CN114887641A - Single-atom catalyst with nitrogen-doped lignin carbon dots as carrier and application thereof - Google Patents
Single-atom catalyst with nitrogen-doped lignin carbon dots as carrier and application thereof Download PDFInfo
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- CN114887641A CN114887641A CN202210490097.3A CN202210490097A CN114887641A CN 114887641 A CN114887641 A CN 114887641A CN 202210490097 A CN202210490097 A CN 202210490097A CN 114887641 A CN114887641 A CN 114887641A
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- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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Abstract
The invention discloses a single-atom catalyst taking nitrogen-doped lignin carbon dots as a carrier and application thereof, wherein the catalyst comprises the lignin carbon dots and noble metal atoms in a limited range. The method specifically comprises the following steps: preparing nitrogen-doped lignin carbon points by using a hydrothermal method by taking lignin as a carbon source and taking a nitrogen-containing reagent as a doping agent and a passivating agent; the supported metal monoatomic catalyst is prepared by a simple liquid phase method, and the metal monoatomic support is 0.01-10.00 wt% based on the total mass of the catalyst. The nitrogen-doped lignin carbon dots and the metal monoatomic catalyst thereof prepared by the invention have the characteristics of regular appearance, uniform particle size, excellent photoelectric corresponding performance and the like; meanwhile, the monatomic catalyst shows good photocatalytic hydrogen production activity and stability in the photocatalytic hydrogen production process.
Description
Technical Field
The invention belongs to the field of nano materials and catalysis, and particularly relates to a preparation method and application of a single-atom catalyst taking nitrogen-doped lignin carbon dots as a carrier.
Background
Carbon Dots (CDs), also called Carbon quantum dots or Carbon nanodots, are a class of Carbon-based zero-dimensional materials with the size within 10 nm, have the characteristics of unique optical performance, good water solubility, high stability, low toxicity, excellent biocompatibility, low environmental impact and the like, and are considered to be a novel fluorescent Carbon material with great application prospect. In 2004, Xu et al discovered the carbon quantum dots capable of emitting weak fluorescence for the first time in the process of electrophoretic purification of single-walled carbon nanotubes, and thus the research on carbon dots has attracted the attention of scholars at home and abroad, and in recent years, the research heat tide of synthesizing carbon dots by using natural substances as carbon sources has been raised.
The lignin is an aromatic natural high molecular compound with the content second to that of cellulose, has the advantages of large reserves, wide sources, no toxicity, low price, easy decomposition, higher carbon content and rich aromatic structures, and is an excellent carbon source for preparing carbon dots. How to utilize lignin resources with high efficiency and high value has important significance for relieving environmental pressure, developing low-carbon economy, optimizing related industrial structures, promoting economic sustainable development and the like, and is one of important subjects which need to be overcome urgently. Patent CN202110229688.0 discloses a modified lignin carbon dot and a preparation method and application thereof, wherein lignin, water and a silane coupling agent are subjected to hydrothermal reaction to obtain the modified lignin carbon dot which is used as the heat resistance, oxidation resistance and scratch resistance of a polypropylene composite material, but the addition of the silane coupling agent can greatly change the chemical environment of the surface of the carbon dot and inhibit the application of the carbon dot in the field of catalysis.
The monatomic catalysis, i.e. the active metal is loaded on the surface of the carrier in the form of a single atom and is mainly connected to the surface of the carrier in a bonding way with a hetero atom, and the coordination environment of the metal atom may not be completely consistent. Monatomic catalysis is also single-site catalysis when the coordination environment of each monodisperse active metal atom is completely identical. The monatomic catalyst does not mean that a single zero-valent metal atom is an active center, the monatomic atom also has coordination effects such as electron transfer and the like with other atoms of the carrier, and often has certain charge property, and the synergistic effect of the metal atom and peripheral coordination atoms is a main reason of high activity of the catalyst. Monatomic catalysts with unique geometry and electronic properties, and maximum atomic utilization, have been shown to not only greatly increase the catalytic active sites, but also ensure the inherent activity of each individual active site. However, the atomically dispersed metals tend to migrate and aggregate, which severely hampers the development of monatomic catalysts. Therefore, the selection of a proper single metal atom catalyst carrier is very important, which has great significance to the preparation and application research of the catalytic material on the atomic level.
Disclosure of Invention
The invention aims to provide a preparation method and application of a single-atom catalyst taking nitrogen-doped lignin carbon dots as a carrier.
In order to achieve the purpose, the invention adopts the following technical scheme: the method comprises the steps of preparing nitrogen-doped lignin carbon dots by utilizing a hydrothermal reaction of lignin, a nitrogen-containing reagent and hydrogen peroxide, and preparing a supported metal monatomic catalyst by a simple liquid phase method. The method specifically comprises the following steps: mixing lignin, a nitrogen-containing reagent and hydrogen peroxide according to a mass ratio of 1: (1-10): (5-50) dispersing in deionized water to prepare a uniform solution, transferring the uniform solution into a high-pressure reaction kettle, and heating to 100-220 ℃ for hydrothermal reaction for 4-48 hours; cooling to room temperature, performing centrifugal separation on the hydrothermal product, collecting supernatant, and performing dialysis and purification treatment by using a filter membrane to obtain a nitrogen-doped lignin carbon dot solution; and (2) dropwise adding a metal inorganic salt solution into the nitrogen-doped lignin carbon dot solution, and stirring to obtain the nitrogen-doped lignin carbon dot-supported monatomic catalyst, wherein the metal monatomic loading is 0.01-10.00 wt% based on the total mass of the catalyst.
Preferably, the lignin carbon source may be one or more of common lignin such as enzymatic lignin, alkali lignin, lignosulfonate, kraft lignin, organic lignin, etc. The nitrogen-containing reagent comprises one or more of ethylenediamine, propylenediamine, polyethyleneimine and urea. The mass ratio of the lignin, the nitrogen-containing reagent and the hydrogen peroxide is 1: (1-10): (5-20).
Preferably, the technological parameter of the hydrothermal reaction is that the reaction is carried out for 4-48 hours in the hydrothermal reaction at the temperature of 100-220 ℃.
Preferably, the metal atom precursor can be one or more of metal inorganic salts such as Pt, Pd, Au, Ru, Cu, Fe, Co, Ni, Mn and the like, and the loading amount of metal single atoms is 0.01-10.00 wt% based on the total weight of the catalyst.
The application comprises the following steps: the application of the monatomic catalyst taking the nitrogen-doped lignin carbon dots as the carrier in photocatalytic hydrogen production.
The invention has the beneficial effects that: the invention 1) prepares carbon dots by using natural renewable lignin as a main raw material, the used lignin can be derived from papermaking black liquor, and the method has important significance for protecting the environment and realizing the double-carbon target; 2) compared with other biomass carbon sources, the lignin macromolecules not only have rich aromatic structures and higher carbon content, but also contain endogenous heteroatoms and rich functional groups, so that the carbon quantum dots which are high in graphitization degree and doped and modified by specific elements are easy to synthesize; 3) the preparation method has the advantages of simple and convenient operation, low raw material cost, environmental friendliness, no need of large-scale precise instruments, capability of amplifying the yield, good repeatability and the like. 4) The prepared nitrogen-doped woodThe plain carbon dots and the metal monatomic catalyst thereof have the characteristics of regular appearance, uniform particle size, good stability, excellent photoelectric corresponding performance and the like; 5) the material utilizes active sites rich on the surface of nitrogen-doped carbon dots to form pyridine nitrogen in the carbon dots, and Me-N can be formed between the pyridine nitrogen and noble metal atoms 4 The coordination function (Me represents metal atom) anchors the metal monoatomic atom, and an effective solution is provided for the problems of atom migration and agglomeration of the metal monoatomic catalyst in the preparation and application processes; 6) the material fully utilizes the advantages of metal monatomic site catalysis, shows excellent catalytic activity and structural stability, and has extremely high research value and industrial application prospect.
Drawings
Fig. 1 is an ultraviolet-visible absorption spectrum and a fluorescence spectrum of a nitrogen-doped lignin carbon dot solution, inset: pure water is arranged at the upper left, carbon dot solution is arranged at the upper right, and ultraviolet light with the wavelength of 254nm is arranged at the lower left and ultraviolet light with the wavelength of 365nm is arranged at the lower right.
FIG. 2 is a Transmission Electron Microscope (TEM) photograph and a particle size distribution chart of nitrogen-doped lignin carbon dots.
Fig. 3 is a raman spectrum of nitrogen-doped lignin carbon dots.
FIG. 4 is a Transmission Electron Microscope (TEM) photograph of a nitrogen-doped lignin carbon dot-Pt monatomic catalyst (2.63 wt%).
Figure 5 is a spherical aberration corrected high angle annular dark field image of a nitrogen doped lignin carbon dot-Pt monatomic catalyst.
Figure 6 is a spherical aberration corrected high angle annular dark field image of an undoped lignin carbon dot-Pt monatomic catalyst.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and examples. It is also to be understood that the following examples are intended to illustrate the present invention and are not to be construed as limiting the scope of the invention, and that the particular materials, reaction times and temperatures, process parameters, etc. listed in the examples are exemplary only and are intended to be exemplary of suitable ranges, and that insubstantial modifications and adaptations of the invention by those skilled in the art in light of the foregoing description are intended to be within the scope of the invention.
In the present invention, the production method is a conventional method unless otherwise specified, and the raw materials used are commercially available from public or produced according to the prior art without specifically specified, and the percentages are mass percentages without specifically specified.
Example 1: preparation of nitrogen-doped lignin carbon dots
Ultrasonically dispersing 1 g of alkali lignin and 4 g of ethylenediamine into 100mL of deionized water, and then dripping 10mL of 30wt% hydrogen peroxide to prepare a uniform mixed solution; transferring the solution into a hydrothermal reaction kettle, and reacting for 12 hours at 190 ℃; after the hydrothermal kettle is cooled to room temperature, carrying out centrifugal separation (9000 rpm for 10 min) on the obtained hydrothermal product to remove insoluble substances and large particles to obtain a clear solution, and carrying out dialysis purification by using a dialysis bag with the molecular weight cutoff of 3000 Da to obtain a lignin carbon dot solution with the nitrogen atom doping concentration of about 9wt%, wherein the concentration is about 28.6 mg/mL. The carbon spot spectrum was measured with an ultraviolet-visible spectrophotometer and a fluorescence spectrophotometer, as shown in fig. 1, and as can be seen from fig. 1, the optimum excitation wavelength was 400nm and the optimum emission wavelength was 475 nm. TEM representation is carried out on carbon dots, as shown in FIG. 2, the sizes of the carbon dots are mainly distributed between 1.5nm and 2.8nm, and obvious graphite carbon lattice fringes can be seen in the carbon dots. Meanwhile, the Raman spectrum analysis spectrogram is shown in FIG. 3, and the peak intensity ratio I of the D peak to the G peak in the spectrum D ：I G = 0.48, indicating a higher degree of graphitization of the synthesized carbon dots.
TABLE 1 Synthesis Process parameters for different carbon spots and fluorescence intensity data thereof
Table 1 lists and analyzes the synthesis process parameters of different carbon points and fluorescence intensity data thereof, and it can be seen that when the hydrothermal temperature is 190 ℃, the lignin: the mass ratio of the ethylenediamine is 1: 4, the hydrothermal time is 12 hours, and the fluorescence intensity of the prepared nitrogen-doped lignin carbon dot is strongest, so that the condition is used as the optimized preparation condition of the carbon dot used below.
Example 2: preparation of Pt monatomic catalyst with nitrogen-doped lignin carbon dots as carrier (load capacity of 2.63 wt%)
25mL of the nitrogen-doped lignin carbon dot solution (with the concentration of 28.6 mg/mL) in example 1 is taken, 5mL of chloroplatinic acid solution (with the concentration of about 10 mg/mL) is dropped, the mixture is vigorously stirred for 10min under the irradiation of visible light, and the platinum-based catalyst supported by the lignin carbon dots is obtained by freeze-drying, wherein the theoretical content of Pt atoms is about 2.63 wt%, and the actual loading amount of Pt measured by ICP-MS is about 1.64 wt%. TEM characterization of the monatomic catalyst was performed, and as shown in FIG. 4, it can be seen that the carbon dot size and morphology did not change after loading Pt atoms. And further characterizing the sample by using a spherical aberration correction TEM, wherein as shown in a dark field image of the sample in FIG. 5, Pt metal is mainly loaded on the surface of the carbon dot in a single atom form, and the particle size is about 0.1-0.2 nm.
Example 3: preparation of Pt monatomic catalyst with nitrogen-doped lignin carbon dots as carrier (load amount is 5.26 wt%)
25mL of the nitrogen-doped lignin carbon dot solution (with the concentration of 28.6 mg/mL) in example 1 is taken, 10mL of chloroplatinic acid solution (with the concentration of about 10 mg/mL) is dropped, the mixture is vigorously stirred for 10min under the irradiation of visible light, and the Pt monatomic catalyst supported by the lignin carbon dots is obtained through freeze-drying, wherein the theoretical content of Pt atoms is about 5.26 wt%.
Example 4: preparation of Pt monatomic catalyst with nitrogen-doped lignin carbon dots as carrier (load amount is 1.05 wt%)
25mL of the nitrogen-doped lignin carbon dot solution (with the concentration of 28.6 mg/mL) in example 1 is taken, 2 mL of chloroplatinic acid solution (with the concentration of about 10 mg/mL) is dropped, the mixture is vigorously stirred for 10min under the irradiation of visible light, and the Pt monatomic catalyst supported by the lignin carbon dots is obtained through freeze-drying, wherein the theoretical content of Pt atoms is about 1.05 wt%.
Example 5: preparation of Pt monatomic catalyst with nitrogen-doped lignin carbon dots as carrier (load amount is 0.53 wt%)
25mL of the nitrogen-doped lignin carbon dot solution (with the concentration of 28.6 mg/mL) in example 1 is taken, 1 mL of chloroplatinic acid solution (with the concentration of about 10 mg/mL) is dropped, the mixture is vigorously stirred for 10min under the irradiation of visible light, and the Pt monatomic catalyst supported by the lignin carbon dots is obtained through freeze-drying, wherein the theoretical content of Pt atoms is about 0.53 wt%.
Example 6: preparation of Cu monatomic catalyst with nitrogen-doped lignin carbon dots as carrier (2.63 wt% of load)
25mL of the nitrogen-doped lignin carbon dot solution (with the concentration of 28.6 mg/mL) in example 1 is taken, 5mL of copper chloride solution (with the concentration of about 7.97 mg/mL) is dropped into the solution, the solution is vigorously stirred for 10min under the irradiation of visible light, and the Cu monatomic catalyst supported by the lignin carbon dots is obtained through freeze-drying, wherein the theoretical content of Cu atoms is about 2.63 wt%.
Example 7: preparation of Co single-atom catalyst with nitrogen-doped lignin carbon dots as carrier (2.63 wt% of load)
25mL of the nitrogen-doped lignin carbon dot solution (with the concentration of 28.6 mg/mL) obtained in example 1 is taken, 5mL of cobalt chloride solution (with the concentration of about 8.3 mg/mL) is dropped into the solution, the solution is vigorously stirred for 10min under the irradiation of visible light, and the Co monatomic catalyst supported by the lignin carbon dots is obtained through freeze-drying, wherein the theoretical content of Co atoms is about 2.63 wt%.
Example 8: preparation of Ni single-atom catalyst with nitrogen-doped lignin carbon dots as carrier (2.63 wt% of load)
25mL of the nitrogen-doped lignin carbon dot solution (with the concentration of 28.6 mg/mL) in example 1 is taken, 5mL of nickel chloride solution (with the concentration of about 8.32 mg/mL) is dropwise added, the mixture is vigorously stirred for 10min under the irradiation of visible light, and the Ni monatomic catalyst supported by the lignin carbon dots is obtained through freeze-drying, wherein the theoretical content of Ni atoms is about 2.63 wt%.
Comparative example 1
In the preparation of the nitrogen-doped lignin carbon dot in example 1, the lignin carbon dot without nitrogen doping was prepared by the same operation as in example 1 except that ethylenediamine was not added.
25mL of lignin carbon dots without nitrogen doping are taken, 5mL of chloroplatinic acid solution (the concentration is about 10 mg/mL) is dripped into the lignin carbon dots, the lignin carbon dots are vigorously stirred for 10min under the irradiation of visible light, and the Pt monatomic catalyst supported by the lignin carbon dots is obtained by freeze-drying, wherein the theoretical content of Pt atoms is about 2.63 wt%, and the actual load amount of Pt measured by ICP-MS is about 0.55 wt%. And further, a sample is characterized by using a spherical aberration correction TEM, and as shown in a dark field image of the sample in FIG. 6, Pt metal is mainly loaded on the surface of a carbon dot in a form of nano particles, the size of the Pt metal is about 1-2 nm, and local agglomeration is serious and exceeds 4 nm.
Application of different monatomic catalysts in photocatalytic hydrogen production and performance evaluation
Adding 2mg of single-atom catalyst powder into 50mL of aqueous solution containing CdS (23 mg) and lactic acid (5 mL), uniformly dispersing and stirring the catalyst by magnetic stirring, and putting the solution into a Lab-solar 6A photocatalytic hydrogen production on-line analysis system for photocatalytic hydrogen production performance analysis. The PLS-SXE300 xenon lamp is used as a light source, the incident wavelength is controlled to be more than or equal to 420nm by using an optical filter, and the content of hydrogen generated in the reaction is detected by using a GC-7806 gas chromatograph. As a comparison, table 2 comparatively analyzes hydrogen production performance data of different monatomic catalysts, and the results show that the different monatomic catalysts prepared by the method all show good catalytic activity in visible light catalytic hydrogen production applications, wherein the monatomic catalyst in example 2 has the best performance. This is mainly due to the fact that in example 2, Pt metal exists mainly in the form of a single atom, and if the loading is too high, the Pt single atom is prone to agglomeration; when the loading amount is too low, the performance may be deteriorated due to the small content of the active component. Meanwhile, with comparative example 1, since nitrogen doping was not performed, the Pt metal atoms were less supported on the carbon dots and were mainly present in the form of agglomerates, and thus a sharp drop in catalytic efficiency occurred.
TABLE 2 comparison of parameters of different monatomic catalysts and their photocatalytic hydrogen production performance
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (9)
1. A single atom catalyst taking nitrogen-doped lignin carbon dots as a carrier is characterized in that: the method comprises the steps of preparing nitrogen-doped lignin carbon dots by utilizing a hydrothermal reaction of lignin, a nitrogen-containing reagent and hydrogen peroxide, and preparing a supported metal monatomic catalyst by a simple liquid phase method.
2. The nitrogen-doped lignin carbon dot supported monatomic catalyst according to claim 1, wherein: the lignin is used as a carbon source, and is specifically one or more of enzymatic hydrolysis lignin, alkali lignin, lignosulfonate, sulfate lignin and organic lignin.
3. The nitrogen-doped lignin carbon dot supported monatomic catalyst according to claim 1, wherein: the nitrogen-containing reagent comprises one or more of ethylenediamine, propylenediamine, polyethyleneimine and urea.
4. The nitrogen-doped lignin carbon dot supported monatomic catalyst according to claim 1, wherein: the mass ratio of the lignin to the nitrogen-containing reagent to the hydrogen peroxide is 1: (1-10): (5-20).
5. The nitrogen-doped lignin carbon dot supported monatomic catalyst according to claim 1, wherein: the temperature of the hydrothermal reaction is 100-220 ℃, and the reaction time is 4-48 hours.
6. The nitrogen-doped lignin carbon dot supported monatomic catalyst according to claim 1, wherein: the metal atom precursor is one or more of Pt, Pd, Au, Ru, Cu, Fe, Co, Ni and Mn metal inorganic salts.
7. The nitrogen-doped lignin carbon dot supported monatomic catalyst according to claim 1, wherein: the load of the metal single atom is 0.01-10.00 wt% of the total weight of the catalyst.
8. The nitrogen-doped lignin carbon dot supported monatomic catalyst according to claim 1, comprising the steps of: mixing lignin, a nitrogen-containing reagent and hydrogen peroxide according to a mass ratio of 1: (1-10): (5-20) dispersing in deionized water to prepare a uniform solution, transferring the uniform solution into a high-pressure reaction kettle, and heating to 100-220 ℃ for hydrothermal reaction for 4-48 hours; cooling to room temperature, performing centrifugal separation on the hydrothermal product, collecting supernatant, and performing dialysis and purification treatment by using a filter membrane to obtain a nitrogen-doped lignin carbon dot solution; and (3) dropwise adding a metal inorganic salt solution into the solution, and stirring to obtain the nitrogen-doped lignin carbon dot-supported monatomic catalyst.
9. The use of the nitrogen-doped lignin carbon dot supported monatomic catalyst of claim 1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116161616A (en) * | 2022-12-30 | 2023-05-26 | 合肥工业大学 | Method for catalyzing sodium borohydride to quickly produce hydrogen at low temperature by nonmetal catalyst |
| CN117239156A (en) * | 2023-09-07 | 2023-12-15 | 广东工业大学 | High-dispersion lignin derived Ru in-situ N-doped carbon material and preparation method and application thereof |
| CN117723526A (en) * | 2024-02-04 | 2024-03-19 | 云南伦扬科技有限公司 | Method for rapidly detecting glyphosate and cadmium by monoatomic nano enzyme-based fluorescent probe |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109777410A (en) * | 2019-03-13 | 2019-05-21 | 大连工业大学 | A kind of preparation method of the lignin-base fluorescent carbon quantum dot of high yield pulp1 |
| CN111517302A (en) * | 2020-04-23 | 2020-08-11 | 延边大学 | Detection of amino acid by luteolin-based carbon dot as MALDI-TOF MS matrix |
| CN113003563A (en) * | 2021-03-02 | 2021-06-22 | 湖南工业大学 | Modified lignin carbon dots and preparation method and application thereof |
| CN113089015A (en) * | 2021-03-29 | 2021-07-09 | 西北大学 | Nitrogen-doped carbon quantum dot and preparation method thereof, reduced graphene oxide and preparation method and application thereof |
| CN114277399A (en) * | 2021-12-03 | 2022-04-05 | 电子科技大学长三角研究院(湖州) | Ni monatomic-nitrogen-doped carbon nano-catalyst, preparation method thereof and flue gas conversion application |
-
2022
- 2022-05-07 CN CN202210490097.3A patent/CN114887641A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109777410A (en) * | 2019-03-13 | 2019-05-21 | 大连工业大学 | A kind of preparation method of the lignin-base fluorescent carbon quantum dot of high yield pulp1 |
| CN111517302A (en) * | 2020-04-23 | 2020-08-11 | 延边大学 | Detection of amino acid by luteolin-based carbon dot as MALDI-TOF MS matrix |
| CN113003563A (en) * | 2021-03-02 | 2021-06-22 | 湖南工业大学 | Modified lignin carbon dots and preparation method and application thereof |
| CN113089015A (en) * | 2021-03-29 | 2021-07-09 | 西北大学 | Nitrogen-doped carbon quantum dot and preparation method thereof, reduced graphene oxide and preparation method and application thereof |
| CN114277399A (en) * | 2021-12-03 | 2022-04-05 | 电子科技大学长三角研究院(湖州) | Ni monatomic-nitrogen-doped carbon nano-catalyst, preparation method thereof and flue gas conversion application |
Non-Patent Citations (1)
| Title |
|---|
| HUI LUO等: ""Pt single-atoms supported on nitrogen-doped carbon dots for highly efficient photocatalytic hydrogen generation"", J. MATER. CHEM. A, vol. 8, pages 2 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116161616A (en) * | 2022-12-30 | 2023-05-26 | 合肥工业大学 | Method for catalyzing sodium borohydride to quickly produce hydrogen at low temperature by nonmetal catalyst |
| CN116161616B (en) * | 2022-12-30 | 2024-04-19 | 合肥工业大学 | Method for catalyzing sodium borohydride to quickly produce hydrogen at low temperature by nonmetal catalyst |
| CN117239156A (en) * | 2023-09-07 | 2023-12-15 | 广东工业大学 | High-dispersion lignin derived Ru in-situ N-doped carbon material and preparation method and application thereof |
| CN117239156B (en) * | 2023-09-07 | 2024-02-23 | 广东工业大学 | High-dispersion lignin derived Ru in-situ N-doped carbon material and preparation method and application thereof |
| CN117723526A (en) * | 2024-02-04 | 2024-03-19 | 云南伦扬科技有限公司 | Method for rapidly detecting glyphosate and cadmium by monoatomic nano enzyme-based fluorescent probe |
| CN117723526B (en) * | 2024-02-04 | 2024-04-12 | 云南伦扬科技有限公司 | Method for rapidly detecting glyphosate and cadmium by monoatomic nano enzyme-based fluorescent probe |
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