CN115196620A - Method for preparing multi-nitrogen-doped wood macromolecular-based carbon quantum dots by using ethylenediamine and application - Google Patents
Method for preparing multi-nitrogen-doped wood macromolecular-based carbon quantum dots by using ethylenediamine and application Download PDFInfo
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Abstract
The invention discloses a method for preparing a multi-nitrogen doped wood macromolecular-based carbon quantum dot by using ethylenediamine and application thereof, relates to the field of nano material preparation, and aims to solve the problems that the utilization rate of biomass raw materials in nature is poor in the preparation of the carbon quantum dot, and the pi-pi of the aromatic ring of the prepared carbon quantum dot * The problem of poor electron transfer capability, the carbon quantum dot of the invention is prepared by the following steps: heating sodium carboxymethylcellulose and o-phenylenediamine to obtain a carbon dot solution; centrifuging to remove precipitate, and filtering with water phase filtering membrane; freezing with liquid nitrogen, and lyophilizing in a lyophilizer. The macromolecular raw material resources of the wood are rich and easily obtained, are almost everywhere visible, and are wood-basedThe preparation method of the carbon dots is simple, efficient, environment-friendly and low in cost, and the microbial power generation application of the wood-based carbon dots not only realizes the energy conversion and utilization of wood, but also is environment-friendly. The electron transfer capacity of the microorganism is improved, and the effects of promoting the activity of the microorganism and improving the metabolism of the microorganism are further realized.
Description
Technical Field
The invention belongs to the field of nano material preparation, and particularly relates to a method for preparing multi-nitrogen doped wood macromolecular-based carbon quantum dots by using ethylenediamine and application of the method.
Background
At present, carbon nano materials attract people to pay extensive attention due to excellent performance and wide application prospect, fluorescent carbon quantum dots have the specific electronic and optical characteristics of semiconductor quantum dots, and the synthetic raw materials are wide in source, low in toxicity and low in cost and are always hot spots for domestic and foreign research. With the research of carbon dots, more and more raw materials for preparing the carbon dots are available, and organic small molecules, polymer macromolecules, fruits and vegetables, food and the like can be used for preparing the carbon dots. There are also many methods for producing carbon dots, such as oxidation, hydrothermal synthesis, microwave synthesis, and the like. Biomass raw materials have been used to produce carbon dots with excellent properties due to their wide sources, non-toxicity, and renewable characteristics.
The carbon dot is a novel carbon-based quantum dot fluorescent material with fluorescence property, has the advantages of excellent photoluminescence effect, stable structure, low toxicity, good water solubility and easy synthesis, has the size of less than 10nm, and is widely applied to the fields of microbial detection and marking, biological imaging, photocatalysis, fluorescent ink and the like. At present, most of carbon dots are complex in preparation process and low in yield, and in order to further expand the application range of the carbon dots, non-metal doping or surface modification such as N, B, S is usually carried out on the carbon dots. The biomass resource is low in cost and environment-friendly, contains a large amount of organic matters, can effectively reduce the preparation cost of the carbon dots by using the biomass resource as a raw material, provides possibility for large-scale commercial application, and can form a large amount of oxygen-containing and nitrogen-containing functional groups in the carbonization process of the biomass material, thereby effectively improving the hydrophilic performance of the prepared carbon dots.
The preparation methods and methods for biomass carbon quantum dots are various, however, reports on the preparation of carbon nanospheres based on biomass materials are less, and the photo-thermal performance of the carbon nanospheres is less, and the previous research is usually about the optical performance of the carbon dots in a liquid state. The carbon dots have many excellent properties such as self-sintering property, chemical inertness, high packing density, excellent electrical and thermal conductivity and the like due to large surface area, and show good application potential in the fields of medicine and photoelectricity.
In recent years, natural and biological waste carbon nano materials have become a new field of green synthesis, and have wide economic application advantages. In the aspect of nano material synthesis, a carbon source can be obtained from natural biological resources, and the carbon nano material can be simply, economically and greenly synthesized. According to different experimental conditions, different types of carbon nano materials, such as porous carbon, carbon dots and the like, can be prepared from the biological waste. During the last few years, a great deal of research has been reported on the synthesis of carbon nanomaterials from biological waste, natural resources and waste materials.
With the continuous development of biomass materials, people have more and more researches on non-metal carriers. Among them, carbon element is widely present in nature as the most basic element constituting biomass, and research on carbon materials is increasing. Carbon has also received attention from researchers in the field of catalysis as a catalyst support. Cellulose, which is a substance having a large content in nature, serves as a precursor of a synthetic carbon material.
The design and synthesis of carbon dots has recently received much attention because of their widespread use in many areas of research, including energy storage and conversion, catalysis, water and air purification, and adsorption. These applications are attributed to the very unique properties of carbon spheres, such as tunable porous structure, controllable particle size, high surface area and controllable surface chemistry. In the existing reports, biomass-derived carbohydrate sources (such as glucose, fructose and sucrose) have been used for preparing carbon spheres, but the preparation of carbon spheres by using biomass such as cellulose, hemicellulose and the like as a carbon source is less reported.
Small molecular saccharides such as glucose, sucrose, fructose and the like are all easily soluble in water, and are common carbon sources for preparing hydrothermal carbon points and researching reaction mechanisms. Liu et al have studied the influence of different reaction conditions on the particle weight and physicochemical properties of the obtained hydrothermal carbon spheres in the hydrothermal carbonization process of glucose in detail. The morphology and chemical composition of the hydrothermal carbon spheres are greatly influenced by the reaction temperature, and when the temperature exceeds 230 ℃, the hydrophilic groups of the carbon spheres are obviously reduced, and the internal carbon structure is gradually converted from amorphous to graphitized.
Cellulose and starch are two natural high molecular carbohydrates with highest yield and most extensive distribution in nature. Among them, starch is the most common storage form of carbohydrate in plant cells, and is abundant in organs such as seeds, tubers and root tubers of most plants. Cellulose is a main component of plant cell walls, is a natural high molecular compound which is most abundant in the world and accounts for more than half of the carbon content of plant boundaries. The two types of carbohydrates which are more primitive and have stronger renewability are used as raw materials to prepare the carbon spheres, so that the method is more economical and more suitable for sustainable development. In addition to the starch and cellulose, high molecular carbohydrates such as cyclodextrin and chitosan can be synthesized into carbon spheres through a hydrothermal carbonization process.
Compared with carbohydrates which need to be prepared in advance, biomass raw materials in nature, such as wood, straws, various grains and the like, obviously have more advantages in cost and are generally regarded by researchers. The electron transfer of microorganisms plays an important role in microbial metabolism, and therefore, the improvement of the electron transfer capability of microorganisms contributes to the improvement of microbial metabolism and activity.
Disclosure of Invention
The invention aims to solve the problems that the utilization rate of biomass raw materials in nature is poor in the preparation of carbon quantum dots, and pi-pi of aromatic rings of the prepared carbon quantum dots * Poor electron transfer ability. The second purpose of the invention is to provide a method for applying the carbon quantum dots to microorganisms so as to improve the activity and the metabolic capability of the microorganisms.
The invention relates to a method for preparing multi-nitrogen doped wood macromolecular-based carbon quantum dots by using ethylenediamine, which is carried out according to the following steps:
step one, rough preparation of carbon dots:
adding lignosulfonate and ethylenediamine into the inner liner of the reaction kettle, adding deionized water, heating to 160-200 ℃, and reacting for 7-10 hours to obtain a carbon point primary product;
the mass volume ratio of the lignosulfonate to the ethylenediamine to the deionized water is 1g: 4-6 mL: 80-120 mL;
step two, purifying the carbon point crude product:
centrifuging the carbon point primary product, collecting supernatant, adding into a dialysis bag, and dialyzing with deionized water for 70-72 h; and (3) freezing by adopting liquid nitrogen, putting the frozen particles into a freeze dryer, and carrying out freeze-drying treatment to obtain the ethylenediamine multi-nitrogen doped wood macromolecular-based carbon quantum dots.
Further, the reaction is carried out for 8 hours under the temperature of heating to 180 ℃ in the step one, and a carbon point primary product is obtained.
Further, the centrifugation conditions of the carbon dot primary product in the step two are as follows: centrifugation was carried out at 10000rpm for 10min.
Further, the dialysis bag in the second step is an 800MD standard dialysis bag.
Further, the mass volume ratio of the lignosulfonate to the ethylenediamine to the deionized water is 1g: 5-6 mL: 80-100 mL.
The application of the multi-nitrogen-doped wood macromolecular-based carbon quantum dots prepared from ethylenediamine is used for promoting microbial activity and improving metabolic capability.
The invention has the following remarkable advantages:
the wood macromolecular raw material resources are rich and easily available and are almost visible everywhere, the preparation method of the wood-based carbon dots is simple, efficient, environment-friendly and low in cost, and the microbial power generation application of the wood-based carbon dots not only realizes the energy conversion and utilization of wood, but also is environment-friendly. The invention has important guiding significance for understanding the internal relation between the photoelectric physical property and the structure of the wood-based carbon dot by mastering the basic rule of carbon formation.
Preparation of carbon quantum dots by lignosulfonate and ethylenediamineCan obviously improve the pi-pi of the carbon point aromatic ring * The electron transfer improves the electron transfer capability of the microorganism, thereby realizing the functions of promoting the activity of the microorganism and improving the metabolism of the microorganism.
Drawings
FIG. 1 is a graph of steady state absorption spectrum and fluorescence spectrum of carbon quantum dots prepared in example 1; wherein A is 400nm, B is 380nm, C is 420nm, D is 360nm, E is 320nm, F is 440nm, G is 460nm, H is 300nm, I is 340nm;
FIG. 2 is a plot of carbon quantum dot Fourier transform infrared spectroscopy (FTIR) prepared in example 1, wherein A is CDs-1,B, CDs-2,C, CDs-3,D is lignosulfonate;
FIG. 3 is a carbon quantum dot X-ray electron spectroscopy (XPS) chart prepared in example 1;
FIG. 4 is an XPS survey scan of the carbon quantum dots L-CDs prepared in example 1;
FIG. 5 is a DC voltage test curve of carbon quantum dots promoting the electron transfer in the microbial cell.
Detailed Description
For the purpose of promoting a clear understanding of the objects, aspects and advantages of the embodiments of the invention, reference will now be made in detail to the embodiments of the present disclosure, and it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the disclosure.
The exemplary embodiments and descriptions of the present invention are provided to explain the present invention and should not be interpreted as limiting the present invention.
Example 1
The preparation method of the multi-nitrogen-doped wood macromolecular-based carbon quantum dot comprises the following steps:
this example uses a controlled variable method to change the fluorescence color of a carbon dot by changing the volume of ethylenediamine. The volumes of the three groups of experimental ethylenediamine are 0 muL, 100 muL and 1000 muL respectively.
1. The method comprises the following specific steps:
firstly weighing 0.2g of sodium lignosulfonate, adding ethylenediamine with different volumes, adding 20ml of deionized water, uniformly stirring, pouring into a prepared hydrothermal reaction kettle, putting the reaction kettle into an oven, setting the temperature to be 180 ℃, starting timing when the temperature rises to 180 ℃, closing the oven after reacting for 8 hours, naturally cooling the reaction kettle, taking out the reaction kettle after cooling, pouring into a centrifugal tube, putting the centrifugal tube into a high-speed centrifuge, setting the rotating speed to be 10000rpm, centrifuging for 10min, taking out the centrifugal tube after centrifuging is finished, removing sediment, then adding into a dialysis bag with the treated 800MD specification, and dialyzing for 72 hours by using the deionized water. Freezing with liquid nitrogen, and freeze-drying in a freeze-dryer for 48h.
And (3) putting the prepared carbon dot liquid sample into a vacuum drying oven for drying to obtain a carbon dot solid, scraping the solid sample from a sample bottle, grinding the solid sample to Cheng Fenmo, putting the solid sample into a small centrifuge tube, sealing the centrifuge tube by using a sealing film, and storing the centrifuge tube for later use.
2. Characterization of carbon quantum dots
1. Ultraviolet-visible absorption spectroscopy (UV-vis) and fluorescence spectroscopy measurements
The UV-Vis spectrum is a spectrum generated by orbital transition of valence electrons in molecules at different energies, and is an important characterization method for researching the absorption spectrum of the molecules in an article in an ultraviolet-visible light interval (200-800 nm). Basic operation: opening the instrument, opening the software, connecting the instrument and the computer, drawing a spectrum base line by using deionized water, and then putting into dilute solution for scanning, wherein the scanning range is 360-800 nm. The carbon quantum dots of example 1 were examined in this way.
When some atoms are irradiated with light, electrons around the atomic nucleus absorb energy emitted from the light and then transit from a ground state to an excited state by the transition of an electron orbit, but are transited from the excited state to the ground state due to instability of the excited state, and when the electrons return from the excited state to the ground state, the released energy is expressed in the form of light, thereby generating fluorescence. The liquid sample containing the carbon quantum dots of example 1 was taken out of the sample bottle and diluted 500-fold for use. And opening the instrument and corresponding software for preheating, and starting to scan the sample after setting parameters to obtain a corresponding fluorescence spectrum.
The results are shown in FIG. 1 byTwo obvious peaks can be seen in the ultraviolet visible light spectrum, wherein one carbon point has an obvious strong peak at 220nm and is a characteristic absorption peak of the carbon point, and the reason why the peak appears is that aromatic sp in the carbon point is generally aromatic sp 2 The pi-pi + bond transition of the structure. An absorption peak also appears near 280nm, where the absorption peak is mainly due to n-pi x transitions.
In order to examine the fluorescence characteristics of the carbon quantum dots of example 1, corresponding fluorescence spectra were prepared with excitation wavelengths from 300nm to 460nm. As can be seen from FIG. 1, the emission peak of the fluorescence spectrum starts to be red-shifted, the optimum excitation wavelength is 400nm, and the peak of the strongest intensity is at 470 nm. The carbon dots have a blue-green fluorescent color.
2. Fourier Transform Infrared Spectroscopy (FT-IR)
The principle of Fourier Infrared Spectroscopy (FTIR-650) is due to the chemical bonds that make up organic compounds and the atoms in the clusters of tubes are always in a vibrational state. Furthermore, the vibration frequencies of atoms in the functional group and the chemical bond are substantially the same as the infrared light frequency, so when organic molecules are irradiated, the infrared light is absorbed by the vibrating atoms due to the vibration of the chemical bond and the functional group atoms, the absorption frequencies of different organic molecules are greatly different due to the difference between the functional group and the chemical bond, and the positions on the infrared spectrum are not the same, and the functional group and the chemical bond of the organic molecule can be determined through the absorption peak on the infrared spectrum. The carbon quantum dot powder of example 1 was put into a grinding tool and pressed into small pieces, and then infrared spectroscopy was performed after setting parameters.
The Fourier infrared spectrum of the carbon quantum dots of example 1 is shown in FIG. 2, where CDs-1 is the carbon dots produced by hydrothermal synthesis without adding ethylenediamine to sodium lignosulfonate, and is shown at 1631cm -1 The characteristic absorption peak of phenylpropyl alkyl skeleton specific to lignin is 1176cm -1 The absorption peak caused by the C-O is observed at 630cm -1 Is equivalent to C-H, which causes the absorption peak to appear.
0.1ml and 1ml of ethylenediamine were added to CDs-2 and CDs-3, respectively, and the reagents were the same, so thatThe IR spectra of the two samples were similar at 3300cm -1 The small absorption peak at (A) is caused by stretching vibration of-OH at 2956cm -1 And 1360cm -1 The absorption peak is caused by the C-H stretching vibration and bending vibration of methyl and methylene, the absorption peak is formed at 1867cm-1 due to the C = O stretching vibration of the esterphenolic acid, and the absorption peak is formed at 1675cm -1 The absorption peak is 1463cm because of C = N stretching vibration -1 The absorption peak of (1) is that C-O is deformed and vibrated to generate an absorption peak at 1256cm -1 And (b) an absorption peak appears due to ester bond conjugate C = O stretching vibration in lignin. The analysis of infrared spectrum shows that the carbon point contains hydrophilic groups such as hydroxyl and carboxyl, and therefore, the carbon point is inferred to have good water solubility.
Visible at 1621cm by infrared spectrum -1 The characteristic absorption peak of the phenylpropyl alkyl skeleton which is specific to lignin and has the same carbon point with the preparation place is contained in the position, and is 1136cm -1 The absorption peak at (b) is due to ester bond conjugation C = O in lignin occurring by stretching vibration.
3. X-ray photoelectron Spectroscopy (XPS)
When a beam of light irradiates the surface of the sample, electrons on one of the atom orbitals escape from the nucleus after absorbing photons, and the atoms become ions due to the lack of electrons. The carbon quantum dots of example 1 were determined using AlK α X-ray excitation.
In order to identify the elements contained in the carbon quantum dots of example 1, the carbon dots produced by the analysis of the X-ray photoelectron spectroscopy contain C and O elements as shown in fig. 3. Doping with the N element can be observed on the X-ray photoelectron spectrum after addition of ethylenediamine.
Analysis of the binding energy of the carbon dots by XPS gave:
to further explore the surface elements of L-CDs, they were characterized using XPS. FIG. 4 shows XPS survey of L-CDs, which shows the existence of C (1S), O (1S), N (1S) and S (2 p) in the survey spectrum, and the main component elements of L-CDs are C, O, N, S. From the results of XPS elemental composition measurements, it was found that C, O, N, S has high carbon contents of 78.16%, 19.84%, 0.66%, 0.78% in the elemental ratios, respectively, indicating that the dealkalized lignin was reduced in a high temperature environment and a part of the oxygen-containing groups were removed.
FIG. 3.a is a spectrogram of C1s that can be fit decomposed into two peaks with binding energies at 284.74eV and 286.18eV, corresponding to C = C/C-C bond and C-O bond, respectively. XPS allowed semi-quantitative analysis, with a peak area ratio of C = C/C-C to C-O of about 2.2, indicating that the content of C = C/C-C structures occupies a substantial portion of the chemical bonds in L-CDs, and that the majority of C = C bonds are primarily due to the contribution of aromatic ring conjugated structures, consistent with the structural features of lignin.
Fig. 3.b is a histogram of O1s, which can be decomposed into 2 peaks, resulting in two peaks with binding energies at 531.9eV, 533.34eV, corresponding to C = O bond and C-O bond, respectively, with a peak area ratio of C = O to C-O of 1.
5. Carbon quantum dot for promoting microbial extracellular electron transfer
The carbon quantum dot of example 1 was subjected to a microorganism-promoted extracellular electron transfer test using a microbial fuel cell in which the anode was a sodium lactate PBS solution (1.49 g/L sodium lactate, 50mM PBS solution), the cathode was potassium ferricyanide PBS solution (50 mM potassium ferricyanide solution, 50mM PBS solution), and a cation exchange membrane was interposed between the anode and cathode; the cathode and anode are externally connected with a 1000 omega resistor, and a direct current voltmeter is used for testing the voltage at the two ends of the battery.
As shown in FIG. 5, the voltage across the microbial fuel cell is the capability of transferring electrons from the outside of the microbial cells, and the comparison and observation of the two experiments show that the voltage across the cell of the experimental group with carbon dots added (the amount of the carbon dots added is 100 μ g/mL) is higher, and the voltage of the cell of the experimental group is reduced earlier and faster, so that the carbon dots added can be obtained to facilitate the transfer of electrons from the outside of the microbial cells.
Claims (7)
1. A method for preparing multi-nitrogen doped wood macromolecular-based carbon quantum dots by using ethylenediamine is characterized by comprising the following steps:
step one, rough preparation of carbon dots:
adding lignosulfonate and ethylenediamine into the inner liner of the reaction kettle, adding deionized water, heating to 160-200 ℃, and reacting for 7-10 hours to obtain a carbon point primary product;
the mass volume ratio of the lignosulfonate to the ethylenediamine to the deionized water is 1g: 4-6 mL: 80-120 mL;
step two, purifying the carbon point crude product:
centrifuging the carbon point primary product, collecting supernatant, adding into a dialysis bag, and dialyzing with deionized water for 70-72 h; and (3) freezing by adopting liquid nitrogen, putting the frozen particles into a freeze dryer, and carrying out freeze-drying treatment to obtain the ethylenediamine multi-nitrogen doped wood macromolecular-based carbon quantum dots.
2. The method for preparing multi-nitrogen-doped wood macromolecular-based carbon quantum dots by using ethylenediamine as claimed in claim 1, characterized in that the reaction is carried out for 8 hours at the temperature of 180 ℃ in the step one to obtain a carbon dot primary product.
3. The method for preparing the multi-nitrogen-doped wood macromolecular-based carbon quantum dot by using the ethylenediamine as claimed in claim 1, wherein the centrifugation conditions of the carbon dot primary product in the second step are as follows: centrifugation was carried out at 10000rpm for 10min.
4. The method for preparing the multi-nitrogen-doped wood macromolecular-based carbon quantum dots by using the ethylenediamine as claimed in claim 1, wherein the dialysis bag in the second step is an 800MD dialysis bag.
5. The method for preparing the multi-nitrogen-doped wood macromolecular-based carbon quantum dot by using the ethylenediamine as claimed in claim 1, wherein the mass-to-volume ratio of the lignosulfonate to the ethylenediamine to the deionized water is 1g: 5-6 mL: 80-100 mL.
6. The use of ethylenediamine as in any of claims 1-5 for preparing nitrogen-rich wood macromolecular-based carbon quantum dots, wherein said nitrogen-rich wood macromolecular-based carbon quantum dots are used for promoting microbial activity and improving metabolic capability.
7. The application of the ethylenediamine for preparing the multi-nitrogen-doped wood macromolecular-based carbon quantum dot according to claim 6, wherein the application amount of the carbon quantum dot is 25-100 μ g/mL.
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