CN107824797A - Nano-particle modified nitrogen-doped carbon nanometer sheet material of a kind of bismuth of porous high-specific surface area and its preparation method and application - Google Patents
Nano-particle modified nitrogen-doped carbon nanometer sheet material of a kind of bismuth of porous high-specific surface area and its preparation method and application Download PDFInfo
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Abstract
The invention belongs to field of nanometer material technology, discloses nano-particle modified nitrogen-doped carbon nanometer sheet material of a kind of bismuth of porous high-specific surface area and its preparation method and application.This method comprises the following steps：Using polyvinylpyrrolidonesolution solution as nitrogen source and carbon source, add in beaker；Bismuth salt is added into the nitrogen source solution, stirs and adjusts pH value with weak acid solution, bismuth salt is all dissolved；The solution prepared is placed in electric drying oven with forced convection and is dried to obtain solid precursors；It is put into after solid precursors are ground into fine powder in porcelain boat, under protective gas, is placed in tube furnace and heats roasting, obtain nanometer sheet material.It is one that the synthesis of carbon nanomaterial, doping and the modification of bismuth nano particle are closed into three by this method, the structure and stable performance of the nano-particle modified nitrogen-doped carbon nanometer sheet material of the bismuth of gained, shows preferable heavy metal analysis performance.Preparation method process provided by the invention is simple and easy, and cost is low, suitable large-scale production.
Description
Technical field
The invention belongs to field of nanometer material technology, is related to nitrogen-doped carbon technical field of nano material, and in particular to a kind of porous
Nano-particle modified nitrogen-doped carbon nanometer sheet material of the bismuth of high-specific surface area and its preparation method and application.
Background technology
Carbon nanomaterial is most common a kind of material in nature, very important in the energy and Material Field holder
Status.Carbon nanomaterial has high electric conductivity, and high-specific surface area, chemical stability is good and can facilitate the spy of large-scale production
Property, it has been widely used in energy storage, gas separation, the field such as heavy metal adsorption and detection.However, pure carbon material parent
Water poor performance, activity is relatively low, is unfavorable for heavy metal and deposits, disperses and interact on its surface, limits to a certain extent
Its application.At present, conventional method is exactly that carbon nanomaterial is modified and adulterated.Such as the foreign atom such as N, S, P
Effect, makes carbon nanomaterial carrier have polarity, more avtive spot is provided for the deposition of metallic particles.
In numerous hetero atoms, the doping of nitrogen-atoms is to be studied earliest by people, and the doped chemical of most study.
At present, the carbon material of N doping mainly has following several synthesis modes：Original position doping and post processing doping method.Doping method in situ is
Chemical vapor deposition growth is carried out using the organic molecule (such as urea, melamine etc.) of Nitrogen element and obtains nitrogen-doping
Carbon material, this method needs expensive instrument and equipment, and shortcoming is can not to meet large-scale industrial production.Post processing doping
Rule is the functionalization that the carbon material that will be prepared carries out the later stage in the activated gas of Nitrogen element, but this activation process
It is generally necessary to complete at a higher temperature, therefore it is to restrict two big major issues of its development to produce power consumption and safety factor.
Bismuth nano particle has unique physicochemical properties and widely paid close attention to, be widely used in heavy metal from
The analysis of son and biological micromolecule detects, electro-catalysis and battery industry.The conventional nitrogen for preparing metal nanoparticle modification is mixed
The method of miscellaneous carbon nanosheet material is divided into two steps：Carbon material is prepared first, then carries out the doping of nitrogen.It is this conventional
Preparation method, operating process is more complicated, complex steps, so as to limit its extensive use.Moreover, other materials are as nitrogen
Source, cost is not only increased, and easily cause mixing inequality, surface area is smaller, finally makes N doping also uneven.Meanwhile
Carbon nanosheet frame material with more high nitrogen doped amount and high-specific surface area is also without the related report of document and patent progress
Road and openly.Therefore, the nano-particle modified nitrogen-doped carbon of the bismuth with porous high-specific surface area that is convenient, easily realizing is inquired into out
Nano sheet material preparation method for material, and its application, tool are of great significance.
The content of the invention
The shortcomings that in order to overcome prior art and weak point, primary and foremost purpose of the invention are to provide a kind of porous high ratio
The preparation method of the nano-particle modified nitrogen-doped carbon nanometer sheet material of the bismuth of surface area.It is easy to implement the method, it is simple to operate, with poly- second
Alkene pyrrolidone solution is as nitrogen source, and bismuth salt provides metal bismuth ion, by the way of roasting direct, by carbon nanosheet material
It is one that synthesis, doping and the modification of bismuth nano particle, which close three, and obtained carbon nanometer frame material has porous, high-ratio surface
Product, structure and stable performance, it can be used for the quick analysis detection of trace heavy metal ion.
A kind of bismuth for the porous high-specific surface area being prepared another object of the present invention is to provide above-mentioned preparation method
Nano-particle modified nitrogen-doped carbon nanometer sheet material.
It is still another object of the present invention to provide a kind of nano-particle modified nitrogen of bismuth of above-mentioned porous high-specific surface area to mix
The application of miscellaneous carbon nanosheet material.
The purpose of the present invention is realized by following technical proposals：
A kind of preparation method of the nano-particle modified nitrogen-doped carbon nanometer sheet material of the bismuth of porous high-specific surface area, including
Following steps：
(a) using polyvinylpyrrolidone as carbon source and nitrogen source, add solvent and fully dissolve, obtain nitrogen source solution；
(b) bismuth salt is added into nitrogen source solution obtained by step (a), stirs and adjusts pH value with weak acid solution, make bismuth salt complete
Portion dissolves, and obtains mixed solution；
(c) nitrogen source solution obtained by step (b) is placed in electric drying oven with forced convection and is dried to obtain solid precursors；
(d) it is put into after the solid precursors of gained being ground into fine powder in porcelain boat, under protective gas atmosphere, is placed in tubular type
Roasting is heated in stove, obtains the nano-particle modified nitrogen-doped carbon nanometer sheet material of the bismuth of porous high-specific surface area.
In polyvinylpyrrolidone of step (a) polyvinylpyrrolidone between molecular weight ranges K25~K30
It is one or more kinds of.
Step (a) solvent be deionized water, absolute ethyl alcohol, ethylene glycol, glycerine and polyethylene glycol in one kind or
It is two or more；The nitrogen source solution concentration is 0.01g/mL-0.1g/mL.
Step (b) bismuth salt is bismuth nitrate, bismuth acetate or bismuth chloride；The weak acid solution be glacial acetic acid, dust technology or
Dilute sulfuric acid；The regulation pH value is regulation between 4.0-5.5.
The mass ratio of bismuth salt described in polyvinylpyrrolidone described in step (a) and step (b) is 1：0.1-5.
The temperature dried in step (c) electric drying oven with forced convection is 110-130 DEG C, drying time 12-14h.
Step (d) protective gas is one or two kinds of in nitrogen and argon gas, and its flow is 30-60mL/min.
Step (d) tube furnace under protective gas atmosphere using 2-8 DEG C/min heating rate rise to calcining heat as
600-900 DEG C, it is carbonized 1-3 hours.
A kind of nano-particle modified nitrogen-doped carbon of bismuth that porous high-specific surface area is prepared by above-mentioned preparation method
Nanometer sheet material, the carbon nanomaterial are nanometer sheet frame structure, specific surface area 400-800m2/ g, pore volume 0.7-
1.2cm3/ g, pore-size distribution is in 1.0-5nm, and the mass content of nitrogen is between 4%-10%.
The nano-particle modified nitrogen-doped carbon nanometer sheet material of the bismuth of above-mentioned porous high-specific surface area is in trace heavy metal
Application in the electrochemical analysis detection of ion.
The present invention is had the following advantages relative to prior art and effect：
(1) present invention directly prepares the nano-particle modified nitrogen-doped carbon nanometer sheet material of bismuth by the way of roasting,
The synthesis of carbon nanosheet material, doping and the step syntheti c route of the modification of bismuth nano particle three are simplified to a step, it is simple to operate, hold
Easily realize.
(2) present invention is made using carbon source and nitrogen source prepares nitrogen-doped carbon nanometer by the way of roasting direct after presoma
Material, the carbon nanosheet frame material with porous high-specific surface area can be obtained, cost is low, structure and stable performance, fits
Preferably mass produce.
(3) the nano-particle modified nitrogen-doped carbon nanometer sheet material of the obtained bismuth of the present invention, can be used for heavy metal ion
The detections such as quick trace analysis detection, such as zinc, lead, cadmium, copper, mercury.
Brief description of the drawings
Fig. 1 is the nano-particle modified nitrogen-doped carbon nanometer sheet material XRD of bismuth used in the embodiment of the present invention 1.
Fig. 2 is the nano-particle modified nitrogen-doped carbon nanometer sheet material SEM figures of bismuth used in the embodiment of the present invention 1.
Fig. 3 is the nano-particle modified nitrogen-doped carbon nanometer sheet material TEM figures of bismuth used in the embodiment of the present invention 1.
Fig. 4 schemes for XPS, and wherein a is the nano-particle modified nitrogen-doped carbon nanometer of bismuth used in the embodiment of the present invention 1
Sheet material XPS figure full figures；B is the feature XPS figures of carbon in the embodiment of the present invention 1；C is the feature XPS of oxygen in the embodiment of the present invention 1
Figure；D is the feature XPS figures of nitrogen in the embodiment of the present invention 1；E is the feature XPS figures of bismuth in the embodiment of the present invention 1.
Fig. 5 is the nitrogen of the nano-particle modified nitrogen-doped carbon nanometer sheet material of bismuth used in the embodiment of the present invention 1
Adsorption-desorption curve map.
Fig. 6 is the peak shape figure obtained in the embodiment of the present invention 2 using Square wave anodic stripping voltammetry method.
Embodiment
Further the present invention is illustrated below by specific embodiment and with reference to the mode of accompanying drawing, but it is not intended that
Limiting the scope of the invention, those skilled in the art make some nonessential changes according to the content of foregoing invention
And adjustment, belong to protection scope of the present invention.
Embodiment 1
A kind of preparation method of the nano-particle modified nitrogen-doped carbon nanometer sheet material of porous surface high-specific surface area bismuth, tool
Body comprises the following steps：
(1) using 0.5g polyvinylpyrrolidone K28 as carbon source and nitrogen source, the ethylene glycol (carbon source) for adding 50mL is abundant
Dissolving, obtains 0.01g/L nitrogen source solution；
(2) 0.05g bismuth nitrate is added into nitrogen source solution obtained by step (1), stir and with vinegar acid for adjusting pH value extremely
5.5, now bismuth nitrate fully dissolved, obtains mixed solution；
(3) mixed solution obtained by step (2) is placed in 14h in 110 DEG C of electric drying oven with forced convections until obtaining pale yellow colored solid
Body predecessor；
(4) it is put into after the faint yellow solid predecessor of gained being ground into fine powder in porcelain boat, is 40mL/min's in flow velocity
Under nitrogen protective condition, it is placed in tube furnace and heats roasting, roasting process is heated to 5 DEG C/min heating rate from room temperature
600 DEG C, 2h is then incubated under 600 DEG C of high temperature, is finally down to room temperature, takes out sample, that is, obtains the bismuth of porous high-specific surface area
Nano-particle modified nitrogen-doped carbon nanometer sheet material.
Structural behaviour is tested：Using XRD (solid powder X-ray diffraction analysis) technologies to above-mentioned gained bismuth metal nanometer
The nitrogen-doped carbon nanometer sheet material of grain modification is characterized (such as Fig. 1), occurs C (002) graphitization of 2 θ=28.4 ° in material
The Bi (012) of the diffraction maximum at diffractive features peak and Bi, i.e. respectively 2 θ=28.2 °, the Bi (104) of 2 θ=38.1 °, and 2 θ=
39.7 ° of Bi (110) characteristic diffraction peak.The material is characterized using SEM (SEM) technology (as schemed
2), material is shown as carbon nanosheet frame structure skeleton and has loose structure.Using transmission electron microscope (TEM) technology pair
The material is characterized (such as Fig. 3), as a result shows Bi nanoparticle sizes between 5-20nm, and be evenly distributed on carbon nanosheet
In framework.Using x-ray photoelectron power spectrum (XPS) technical Analysis material (such as Fig. 4), there is C 1s peak in 284.8eV,
There is N 1s peak in 400.1eV, and O 1s peak occurs in 530.5eV；157.2eV(Bi 4f7/2) and 162.7eV (Bi 4f5/2)
There is two Bi peak, show to contain C, N, O, tetra- kinds of elements of Bi in prepared material, and tested by elementary analysis,
The constituent content for understanding N in the carbon material is 5.71, and according to the difference of initial feed (nitrogen source), the content of N element is in 4%-
Between 10%.Using the specific surface area (such as Fig. 5) of BET specific surface area tester test material, specific surface area 400-600m2/
G, pore volume 0.7-1.2cm3/ g, pore-size distribution are 1.0-5nm (according to the different and different of initial feed)；
Heavy metal analysis performance test：The nano-particle modified nitrogen-doped carbon of the bismuth of obtained porous high-specific surface area is received
Rice sheet material is used as the analysis detection of heavy metal lead and cadmium in running water.Specific experiment step is as follows：
2mg carbon materials are accurately weighed with assay balance, add 2mL 0.125% Nafion ethanol solutions, ultrasonic vibration
Material is set to be uniformly dispersed, then pipettor takes 10 μ L to be applied to the glassy carbon electrode surface polished, and infrared lamp is dried, standby
With.Heavy metal analysis uses Square wave anodic stripping voltammetry method (SWASV), by glass-carbon electrode, to electrode (platinum electrode) and Ag-AgCl
Electrode form three-electrode system, take 10mL Acetic acid-sodium acetate buffer solution (pH 4.5) add with agitator electrolytic cell, three
In branch electrode submergence buffer solution, electrochemical analyser square wave anodic stripping voltammetry detection parameters are set：Amplitude：25mV；Current potential increases
Amount：4mV；Frequency：15mV；Accumulating potential -1.2V；Enrichment time 360s, 500 revs/min of stir speed (S.S.)；Time of repose 15s；It is molten
Go out take-off potential -1.0V, terminate current potential 0V.The μ g/L of sequentially determining 0.1,0.3,0.5,0.7,1.0,2,4,6,8,10 electric current rings
It should be worth, obtain working curve (such as Fig. 6).Then modified electrode again, running water 5mL, mixing 5mL pH 4.5 acetic acid-vinegar are taken
Then sour sodium buffer solution, mensuration mode sequentially add standard specimen three times, obtain lead cadmium in running water with the formulation process of working curve
Content is respectively 0.2 μ g/L and 0.35 μ g/L.Meet the standard of national drinking water.
Embodiment 2
A kind of preparation method of the nano-particle modified nitrogen-doped carbon nanometer sheet material of porous surface, high-specific surface area bismuth,
Specifically comprise the following steps：
Using 1.0g PVP K30 as carbon source and nitrogen source, the water for adding 10mL is substantially dissolved in beaker
Again into beaker add 5g bismuth acetate, stir and with alkene nitric acid regulation mixed solution pH value to 4.5, now bismuth nitrate is entirely molten
Solution.It is 12h in 130 DEG C of electric drying oven with forced convections until obtaining faint yellow solid forerunner that the solution prepared is placed in into temperature
Thing, it is put into after the faint yellow solid predecessor of gained is ground into fine powder in porcelain boat, in the nitrogen and argon that flow velocity is 30mL/min
Under oxygen mixture protective condition, it is placed in tube furnace and heats roasting.Roasting process is added with 8 DEG C/min heating rate from room temperature
Then heat is incubated 3h to 900 DEG C under 900 DEG C of high temperature, be finally down to room temperature, takes out sample, that is, obtains porous high-specific surface area
The nano-particle modified nitrogen-doped carbon nanometer sheet material of bismuth.
Heavy metal analysis performance test：The nano-particle modified nitrogen-doped carbon of the bismuth of obtained porous high-specific surface area is received
Rice sheet material is used as the analysis detection of heavy metal lead and cadmium in lake water.Specific experiment step is as follows：
2mg carbon materials are accurately weighed with assay balance, add 2mL 0.125% Nafion ethanol solutions, ultrasonic vibration
Material is set to be uniformly dispersed, then pipettor takes 10 μ L to be applied to the glassy carbon electrode surface polished, and infrared lamp is dried, standby
With.Heavy metal analysis uses Square wave anodic stripping voltammetry method (SWASV), glass-carbon electrode, to electrode (platinum electrode) and Ag-AgCl groups
Into three-electrode system, 10mL Acetic acid-sodium acetate buffer solution (pH4.5) is taken to add the electrolytic cell with agitator, three electrodes
Submerge in buffer solution, set electrochemical analyser square wave anodic stripping voltammetry detection parameters：Amplitude：25mV；Current potential increment：4mV；
Frequency：15mV；Accumulating potential -1.2V；Enrichment time 360s, 500 revs/min of stir speed (S.S.)；Time of repose 15s；Dissolution originates
Current potential -1.0V, terminate current potential 0V.The μ g/L of sequentially determining 0.1,0.3,0.5,0.7,1.0,2,3 current-responsive value, obtain work
Curve.Then modified electrode again, lake water 8mL, mixing 2mL pH4.5 Acetic acid-sodium acetate buffer solution, the same work of mensuration mode are taken
Make the formulation process of curve, then sequentially add standard specimen three times, it is respectively 2.1 μ g/L and 1.6 μ g/ to obtain lead cadmium content in lake water
L。
Other implementation steps are in the same manner as in Example 1.
Embodiment 3
A kind of preparation method of the nano-particle modified nitrogen-doped carbon nanometer sheet material of porous surface, high-specific surface area bismuth,
Specifically comprise the following steps：
Using 5.0g polyvinylpyrrolidone K25 as carbon source and nitrogen source, the water for adding 100mL is substantially dissolved in beaker
In, then 10g bismuth acetate is added into beaker, stirred and with the pH value of alkene nitric acid regulation mixed solution to 5.0, now bismuth nitrate
Fully dissolved.By the solution prepared be placed in temperature for 13h in 120 DEG C of electric drying oven with forced convections until obtaining faint yellow solid before
Drive thing, be put into after the faint yellow solid predecessor of gained is ground into fine powder in porcelain boat, flow velocity be 60mL/min nitrogen with
Under the conditions of argon gas is mixed gas protected, it is placed in tube furnace and heats roasting.Roasting process is with 5 DEG C/min heating rate from room temperature
800 DEG C are heated to, 1h is then incubated under 800 DEG C of high temperature, is finally down to room temperature, sample is taken out, that is, obtains porous high-ratio surface
The nano-particle modified nitrogen-doped carbon nanometer sheet material of long-pending bismuth.
Heavy metal analysis performance test：The nano-particle modified nitrogen-doped carbon of the bismuth of obtained porous high-specific surface area is received
Rice sheet material is used as the analysis detection of heavy metal lead and cadmium in papermaking sewage discharge.Specific experiment step is as follows：
4mg carbon materials are accurately weighed with assay balance, add 4mL 0.125% Nafion ethanol solutions, ultrasonic vibration
Material is set to be uniformly dispersed, then pipettor takes 10 μ L to be applied to the glassy carbon electrode surface polished, and infrared lamp is dried, standby
With.Heavy metal analysis uses Square wave anodic stripping voltammetry method (SWASV), glass-carbon electrode, to electrode (platinum electrode) and Ag-AgCl groups
Into three-electrode system, 10mL Acetic acid-sodium acetate buffer solution (pH4.5) is taken to add the electrolytic cell with agitator, three electrodes
Submerge in buffer solution, set electrochemical analyser square wave anodic stripping voltammetry detection parameters：Amplitude：25mV；Current potential increment：4mV；
Frequency：15mV；Accumulating potential -1.2V；Enrichment time 360s, 500 revs/min of stir speed (S.S.)；Time of repose 15s；Dissolution originates
Current potential -1.0V, terminate current potential 0V.The μ g/L of sequentially determining 0.1,0.3,0.5,0.7,1.0,2,3 current-responsive value, obtain work
Curve.Then modified electrode again, sewage 5mL, mixing 5mL pH4.5 Acetic acid-sodium acetate buffer solution, the same work of mensuration mode are taken
Make the formulation process of curve, then sequentially add standard specimen three times, it is respectively 3.8 μ g/L and 4.5 μ g/ to obtain lead cadmium content in sewage
L。
Other implementation steps are in the same manner as in Example 1.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the nano-particle modified nitrogen-doped carbon nanometer sheet material of bismuth of porous high-specific surface area, its feature
It is to comprise the following steps：
(a) using polyvinylpyrrolidone as carbon source and nitrogen source, add solvent and fully dissolve, obtain nitrogen source solution；
(b) bismuth salt is added into nitrogen source solution obtained by step (a), stirs and adjusts pH value with weak acid solution, make bismuth salt all molten
Solution, obtains mixed solution；
(c) nitrogen source solution obtained by step (b) is placed in electric drying oven with forced convection and is dried to obtain solid precursors；
(d) it is put into porcelain boat after the solid precursors of gained being ground into fine powder, under protective gas atmosphere, is placed in tube furnace
Heating roasting, obtains the nano-particle modified nitrogen-doped carbon nanometer sheet material of the bismuth of porous high-specific surface area.
2. preparation method according to claim 1, it is characterised in that：Step (a) polyvinylpyrrolidone is molecule
Measure more than one or both of polyvinylpyrrolidone between scope K25~K30.
3. preparation method according to claim 1, it is characterised in that：Step (a) solvent is deionized water, anhydrous second
It is more than one or both of alcohol, ethylene glycol, glycerine and polyethylene glycol；The nitrogen source solution concentration is 0.01g/mL-0.1g/
mL。
4. preparation method according to claim 1, it is characterised in that：Step (b) bismuth salt be bismuth nitrate, bismuth acetate or
Bismuth chloride；The weak acid solution is glacial acetic acid, dust technology or dilute sulfuric acid；The regulation pH value is regulation between 4.0-5.5.
5. preparation method according to claim 1, it is characterised in that：Polyvinylpyrrolidone described in step (a) and step
Suddenly the mass ratio of bismuth salt described in (b) is 1：0.1-5.
6. preparation method according to claim 1, it is characterised in that：Dried in step (c) electric drying oven with forced convection
Temperature be 110-130 DEG C, drying time 12-14h.
7. preparation method according to claim 1, it is characterised in that：Step (d) protective gas is nitrogen and argon gas
In it is one or two kinds of, its flow is 30-60mL/min.
8. preparation method according to claim 1, it is characterised in that：Step (d) tube furnace is in protective gas atmosphere
Under calcining heat risen to as 600-900 DEG C using 2-8 DEG C/min heating rate, be carbonized 1-3 hours.
9. the bismuth nano particle of porous high-specific surface area is prepared in a kind of preparation method as described in claim any one of 1-8
The nitrogen-doped carbon nanometer sheet material of modification, it is characterised in that：The carbon nanomaterial is nanometer sheet frame structure, and specific surface area is
400-800m2/ g, pore volume 0.7-1.2cm3/ g, pore-size distribution is in 1.0-5nm, and the mass content of nitrogen is between 4%-10%.
10. the nano-particle modified nitrogen-doped carbon nanometer sheet material of the bismuth of porous high-specific surface area according to claim 9
Application in the electrochemical analysis detection of trace heavy metal ion.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111330565A (en) * | 2020-03-03 | 2020-06-26 | 徐州工程学院 | Carbon-loaded nano bismuth composite material and preparation method and application thereof |
| CN111330565B (en) * | 2020-03-03 | 2022-12-16 | 徐州工程学院 | Carbon-loaded nano bismuth composite material and preparation method and application thereof |
| CN114524429A (en) * | 2022-02-21 | 2022-05-24 | 周口师范学院 | Nitrogen-doped carbon nano material and preparation method and application thereof |
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