CN103407991A - Preparation method of nickel/nickel oxide-decorated nitrogen-doped graphene material - Google Patents
Preparation method of nickel/nickel oxide-decorated nitrogen-doped graphene material Download PDFInfo
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Abstract
The invention provides a preparation method of a nickel/nickel oxide-decorated nitrogen-doped graphene material. The method comprises the following steps of: evenly dopping nitrogen elements in phene into a graphene slice; distributing nickel/nickel oxide particles on the graphene slice. The nickel/nickel oxide-decorated nitrogen-doped graphene material can be possibly applied to the fields of fuel cells, photocatalysis, biological catalysis, supercapacitors and the like. The nickel/nickel oxide-decorated nitrogen-doped graphene material has the beneficial effects that 1, compared with the pure graphene, the prepared graphene material decorated by nickel, nickel oxide and nitrogen has new properties; 2, a high-temperature heat treatment method is adopted, so that the equipment is simple and the production cost is low; 3, the adopted nickel phthalocyanine can be used for providing a nitrogen source and a nickel source simultaneously, so that the graphene material can be prepared by one step; 4, the graphene material is high in yield, so that the requirement of quantitative production is satisfied.
Description
Technical field
The present invention relates to a kind of nickel/nickel oxide and modify the preparation method of nitrogen-doped graphene material.
Background technology
Graphene is a kind of novel 2D carbon structure that the people such as the strong K of the peace moral of Univ Manchester UK in 2004 sea nurse (Andre K.Geim) finds, due to its unique structure and physical and chemical performance, has been subject to people's extensive attention.Graphene has that specific surface area is large, the conductivity high, has important researching value and application prospect in fields such as fuel cell, ultracapacitor, biocatalysis, lithium ion batteries.
Doping is a kind of method of adjustment Graphene performance commonly used, can effectively widen and promote the practical application of grapheme material.Correlative study shows: the nitrogen doping can change electronic structure and the energy band structure of Graphene, increases the reactive behavior point on Graphene surface, strengthens oxygen reduction catalysis, the biocatalysis performance of Graphene; Nitrogen is entrained on Graphene also can introduce avtive spot, help the immobilized of metallic particles, widen application (Haibo Wang, Thandavarayan Maiyalagan, and Xin Wang at catalytic field, Review on recent progress in nitrogen-doped graphene:synthesis, characterization, and its potential applications[J], ACS Catalysis, 2 (2012), 781-794.).Recent research shows: the Graphene catalysis water-splitting effectively that Ni and NiO modify, improve hydrogen yield; This material also be expected to for fuel cell, lithium ion battery, sensor field (A K Agegnechu et al.Enhanced hydrogen generation by cocatalytic Ni and NiO nanoparticles loaded on graphene oxide sheets[J], J.Mater.Chem., 22 (2012), 13849-13854.).Therefore, the doping of research Graphene is a significant problem.
Summary of the invention
The technical problem solved
For fear of the deficiencies in the prior art part, the present invention proposes the preparation method that a kind of nickel/nickel oxide is modified the nitrogen-doped graphene material, and by alkene, nitrogen element Uniform Doped is in graphene film, nickel/nickel oxide is distributed on graphene film with particle form.This nickel/nickel oxide is modified nitrogen-doped graphene and is expected to for fields such as fuel cell, photochemical catalysis, biocatalysis, ultracapacitors.
Technical scheme
A kind of nickel/nickel oxide is modified the preparation method of nitrogen-doped graphene material, it is characterized in that step is as follows:
The preparation of step 1, graphite oxide: container is positioned in ice-water bath, pours the vitriol oil into; By 3g crystalline graphite powder, 1.5g NaNO
3Pour in flask, stir, cooling 3h then, making system temperature is 0 ℃; In mixing solutions, add 9g KMnO
4, stir, during keep system temperature below 20 ℃; Container is moved into to oil bath pan, after 35 ℃ of constant temperature 2h, add deionized water, after 10min, add the hydrogen peroxide of dilution, obtain bright yellow solution; Filter reactant, use respectively 10% hydrochloric acid and distilled water repetitive scrubbing, suction filtration, dialysis gained sticky solid approaches neutral to the pH value; Dry, grinding gained solid is graphite oxide;
The dispersion of step 2, graphene oxide: take the graphite oxide of 60～100mg, measure 300～500mL dehydrated alcohol, ultrasonic with the conventional ultrasound cleanser, with 40kHz, 100W disperses 5h, the alcohol dispersion liquid of configuration graphene oxide.Keeping during this time temperature is 25 ℃;
Step 3, graphene oxide/Nickel Phthalocyanine compound: take 60～100mg Nickel Phthalocyanine, pour in the alcohol dispersion liquid of the graphene oxide that step 2 configures, ultrasonic with the conventional ultrasound cleanser, with 40kHz, 100W disperses 6h, and keeping temperature during ultrasonic is 25 ℃; Then mixing solutions is put into to baking oven, 80 ℃ of oven dry, to the sample complete drying; Take out beaker, scrape reactant, put into mortar and fully grind, obtain graphene oxide/Nickel Phthalocyanine powder;
The preparation that step 4, nickel/nickel oxide are modified nitrogen-doped graphene: pour the resulting graphene oxide of step 3/Nickel Phthalocyanine powder into porcelain boat, the silica tube heating zone of then porcelain boat being packed into, rubber stopper seal is adopted at two ends; After the rubber plug of jam-pack silica tube two ends, be evacuated to vacuum tightness and be less than 0.10MPa, then pass into argon gas to normal pressure, repeat to vacuumize; Triplicate, guarantee in silica tube without obviously oxygen is remaining; Continue to pass into argon gas, and be warming up to 800～1000 ℃ with the speed of 10 ℃/min; By powder 800～1000 ℃ of annealing 1h in argon gas atmosphere; Argon flow amount is 100sccm during this time; After annealing finished, powered-down, be chilled to room temperature by the porcelain boat stove; Stop ventilation, take out porcelain boat, collecting reaction product, obtain nickel/nickel oxide and modify the nitrogen-doped graphene material.
Beneficial effect
A kind of nickel that the present invention proposes/nickel oxide is modified the preparation method of nitrogen-doped graphene material, and by black alkene, nitrogen element Uniform Doped is in graphene film, nickel/nickel oxide is distributed on graphene film with particle form.This nickel/nickel oxide is modified nitrogen-doped graphene and is expected to for fields such as fuel cell, photochemical catalysis, biocatalysis, ultracapacitors.
Beneficial effect of the present invention:
1, prepare a kind of nickel/nickel oxide and modified the nitrogen-doped graphene material.With pure Graphene, compare, nickel, nickel oxide, the co-modified Graphene of nitrogen have new character.
2, use the high-temperature heat treatment method, equipment is simple, and production cost is low.
3, the Nickel Phthalocyanine adopted can provide nitrogenous source, nickel source simultaneously, realizes a step preparation of nickel/nickel oxide modification nitrogen-doped graphene material.
4, the productive rate of product is high, can reach and quantize the requirement of producing.
The accompanying drawing explanation
Fig. 1 is thermal treatment unit schematic diagram of the present invention;
Fig. 2 is the transmission electron microscope photo that the prepared nickel of the embodiment of the present invention one/nickel oxide is modified the nitrogen-doped graphene material;
Fig. 3 is the XPS collection of illustrative plates that the prepared nickel of the embodiment of the present invention one/nickel oxide is modified the nitrogen-doped graphene material;
Fig. 4 is the XRD figure spectrum that the prepared nickel of the embodiment of the present invention one/nickel oxide is modified the nitrogen-doped graphene material.
Embodiment
Now in conjunction with the embodiments, the invention will be further described for accompanying drawing:
Embodiment 1:
(1) preparation of graphite oxide: flask is positioned in ice-water bath, pours the appropriate vitriol oil into; By 3g crystalline graphite powder, 1.5g NaNO
3Pour in flask, stir, cooling 3h then, making system temperature is 0 ℃; In mixing solutions, add 9g KMnO
4, stir, during keep system temperature below 20 ℃; Flask is moved into to oil bath pan, after 35 ℃ of constant temperature 2h, add deionized water, after 10min, add the hydrogen peroxide of dilution, obtain bright yellow solution; Filter reactant, use respectively 10% hydrochloric acid and distilled water repetitive scrubbing, suction filtration, dialysis gained sticky solid approaches neutral to the pH value; Dry, grinding gained solid, obtain graphite oxide.
(2) dispersion of graphene oxide: take the 60mg graphite oxide that step 1 is prepared, measure the 500mL dehydrated alcohol, pour in beaker, disperse 5h with conventional ultrasound cleanser ultrasonic (40kHz, 100W), the alcohol dispersion liquid of configuration graphene oxide.Keeping during this time temperature is 25 ℃.
(3) graphene oxide/Nickel Phthalocyanine is compound: take the 60mg Nickel Phthalocyanine, pour in the alcohol dispersion liquid of the graphene oxide that step 2 configures, disperse 6h with conventional ultrasound cleanser ultrasonic (40kHz, 100W).During ultrasonic, keeping temperature is 25 ℃.Mixing solutions is put into to baking oven, and 80 ℃ of oven dry, to the sample complete drying.Take out beaker, scrape sample, put into mortar and fully grind, obtain graphene oxide/Nickel Phthalocyanine powder.
(4) nickel/nickel oxide is modified the preparation of nitrogen-doped graphene: pour the resulting graphene oxide of step 3/Nickel Phthalocyanine powder into porcelain boat, and the silica tube heating zone of then porcelain boat being packed into, rubber stopper seal is adopted at two ends.After the rubber plug of jam-pack silica tube two ends, be evacuated to vacuum tightness and be less than 0.10MPa, then pass into argon gas to normal pressure, repeat to vacuumize.Triplicate, guarantee in silica tube without obviously oxygen is remaining.Continue to pass into argon gas, and be warming up to 1000 ℃ with the speed of 10 ℃/min.Powder 1000C thermal treatment 1h(experimental installation in argon gas atmosphere is shown in to Fig. 1).Argon flow amount is 100sccm during this time.After annealing finished, powered-down, be chilled to room temperature by the porcelain boat stove.Stop ventilation, take out porcelain boat, collecting reaction product, obtain nickel/nickel oxide and modify the nitrogen-doped graphene material.
The transmission electron microscope photo of this nickel/nickel oxide modification nitrogen-doped graphene as shown in Figure 2.Can see, metallic particles is not of uniform size, loads on graphene film.Fig. 3 is its corresponding XPS collection of illustrative plates.As seen from the figure, than graphene oxide, in product, there are N, Ni, show the successful doping of N, Ni.In Fig. 3, the O peak intensity falls sharply, and shows that the graphene oxide in raw material is successfully reduced.The XPS quantitative analysis shows, in product, N content is 2.54at.%, and Ni content is 0.25at.%.Fig. 4 is its corresponding XRD figure spectrum.℃ peak in figure (2 θ=26.1 °) comes from Graphene; Ni and NiO peak come from Nickel Phthalocyanine.In figure, 44.36 °, 51.71 °, 76.09 °, three of Ni peaks correspond respectively to (111), (200), (220) three crystal faces.43.28 °, 51.75 °, 76.09 °, three peaks of NiO correspond respectively to (012), (003), (110) three crystal faces.
Embodiment 2:
(1) preparation of graphite oxide: flask is positioned in ice-water bath, pours the appropriate vitriol oil into; By 3g crystalline graphite powder, 1.5g NaNO
3Pour in flask, stir, cooling 3h then, making system temperature is 0 ℃; In mixing solutions, add 9g KMnO
4, stir, during keep system temperature below 20 ℃; Flask is moved into to oil bath pan, after 35 ℃ of constant temperature 2h, add deionized water, after 10min, add the hydrogen peroxide of dilution, obtain bright yellow solution; Filter reactant, use respectively 10% hydrochloric acid and distilled water repetitive scrubbing, suction filtration, dialysis gained sticky solid approaches neutral to the pH value; Dry, grinding gained solid, obtain graphite oxide.
(2) dispersion of graphene oxide: take the 20mg graphite oxide that step 1 is prepared, measure the 300mL dehydrated alcohol, pour in beaker, disperse 5h with conventional ultrasound cleanser ultrasonic (40kHz, 100W), the alcohol dispersion liquid of configuration graphene oxide.Keeping during this time temperature is 25 ℃.
(3) graphene oxide/Nickel Phthalocyanine is compound: take the 100mg Nickel Phthalocyanine, pour in the alcohol dispersion liquid of the graphene oxide that step 2 configures, disperse 6h with conventional ultrasound cleanser ultrasonic (40kHz, 100W).During ultrasonic, keeping temperature is 25 ℃.Mixing solutions is put into to baking oven, and 80 ℃ of oven dry, to the sample complete drying.Take out beaker, scrape sample, put into mortar and fully grind, obtain graphene oxide/Nickel Phthalocyanine powder.
(4) nickel/nickel oxide is modified the preparation of nitrogen-doped graphene: pour the resulting graphene oxide of step 3/Nickel Phthalocyanine powder into porcelain boat, and the silica tube heating zone of then porcelain boat being packed into, rubber stopper seal is adopted at two ends.After the rubber plug of jam-pack silica tube two ends, be evacuated to vacuum tightness and be less than 0.10MPa, then pass into argon gas to normal pressure, repeat to vacuumize.Triplicate, guarantee in silica tube without obviously oxygen is remaining.Continue to pass into argon gas, and be warming up to 1000 ℃ with the speed of 10 ℃/min.Powder 1000 ℃ of thermal treatment 1h(experimental installations in argon gas atmosphere are shown in to Fig. 1).Argon flow amount is 100sccm during this time.After annealing finished, powered-down, be chilled to room temperature by the porcelain boat stove.Stop ventilation, take out porcelain boat, collecting reaction product, can obtain nickel/nickel oxide and modify the nitrogen-doped graphene material.
Embodiment 3:
(1) preparation of graphite oxide: flask is positioned in ice-water bath, pours the appropriate vitriol oil into; By 3g crystalline graphite powder, 1.5g NaNO
3Pour in flask, stir, cooling 3h then, making system temperature is 0 ℃; In mixing solutions, add 9g KMnO
4, stir, during keep system temperature below 20 ℃; Flask is moved into to oil bath pan, after 35 ℃ of constant temperature 2h, add deionized water, after 10min, add the hydrogen peroxide of dilution, obtain bright yellow solution; Filter reactant, use respectively 10% hydrochloric acid and distilled water repetitive scrubbing, suction filtration, dialysis gained sticky solid approaches neutral to the pH value; Dry, grinding gained solid, obtain graphite oxide.
(2) dispersion of graphene oxide: take the 60mg graphite oxide that step 1 is prepared, measure the 500mL dehydrated alcohol, pour in beaker, disperse 5h with conventional ultrasound cleanser ultrasonic (40kHz, 100W), the alcohol dispersion liquid of configuration graphene oxide.Keeping during this time temperature is 25 ℃.
(3) graphene oxide/Nickel Phthalocyanine is compound: take the 60mg Nickel Phthalocyanine, pour in the alcohol dispersion liquid of the graphene oxide that step 2 configures, disperse 6h with conventional ultrasound cleanser ultrasonic (40kHz, 100W).During ultrasonic, keeping temperature is 25 ℃.Mixing solutions is put into to baking oven, and 80 ℃ of oven dry, to the sample complete drying.Take out beaker, scrape sample, put into mortar and fully grind, obtain graphene oxide/Nickel Phthalocyanine powder.
(4) nickel/nickel oxide is modified the preparation of nitrogen-doped graphene: pour the resulting graphene oxide of step 3/Nickel Phthalocyanine powder into porcelain boat, and the silica tube heating zone of then porcelain boat being packed into, rubber stopper seal is adopted at two ends.After the rubber plug of jam-pack silica tube two ends, be evacuated to vacuum tightness and be less than 0.10MPa, then pass into argon gas to normal pressure, repeat to vacuumize.Triplicate, guarantee in silica tube without obviously oxygen is remaining.Continue to pass into argon gas, and be warming up to 1000 ℃ with the speed of 10 ℃/min.Powder 800 ℃ of thermal treatment 1h(experimental installations in argon gas atmosphere are shown in to Fig. 1).Argon flow amount is 100sccm during this time.After annealing finished, powered-down, be chilled to room temperature by the porcelain boat stove.Stop ventilation, take out porcelain boat, collecting reaction product, can obtain nickel/nickel oxide and modify the nitrogen-doped graphene material.
Claims (1)
1. a nickel/nickel oxide is modified the preparation method of nitrogen-doped graphene material, it is characterized in that step is as follows:
The preparation of step 1, graphite oxide: container is positioned in ice-water bath, pours the vitriol oil into; By 3g crystalline graphite powder, 1.5g NaNO
3Pour in flask, stir, cooling 3h then, making system temperature is 0 ℃; In mixing solutions, add 9g KMnO
4, stir, during keep system temperature below 20 ℃; Container is moved into to oil bath pan, after 35 ℃ of constant temperature 2h, add deionized water, after 10min, add the hydrogen peroxide of dilution, obtain bright yellow solution; Filter reactant, use respectively 10% hydrochloric acid and distilled water repetitive scrubbing, suction filtration, dialysis gained sticky solid approaches neutral to the pH value; Dry, grinding gained solid is graphite oxide;
The dispersion of step 2, graphene oxide: take the graphite oxide of 60～100mg, measure 300～500mL dehydrated alcohol, ultrasonic with the conventional ultrasound cleanser, with 40kHz, 100W disperses 5h, the alcohol dispersion liquid of configuration graphene oxide.Keeping during this time temperature is 25 ℃;
Step 3, graphene oxide/Nickel Phthalocyanine compound: take 60～100mg Nickel Phthalocyanine, pour in the alcohol dispersion liquid of the graphene oxide that step 2 configures, ultrasonic with the conventional ultrasound cleanser, with 40kHz, 100W disperses 6h, and keeping temperature during ultrasonic is 25 ℃; Then mixing solutions is put into to baking oven, 80 ℃ of oven dry, to the sample complete drying; Take out beaker, scrape reactant, put into mortar and fully grind, obtain graphene oxide/Nickel Phthalocyanine powder;
The preparation that step 4, nickel/nickel oxide are modified nitrogen-doped graphene: pour the resulting graphene oxide of step 3/Nickel Phthalocyanine powder into porcelain boat, the silica tube heating zone of then porcelain boat being packed into, rubber stopper seal is adopted at two ends; After the rubber plug of jam-pack silica tube two ends, be evacuated to vacuum tightness and be less than 0.10MPa, then pass into argon gas to normal pressure, repeat to vacuumize; Triplicate, guarantee in silica tube without obviously oxygen is remaining; Continue to pass into argon gas, and be warming up to 800～1000 ℃ with the speed of 10 ℃/min; By powder 800～1000 ℃ of annealing 1h in argon gas atmosphere; Argon flow amount is 100sccm during this time; After annealing finished, powered-down, be chilled to room temperature by the porcelain boat stove; Stop ventilation, take out porcelain boat, collecting reaction product, obtain nickel/nickel oxide and modify the nitrogen-doped graphene material.
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| CN103871755A (en) * | 2014-03-05 | 2014-06-18 | 南京理工大学 | N-doped graphene/nickel ferrite nanometer compound material and preparation thereof |
| CN104449239A (en) * | 2014-12-18 | 2015-03-25 | 四川环碳科技有限公司 | Nitrogen-doped graphene composited electromagnetic shielding type electricity conductive primer and preparation method thereof |
| CN105110321A (en) * | 2015-07-29 | 2015-12-02 | 浙江工业大学 | Preparation method for nano-pores on surface of graphene by metal phthalocyanine and its alloy precursor |
| CN106158418A (en) * | 2016-07-14 | 2016-11-23 | 江苏大学 | A kind of preparation method of NiO/ nitrogen-doped graphene composite nano-electrode material |
| CN106944066A (en) * | 2017-03-30 | 2017-07-14 | 常州大学 | A kind of preparation method of hud typed nickel oxide/nickel photochemical catalyst |
| CN109529931A (en) * | 2018-11-16 | 2019-03-29 | 中北大学 | A kind of covalent immobilized metal phthalocyanine catalyst and its preparation method and application of graphene oxide |
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| CN103871755A (en) * | 2014-03-05 | 2014-06-18 | 南京理工大学 | N-doped graphene/nickel ferrite nanometer compound material and preparation thereof |
| CN104449239A (en) * | 2014-12-18 | 2015-03-25 | 四川环碳科技有限公司 | Nitrogen-doped graphene composited electromagnetic shielding type electricity conductive primer and preparation method thereof |
| CN105110321A (en) * | 2015-07-29 | 2015-12-02 | 浙江工业大学 | Preparation method for nano-pores on surface of graphene by metal phthalocyanine and its alloy precursor |
| CN106158418A (en) * | 2016-07-14 | 2016-11-23 | 江苏大学 | A kind of preparation method of NiO/ nitrogen-doped graphene composite nano-electrode material |
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| CN106944066A (en) * | 2017-03-30 | 2017-07-14 | 常州大学 | A kind of preparation method of hud typed nickel oxide/nickel photochemical catalyst |
| CN109529931A (en) * | 2018-11-16 | 2019-03-29 | 中北大学 | A kind of covalent immobilized metal phthalocyanine catalyst and its preparation method and application of graphene oxide |
| CN109529931B (en) * | 2018-11-16 | 2021-09-28 | 中北大学 | Graphene oxide covalent immobilized metal phthalocyanine catalyst and preparation method and application thereof |
| CN110400935A (en) * | 2019-07-30 | 2019-11-01 | 南京汉尔斯生物科技有限公司 | A kind of preparation method and fuel cell electrode of fuel cell nano-electrode material |
| CN115368801A (en) * | 2021-05-18 | 2022-11-22 | 江苏科辉环境科技有限公司 | Magnetized graphene coating and preparation method thereof |
| CN113550069A (en) * | 2021-08-04 | 2021-10-26 | 安徽锦鼎织造有限公司 | Preparation process of terahertz hot-air cotton |
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