedance spectrum and a polarization curve are monitored by using a Shanghai Chen Hua CHI660E electrochemical workstation in the soaking process. As shown in FIGS. 4 a-4 b, the impedance of carbon steel after 24h immersion in 3.5% NaCl solution was 185 Ω cm 2 . As shown in FIGS. 11 a-11 b, after adding 25, 50, 100, 200mg/L carbon quantum dot corrosion inhibitor, the impedance of the carbon steel is 630, 1250, 1600, 1900 Ω cm in order 2 Compared with the low-frequency impedance modulus of the carbon steel before the corrosion inhibitor is added, the low-frequency impedance modulus of the carbon steel is improved by 3.4 times, 6.8 times, 8.6 times and 10.3 times in sequence. As shown in FIGS. 15 a-15 b, with the decrease of the heating temperature, after adding 25, 50 and 100mg/L carbon quantum dot corrosion inhibitor, the impedance of the carbon steel is 450, 1200 and 1550 Ω cm in turn 2 A slight drop was also observed compared to example 3. As shown in FIG. 5, the corrosion current density of carbon steel after 24 hours of soaking in 3.5% NaCl solution was 1.7X10 -4 A cm 2 . As shown in fig. 12 a-12 b, compared with the corrosion inhibitor without the corrosion inhibitor, after the addition of the carbon quantum dot corrosion inhibitor of 25, 50, 100 and 200mg/L, the corrosion current density of the carbon steel is reduced by 8.7 times, 16.3 times, 22.9 times and 24.8 times in sequence, and the corresponding corrosion inhibition efficiency is 89.7%, 94.2%, 95.8% and 96.2%, which shows that the corrosion inhibitor has excellent protection effect on the carbon steel in the environment of 3.5% of nacl. As shown in FIG. 13, the corrosion rate of carbon steel after 24h of immersion in 3.5% NaCl solution was highest. As the corrosion inhibitor concentration increases, the corrosion rate of the carbon steel decreases dramatically.
Comparative examples 1, examples 7, 8 lysine-based carbon quantum dot corrosion inhibitors were prepared to provide electrical contact to carbon steel in HCl environmentThe chemical behavior is characterized by immersing carbon steel in 1M HCl solutions with different corrosion inhibitor concentrations for 24 hours, and monitoring alternating current impedance spectrum by using Shanghai Chenhua CHI660E electrochemical workstation. As shown in FIGS. 2 a-2 b, the resistance of carbon steel after 24h of soaking in 1M HCl solution was 70 Ω cm 2 . As shown in FIGS. 16 a-16 b, after adding 25, 50 and 100mg/L carbon quantum dot corrosion inhibitor, the impedance of the carbon steel is 380, 740 and 1050 Ω cm in sequence 2 Compared with the blank environment, the low-frequency impedance modulus of the carbon steel is improved by 5.4 times, 10.6 times and 15 times in sequence. As shown in FIGS. 17 a-17 b, after adding 25, 50 and 100mg/L carbon quantum dot corrosion inhibitor, the impedance of the carbon steel is 370, 720 and 1000 Ω cm in sequence 2 Compared with the blank environment, the low-frequency impedance modulus of the carbon steel is sequentially improved by 5.3 times, 10.3 times and 14.3 times.
The carbon quantum dot corrosion inhibitor prepared in comparative example 3 and example 1 is used for characterizing the electrochemical behavior of carbon steel in an HCl environment, carbon steel is soaked in 1M HCl solution at the concentration of 200mg/L for 24 hours, and an AC impedance spectrum is monitored by using a Shanghai Chenhua CHI660E electrochemical workstation in the soaking process. As shown in FIGS. 6 a-6 b, after 200mg/L of citric acid, threonine, leucine and aspartic acid carbon quantum dot corrosion inhibitor is added, the impedance of the carbon steel is 130, 210, 270 and 330 Ω cm in sequence 2 . After 200mg/L of lysine-based carbon quantum dot corrosion inhibitor is added, as shown in fig. 8 a-8 b, the impedance of the carbon steel is about 1200 Ω cm 2 Compared with the carbon quantum dots of citric acid, threonine, leucine and aspartic acid, the carbon quantum dots are respectively improved by 9.2 times, 5.7 times, 4.4 times and 3.6 times, which shows that the lysine-based carbon quantum dots have better protection effect compared with other amino acid-based carbon quantum dots. The antibacterial performance is compared, and the antibacterial rate of the lysine-based carbon quantum dot to escherichia coli and staphylococcus aureus is 4-6 times that of other amino acid-based carbon quantum dots.
In addition, the inventors have conducted experiments with other materials, process operations, and process conditions as described in this specification with reference to the foregoing examples, and have all obtained desirable results.
It should be understood that the technical solution of the present invention is not limited to the above specific embodiments, and all technical modifications made according to the technical solution of the present invention without departing from the spirit of the present invention and the scope of the claims are within the scope of the present invention.

Claims (10)

1. A lysine-based carbon quantum dot corrosion inhibitor is characterized in that: the lysine-based carbon quantum dot corrosion inhibitor is obtained by cracking lysine at a high temperature of 150-250 ℃ for 1-3 hours, and comprises an aromatic heterocyclic structure formed by C, H, O, N, wherein N exists in the form of pyridine-like nitrogen, pyrrole-like nitrogen or graphite-like nitrogen, and the size of the lysine-based carbon quantum dot corrosion inhibitor is 5-20 nm.
2. The lysine-based carbon quantum dot corrosion inhibitor according to claim 1, wherein: the solubility of the lysine-based carbon quantum dot corrosion inhibitor in water is 5-500 mg/1mL of water.
3. The method for preparing the lysine-based carbon quantum dot corrosion inhibitor according to claim 1 or 2, which is characterized by comprising the following steps: and (3) carrying out high-temperature pyrolysis on lysine for 1-3 hours at the temperature of 150-250 ℃ to obtain the lysine-based carbon quantum dot corrosion inhibitor.
4. A production method according to claim 3, further comprising: and (3) dissolving, centrifuging, filtering, dialyzing and drying the lysine-based carbon quantum dot corrosion inhibitor.
5. The preparation method according to claim 4, characterized by comprising: and mixing the lysine-based carbon quantum dot corrosion inhibitor with water for stirring and carrying out ultrasonic treatment, wherein the stirring treatment time is 10-20 min, and the ultrasonic treatment time is 10-25 min.
6. The method of manufacturing according to claim 4, wherein: the rotational speed of the centrifugal treatment is 8000-15000 r/min.
7. The method of manufacturing according to claim 4, wherein: the molecular weight of a dialysis bag adopted in the dialysis treatment is 1 KD-3 KD.
8. The method of manufacturing according to claim 4, wherein: the temperature of the drying treatment is 60-90 ℃ and the time is 24-48 h.
9. Use of the lysine-based carbon quantum dot corrosion inhibitor according to claim 1 or 2 in the field of corrosion protection of metal substrate surfaces; the metal substrate comprises any one of carbon steel, copper, iron and alloy.
10. A method of protecting a surface of a metal substrate, comprising: immersing the surface of the metal substrate in the lysine-based carbon quantum dot corrosion inhibitor solution according to claim 1 or 2, thereby realizing protection of the metal substrate.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107385456A (en) * 2017-08-17 2017-11-24 中国科学院宁波材料技术与工程研究所 Environmentally friendly restrainer is applied with it
CN108728086A (en) * 2018-06-01 2018-11-02 陕西科技大学 A kind of method of simple synthesis green fluorescence carbon quantum dot
CN109763135A (en) * 2019-02-25 2019-05-17 华中科技大学 A kind of graphene oxide quantum dot and preparation method thereof and the application as corrosion inhibiter
CN111662243A (en) * 2020-05-28 2020-09-15 广州大学 Citric acid-based functionalized carbon dot corrosion inhibitor and preparation method and application thereof
CN113293380A (en) * 2021-05-10 2021-08-24 广州大学 Functionalized glucose-based carbon dot corrosion inhibitor and preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107385456A (en) * 2017-08-17 2017-11-24 中国科学院宁波材料技术与工程研究所 Environmentally friendly restrainer is applied with it
CN108728086A (en) * 2018-06-01 2018-11-02 陕西科技大学 A kind of method of simple synthesis green fluorescence carbon quantum dot
CN109763135A (en) * 2019-02-25 2019-05-17 华中科技大学 A kind of graphene oxide quantum dot and preparation method thereof and the application as corrosion inhibiter
CN111662243A (en) * 2020-05-28 2020-09-15 广州大学 Citric acid-based functionalized carbon dot corrosion inhibitor and preparation method and application thereof
CN113293380A (en) * 2021-05-10 2021-08-24 广州大学 Functionalized glucose-based carbon dot corrosion inhibitor and preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
N, S co-doped carbon dots as effective corrosion inhibitor for carbon steel in CO 2 -saturated 3.5% NaCl solution;Hongyu Cen et al.;Journal of the Taiwan Institute of Chemical Engineers;第99卷;第224-238页 *
氮掺杂对碳纳米颗粒缓蚀性能的影响;王晶等;中国腐蚀与防护学报;第42卷(第1期);第85-92页 *

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