CN103977802A - Nano needle-like nickel-coated graphite compound particle and preparation method and application thereof - Google Patents
Nano needle-like nickel-coated graphite compound particle and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a nano needle-like nickel-coated graphite compound particle and a preparation method and application thereof. The nano needle-like nickel-coated graphite compound particle is a nano needle-like nickel-coated flake graphite particle. The preparation method comprises the steps: processing the flake graphite particle, putting in a chemical nickel-plating solution, stirring while reacting, performing suction filtration, washing and drying to obtain the nano needle-like nickel-coated graphite compound particle. Compared with the prior art, the nano needle-like nickel-coated graphite compound particle has the main advantages that the activity of a catalyst prepared by adopting the preparation method is relatively high, for example, the reaction rate constant (k) for catalyzing reduction paranitrophenol by NaBH4 is 8.61*10<-2>min<-1>, and is greater than the k value (the rate constant is 14.82*10<-3>min<-1>) of a graphene oxide/nickel nano composite prepared by Ji and others and used for catalyzing the reaction. The nano needle-like nickel-coated graphite compound particle prepared by adopting the preparation method is magnetic, and is conveniently recycled. The preparation method disclosed by the invention is simple, low in cost and convenient to popularize and apply.
Description
Technical field
The present invention relates to composite and catalysis technical field, particularly relate to nanometer needle-like nickel bag graphite compound particle and its preparation method and application for a kind of synthetic para-aminophenol.
Background technology
Para-aminophenol (PAP) is a kind of important medicine, dye well organic synthesis intermediate, also can be used for manufacturing various dyestuffs, coloring agent, rubber antioxidant, photographic developer, agricultural chemicals antioxidant and oil dope etc. simultaneously.The synthetic method of para-aminophenol mainly contains p-nitrophenol iron powder reducing method, nitrobenzene method and p-nitrophenol catalytic hydrogenation method at present.Wherein paranitrophenol catalytic hydrogenating reduction method has simple to operate, the advantage such as product yield is high and quality is good, therefore be widely used.In the process of the synthetic p-aminophenol of paranitrophenol catalytic hydrogenating reduction method, the important role of catalyst, the quality of its performance directly affects the quality of reduzate, and the catalyst of high activity, high selectivity can improve the production efficiency of para-aminophenol, reduces production costs.
This catalyst has two classes at present: a class catalyst is with Al
2o
3, TiO
2, SiO
2or the noble metal type catalyst that active carbon etc. are carrier.For example: US Patent No. 4264529 has been used Pt/Al in preparation process
2o
3catalyst, due to Pt/Al
2o
3under acid medium condition, carrier easily dissolves, and causes catalyst heavy losses.Patent CN102658125A be take active carbon as carrier, Pt and MoS
2respectively as major catalyst and co-catalyst, and find when Pt load capacity is 2.5～3% time Pt/MoS
2the catalytic activity of/C is the highest, and it is good repeatedly to recycle rear catalytic activity maintenance.Yet Pt's is expensive, can increase the cost of p-aminophenol.
Another kind of is nickel catalyst, for example: Raney's nickel (Raney Ni), nano-nickel powder, or load the TiO2 of nano nickel, the materials such as SiO2.At present in industrial production large fecund with Raney's nickel (Raney Ni) as catalyst, yet its defect is mainly active low, poor heat resistance, and poor selectivity, as: there is on phenyl ring the problems such as hydrogenation, be difficult to practical requirement.Nano-nickel powder has that size is little, specific area is large and the feature such as Adsorption is many, and exploitation and the application at catalyst receives much attention.The people such as Du Yan (colleges and universities' Chemical Engineering journal 2004; 18 (4): 515-518) adopt the method for liquid-phase reduction to prepare the nano-nickel powder catalyst that average grain diameter is 57nm; Under same experiment condition, the catalytic activity of this catalyst is approximately 16 times of industrial normally used Raney Ni.But the particle diameter of this catalyst is less, there is problems such as being difficult for recovery.Patent CN101259414A has proposed a kind of at TiO
2, SiO
2deng the new method of loaded with nano Raney nickel on material, the carrier of the quantitative derivant of load of take is precursor, and induction hydrazine hydrate reduction nickel salt solution obtains load capacity and be 1～50% nano nickel catalyst, and the size of nanosphere nickel particle is within the scope of 5～25nm.The preparation method of this catalyst is simple, and the nano nickel forming on carrier is spherical or class is spherical, and its catalytic activity is only suitable with Raney's nickel.Therefore develop high activity, low cost, low pollution, selective good nitro compound hydrogenation catalyst significant.
Summary of the invention
Technical problem to be solved by this invention is that the purposes that a kind of nanometer needle-like nickel bag graphite compound particle and preparation method thereof and catalyzing N aBH4 reduction p-nitrophenol are para-aminophenol is provided for above-mentioned prior art, that gained nanometer needle-like nickel bag graphite compound particle possesses skills is simple, with low cost, catalytic activity is high, have the features such as the easy recycling of magnetic, synthetic para-aminophenol is with a wide range of applications in field simultaneously.
The present invention proposes the technological approaches addressing the above problem, nanometer needle-like nickel bag graphite compound particle, and it is the coated flake graphite particle of nickel of nanometer needle-like, for adopting following steps products therefrom: 1) preparation chemical nickel-plating solution; 2) after flake graphite particle is processed, be placed in chemical nickel-plating solution, after stirring reaction, suction filtration, washing, dry, obtain nanometer needle-like nickel bag graphite compound particle, described chemical nickel-plating solution is comprised of distilled water, nickel salt, sodium potassium tartrate tetrahydrate, NaOH and 85% hydrazine hydrate, wherein, the mol ratio of nickel salt and sodium potassium tartrate tetrahydrate is 1～6:30, the mol ratio of nickel salt and NaOH is 2～6:3, the mol ratio of nickel salt and hydrazine hydrate is 1～4:35, and described nickel salt is nickelous sulfate or nickel chloride.
Press such scheme, the flake graphite particle after processing and the w/v of chemical nickel-plating solution are 1～5:1g/L.
Press such scheme, step 2) stirring reaction temperature is 70～90 ℃.
Press such scheme, the processing method of flake graphite particle is:
1) flake graphite particle surface is cleaned to suction filtration, dry;
2) the flake graphite particle after cleaning is inserted to absorbed Ni ion in nickel sulfate solution, suction filtration, dry;
3) reduce the nickel ion of above-mentioned flake graphite particle surface, suction filtration, washing, dry.
The preparation method of described nanometer needle-like nickel bag graphite compound particle, includes following steps: 1) preparation chemical nickel-plating solution; 2) the flake graphite particle after processing is placed in chemical nickel-plating solution, after stirring reaction, suction filtration, washing, dry, obtain nanometer needle-like nickel bag graphite compound particle, described chemical nickel-plating solution is comprised of distilled water, nickel salt, sodium potassium tartrate tetrahydrate, NaOH and 85% hydrazine hydrate, wherein, the mol ratio of nickel salt and sodium potassium tartrate tetrahydrate is 1～6:30, the mol ratio of nickel salt and NaOH is 2～6:3, the mol ratio of nickel salt and hydrazine hydrate is 1～4:35, and described nickel salt is nickelous sulfate or nickel chloride.
Described nanometer needle-like nickel bag graphite compound particle is as the application of the catalyst of the synthetic para-aminophenol of catalyzing N aBH4 reduction p-nitrophenol.
The architectural feature of compound particle prepared by the present invention is that the nickel on graphite particle surface is nanometer needle-like, and this compound particle is with low cost, active high, has the features such as the easy recycling of magnetic simultaneously, can be used for catalyzing N aBH
4the synthetic para-aminophenol of reduction p-nitrophenol.
The present invention compared with prior art has following major advantage:
When the nanometer needle-like nickel bag graphite compound particle that 1, prepared by the present invention synthesizes p-aminophenol for the reduction of catalysis paranitrophenol, this compound particle embodies the advantage of following three aspects: (1) nano nickel loads on micron order graphite flake and can prevent its reunion; (2) thus the transmission that micron order graphite is a kind of conductive material can accelerate electronics improves the activity of catalyst; (3) the nanometer needle-like nickel that in addition, has an one-dimentional structure can further improve the catalytic activity of compound particle;
The activity of the catalyst that 2, prepared by the present invention is higher, for example: it is for catalyzing N aBH
4the reaction rate constant (k) of reduction paranitrophenol is 8.61 * 10
-2min
-1, graphene oxide/nickel nano composite material of preparing than people such as Ji (J.Mater.Chem.2012,22,3471) wants for the k value of this reaction of catalysis that large (its speed constant is 14.82 * 10
-3min
-1);
3, the nanometer needle-like nickel bag graphite compound particle that prepared by the present invention has magnetic, is convenient to recycling;
4, technology of preparing of the present invention is simple, and cost is low, easy to utilize.
Accompanying drawing explanation
Fig. 1 is the SEM figure of commercially available graphite;
Fig. 2 is the XRD spectrum of the synthetic nanometer needle-like nickel bag graphite compound particle of embodiments of the invention 1;
Fig. 3 is the SEM figure of the synthetic nanometer needle-like nickel bag graphite compound particle of embodiments of the invention 1;
Fig. 4 is the SEM figure of the synthetic nanometer needle-like nickel bag graphite compound particle of embodiments of the invention 2;
Fig. 5 is the SEM figure of the synthetic nanometer needle-like nickel bag graphite compound particle of embodiments of the invention 3;
Fig. 6 is the SEM figure of the synthetic nanometer needle-like nickel bag graphite compound particle of embodiments of the invention 4;
Fig. 7 is the VSM figure of the synthetic nanometer needle-like nickel bag graphite compound particle of embodiments of the invention 1;
Fig. 8 is the synthetic nanometer needle-like nickel bag graphite compound particle catalyzing N aBH4 reduction paranitrophenol A-λ time history plots of embodiments of the invention 1;
Fig. 9 is the lnA-t curve map of the synthetic nanometer needle-like nickel bag graphite compound particle of embodiments of the invention 1;
The synthetic schematic diagram of nanometer needle-like nickel bag graphite compound particle that Figure 10 example 1 of the present invention is synthetic.
The specific embodiment
Below in conjunction with embodiment and accompanying drawing, the invention will be further described, but do not limit the present invention.
Embodiment 1
Take 200mL absolute ethyl alcohol as solvent, 10g flake graphite particle is joined to the 8h that refluxes in the apparatus,Soxhlet's of 250mL, filter, vacuum drying is stand-by.In the nickel sulfate solution that graphite particle after cleaning-drying is inserted, adsorb 12h, filtration drying is standby; Get above-mentioned graphite particle again and insert in the ethanolic solution of sodium borohydride standingly, after graphite particle and ethanolic solution layering, filtration drying is standby.Another obtain solution, the hydrazine hydrate solution of getting 2.63g six hydration nickel sulfate, 25.4g Rochelle salt, 0.27g NaOH, 5.2mL85% is mixed with the solution of 100mL; 100mL solution is inserted in there-necked flask and is heated to 90 ℃, add the graphite of 0.5g after pre-treatment, reaction 0.5h.Suction filtration, and with deionized water washing 2 times, completely dry in vacuum drying chamber, obtain the nanometer shape pin nickel bag graphite compound particle shown in Fig. 3.
The contrast JCPDS No.08-0415 card of graphite and the JCPDS No.04-0850 card of nickel, XRD collection of illustrative plates from Fig. 2, the graphite (002) of fcc structure and (111) of Ni have been obtained respectively, and (220) crystal face diffraction maximum, and all do not find other dephasign diffraction maximum (200).The synthetic compound particle of this explanation the present embodiment 1 is comprised of elemental nickel and simple substance graphite.As shown in Figure 3, after liquid phase chemical reduction, the shape of nickel bag graphite compound particle of the present embodiment 1 preparation is identical with the shape of interior nuclear graphite, can be found out that the surface of flake graphite is all coated by nanometer needle-like nickel shell by illustration.
Figure 10 is the synthetic schematic diagram of the synthetic nanometer needle-like nickel bag graphite compound particle of real this example 1.Graphite particle after cleaning is electronegative, based on electrostatic adsorption, at graphite particle surface deposition nickel crystal seed, causes the carrying out of subsequent chemistry nickel plating reaction.Because the reaction rate of system is very low, the growth of nickel nucleus is controlled by surface free energy, thereby along <110> direction, grows the nickel of nanometer needle-like, obtains nanometer needle-like nickel bag graphite compound particle.
For further illustrating the magnetic property of the nanometer needle-like nickel bag graphite compound particle of above-described embodiment 1 preparation, use the magnetic property of PPMS measurement nanometer needle-like nickel bag graphite compound particle as Fig. 7, its saturation magnetization is 34.9emu/g.In like manner, the synthetic nickel bag graphite compound particle of other embodiment also obtains similar results.
For further illustrating the catalytic performance to electron transfer reaction for catalytic reduction paranitrophenol of the nanometer needle-like nickel bag graphite compound particle of above-described embodiment 1 preparation.42.5mg sodium borohydride solids is dissolved in 45ml deionized water solution, after stirring, adds the nanometer needle-like nickel bag graphite compound particle of the above-mentioned preparation of 5mg under 25oC, to stir maintenance 10min.Then add the paranitrophenol of 5ml0.05mM and start immediately timing.Every 2min sampling, by the absorbance within the scope of Uv-vis spectrophotometer scanning 260-500nm.As shown in Figure 8, it is nanometer needle-like nickel bag graphite compound particle catalysis sodium borohydride reduction paranitrophenol A-λ curve time history plot.The absworption peak at 400nm place is the maximum absorption band of paranitrophenol, the absworption peak of 300nm derives from its product p-aminophenol, from figure, can find out, prolongation along with the reaction time, the absworption peak of 400nm declines gradually, and the absworption peak of 300nm is strengthened thereupon, process 28min solution approaches colourless, illustrates to react and has carried out completely.In the experiment of sodium borohydride reduction paranitrophenol, the concentration of sodium borohydride is much larger than the concentration of paranitrophenol, therefore this reaction can be regarded pseudo first order reaction as, according to first-order kinetics lnA=-kt+c, made the curve map of lnA-t, the reaction rate constant that can calculate nanometer needle-like nickel bag graphite compound particle catalyst as Fig. 9 is 0.086min
-1.In like manner, the synthetic nickel bag graphite compound particle of other embodiment also obtains similar results.
Embodiment 2
Take 200mL absolute ethyl alcohol as solvent, 10g flake graphite particle is joined to the 8h that refluxes in the apparatus,Soxhlet's of 250mL, filter, vacuum drying is stand-by.In the nickel sulfate solution that graphite particle after cleaning-drying is inserted, adsorb 12h, filtration drying is standby; Get above-mentioned graphite particle again and insert in the ethanolic solution of sodium borohydride standingly, after graphite particle and ethanolic solution layering, filtration drying is standby.Another obtain solution, the hydrazine hydrate solution of getting 5.25g six hydration nickel sulfate, 28.2g Rochelle salt, 0.4g NaOH, 22mL85% is mixed with the solution of 200mL; 200mL solution is inserted in there-necked flask and is heated to 80 ℃, add the graphite of 0.5g after pre-treatment, reaction 0.5h.Suction filtration, and with deionized water washing 2 times, completely dry in vacuum drying chamber, obtain the nanometer shape pin nickel bag graphite compound particle shown in Fig. 3.
As shown in Figure 4, after liquid phase chemical reduction, the surface of its graphite particle of nickel bag graphite compound particle of the present embodiment 2 preparations is all coated by nanometer needle-like nickel shell.
Embodiment 3
Take 200mL absolute ethyl alcohol as solvent, 10g flake graphite particle is joined to the 8h that refluxes in the apparatus,Soxhlet's of 250mL, filter, vacuum drying is stand-by.In the nickel sulfate solution that graphite particle after cleaning-drying is inserted, adsorb 12h, filtration drying is standby; Get above-mentioned graphite particle again and insert in the ethanolic solution of sodium borohydride standingly, after graphite particle and ethanolic solution layering, filtration drying is standby.Another obtain solution, the hydrazine hydrate solution of getting 7.88g six hydration nickel sulfate, 98.5g Rochelle salt, 1.8g NaOH, 21mL85% is mixed with the solution of 300mL; 300mL solution is inserted in there-necked flask and is heated to 70 ℃, add the graphite of 0.5g after pre-treatment, reaction 0.5h.Suction filtration, and with deionized water washing 2 times, completely dry in vacuum drying chamber, obtain the nanometer shape pin nickel bag graphite compound particle shown in Fig. 4.
As shown in Figure 5, after liquid phase chemical reduction, the surface of its graphite particle of nickel bag graphite compound particle of the present embodiment 3 preparations is all coated by nanometer needle-like nickel shell.
Embodiment 4
Take 200mL absolute ethyl alcohol as solvent, 10g flake graphite particle is joined to the 8h that refluxes in the apparatus,Soxhlet's of 250mL, filter, vacuum drying is stand-by.In the nickel sulfate solution that graphite particle after cleaning-drying is inserted, adsorb 12h, filtration drying is standby; Get above-mentioned graphite particle again and insert in the ethanolic solution of sodium borohydride standingly, after graphite particle and ethanolic solution layering, filtration drying is standby.Another obtain solution, the hydrazine hydrate solution of getting 5.94g Nickel dichloride hexahydrate, 49.3g Rochelle salt, 1g NaOH, 30mL85% is mixed with the solution of 250mL; 250mL solution is inserted in there-necked flask and is heated to 80 ℃, add the graphite of 0.5g after pre-treatment, reaction 0.5h.Suction filtration, and with deionized water washing 2 times, completely dry in vacuum drying chamber, obtain the nanometer shape pin nickel bag graphite compound particle shown in Fig. 5.
As shown in Figure 6, after liquid phase chemical reduction, the surface of its graphite particle of nickel bag graphite compound particle of the present embodiment 4 preparations is all coated by nanometer needle-like nickel shell.
Embodiment 5
Take 200mL absolute ethyl alcohol as solvent, 10g flake graphite particle is joined to the 8h that refluxes in the apparatus,Soxhlet's of 250mL, filter, vacuum drying is stand-by.In the nickel sulfate solution that graphite particle after cleaning-drying is inserted, adsorb 12h, filtration drying is standby; Get above-mentioned graphite particle again and insert in the ethanolic solution of sodium borohydride standingly, after graphite particle and ethanolic solution layering, filtration drying is standby.Another obtain solution, the hydrazine hydrate solution of getting 10.5g six hydration nickel sulfate, 225g Rochelle salt, 2g NaOH, 80mL85% is mixed with the solution of 400mL; 400mL solution is inserted in there-necked flask and is heated to 75 ℃, add the graphite of 0.5g after pre-treatment, reaction 0.5h.Suction filtration, and with deionized water washing 2 times, completely dry in vacuum drying chamber, can obtain the nanometer needle-like nickel bag graphite compound particle similar to example before.
Embodiment 6
Take 200mL absolute ethyl alcohol as solvent, 10g flake graphite particle is joined to the 8h that refluxes in the apparatus,Soxhlet's of 250mL, filter, vacuum drying is stand-by.In the nickel sulfate solution that graphite particle after cleaning-drying is inserted, adsorb 12h, filtration drying is standby; Get above-mentioned graphite particle again and insert in the ethanolic solution of sodium borohydride standingly, after graphite particle and ethanolic solution layering, filtration drying is standby.Another obtain solution, the hydrazine hydrate solution of getting 13g six hydration nickel sulfate, 427g Rochelle salt, 1.67g NaOH, 50mL85% is mixed with the solution of 500mL; 500mL solution is inserted in there-necked flask and is heated to 85 ℃, add the graphite of 0.5g after pre-treatment, reaction 0.5h.Suction filtration, and with deionized water washing 2 times, completely dry in vacuum drying chamber, can obtain the nanometer needle-like nickel bag graphite compound particle similar to example before.
Claims (9)
1. nanometer needle-like nickel bag graphite compound particle, it is the coated flake graphite particle of nickel of nanometer needle-like, is to adopt following steps products therefroms: 1) preparation chemical nickel-plating solution; 2) after flake graphite particle is processed, be placed in chemical nickel-plating solution, after stirring reaction, suction filtration, washing, dry, obtain nanometer needle-like nickel bag graphite compound particle, described chemical nickel-plating solution is comprised of distilled water, nickel salt, sodium potassium tartrate tetrahydrate, NaOH and hydrazine hydrate, wherein, the mol ratio of nickel salt and sodium potassium tartrate tetrahydrate is 1～6:30, and the mol ratio of nickel salt and NaOH is 2～6:3, the mol ratio of nickel salt and hydrazine hydrate is 1～4:35, and described nickel salt is nickelous sulfate or nickel chloride.
2. according to the nanometer needle-like nickel bag graphite compound particle described in claim 1, it is characterized in that flake graphite particle after processing and the w/v of chemical nickel-plating solution are 1～5:1g/L.
3. according to the nanometer needle-like nickel bag graphite compound particle described in claim 1, it is characterized in that step 2) stirring reaction temperature is 70～90 ℃.
4. according to the nanometer needle-like nickel bag graphite compound particle described in claim 1, it is characterized in that the processing method of flake graphite particle is:
1) flake graphite particle surface is cleaned to suction filtration, dry;
2) the flake graphite particle after cleaning is inserted to absorbed Ni ion in nickel sulfate solution, suction filtration, dry;
3) reduce the nickel ion of above-mentioned flake graphite particle surface, suction filtration, washing, dry.
5. the preparation method of nanometer needle-like nickel bag graphite compound particle claimed in claim 1, includes following steps: 1) preparation chemical nickel-plating solution; 2) the flake graphite particle after processing is placed in chemical nickel-plating solution, after stirring reaction, suction filtration, washing, dry, obtain nanometer needle-like nickel bag graphite compound particle, described chemical nickel-plating solution is comprised of distilled water, nickel salt, sodium potassium tartrate tetrahydrate, NaOH and 85% hydrazine hydrate, wherein, the mol ratio of nickel salt and sodium potassium tartrate tetrahydrate is 1～6:30, the mol ratio of nickel salt and NaOH is 2～6:3, the mol ratio of nickel salt and hydrazine hydrate is 1～4:35, and described nickel salt is nickelous sulfate or nickel chloride.
6. according to the nanometer needle-like nickel bag graphite compound particle described in claim 5, it is characterized in that flake graphite particle after processing and the w/v of chemical nickel-plating solution are 1～5:1g/L.
7. according to the nanometer needle-like nickel bag graphite compound particle described in claim 5, it is characterized in that step 2) stirring reaction temperature is 70～90 ℃.
8. according to the nanometer needle-like nickel bag graphite compound particle described in claim 5, it is characterized in that the processing method of flake graphite particle is:
1) flake graphite particle surface is cleaned to suction filtration, dry;
2) the flake graphite particle after cleaning is inserted to absorbed Ni ion in nickel sulfate solution, suction filtration, dry;
3) reduce the nickel ion of above-mentioned flake graphite particle surface, suction filtration, washing, dry.
9. the nanometer needle-like nickel bag graphite compound particle described in claim 1 is as catalyzing N aBH
4the application of the catalyst of the synthetic para-aminophenol of reduction p-nitrophenol.
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| JP2018103172A (en) * | 2016-12-22 | 2018-07-05 | 国立成功大学 | Nano-nickel catalyst and carbon oxide hydrogenation method |
| CN109536933A (en) * | 2018-12-06 | 2019-03-29 | 江苏大学 | A kind of method of graphite flake plating nickel on surface nano particle |
| CN109626549A (en) * | 2019-01-17 | 2019-04-16 | 上海理工大学 | A kind of method of quick catalysis degradation 4- nitrophenol |
| CN111408713A (en) * | 2020-03-17 | 2020-07-14 | 苏州逸峰新材料科技有限公司 | Preparation method of nickel-coated graphite composite powder material with high coating rate |
| CN111424266A (en) * | 2020-03-19 | 2020-07-17 | 西安工程大学 | Preparation method of nickel-coated graphite composite particles |
| WO2021212775A1 (en) * | 2020-04-24 | 2021-10-28 | 南京同诚节能环保装备研究院有限公司 | Preparation method for nickel-coated graphene silicon carbide |
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| CN106563473A (en) * | 2015-10-08 | 2017-04-19 | 南京理工大学 | A high-efficiency surface plasma visible-light-induced photocatalyst composite material (Ag@AgCl)-Ni/RGO having magnetic responsibility |
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| CN109626549B (en) * | 2019-01-17 | 2021-11-30 | 上海理工大学 | Method for rapidly catalyzing and degrading 4-nitrophenol |
| CN111408713A (en) * | 2020-03-17 | 2020-07-14 | 苏州逸峰新材料科技有限公司 | Preparation method of nickel-coated graphite composite powder material with high coating rate |
| CN111424266A (en) * | 2020-03-19 | 2020-07-17 | 西安工程大学 | Preparation method of nickel-coated graphite composite particles |
| WO2021212775A1 (en) * | 2020-04-24 | 2021-10-28 | 南京同诚节能环保装备研究院有限公司 | Preparation method for nickel-coated graphene silicon carbide |
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