CN106946247B - A kind of laser irradiation synthesizes the preparation method of more active sites nitrogen-doped graphenes - Google Patents

A kind of laser irradiation synthesizes the preparation method of more active sites nitrogen-doped graphenes Download PDF

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CN106946247B
CN106946247B CN201710108192.1A CN201710108192A CN106946247B CN 106946247 B CN106946247 B CN 106946247B CN 201710108192 A CN201710108192 A CN 201710108192A CN 106946247 B CN106946247 B CN 106946247B
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nitrogen
laser irradiation
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laser
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CN106946247A (en
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杨静
王学瑞
杜希文
毛晶
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Tianjin University
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    • 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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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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Abstract

The invention discloses the preparation methods that a kind of laser irradiation synthesizes more active sites nitrogen-doped graphenes, obtain exposing the graphene oxide raw material of more edge active positions using nanosecond laser irradiating soln, raw material can be regulated and controled by laser energy and irradiation time with exposed edge active position, available more controllable pyridine N structures in later period hydrothermal synthesis nitrogen-doped graphene, to promote the catalytic activity of nitrogen-doped graphene.The present invention takes the lead in proposing a kind of controllable method for promoting pyridine nitrogen content in nitrogen-doped graphene, and the synthetic method of nitrogen of high activity doped graphene is realized in the water phase under benign environment.In addition, synthetic method craft of the present invention is simple and convenient to operate, is easily controllable, and is not used toxic reaction raw materials, it is a kind of environmental-friendly green synthesis process.

Description

A kind of laser irradiation synthesizes the preparation method of more active sites nitrogen-doped graphenes
Technical field
The present invention relates to a kind of preparation methods of nitrogen-doped graphene, mostly active more particularly to a kind of synthesis of laser irradiation The preparation method of position nitrogen-doped graphene.
Background technique
Currently, energy crisis and environmental problem brought by fossil fuel are got worse, and people more and more pay close attention to can The development and utilization of the renewable sources of energy.Renewable energy conversion and the key technology of storage include fuel cell, chargeable metal-air Battery, photocatalytic water etc., and its key problem is to find efficient, cheap oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) Catalyst, to replace expensive and rare storage noble metal (Pt, Pt alloy) and its oxide (IrO2、RuO2), this for The commercialization process of promotion renewable energy utilization technology has and its important meaning.Based on earth carbon material abundant, one Kind of the carbon-based non-metal catalyst of new catalyst be found to be it is a kind of efficiently, low cost, no metal and alternative platinum is for firing Expect the catalyst of the oxygen reduction reaction in battery, wherein nitrogen-doped graphene has been proved to be very effective in carbon-based no metal The catalyst of oxygen reduction reaction.
Since 2009, nitrogen-doped carbon nanometer pipe was reported with efficient oxygen reduction catalytic activity while also having for the first time There are the methanol tolerance and stability better than platinum carbon, the oxygen reduction catalytic activity of carbon-based non-metal catalyst obtains extensively from there on General research.N doping, sulfur doping, phosphorus doping, I2 doping graphene and edge halogenation doped graphite are then reported in succession The high-efficiency catalytic activity that alkene has in oxygen reduction reaction.Wherein, Dai et al. first reported nitrogen-doped carbon nanometer pipe with good Good catalytic activity and stability and methanol tolerance better than platinum carbon.Referring to: Kuanping Gong, Feng Du, Liming Dai.Science 323,760–764(2009).Subsequent Yang et al. and Jeon etc. reports sulfur doping, phosphorus in succession Doping, the performance of I2 doping graphene and edge halogenation doped graphene in oxygen reduction reaction.
Currently, nitrogen-doped graphene is main research hotspot.Dai et al. passed through CVD method synthetic nitrogen in 2010 first Doped graphene shows good oxygen reduction catalytic activity.Referring to: Kuanping Gong, Feng Du, Liming Dai.ACS Nano 4,1321–1326(2010)；James in 2014 et al. on graphene oxide by growing graphite oxide The synthesis of alkene quantum dot has the nitrogen-doped graphene of more marginal textures, testing the result is that the catalysis of nitrogen-doped graphene is living Property, which has, to be obviously improved, referring to: Huilong Fei, James M.Tour.ACS Nano 10,10837-10843 (2014)； Zhang et al. carries out theoretical modeling, gained knot using mechanism of the density functional theory to oxygen reduction reaction on nitrogen-doped graphene Fruit is consistent with Germicidal efficacy, i.e., ORR is direct 4 electronic channel on NG；Guo in 2016 et al. passes through experiment card pyridine Nitrogen is the key that promote oxygen reduction reaction catalytic activity.Referring to: Guo, D.H.et al.Science 351,361-365 (2016).But up to the present, the condition for synthesizing nitrogen-doped graphene is harsher, and not someone's system research how The pyridine nitrogen content of nitrogen-doped graphene is promoted to promote the catalytic activity of material.
Summary of the invention
In order to solve the problems in the existing technology, the present invention provides a kind of laser irradiation synthesis more active sites N dopings The preparation method of graphene, overcome in the prior art synthesis technology can not be synthesized under low-temp low-pressure there is high-efficiency catalytic activity Nitrogen-doped graphene and the problem of not can be effectively controlled pyridine nitrogen content in nitrogen-doped graphene.
The technical solution adopted by the present invention is that:
A kind of laser irradiation synthesizes the preparation method of more active sites nitrogen-doped graphenes, comprising the following steps:
(1) graphene oxide prepared using improved Hummers method as raw material, by graphene oxide and ethanol solution with The mixing of 1mg:1ml~1mg:10ml ratio, ultrasonication are uniform；
(2) the resulting 10~50ml of sample of step (1) is put into conical flask, with nanosecond parallel pulse laser irradiation 10~ 50min solution；
(3) the resulting sample of step (2) is subjected to high speed centrifugation, 12000~20000 revs/min of revolving speed, obtains precipitating simultaneously Freeze-drying；
(4) the resulting sample of step (3) and ammonium hydrogen carbonate is soluble in water with mass ratio 1:1~1:50 mixing, it will mix It closes solution to pour into reaction kettle, be reacted 5~20 hours at a temperature of 90~200 DEG C；
(5) three times by the resulting sample centrifugation of step (4), washing, freeze-drying.
When step (2) the ps pulsed laser and ns pulsed laser effect irradiation, the energy of laser is 270mJ, wavelength 1064nm, laser Repetition rate is 10Hz.
It to be stirred during step (2) laser irradiation, mixing speed is controlled at 500 revs/min -800 revs/min, So that solution is evenly dispersed.
Whole preparation process all carries out in the exposed environment, without being passed through protection gas.
The beneficial effects of the present invention are: the present invention obtains exposing more edge active positions using nanosecond laser irradiating soln Graphene oxide raw material can regulate and control raw material with exposed edge active position, in later period water by laser energy and irradiation time Available more controllable pyridine N structures when thermal synthesis nitrogen-doped graphene, live to promote the catalysis of nitrogen-doped graphene Property.The present invention takes the lead in proposing a kind of controllable method for promoting pyridine nitrogen content in nitrogen-doped graphene, under benign environment The synthetic method of nitrogen of high activity doped graphene is realized in water phase.In addition, synthetic method craft letter of the present invention It is single, easy to operate, easily controllable, and toxic reaction raw materials are not used, it is a kind of environmental-friendly green synthesis process.
Detailed description of the invention
Fig. 1 is the process device figure using the more edge active positions of nanosecond laser irradiation oxidation graphene exposure；
Fig. 2 (a) is the low power transmission electron microscope photo of raw material graphene oxide；(b) it is aoxidized later for laser irradiation Graphene low power transmission electron microscope photo；(c) graphene oxide high power transmission electron microscope photo after laser irradiation； It (d) is the Raman figure of graphene oxide before and after laser irradiation；
Fig. 3 (a) is the nitrogen-doped graphene without laser irradiation, (b) nitrogen-doped graphene that laser treatment synthesizes later X-ray photoelectron spectroscopic analysis figure；Analyze data discovery laser irradiation after pyridine nitrogen content by before 24% promoted to 53%, improve 120%；
The oxygen for the nitrogen-doped graphene that Fig. 4 is nitrogen-doped graphene without laser irradiation and laser treatment synthesizes later is also Originality energy comparison diagram (b) is the tafel slope of oxygen reduction reaction, (c) is wherein (a) is the polarization curve of oxygen reduction reaction Dynamics current density and electron transfer number (d) are answered for methanol tolerance；It can be seen that the nitrogen-doped graphene after laser irradiation Take-off potential improves 60mv, and diffusion current density is by 4.6mA/cm before2Promote 5.3mA/cm2, electron transfer number is by it Preceding 3.78 are promoted to 3.95, and dynamics current density is by 8.2mA/cm before2Promote 17.6mA/cm2, tafel slope It is promoted from 72mv/dec to 56mv/dec, and still keeps good methanol tolerance.
Specific embodiment
As shown in Fig. 1 synthesizer figure, the mixing speed of magneton should not be too slow also unsuitable too fast, and too time slack solution mixes not Uniformly, solution may be made to sputter out fastly very much, mixing speed is suitable for control between 500 revs/min -800 revs/min.It receives When pulse per second (PPS) laser action irradiates, the energy of laser is 270mJ, wavelength 1064nm, laser repetition rate 10Hz.Entire system Standby process all carries out in the exposed environment, without being passed through protection gas.
Embodiment 1:
Laser irradiation synthesizes the preparation method of more active sites nitrogen-doped graphenes, comprising the following steps:
(1) using the graphene oxide of improved Hummers method preparation as raw material, graphene oxide 10mg is dissolved in 20ml Ethanol solution in (analysis pure), five minutes broken under conditions of 400w power is broken, then ultrasonic vibration 10 minutes.
(2) 20ml is taken to be put into conical flask in step (1) resulting sample, with nanosecond parallel veins impulse actinometric solutions, Time is 10min.
(3) the resulting sample of step (2) is subjected to (16000 revs/min) centrifugation 25min of high speed, is precipitated and is lyophilized.
(4) the resulting sample 10mg of step (3) is dissolved in 30ml water and is added 100mg ammonium hydrogen carbonate, by mixed solution Pour into 40ml reaction kettle, 90 DEG C at a temperature of react 12 hours.
(5) three times by the resulting sample centrifugation of step (4), washing, it is centrifuged 20 minutes, freezes under 20000 revs/min of revolving speed It is dry.
Embodiment 2:
Laser irradiation synthesizes the preparation method of more active sites nitrogen-doped graphenes, comprising the following steps:
(1) using the graphene oxide of improved Hummers method preparation as raw material, graphene oxide 60mg is dissolved in In the ethanol solution of 180ml (analysis is pure), 40 minutes broken under conditions of 300w power is broken, then ultrasonic vibration 20 divides Clock.
(2) 30ml is taken to be put into conical flask in step (1) resulting sample, with nanosecond parallel veins impulse actinometric solutions, Time is 30min.
(3) the resulting sample of step (2) is subjected to (20000 revs/min) centrifugation 30min of high speed, is precipitated and is lyophilized.
(4) the resulting sample 15mg of step (3) is dissolved in 30ml water and is added 75mg ammonium hydrogen carbonate, mixed solution is fallen Enter in 40ml reaction kettle, 150 DEG C at a temperature of react 12 hours.
(5) three times by the resulting sample centrifugation of step (4), washing, it is centrifuged 20 minutes under 20000 revs/min of revolving speed.
Embodiment 3:
Laser irradiation synthesizes the preparation method of more active sites nitrogen-doped graphenes, comprising the following steps:
(1) using the graphene oxide of improved Hummers method preparation as raw material, graphene oxide 30mg is dissolved in In the ethanol solution of 300ml (analysis is pure), 20 minutes broken under conditions of 450w power is broken, then ultrasonic vibration 40 divides Clock.
(2) 40ml is taken to be put into conical flask in step (1) resulting sample, with nanosecond parallel veins impulse actinometric solutions, Time is 40min.
(3) the resulting sample of step (2) is subjected to (18000 revs/min) centrifugation 35min of high speed, is precipitated and is lyophilized.
(4) the resulting sample 20mg of step (3) is dissolved in 80ml water and is added 1g ammonium hydrogen carbonate, mixed solution is poured into In 100ml reaction kettle, 200 DEG C at a temperature of react 16 hours.
(5) three times by the resulting sample centrifugation of step (4), washing, it is centrifuged 40 minutes under 20000 revs/min of revolving speed.
Although above in conjunction with figure, invention has been described, and the invention is not limited to above-mentioned specific embodiment parties Formula, the above mentioned embodiment is only schematical, rather than restrictive, and those skilled in the art are in this hair Under bright enlightenment, without deviating from the spirit of the invention, many variations can also be made, these belong to guarantor of the invention Within shield.

Claims (2)

1. the preparation method that a kind of laser irradiation synthesizes more active sites nitrogen-doped graphenes, which comprises the following steps:
(1) using the graphene oxide of improved Hummers method preparation as raw material, by graphene oxide and ethanol solution with 1mg: The mixing of 1ml~1mg:10ml ratio, ultrasonication are uniform；
(2) the resulting 10~50ml of sample of step (1) is put into conical flask, with nanosecond parallel pulse laser irradiation 10~ 50min solution；When step (2) the ps pulsed laser and ns pulsed laser effect irradiation, the energy of laser is 270mJ, wavelength 1064nm, is swashed Light repetition rate is 10Hz；
(3) the resulting sample of step (2) is subjected to high speed centrifugation, 12000~20000 revs/min of revolving speed, is precipitated and frozen It is dry；
(4) the resulting sample of step (3) and ammonium hydrogen carbonate is soluble in water with mass ratio 1:1~1:50 mixing, it will mix molten Liquid pours into reaction kettle, reacts 5~20 hours at a temperature of 90~200 DEG C；
(5) three times by the resulting sample centrifugation of step (4), washing, freeze-drying；
Whole preparation process all carries out in the exposed environment, without being passed through protection gas.
2. laser irradiation synthesizes the preparation method of more active sites nitrogen-doped graphenes according to claim 1, which is characterized in that It to be stirred during step (2) laser irradiation, mixing speed is controlled at 500 revs/min -800 revs/min.
CN201710108192.1A 2017-02-27 2017-02-27 A kind of laser irradiation synthesizes the preparation method of more active sites nitrogen-doped graphenes Expired - Fee Related CN106946247B (en)

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CN108914251B (en) * 2018-07-09 2020-10-30 杭州高烯科技有限公司 Nitrogen-doped graphite fiber and preparation method thereof
CN109289892B (en) * 2018-09-30 2020-12-29 天津大学 Manganese-based mullite/nitrogen-doped graphene composite oxygen electrocatalyst and preparation method thereof
CN109279598A (en) * 2018-11-16 2019-01-29 中科院合肥技术创新工程院 A kind of method of liquid laser auxiliary synthesis heteroatom doped graphene aeroge
CN109590008B (en) * 2018-12-25 2021-06-25 天津大学 Preparation method of laser-synthesized oxygen vacancy adjustable cobaltosic oxide nitrogen-doped graphene
CN110040723B (en) * 2019-04-26 2022-06-10 辽宁烯旺石墨科技有限公司 Method for preparing graphene by using ion sputtering and laser composite technology
CN110586156B (en) * 2019-09-03 2022-06-10 天津大学 Preparation method for synthesizing mesoporous nitrogen-doped graphene-loaded molybdenum disulfide through laser irradiation and application of mesoporous nitrogen-doped graphene-loaded molybdenum disulfide in electro-catalysis hydrogen production
CN110624587A (en) * 2019-09-23 2019-12-31 天津大学 Preparation method for synthesizing cobalt ferrite composite nitrogen-doped three-dimensional porous graphene with assistance of laser
CN113725073A (en) * 2020-05-25 2021-11-30 国家纳米科学中心 Manufacturing method of nitrogen-doped graphene field effect transistor
CN113066976B (en) * 2021-03-19 2023-03-17 中国科学院上海应用物理研究所 Application of nitrogen-doped carbon nanotube in lithium ion battery cathode material
CN113789663A (en) * 2021-08-22 2021-12-14 北京工业大学 Preparation method and application of N, F doped carbon material dual-function integrated catalyst
WO2023225921A1 (en) * 2022-05-25 2023-11-30 北京小米移动软件有限公司 Conductive agent processing method, conductive agent, electrode, and battery

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