CN109248700B - Preparation method and application of nitrogen-doped carbon material catalyst - Google Patents
Preparation method and application of nitrogen-doped carbon material catalyst Download PDFInfo
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Abstract
The invention provides a preparation method of a nitrogen-doped carbon material catalyst, which comprises the following steps: A. adding nitrogen-containing compound and carbon material into ethanol respectively, and stirring at 0-70 deg.C for 5-20 hr; B. b, carrying out solid-liquid separation on the liquid obtained in the step A, and drying the solid obtained after separation; C. and D, grinding the dried solid obtained in the step B, and calcining in an inert atmosphere to obtain the nitrogen-doped carbon material catalyst. The catalyst provided by the invention can be used for efficiently and selectively catalyzing aromatic compound hydrogenation under mild conditions, reduces the usage amount of metals, reduces the catalyst cost, improves the activity, stability and hydrogenation selectivity of the catalyst, and also has good electrocatalysis performance.
Description
Technical Field
The invention belongs to the technical field of non-metallic catalysts, and particularly relates to a preparation method and application of a nitrogen-doped carbon material catalyst.
Background
The arylamine compound is an important raw material for producing chemical products such as medicines, pesticides, dyes, rubber auxiliaries, photosensitive materials, petroleum solvents and the like, and is mainly prepared by catalytic hydrogenation of aromatic nitro compounds, so that the invention of the novel nonmetal catalyst which can efficiently catalyze the hydrogenation of the aromatic nitro compounds under mild conditions has great significance. The prior hydrogenation catalyst usually adopts a supported noble metal catalyst, has good catalytic effect but high cost, and simultaneously has the problems of uneven dispersion of active metal, large particle size, small metal surface area and the like. At present, a part of nonmetal catalysts can also be used for catalyzing hydrogenation reaction, but the catalysts are often in the problems of harsh reaction conditions, unsatisfactory effect, low yield and the like.
The catalytic hydrogenation reaction of the aromatic nitro compound mainly selects a nickel catalyst and a carrier type noble metal catalyst. The conventional nickel catalyst is mainly a raney nickel catalyst. The active component of the Raney nickel is skeleton nickel, which is unstable in air, easy to catch fire and not suitable for storage. And when the nickel catalyst is used for catalytic hydrogenation reaction, the reaction conditions are harsh, the catalyst consumption is large, the hydrogenation selectivity is poor, and the product yield is low. The Wangdi et al invented a supported platinum-ruthenium catalyst and used it in the hydrogenation process of aromatic nitro compound. The catalyst has high catalytic activity and selectivity, but the active component is mainly noble metal, so the catalyst has high cost and faces the problems of catalyst poisoning and the like.
Liuping et al, a university of Hunan Tan, invented a nitrogen-doped carbon-modified nickel-based catalyst and used in the hydrogenation reaction of catalytic nitrocyclohexane. In the preparation process of the nitrogen-doped carbon carrier of the catalyst, the selected solvent is organic solvents such as ethylenediamine and dimethyl sulfoxide, so that great pressure is brought to the environment, and meanwhile, the active component of the catalyst is metal Ni, so that the catalyst is high in cost compared with a non-metal catalyst and faces the condition of uneven distribution of the active component.
A nano nickel/copper composite catalyst is invented by Wangli et al at the university of Jiangsu and is used for the hydrogenation reaction of p-nitrophenol. The catalyst has a complex preparation process, uses bimetal as a raw material, increases the cost of the catalyst, uses toxic solvents such as tetrahydrofuran and the like in the preparation process, has great harm to the environment, and can reach a conversion rate of more than 90 percent after reacting for 8 hours.
At present, the catalysts disclosed in the prior patents mainly include unsupported catalysts and metal supported catalysts. The non-supported catalyst mainly comprises framework nickel and nano nickel, and the effective active components of the metal supported catalyst mainly comprise transition elements of a VI group and a VIII group, and the transition elements have strong affinity to hydrogen. The common problems encountered with these catalysts are the relatively high cost of the metals and the relatively poor stability. In addition, the prior catalyst used for hydrogenation reaction of aromatic nitro compound often requires harsh conditions, high temperature and high pressure.
Disclosure of Invention
In view of this, the present invention is directed to a method for preparing a nitrogen-doped carbon catalyst, which can implement highly efficient selective catalytic hydrogenation of aromatic compounds under mild conditions, thereby reducing the usage amount of metals, reducing the catalyst cost, and improving the activity, stability and hydrogenation selectivity of the catalyst.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of a nitrogen-doped carbon material catalyst comprises the following steps:
A. adding nitrogen-containing compound and carbon material into ethanol respectively, and stirring at 0-70 deg.C for 5-20 hr;
B. b, carrying out solid-liquid separation on the liquid obtained in the step A, and drying the solid obtained after separation;
C. and D, grinding the dried solid obtained in the step B, and calcining in an inert atmosphere to obtain the nitrogen-doped carbon material catalyst.
Preferably, the nitrogen-containing compound in step a is a pyrrole nitrogen-containing compound.
Preferably, the compound containing pyrrole nitrogen comprises one of melanin, protoporphyrin, uroporphyrin, coproporphyrin, hemocyanin, heme, chlorophyll, vitamin B12 or tetraphenylporphyrin.
Preferably, the carbon material in step a includes one of activated carbon, graphene oxide, single-walled carbon nanotube, multi-walled carbon nanotube or fullerene.
Preferably, the solid-liquid separation method in step B includes one of centrifugal separation, reduced pressure filtration or rotary evaporation.
The invention also aims to provide a nitrogen-doped carbon material catalyst prepared by the preparation method.
The invention also aims to provide the application of the nitrogen-doped carbon material catalyst prepared by the preparation method in catalytic hydrogenation reaction.
Preferably, the use is the use of a nitrogen-doped carbon material catalyst for selective catalytic hydrogenation of unsaturated compounds.
The invention also aims to provide the application of the nitrogen-doped carbon material catalyst prepared by the preparation method in electrocatalytic reaction.
Compared with the prior art, the invention has the following advantages: compared with a supported noble metal catalyst, the nitrogen-doped carbon material catalyst prepared by the invention reduces the usage amount of metal, avoids the occurrence of metal poisoning, reduces the cost of the catalyst, and does not have the condition of uneven distribution of active components. In addition, compared with the existing nonmetal hydrogenation catalyst, the catalyst has the advantages of short preparation period, high stability, high catalytic activity and hydrogenation selectivity under relatively mild reaction conditions, production cost reduction, environmental friendliness due to the fact that the catalyst only contains C, N and other elements, and accordance with the sustainable development strategy.
The preparation method is simple, short in period and low in equipment requirement; the solvent used in the preparation process is only ethanol, toxic and harmful organic solvents are not involved, the preparation method is green and environment-friendly, the needed nitrogen-containing compounds are all biological macromolecules, the preparation method is green and pollution-free, the synthesis process conditions are mild, and the strategic target of sustainable development is met; the prepared catalyst is a heat treatment product of a nitrogen-containing polymer, and has extremely high stability, and the nitrogen doping amount is 1-10 wt%.
In a word, the invention simply and effectively prepares a non-metal catalyst, the catalyst has higher catalytic activity and selectivity for hydrogenation reaction of aromatic compounds, the required reaction conditions are relatively mild, the production cost is low, the economy is good, the environment is friendly, the equipment is not corroded, and the catalyst has strong stability and can be recycled.
Drawings
FIG. 1 is a process flow diagram of a preparation method according to the present invention;
FIG. 2 is a rotating disk voltammogram (current density per unit area of catalyst) of nitrogen-doped carbon catalyst prepared in example 10 at different rates in 0.1M KOH solution under a standard hydrogen electrode at a scan rate of 10 mV. s-1；
FIG. 3 is a rotating disk voltammogram (current density per unit area of catalyst) of nitrogen-doped carbon catalyst prepared in example 12 at different rates in 0.1M KOH solution under a standard hydrogen electrode, with a scan rate of 10 mV. s-1。
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to the following examples and accompanying drawings.
The flow chart of the preparation process of the nitrogen-doped catalyst is shown in figure 1.
Example 1
Dissolving a certain amount of melanin in 16mL of absolute ethyl alcohol, adding 0.1806g of carbon nano tubes with the tube diameter less than 8nm to ensure that the mass fraction of nitrogen is 6 wt%, fully stirring the mixed solution at 60 ℃ for 5h, cooling to room temperature, centrifuging to remove supernatant, fully drying the precipitate at 60 ℃ under a vacuum condition, completely removing the solvent, grinding into powder, calcining for 2h at 800 ℃ in a nitrogen atmosphere, and cooling to room temperature to obtain the nitrogen-doped carbon material catalyst.
Example 2
The procedure of example 1 was repeated except that melanin and carbon nanotubes were added to ethanol, and the mixture was stirred at 70 ℃ for 5 hours.
Example 3
The procedure of example 1 was repeated except that melanin and carbon nanotubes were added to ethanol, and the mixture was stirred at 60 ℃ for 10 hours.
Example 4
The procedure of example 1 was repeated except that melanin and carbon nanotubes were added to ethanol, and the mixture was stirred at 60 ℃ for 15 hours.
Example 5
The procedure of example 1 was repeated except that melanin and carbon nanotubes were added to ethanol, and the mixture was stirred at 60 ℃ for 20 hours.
Example 6
The procedure of example 1 was repeated except that after adding melanin and carbon nanotubes to ethanol, the mixture was stirred at room temperature (20 ℃ C.) for 10 hours.
Example 7
On the basis of example 6, calcination in a nitrogen atmosphere at 800 ℃ for 2 hours was replaced with calcination in a nitrogen atmosphere at 600 ℃ for 2 hours, and the remaining preparation steps were the same as in example 6.
Example 8
On the basis of example 6, calcination in a nitrogen atmosphere at 800 ℃ for 2 hours was replaced with calcination in a nitrogen atmosphere at 700 ℃ for 2 hours, and the remaining preparation steps were the same as in example 6.
Example 9
On the basis of example 7, calcination in a nitrogen atmosphere at 800 ℃ for 2 hours was replaced with calcination in a nitrogen atmosphere at 900 ℃ for 2 hours, and the remaining preparation steps were the same as in example 7.
Example 10
On the basis of the embodiment 4, the carbon nano tube with the tube diameter less than 8nm is replaced by the carbon nano tube with the tube diameter of 10-20nm, and the rest preparation steps are the same as the embodiment 4.
Example 11
On the basis of example 4, melanin is replaced by protoporphyrin, the use amounts of the carbon nanotube and absolute ethanol are kept unchanged, the addition amount of the protoporphyrin ensures that the mass fraction of nitrogen is 6 wt%, and the rest preparation steps are the same as those in example 4.
Example 12
Based on the embodiment 11, the carbon nano tube with the tube diameter less than 8nm is replaced by the carbon nano tube with the tube diameter of 10-20nm, and the rest preparation steps are the same as the embodiment 11.
Example 13
Based on the example 12, protoporphyrin is replaced by tetraphenylporphyrin, the use amounts of carbon nanotubes and absolute ethyl alcohol are kept unchanged, the addition amount of tetraphenylporphyrin ensures that the mass fraction of nitrogen is 6 wt%, and the rest of the preparation steps are the same as those in the example 12.
Catalytic hydrogenation reaction of the catalyst:
the solvent in the catalytic hydrogenation reaction related by the invention is selected from hydrocarbons, alcohols, ethers or esters with good stability, and preferably, the solvent is one or a mixture of more of methanol, ethanol, isopropanol, propionic acid, diethyl ether, ethyl acetate, methyl acetate and tetrahydrofuran.
The aromatic nitro compound has the following structural general formula (I):
r is a substituent group, m is an integer of 1-2, t is 0 or an integer of 1-4, and (m + t) is less than or equal to 6.
Before the hydrogenation reaction using the catalyst, the catalyst is first subjected to a pre-adsorption treatment. Preparing 10mL of tertiary amyl alcohol solution of a compound with the same concentration as that of the compound participating in the catalytic hydrogenation reaction in a 20mL glass bottle, then adding a certain amount of the prepared nitrogen-doped carbon material catalyst, fully stirring for 1h to ensure that the catalyst is adsorbed and saturated, centrifuging for many times to remove supernatant, and keeping the catalyst in a centrifuge tube for later use. Subsequently, a catalytic hydrogenation reaction is carried out. Adding 10mL of prepared tert-amyl alcohol solution of a compound to be reacted with a certain concentration into a stainless steel high-temperature high-pressure reaction kettle (100mL), adding a nitrogen-doped carbon material catalyst with adsorption saturation, selecting C12 as an internal standard substance, adding 20 mu L of C12 into the kettle, uniformly stirring, and taking 1mL of a reaction sample before hydrogenation into a centrifuge tube to be tested. Strictly sealing the reaction kettle, connecting a hydrogenation pipeline, checking the air tightness, evacuating for about 5 times by using nitrogen, starting stirring (800rpm) and starting heating, introducing hydrogen and keeping the pressure of the hydrogen stable at 2MPa after the temperature reaches 120 ℃ and is stable, and starting timing, wherein the reaction time is 1-8 h.
Detection of catalytic hydrogenation products:
qualitative determination of the reaction product was carried out by analysis and confirmation using HP6890/Agilent5975 GC (gas chromatography model: HP 6890; mass spectrometry model: 5975) of Agilent Analyzer. The analysis conditions were as follows: a chromatographic column: HP-5 capillary column (30 m.times.0.25 mm.times.0.25 μm); carrier gas: high purity helium gas; column temperature: the initial temperature is 60 ℃, the temperature is raised to 280 ℃ at the speed of 20 ℃/min, and the temperature is kept for 3 min; column flow rate: 1 mL/min; electron bombardment source: EI; electron energy: 70 eV; interface temperature: 280 ℃; mass scan range: 30-300 mu.
After the reaction is finished, the contents of the raw materials and the reaction products are quantitatively analyzed through Bruker456-GC model gas chromatography of Bruker analytical instruments company under the following analysis conditions: a chromatographic column: BR-1PONA capillary column (50 m.times.0.25 mm. times.0.50 μm); a detector: FID; detector temperature: 300 ℃; vaporization chamber temperature: 300 ℃; carrier gas: high-purity nitrogen; column flow rate: 1 mL/min; column temperature: the initial temperature is 80 deg.C, the temperature is raised to 200 deg.C at 20 deg.C/min, the temperature is maintained for 2min, the temperature is raised to 260 deg.C at 10 deg.C/min, and the temperature is maintained for 5 min. The amount of the sample was 0.2. mu.L.
The reaction sample taken before hydrogenation was designated as sample 1. After completion of the reaction, 1mL of the reaction mixture was designated as sample 2. And centrifuging the samples 1 and 2 to separate supernatant, placing the supernatant into a centrifuge tube, absorbing water in the samples by using a 4A molecular sieve, and filtering the samples by using a filter membrane to remove residual catalyst to obtain the samples meeting the chromatographic detection requirement. The product peak of the catalyst was qualitatively analyzed by GC, and the product was quantitatively analyzed by GC, with a sample size of 0.2. mu.L each time. The reaction conversion rate can be calculated by comparing the peak area ratio change of the p-nitrophenol and C12 before and after the reaction.
The catalysts prepared in examples 1 to 13 were applied to the catalytic hydrogenation of p-nitrophenol, and the reaction product was analyzed by gas chromatograph-mass spectrometer and gas chromatograph, the catalytic hydrogenation equation is as shown in formula 1:
the results of the p-nitrophenol hydrogenation reaction catalyzed by the nitrogen-doped carbon material catalyst prepared by the invention are shown in the following table:
TABLE 1 catalytic hydrogenation of p-nitrophenol
As can be seen from Table 1, when the stirring time reaches 5 hours, the catalyst has higher activity and selectivity for catalyzing the hydrogenation of p-nitrophenol, which are superior to the selectivity reported in the prior literature and patents, and the reaction conditions are mild, and the production energy consumption is greatly reduced. In addition, the catalytic hydrogenation performance of the nitrogen-doped carbon material catalyst is greatly influenced by the calcination temperature, wherein the hydrogenation effect of the nitrogen-doped carbon material catalyst prepared in the embodiment 6 is similar to that of the nitrogen-doped carbon material catalyst prepared in the embodiment 9, and the optimum calcination temperature for preparing the nitrogen-doped carbon material catalyst is 800 ℃ in terms of energy saving and energy consumption reduction. The gas chromatographic analysis is carried out on the liquid after the reaction, and the result shows that only an internal standard substance, a reactant and a single product peak exist in a detected substance after the reaction, which indicates that the selectivity of the reaction catalyzed by all the catalysts involved in the invention can reach 100%.
The prepared nitrogen-doped carbon material catalyst (prepared in example 6) is used for carrying out catalytic hydrogenation on other compounds except for p-nitrophenol, and the reaction results are shown in table 2:
TABLE 2 catalytic hydrogenation results for other nitro compounds
As can be seen from Table 2, the nitrogen-doped carbon material catalyst has a good catalytic hydrogenation effect on most of the nitro compounds, and can achieve high conversion rate and selectivity.
Therefore, when the nitrogen-doped carbon material catalyst prepared by the invention is used in the selective hydrogenation process of compounds, the nitrogen-doped carbon material catalyst has the advantages of mild reaction conditions, low equipment requirement, low energy consumption, good selectivity, high yield, no additional auxiliary agent, high product purity, small reaction pollution, high reaction rate, small catalyst consumption and low production cost. And the component proportion can be flexibly adjusted according to production needs so as to meet different requirements on reaction rate, selectivity and production cost, and the method has extremely high market potential and wide adaptability.
And (3) testing the electrochemical performance of the nitrogen-doped carbon material catalyst:
the oxygen reduction electrocatalytic activity test of the catalyst was mainly performed by the electrochemical workstation compactstat.h10800 and the rotating disk device. The invention adopts a three-electrode system: the working electrode is a glassy carbon electrode with the surface loaded with the nitrogen-doped carbon material catalyst prepared by the preparation method, the reference electrode adopts an Ag/AgCl electrode, and the counter electrode adopts a platinum wire. The diameter of the glassy carbon electrode for Cyclic Voltammetry (CV) test in the invention is 5.0mm, and the diameter of the glassy carbon electrode for Linear Voltammetry (LSV) scan is 5.0 mm.
The preparation of the electrode comprises the following steps: (1) preparation of catalyst dispersion: 3mg of the nitrogen-doped carbon material catalyst samples prepared in example 10 and example 12 were accurately weighed, respectively, and dispersed in 1mL of 75% (volume fraction) isopropanol aqueous solution, after 30 minutes of ultrasound, 25 μ L of Nafion solution was added dropwise, and after several hours of ultrasound, the catalyst dispersion liquid ink (ink) was obtained by sufficiently and uniformly dispersing the Nafion solution; (2) preparation of a working electrode: a certain amount (15. mu.L) of the catalyst dispersion ink was accurately measured, and dropped on the surface of the glassy carbon electrode, and the surface was covered with a lid to sufficiently dry the dispersion.
The measurement process comprises the following steps: (1) a rotary disc device is connected, and argon is introduced for 30 min. (2) Performing Cyclic Voltammetric (CV) sweeps: cyclic voltammetry is a common electrochemical study method, and CV is implemented by applying a voltage signal with a triangular waveform to a working electrode and simultaneously measuring the current response of the working electrode. For the oxygen reduction reaction process, the electrocatalytic oxygen reduction capability of the catalyst is evaluated mainly by the initial potential and the peak current value of the reverse sweep peak of cyclic voltammetry, and the more positive the initial potential and the larger the peak current value of the oxygen reduction peak are, the better the oxygen reduction electrocatalytic performance of the catalyst is. The test conditions of the cyclic voltammetry curve are-0.8 to +0.2V (vs Ag/AgCl) under the alkaline condition and the scanning rate is 50mV s-1。
Linear voltammetry (LSV) is a method in which a rapidly linearly changing voltage is applied to an electrode and the electrochemical properties of a sample are analyzed based on the resulting I-E curve. By linear voltammetryThe scanning method can obtain a polarization curve of the sample, and the relation between the electrode potential and the polarization current or the polarization current density can be obtained by analyzing the polarization curve. The test conditions were: in 0.1M KOH, the scanning range is-0.8- +0.2V (vs Ag/AgCl); the scanning rate is 10 mV/s; the rotating speed of the rotating disk electrode was 400, 800, 1200, 1600, 2000, 2400 rpm. The test results are shown in fig. 2 and 3. FIGS. 2 and 3 are voltammograms of a rotating disk at different rotation rates in 0.1M KOH oxygen saturated solution at a scan rate of 10mV s for catalysts prepared in examples 10 and 12, respectively-1. Fig. 2 and 3 are both current densities per unit area of catalyst under a standard hydrogen electrode. As can be seen from fig. 2 and 3, in the alkaline electrolyte, when the reference electrode is converted to the standard hydrogen electrode, the initial potential is 0.85V, which indicates that the nitrogen-doped carbon material catalyst prepared by the present invention has good electrocatalytic activity for Oxygen Reduction Reaction (ORR) in the fuel cell.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (6)
1. A preparation method of a nitrogen-doped carbon material catalyst is characterized by comprising the following steps: the method comprises the following steps:
A. adding nitrogen-containing compound and carbon material into ethanol respectively, and stirring at 0-70 deg.C for 5-20 hr; the nitrogen-containing compound is a compound containing pyrrole nitrogen; the compound containing pyrrole nitrogen comprises one of melanin, protoporphyrin, uroporphyrin, coproporphyrin, hemocyanin, heme, chlorophyll, vitamin B12 or tetraphenylporphyrin; the carbon material comprises one of activated carbon, graphene oxide, single-walled carbon nanotubes, multi-walled carbon nanotubes or fullerene;
B. b, carrying out solid-liquid separation on the liquid obtained in the step A, and drying the solid obtained after separation;
C. and D, grinding the dried solid obtained in the step B, and calcining in an inert atmosphere to obtain the nitrogen-doped carbon material catalyst.
2. The method of claim 1, wherein: the solid-liquid separation method in the step B comprises one of centrifugal separation, reduced pressure filtration or rotary evaporation.
3. A nitrogen-doped carbon material catalyst prepared by the preparation method according to any one of claims 1 to 2.
4. Use of the nitrogen-doped carbon material catalyst of claim 3 for catalytic hydrogenation reactions.
5. Use according to claim 4, characterized in that: the application is the application of the nitrogen-doped carbon material catalyst in selective catalytic hydrogenation of unsaturated compounds.
6. Use of the nitrogen-doped carbon material catalyst of claim 3 in electrocatalytic reactions.
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| CN112138698B (en) * | 2020-09-16 | 2021-03-16 | 吉林化工学院 | Preparation method of nitrogen-doped carbon nano material and application of nitrogen-doped carbon nano material in nitrobenzene hydrogenation reaction |
| CN113889630B (en) * | 2021-09-29 | 2022-09-13 | 陕西科技大学 | Preparation method of composite structure oxygen reduction electrocatalyst for fuel cell cathode |
| CN114433160B (en) * | 2021-12-22 | 2023-09-01 | 重庆工商大学 | Fullerene C 60 Process for preparing derivative electrocatalyst |
| CN114990575B (en) * | 2022-06-09 | 2023-12-29 | 陕西科技大学 | Nano flower derived carbon-supported nickel particle electrocatalyst and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103985884A (en) * | 2014-05-21 | 2014-08-13 | 华中科技大学 | Nitrogen-doped carbon nano-material as well as preparation method and application thereof |
| CN105669464A (en) * | 2016-04-01 | 2016-06-15 | 湘潭大学 | Application of metal-free hydrogenation catalyst in catalyzing hydrogenation reaction of nitrobenzene and derivatives thereof |
| CN106694014A (en) * | 2015-11-13 | 2017-05-24 | 天津大学 | Nitrogen-doped nonmetallic catalyst as well as preparation method and use thereof |
-
2017
- 2017-07-14 CN CN201710575733.1A patent/CN109248700B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103985884A (en) * | 2014-05-21 | 2014-08-13 | 华中科技大学 | Nitrogen-doped carbon nano-material as well as preparation method and application thereof |
| CN106694014A (en) * | 2015-11-13 | 2017-05-24 | 天津大学 | Nitrogen-doped nonmetallic catalyst as well as preparation method and use thereof |
| CN105669464A (en) * | 2016-04-01 | 2016-06-15 | 湘潭大学 | Application of metal-free hydrogenation catalyst in catalyzing hydrogenation reaction of nitrobenzene and derivatives thereof |
Non-Patent Citations (2)
| Title |
|---|
| Mesoporous metal–nitrogen-doped carbon electrocatalysts for highly efficient oxygen reduction reaction;Hai-Wei Liang等;《JACS》;20131015;第135卷;全文 * |
| 氮掺杂多孔炭材料的制备及在多相催化中的应用;杨勇 等;《化学通报》;20161231;第79卷(第10期);全文 * |
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