CN103950922A - Preparation method of nano-hydroxyapatite/nano-hydroxyapatite gas sensing material - Google Patents
Preparation method of nano-hydroxyapatite/nano-hydroxyapatite gas sensing material Download PDFInfo
- Publication number
- CN103950922A CN103950922A CN201410172636.4A CN201410172636A CN103950922A CN 103950922 A CN103950922 A CN 103950922A CN 201410172636 A CN201410172636 A CN 201410172636A CN 103950922 A CN103950922 A CN 103950922A
- Authority
- CN
- China
- Prior art keywords
- preparation
- graphene
- hydroxyapatite
- gas sensing
- phosphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The invention relates to a preparation method of a nano-hydroxyapatite/nano-hydroxyapatite gas sensing material. The preparation method comprises the following steps: first, preparing a graphene oxide dispersion liquid by an ultrasonic method; preparing hydroxylated modified graphene through reduction and modification of a mussel foot fibronectin analogue; in-situ reducing nucleation and growth of nucleation by a chemical precipitation method; and centrifugalizing, washing and drying to obtain the nano-hydroxyapatite/nano-hydroxyapatite gas sensing material. A gas sensor element can be prepared by the following steps: preparing the obtained gas sensing material with a binder to slurry; coating the slurry on a base body with an electrode; and then, sintering and welding for 3 hours at 300 DEG C under a nitrogen protective atmosphere.
Description
Technical field
The present invention relates to nano gas sensing material and gas field of sensing technologies, especially a kind of preparation method of nanometer hydroxyapatite/Graphene gas sensing material and the application on gas sensor thereof.
Background technology
Nano material has the features such as electricity that specific surface area is large, superior and absorption property, in gas sensing field, has obtained significant progress.And Graphene is as a kind of special two-dimensional nano material, there is high active surface and specific conductivity, in air-sensitive performance detects, signal to noise ratio is high, has obtained increasing concern.In theory, Graphene can reach molecular level to the response of gas, but in practical application, Graphene, in gas response process, often occurs that resistance reply is less than original level, and forward or negative sense drift occur.At present, investigator generally adopts doping heavy metal ion and prepares response sensitivity and the stability that the modes such as graphene/nanometer oxide semiconductor improve graphene-based gas sensor.
(Hydroxyapatite, chemical formula is Ca to hydroxyapatite
10(PO
4)
6(OH)
2, be abbreviated as HA) and be the main grey matter composition of vertebrates bone and tooth.Hydroxyapatite has special three-dimensional netted tunnel structure, in its tunnel, has Ca
2+and OH
-ion, can be for ion-exchange.In addition, there is multiple adsorption site on hydroxyapatite crystal surface, is respectively the C site of positively charged and the P site of the negative point of band, to having the material of different charged character, comprises gas, shows superior absorption property.HA has been widely used in Electrochemical Detection and chromatographic separation, and its report as the research of gas sensing is still few.HA can be applied to ethanol, CO and CO
2gas sensing, investigator thinks that these gas molecules react with the OH-on HA surface and generates CO
3 2-, enter in the lattice of HA, or carry out room doping, thereby cause the variation of HA specific conductivity.Although hydroxyapatite has very superior absorption property, its conductive capability is poor, and service temperature is higher, and this has limited the application of HA in gas sensing greatly.The people such as M Nagai (Sensors and Actuators.1988,15,145-151) by doped with Cl in HA
-change the unit cell parameters of HA, thereby reduce CO
3 2-displacement OH
-the stress of Shi Yinqi, and then the air-sensitive performance of raising HA.The people such as Mene (Journal of Alloys and Compounds.2014,584,487-493) by ionizing radiation technology (Swift heavy ions irradiation, SHI) and doped F e element, physical attribute and the crystalline structure of HA have been changed, comprise and improve material surface electronegativity, formed new chemical bond and defect etc., thereby made HA to CO
2the response sensitivity of gas sensing is improved, and service temperature decreases.Therefore, for above-mentioned technical problem, the present invention adopts the gas sensing material of nanometer hydroxyapatite and Graphene initiatively, and the superior absorption property of hydroxyapatite and the conductivity of Graphene are combined, and will improve largely sensitivity and the stability of sensor.
At present, about preparing the research of nanometer hydroxyapatite and carbon material (as carbon nanotube and Graphene) mixture and reporting seldom.The people such as Zhu reported the effect that adopts the method for discharge plasma sintering to realize graphene sheet layer to strengthen HA pottery (Advanced Engineering Materials.2011,13,336-341).Yet this method need to be carried out under comparatively high temps, the microstructure of mixture inside is difficult to control.Gururaj M etc. utilizes quadrol redox graphene to obtain Graphene presoma, and obtain Graphene/hydroxyapatite composite material (J. Materials Research Bulletin. (2010) .08.077) by coprecipitation method, this method has been used toxic agent quadrol, and batch production process will produce pollution to environment.Chinese patent CN201210055981.0 and CN201310296678.4 are usingd graphene oxide as presoma, adopt hydrothermal method redox graphene to prepare nanometer hydroxyapatite simultaneously, thereby obtain Graphene/HA mixture, equipment and the energy cost of this method are high, and long reaction time, the having little significance of scale operation.HongyanLiu etc. utilize Dopamine HCL reduction and modify graphene oxide, again by method synthesizing graphite alkene/hydroxyapatite composite material (J.Phys.Chem.C2012 of biomineralization, 116,3334-3341), the hydroxyapatite that the method obtains is that nanometer is spherical, but crystallinity is poor, because reaction is carried out in simulated body fluid, reaction time is long, and the HA of load on graphene sheet layer amount seldom.
Summary of the invention
The preparation method who the object of the present invention is to provide a kind of nanometer hydroxyapatite/Graphene gas sensing material, technique is simple, and nanometer hydroxyapatite/Graphene gas sensing material of preparation has higher adsorption activity and conductive capability.
The present invention also aims to provide a kind of gas sensor, it comprises the nanometer hydroxyapatite/Graphene gas sensing material being made by above-mentioned preparation method, has higher sensitivity and stability.
For realizing its goal of the invention, the preparation method of nanometer hydroxyapatite/Graphene gas sensing material of the present invention, concrete steps are as follows:
The reduction of a, graphene oxide and modification
By concentration, be the ultrasonic 40 ~ 120kHz supersound process of graphene oxide 1 ~ 6h of 0.2 ~ 2 mg/ml, form the monolithic graphene oxide suspension liquid of favorable dispersity, mussel foot Fibronectin analogue is dissolved in Tris-HCl solution (10mM, pH=8.5).Above-mentioned two kinds of solution equal-volumes are mixed, magnetic agitation 0.5 ~ 16h, solid is separated from suspension liquid, washing, 60 ~ 80 ℃ of vacuum-drying 12 ~ 24h obtain powder;
Described mussel foot Fibronectin analogue is selected from dopamine hydrochloride and norepinephrine.
The concentration of described mussel foot Fibronectin analogue in Tris-HCl solution is 0.5 ~ 4mg/ml.
The Tris-HCl solution of described mussel foot Fibronectin analogue need to dissolve in air, and magnetic agitation 20 ~ 60s, mixes this solution rapidly with the dispersion liquid of graphene oxide.
The described method that solid is separated from suspension liquid is centrifugation or suction filtration, and centrifugation rate is 6000 ~ 12000rpm, and it is the microfiltration membrane of 0.22 ~ 0.45 μ m that suction filtration adopts aperture.
The preparation of b, nanometer hydroxyapatite/Graphene gas sensing material
What in accurate weighing step a, obtain is hydroxylated grapheme modified, 40 ~ 120kHz is ultrasonic to be scattered in the ionic calcium soln of the 0.05 ~ 0.5mol/L preparing in advance, the concentration of Graphene is controlled at 0.2 ~ 2mg/ml, then the phosphate solution that is 0.03 ~ 0.3mol/L with equal-volume, concentration mixes, by pH adjusting agent, regulating the pH value of mixing solutions is 9 ~ 13, temperature of reaction is controlled at 15 ~ 80 ℃, then strong magnetic agitation 2h, still aging 12 ~ 48h, separated, washing, ethanol is washed, and 60 ℃ of dry 12 ~ 24h of vacuum obtain powder.
Described hydroxylated grapheme modified and mass ratio calcium solution are (10 ~ 100): 1.
Described concentration is that the ionic calcium soln of 0.05 ~ 0.5mol/L is ca nitrate soln, calcium acetate solution, calcium chloride solution, calcium hydroxide suspension liquid or calcium carbonate soln.
Described concentration is that the phosphate solution of 0.03 ~ 0.3mol/L is primary ammonium phosphate, Secondary ammonium phosphate, Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC, potassium primary phosphate, dipotassium hydrogen phosphate, tetra-sodium, trisodium phosphate or tripoly phosphate sodium STPP.
Described pH adjusting agent is sodium hydroxide, potassium hydroxide, urea, ammoniacal liquor or dimethyl formamide.
The method of described separation is centrifugation or suction filtration, and centrifugation rate is 2000 ~ 8000rpm, and it is the microfiltration membrane of 0.22 ~ 0.45 μ m that suction filtration adopts aperture.
The present invention also provides a kind of gas sensor, comprises with the matrix of electrode and is coated on the nanometer hydroxyapatite/graphene composite material on matrix, and nanometer hydroxyapatite/grapheme material is made by above-mentioned preparation method.
Concrete grammar is: the nanometer hydroxyapatite/graphene complex preparing in step b is placed in to agate mortar; add wherein a small amount of binding agent; fully grind; the slurry obtaining is evenly coated on the matrix with electrode; 60 ~ 100 ℃ of vacuum-dryings; then matrix is placed in to tube furnace, in nitrogen protection atmosphere in 250 ~ 700 ℃ of sintering 2 ~ 6h.
Described binding agent is ethanol, ultrapure water, glycerine, Terpineol 350 and polyvinyl alcohol glue.
The described matrix with electrode is microcrystalline glass, Al
2o
3ceramic plate or high resistant silicon chip are made.
Electrode on described matrix is two gold electrodes, by means of electron beam deposition, obtains, and thickness is 400 ~ 800nm, and positive and negative electrode spacing is 1 ~ 2mm, in deposition process, draws two platinum wire electrode lead-in wires respectively from two gold electrodes.
This preparation method's environmental friendliness, method is simple, conveniently regulating and controlling, and be beneficial to large-scale mass production, nanometer hydroxyapatite/Graphene gas sensing material of preparing by aforesaid method at room temperature has excellent sensing capabilities to ammonia molecule, is suitable for a large amount of preparations of gas sensor.
Accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme in the embodiment of the present invention, below the accompanying drawing of required use during embodiment is described is briefly described, apparently, accompanying drawing relevant of the present invention in the following describes is only some embodiments of the present invention, for those of ordinary skills, do not paying under the prerequisite of creative work, can also obtain other accompanying drawing according to these accompanying drawings.
Fig. 1 is the preparation process schematic diagram of the nanometer hydroxyapatite/Graphene gas sensing material in embodiment 1 provided by the invention.
Fig. 2 is the transmission electron microscope picture of nanometer hydroxyapatite/Graphene gas sensing material of the embodiment of the present invention 1 preparation.
Fig. 3 is the X-ray diffraction analysis spectrogram of nanometer hydroxyapatite/Graphene gas sensing material of the embodiment of the present invention 1 preparation.
Fig. 4 is the at room temperature response correlation curve figure to different concns ammonia molecule of nanometer hydroxyapatite/Graphene gas sensing material of the embodiment of the present invention 1 preparation and pure reduced graphene.
Fig. 5 is nanometer hydroxyapatite/Graphene gas sensing material response curve in three continuous ammonia concentration intervals of the embodiment of the present invention 1 preparation.
Wherein gas sensing response sensitivity is S=(Rg-Ra)/Ra, the resistance value that wherein Ra and Rg are respectively element in air and in atmosphere to be measured.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is described in detail.
The preparation method of the gas sensor of the present embodiment based on nanometer hydroxyapatite/Graphene gas sensing material (can with reference to figure 1), comprises the steps.
A, by the ultrasonic 60kHz supersound process of graphene oxide 0.02g 2h, form the monolithic graphene oxide suspension liquid 1mg/ml of favorable dispersity.0.04mg dopamine hydrochloride is dissolved in Tris-HCl solution (10mM, pH=8.5), and concentration is 2mg/ml, stirs 10s.Then rapidly two kinds of solution equal-volumes are mixed, magnetic agitation 11h, the centrifugal 10min of 12000 rpm, washes respectively 3 times, and ethanol is washed 2 times, and 60 ℃ of vacuum-drying 12h of the throw out obtaining are obtained to powder.
The hydroxylated grapheme modified 10mg obtaining in b, accurate weighing step a, the ultrasonic Ca (NO that is scattered in the 0.05mol/L preparing in advance of 60 kHz
3)
24H
2in O solution, the concentration of Graphene is controlled at 1mg/ml, then with NH isopyknic, that concentration is 0.03mol/L
4h
2pO
4solution mixes, and with strong aqua, regulating the pH value of mixing solutions is 11, and temperature of reaction is controlled at 37 ℃, then strong magnetic agitation 2h, still aging 12h, the centrifugal 10min of 6000rpm, wash 3 times, ethanol is washed 2 times, and 60 ℃ of vacuum-drying 12h of the precipitation obtaining are obtained to powder.
C, employing micro-processing technology are at Al
2o
3on ceramic plate matrix, by means of electron beam deposition, obtaining thickness is 400 ~ 800nm, and positive and negative electrode spacing is two gold electrodes of 1.5 mm, in deposition process, draws two platinum wire electrode lead-in wires respectively from two gold electrodes.
D, get the nanometer hydroxyapatite/Graphene gas sensing material 10mg preparing in step b; be placed in agate mortar; add wherein a small amount of polyvinyl alcohol glue (2 wt%); fully grind; the slurry obtaining is coated on the matrix with electrode uniformly; 60 ℃ of vacuum-dryings, are then placed in tube furnace by element, in nitrogen protection atmosphere in 500 ℃ of sintering 3h.Thereby obtain nanometer hydroxyapatite/Graphene gas sensing material gas sensor.
From Fig. 2 transmission electron microscope picture, can be clearly seen that nanometer needle-like hydroxyapatite is riveted on graphene nano lamella evenly, dispersedly, without the gathering of bulk composite and stacking.
The thing phase that can find out hydroxyapatite from Fig. 3 X-ray diffraction analysis spectrogram is consistent with standard card (PDF # 09-0432).
From Fig. 4 nanometer hydroxyapatite/Graphene gas sensing material and pure reduced graphene at room temperature to the response curve comparison diagram of different concns ammonia molecule, can be clearly seen that, the former sensitivity has obvious lifting.
Fig. 5 can see nanometer hydroxyapatite/Graphene gas sensing material to only have ~ 5 % of response error in three continuous ammonia concentration intervals, and cyclical stability is good.
Nanometer hydroxyapatite/Graphene gas sensing the material being made by step a, b has higher adsorption activity and conductive capability, except for gas sensor, and can also be for other products.
Embodiment 2:
Method steps and the parameter of the present embodiment and embodiment 1 are basic identical, and different is that the reduction and the modifier that add are norepinephrine.The performance of the nanometer hydroxyapatite/Graphene gas sensing material making by the method step and parameter is substantially the same manner as Example 1.
Embodiment 3:
Method steps and the parameter of the present embodiment and embodiment 1 are basic identical, and different is that calcium solution is the Ca (OH) of 0.01mol/L
2suspension liquid, then the phosphorus solution dropwise the adding H that is 0.006mol/L
3pO
4solution.The performance of the nanometer hydroxyapatite/Graphene gas sensing material making by the method step and parameter is substantially the same manner as Example 1.
Embodiment 4:
Method steps and the parameter of the present embodiment and embodiment 1 are basic identical, and different is that phosphorus solution is diammonium hydrogen phosphate solution.The performance of the nanometer hydroxyapatite/Graphene gas sensing material making by the method step and parameter is substantially the same manner as Example 1.
Embodiment 5:
Method steps and the parameter of the present embodiment and embodiment 1 are basic identical, and the binding agent that different is adopts is ethanol, and sintering process to control temperature be 300 ℃, 2h.The performance of the nanometer hydroxyapatite/Graphene gas sensor making by the method step and parameter is substantially the same manner as Example 1.
Obviously, described embodiment is only the present invention's part embodiment, rather than whole embodiment.Embodiment based in the present invention, the every other embodiment that those of ordinary skills obtain under the prerequisite of not making creative work, belongs to the scope of protection of the invention.
Claims (10)
1. a preparation method for nanometer hydroxyapatite/Graphene gas sensing material, is characterized in that, comprises the steps:
The reduction of a, graphene oxide and modification
By concentration, be graphene oxide supersound process 1 ~ 6h under 40 ~ 120kHz of 0.2 ~ 2 mg/ml, form the monolithic graphene oxide suspension liquid of favorable dispersity, it is 10mM that mussel foot Fibronectin analogue is dissolved in to concentration, in the Tris-HCl solution of pH=8.5, above-mentioned two kinds of solution equal-volumes are mixed, magnetic agitation 0.5 ~ 16h, solid is separated from suspension liquid, washing, 60 ~ 80 ℃ of vacuum-drying 12 ~ 24h obtain powder;
The preparation of b, nanometer hydroxyapatite/Graphene gas sensing material
Weigh obtain in step a hydroxylated grapheme modified, under 40 ~ 120kHz in the ultrasonic ionic calcium soln that is scattered in the 0.05 ~ 0.5mol/L preparing in advance, the concentration of Graphene is controlled at 0.2 ~ 2mg/ml, then the phosphate solution that is 0.03 ~ 0.3mol/L with equal-volume, concentration mixes, by pH adjusting agent, regulating the pH value of mixing solutions is 9 ~ 13, temperature of reaction is controlled at 15 ~ 80 ℃, then strong magnetic agitation 2 ~ 4h, still aging 12 ~ 48h, separated, washing, 60 ~ 80 ℃ of vacuum-drying 12 ~ 24h obtain powder.
2. preparation method according to claim 1, is characterized in that: in step a, mussel foot Fibronectin analogue is dopamine hydrochloride or norepinephrine.
3. preparation method according to claim 1, is characterized in that: in step a, the concentration of mussel foot Fibronectin analogue in Tris-HCl solution is 0.5 ~ 4mg/ml.
4. preparation method according to claim 1, is characterized in that: in step a, the Tris-HCl solution of mussel foot Fibronectin analogue dissolves in air, magnetic agitation 20 ~ 60s, and this solution is mixed with the dispersion liquid of graphene oxide.
5. preparation method according to claim 1, is characterized in that: in step a, the method that solid is separated from suspension liquid is centrifugation or suction filtration, and centrifugation rate is 6000 ~ 12000rpm, and it is the microfiltration membrane of 0.22 ~ 0.45 μ m that suction filtration adopts aperture.
6. preparation method according to claim 1, is characterized in that: in step b, hydroxylated grapheme modified and mass ratio ionic calcium soln are (10 ~ 100): 1.
7. preparation method according to claim 1, is characterized in that: in step b, the ionic calcium soln that concentration is 0.05 ~ 0.5mol/L is ca nitrate soln, calcium acetate solution, calcium chloride solution, calcium hydroxide suspension liquid or calcium carbonate soln.
8. preparation method according to claim 1, it is characterized in that: in step b, the phosphate solution that concentration is 0.03 ~ 0.3mol/L is primary ammonium phosphate, Secondary ammonium phosphate, Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC, potassium primary phosphate, dipotassium hydrogen phosphate, tetra-sodium, trisodium phosphate or tripoly phosphate sodium STPP.
9. preparation method according to claim 1, is characterized in that: in step b, pH adjusting agent is sodium hydroxide, potassium hydroxide, urea, ammoniacal liquor or dimethyl formamide.
10. a gas sensor, it is characterized in that, comprise the matrix with electrode, and the nanometer hydroxyapatite/Graphene gas sensing material that is coated on connection electrode on matrix, nanometer hydroxyapatite/Graphene gas sensing material is made by the preparation method described in claim 1 ~ 9 any one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410172636.4A CN103950922B (en) | 2014-04-28 | 2014-04-28 | The preparation method of nanometer hydroxyapatite/Graphene gas sensing material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410172636.4A CN103950922B (en) | 2014-04-28 | 2014-04-28 | The preparation method of nanometer hydroxyapatite/Graphene gas sensing material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103950922A true CN103950922A (en) | 2014-07-30 |
| CN103950922B CN103950922B (en) | 2016-04-20 |
Family
ID=51328315
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410172636.4A Active CN103950922B (en) | 2014-04-28 | 2014-04-28 | The preparation method of nanometer hydroxyapatite/Graphene gas sensing material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103950922B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107161969A (en) * | 2017-06-08 | 2017-09-15 | 昆明理工大学 | A kind of preparation method of nanometer hydroxyapatite/graphene oxide composite material |
| CN108342109A (en) * | 2018-04-12 | 2018-07-31 | 华东理工大学 | A kind of hydroxyapatite/stannic oxide/graphene nano composite lamainated structure anti-corrosion paint |
| CN108467027A (en) * | 2018-03-13 | 2018-08-31 | 镇江致达新材料科技有限公司 | A kind of method of the microwave radiation technology preparation with wearability CGN/HA composite materials |
| CN109205581A (en) * | 2018-08-29 | 2019-01-15 | 湖北大学 | A kind of preparation method of the composite hydroxylapatite powder with photo-thermal Synergistic antimicrobial performance |
| CN114113240A (en) * | 2021-11-22 | 2022-03-01 | 中南大学 | Room-temperature ammonia sensing material and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101172592A (en) * | 2007-10-22 | 2008-05-07 | 中国科学院上海硅酸盐研究所 | Hydroxyapatite micrometre tube and method of producing the same |
| CN101891174A (en) * | 2009-03-11 | 2010-11-24 | 北京林业大学 | Hydroxyapatite with hollow sphere structure and preparation method thereof |
| CN102616762A (en) * | 2011-02-01 | 2012-08-01 | 中国科学院上海硅酸盐研究所 | Method for hydro-thermal preparation of hydroxyapatite powder by calcium silicate precursor |
| CN102778478A (en) * | 2012-05-15 | 2012-11-14 | 中国科学技术大学 | Graphene-modified doped tin oxide composite material and preparation method thereof |
| CN103083729A (en) * | 2013-01-28 | 2013-05-08 | 西南科技大学 | Production method of three-dimensional porous composite bar |
| CN103420364A (en) * | 2013-07-13 | 2013-12-04 | 西南交通大学 | Preparation method of grapheme/hydroxyapatite composite material |
-
2014
- 2014-04-28 CN CN201410172636.4A patent/CN103950922B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101172592A (en) * | 2007-10-22 | 2008-05-07 | 中国科学院上海硅酸盐研究所 | Hydroxyapatite micrometre tube and method of producing the same |
| CN101891174A (en) * | 2009-03-11 | 2010-11-24 | 北京林业大学 | Hydroxyapatite with hollow sphere structure and preparation method thereof |
| CN102616762A (en) * | 2011-02-01 | 2012-08-01 | 中国科学院上海硅酸盐研究所 | Method for hydro-thermal preparation of hydroxyapatite powder by calcium silicate precursor |
| CN102778478A (en) * | 2012-05-15 | 2012-11-14 | 中国科学技术大学 | Graphene-modified doped tin oxide composite material and preparation method thereof |
| CN103083729A (en) * | 2013-01-28 | 2013-05-08 | 西南科技大学 | Production method of three-dimensional porous composite bar |
| CN103420364A (en) * | 2013-07-13 | 2013-12-04 | 西南交通大学 | Preparation method of grapheme/hydroxyapatite composite material |
Non-Patent Citations (4)
| Title |
|---|
| GURURAJ M. NEELGUND, ET AL.: ""In situ deposition of hydroxyapatite on graphene nanosheets"", 《 MATERIALS RESEARCH BULLETIN》 * |
| HONGYAN LIU ETC.AL: ""Simultaneous Reduction and Surface Functionalization of Graphene Oxide for Hydroxyapatite Mineralization"", 《THE JOURNAL OF PHYSICAL CHEMISTRY C》 * |
| 刘玉荣: "《碳材料在超级电容器中的应用》", 31 January 2013, 国防工业出版社 * |
| 彭继荣: "羟基磷灰石的应用研究进展", 《中国非金属矿工业导刊》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107161969A (en) * | 2017-06-08 | 2017-09-15 | 昆明理工大学 | A kind of preparation method of nanometer hydroxyapatite/graphene oxide composite material |
| CN107161969B (en) * | 2017-06-08 | 2019-07-16 | 昆明理工大学 | A kind of preparation method of nanometer hydroxyapatite/graphene oxide composite material |
| CN108467027A (en) * | 2018-03-13 | 2018-08-31 | 镇江致达新材料科技有限公司 | A kind of method of the microwave radiation technology preparation with wearability CGN/HA composite materials |
| CN108467027B (en) * | 2018-03-13 | 2019-11-05 | 镇江致达新材料科技有限公司 | A kind of method that microwave-assisted preparation has wearability CGN/HA composite material |
| CN108342109A (en) * | 2018-04-12 | 2018-07-31 | 华东理工大学 | A kind of hydroxyapatite/stannic oxide/graphene nano composite lamainated structure anti-corrosion paint |
| CN109205581A (en) * | 2018-08-29 | 2019-01-15 | 湖北大学 | A kind of preparation method of the composite hydroxylapatite powder with photo-thermal Synergistic antimicrobial performance |
| CN114113240A (en) * | 2021-11-22 | 2022-03-01 | 中南大学 | Room-temperature ammonia sensing material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103950922B (en) | 2016-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yue et al. | Synthesis of ZnO nanowire arrays/3D graphene foam and application for determination of levodopa in the presence of uric acid | |
| Saraf et al. | A fascinating multitasking Cu-MOF/rGO hybrid for high performance supercapacitors and highly sensitive and selective electrochemical nitrite sensors | |
| Ma et al. | In situ growth of α-Fe 2 O 3 nanorod arrays on 3D carbon foam as an efficient binder-free electrode for highly sensitive and specific determination of nitrite | |
| Li et al. | Topotactic Transformation of Single‐Crystalline Precursor Discs into Disc‐Like Bi2S3 Nanorod Networks | |
| Fang et al. | Flower-like MoS2 decorated with Cu2O nanoparticles for non-enzymatic amperometric sensing of glucose | |
| Rajesh et al. | High-surface-area nanocrystalline cerium phosphate through aqueous sol− gel route | |
| CN107561133B (en) | A kind of preparation method and application of precious metal doping WO3 base formaldehyde gas sensitive material | |
| CN103950922B (en) | The preparation method of nanometer hydroxyapatite/Graphene gas sensing material | |
| Zhao et al. | Thermal oxidation synthesis hollow MoO3 microspheres and their applications in lithium storage and gas-sensing | |
| Wen et al. | Two birds with one stone: Cobalt-doping induces to enhanced piezoelectric property and persulfate activation ability of ZnO nanorods for efficient water purification | |
| CN102275981B (en) | Preparation method of self-substrate SnO2 nanorod array | |
| CN110346437B (en) | LDHs/MXene-based electrochemical glucose sensor and preparation and application thereof | |
| Wang et al. | Preparation of 3D rose-like NiO complex structure and its electrochemical property | |
| CN108380228A (en) | A kind of preparation method and applications of nickel sulfide/nickel phosphide of 1 dimension/1 dimension nanometer construction assembling | |
| Cheng et al. | Oxygen vacancy enhanced Co3O4/ZnO nanocomposite with small sized and loose structure for sensitive electroanalysis of Hg (II) in subsidence area water | |
| Wang et al. | Ammonium nickel phosphate on nickel foam with a Ni3+-rich surface for ultrasensitive nonenzymatic glucose sensors | |
| CN104261472A (en) | Vanadium pentoxide nanobelt, and room-temperature synthesis method and application of vanadium pentoxide nanobelt | |
| Lv et al. | Hexamethylenetetramine-induced synthesis of hierarchical NiO nanostructures on nickel foam and their electrochemical properties | |
| Wu et al. | A highly sensitive electrochemical sensor for Cd (II) based on protic salt derived nitrogen and sulfur co-doped porous carbon | |
| CN109647482A (en) | A kind of phosphatization cobalt/nano carbon composite material of N doping and its preparation method and application | |
| Lee et al. | Electrochemical properties and characterization of various ZnO structures using a precipitation method | |
| Liu et al. | Au-decorated In2O3 nanospheres/exfoliated Ti3C2Tx MXene nanosheets for highly sensitive formaldehyde gas sensing at room temperature | |
| Khadro et al. | Interfacing a heteropolytungstate complex and gelatin through a coacervation process: design of bionanocomposite films as novel electrocatalysts | |
| Han et al. | Highly sensitive detection of trace Hg2+ via PdNPs/g-C3N4 nanosheet-modified electrodes using DPV | |
| Zhu et al. | Ce-MOFs derived cerium phosphate for high-efficiency electrochemical detection of metronidazole |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |