CN109772382A - A method of preparing phosphating sludge/graphitized carbon composite material - Google Patents
A method of preparing phosphating sludge/graphitized carbon composite material Download PDFInfo
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- CN109772382A CN109772382A CN201811381365.8A CN201811381365A CN109772382A CN 109772382 A CN109772382 A CN 109772382A CN 201811381365 A CN201811381365 A CN 201811381365A CN 109772382 A CN109772382 A CN 109772382A
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- graphitized carbon
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Abstract
A method of phosphating sludge/graphitized carbon composite material being prepared, catalytic activity is low under alkaline condition the present invention relates to existing electrocatalytic hydrogen evolution catalyst is solved the problems, such as, and provides and a kind of prepare phosphating sludge/graphitized carbon composite material method.Preparation method: one, by egg yolk and egg white separate, a certain amount of egg white is placed in a beaker；Two, a certain amount of polyacid is dissolved in the distilled water of certain volume, is added it in egg white, stir a few hours, obtain reaction suspension；Three, the reaction suspension that step 2 obtains is transferred to hydro-thermal process in the water heating kettle with polytetrafluoroethyllining lining, collected by suction solid formation obtains composite material after drying；Four, the composite material for obtaining step 3, which is put into Muffle furnace, calcines, and obtains calcined complex；Five, the composite material for obtaining step 4, which is put into tube furnace, carries out phosphorating treatment, then with furnace natural cooling, obtains phosphating sludge/graphitized carbon composite material.
Description
Technical field
The present invention relates to a kind of phosphating sludge/graphitized carbon composite material preparation methods.
Background technique
Electrocatalytic hydrogen evolution reaction is increasingly interested by researchers.And electrocatalytic hydrogen evolution catalyst is in alkaline condition at present
Under it is low there are unstable or catalytic performance the problems such as, limit development and application, thus find and exploitation under alkaline condition
Stable high activity electrocatalytic hydrogen evolution catalysts are extremely urgent.Transition metal phosphide has the structure of similar hydrogenase,
And phosphide has stronger metallicity, shows higher mechanical strength, strong electron transport ability and chemical stability,
It is widely used in the fields such as catalytic hydrogenation, hydrogen storage and biologic medical.It is nearest the study found that metal phosphide is analysed in electro-catalysis
Also there is preferable catalytic performance in hydrogen reaction.Carbon material, since it is with preferable electric conductivity, and adjust material structure,
It is with the obvious advantage in terms of controlling scantling and preventing material falls back, it is widely used in the design synthesis of nanometer material structure.
Nano particle and carbon material are assembled, composite construction is formed, can both keep two kinds of respective advantages of material, it is also possible to deposit
In synergistic enhancing effect, so that the performance of material be made to obtain unexpected promotion.Meanwhile the size and uniformity of particle are shadows
It rings a very important factor of its catalytic performance, small size and uniform distribution and very must for improving the performance of material
It wants.Heteropoly acid is a kind of discrete polyanionic metal oxygen cluster, and there are various types of molecular structures to be close to the size of nanometer
Prepare the quality raw materials of small size phosphide.The biomass egg white of nitrogenous (carbon) group is enriched as carbon source, original using having
Position reaction obtains phosphating sludge/graphitized carbon composite material, has the advantage that i) enhancing electric conductivity；Ii the dispersion of material) is improved
Degree, to increase the specific surface area of material；Iii reunion and powder of the transition metal phosphide material in catalytic process) are prevented
It is broken, keep structural stability；Iv the corrosion resistance of material in the electrolytic solution) is improved；V) transition metal material and carbon is close
Interfacial effect caused by contacting, can effectively increase active site.
Summary of the invention
The invention aims to solve the problems, such as existing electrocatalytic hydrogen evolution catalyst, catalytic activity is low under alkaline condition,
And it provides and a kind of prepares phosphating sludge/graphitized carbon composite material method.
The present invention prepares phosphating sludge/graphitized carbon composite material method and follows these steps to realize:
One, by egg yolk and egg white separate, a certain amount of egg white is placed in a beaker；
Two, in deionized water by polyacid dissolution, polyacid aqueous solution is obtained, polyacid aqueous solution is added to egg under stirring
In clear, reaction suspension is obtained；
Three, the reaction suspension that step 2 obtains is transferred in the water heating kettle with polytetrafluoroethyllining lining at hydro-thermal
Reason, collected by suction solid formation obtain composite material after drying；
Four, the composite material for obtaining step 3 is put into Muffle furnace, is calcined under air atmosphere, is obtained calcined multiple
It is fit；
Five, calcined complex and sodium hypophosphite being respectively put into tube furnace, sodium hypophosphite is placed in front end, after
Calcined complex is placed at end, is carried out phosphorating treatment then with furnace natural cooling and is obtained phosphating sludge/graphitized carbon composite wood
Material.
The present invention has using biomass egg white enriches nitrogenous, carbon-based group, the strong phase interaction between polyacid presoma
With the method based on coordination assembling prepares phosphating sludge/graphitized carbon composite material, and obtained phosphating sludge/graphitized carbon is compound
Material is tightly combined between having component, phosphide size is small, being evenly distributed is easy the advantages such as regulation with component, using it as electricity
The catalyst of catalytic hydrogen evolution reaction, shows excellent catalytic activity under alkaline condition, has lower take-off potential 5mV,
In 10mA cm-2Current density under, required overpotential is only 96mV, and with good stability, be Future Design and system
The standby electrochemistry liberation of hydrogen catalyst used under alkaline condition lays the foundation.
In summary the present invention also comprising following the utility model has the advantages that
1, the carbon source that the present invention selects is biomass egg white, with abundant nitrogenous and carbon containing group, is conducive to function
Energy component effectively assembles and obtains the composite material haveing excellent performance；
2, the source metal selected is polyacid, has the advantages such as size is small, stability is good, various structures are easy to regulate and control, favorably
The composition of phosphide in regulation complex, and then it is easily achieved the regulation of composite material application performance；
3, the present invention can realize the control of composite structure by changing the parameters such as heat treatment time, material ratio.
Detailed description of the invention
Fig. 1 is phosphating sludge/graphitized carbon composite material X-ray powder diffraction pattern that embodiment one obtains；
Fig. 2 is phosphating sludge/graphitized carbon composite material transmission electron microscope figure；
Fig. 3 is the infrared conversion map of phosphating sludge/graphitized carbon composite material Fourier；
Fig. 4 is phosphating sludge/graphitized carbon composite material raman spectrum；
Fig. 5 is the cyclic voltammetry curve of two kinds of different catalysts, wherein 1-phosphating sludge/graphitized carbon catalyst, 2-quotient
Industry Pt/C catalyst.
Specific embodiment
Specific embodiment 1: present embodiment is phosphating sludge/graphitized carbon composite material method
One, by egg yolk and egg white separate, a certain amount of egg white is placed in a beaker；
Two, in deionized water by polyacid dissolution, polyacid aqueous solution is obtained, polyacid aqueous solution is added to egg under stirring
In clear, reaction suspension is obtained；
Three, the reaction suspension that step 2 obtains is transferred in the water heating kettle with polytetrafluoroethyllining lining at hydro-thermal
Reason, collected by suction solid formation obtain composite material after drying；
Four, the composite material for obtaining step 3 is put into Muffle furnace, is calcined under air atmosphere, is obtained calcined multiple
It is fit；
Five, calcined complex and sodium hypophosphite being respectively put into tube furnace, sodium hypophosphite is placed in front end, after
Calcined complex is placed at end, is carried out phosphorating treatment then with furnace natural cooling and is obtained phosphating sludge/graphitized carbon composite wood
Material.
The phosphating sludge that present embodiment is prepared/graphitized carbon composite material is using a certain amount of egg white as carbon source
And carbon containing and nitrogen functional organic ligand passes through strong phase interaction between the two using polyoxoanion phosphomolybdic acid as molybdenum source
With obtaining polyacid base organic inorganic hybridization object, carry out phosphorating treatment to it and obtain.
The resulting phosphating sludge of present embodiment/graphitized carbon composite material has phosphide good dispersion, and size is small, phosphorus
Compound such as contacts at the advantages with graphitized carbon substrate, and excellent electrocatalytic hydrogen evolution activity is shown in alkaline electrolyte and is stablized
Property.
Specific embodiment 2: the present embodiment is different from the first embodiment in that stirring described in step 2 is fast
Degree is 400~2000rpm, and mixing time is 2~10 hours.Other steps and parameter are same as the specific embodiment one.
Specific embodiment 3: unlike one of present embodiment and specific embodiment one to two described in step 2
Polyacid be ammonium molybdate, silicomolybdic acid or phosphomolybdic acid.Other steps and parameter are identical as one of specific embodiment one to two.
Specific embodiment 4: step 2 presses polyacid unlike one of present embodiment and specific embodiment one to three
Total mass ratio with egg white is 1:(8~42) polyacid is added.Other steps and one of parameter and specific embodiment one to three
It is identical.
Specific embodiment 5: water described in step 3 unlike one of present embodiment and specific embodiment one to four
The temperature of heat treatment is 160~200 DEG C, and the hydro-thermal time is 8~24 hours.Other steps and parameter and specific embodiment one to
One of four is identical.
Specific embodiment 6: being forged described in step 4 unlike one of present embodiment and specific embodiment one to five
The temperature of burning is 250~350 DEG C, and calcination time is 2~8 hours.Other steps and parameter and specific embodiment one to five it
One is identical.
Specific embodiment 7: unlike one of present embodiment and specific embodiment one to six at step 5 phosphatization
The temperature of reason is 400~800 DEG C, and phosphating time is 3~6 hours.Other steps and parameter and specific embodiment one to six it
One is identical.
Embodiment one: the present embodiment prepares phosphating sludge/graphitized carbon composite material method and follows these steps to realize:
One, by egg yolk and egg white separate, weigh 38g egg white and be placed in 100mL beaker；
Two, it is 1:21 by the mass ratio of polyacid and egg white, polyacid is dissolved in 30mL deionized water, polyacid water is obtained
Solution adds it in egg white, is stirred 4 hours with the speed of 500rpm, obtains reaction suspension；
Three, the reaction suspension that step 2 obtains is transferred in the water heating kettle with polytetrafluoroethyllining lining with 180 DEG C
Hydro-thermal 10h, collected by suction solid formation, then drying obtain composite material；
Four, the composite material for obtaining step 3 is put into Muffle furnace, with temperature calcination 5 hours of 300 DEG C, is calcined
Complex afterwards；
Five, calcined complex and sodium hypophosphite being respectively put into tube furnace, sodium hypophosphite is placed in front end, after
Calcined complex is placed at end, is carried out phosphorating treatment and, then with furnace natural cooling, was obtained with temperature calcination 3 hours of 800 DEG C
To phosphating sludge/graphitized carbon composite material.
Phosphating sludge manufactured in the present embodiment/graphitized carbon composite material X-ray powder diffraction pattern as shown in Figure 1, from
As can be seen that there are nine diffraction at 32.3 °, 43.1 °, 57.4 °, 57.9 °, 64.9 °, 67.0 °, 67.8 ° and 74.3 ° in figure
Peak is respectively belonging to (100), (101), (110), (002), (111), (200), (111), (102) and (201) crystal face of MoP.
The MoP of this crystal phase uses class Pt hexagon WC type structure, illustrates to can be used as potential class Pt catalyst in catalysis reaction.
Fig. 2 shows phosphating sludge/graphitized carbon composite material transmission electron microscope figure, it can be seen from the figure that phosphorus
Change molybdenum and lamellar structure is presented, has the characteristics that small size, be evenly dispersed in graphitized carbon substrate.
Fig. 3 shows the infrared conversion map of the Fourier of phosphating sludge, and the spacing of lattice of phosphating sludge can be calculated from figure
It is tungsten nitride (101) crystal face for 0.21nm.
Fig. 4 shows phosphating sludge/graphitized carbon composite material raman spectrum, there are 1381 Hes as we can see from the figure
1590cm-1Place corresponds respectively to D and G the band peak of graphitic carbon, and ID/IG ratio is 0.86, illustrates that degree of graphitization is higher.
Fig. 5 shows that phosphating sludge/graphitized carbon catalyst cyclic voltammetry curve, test process are as follows: it is to be measured to weigh 5mg
Catalyst sample, be scattered in 1mL mixed solution (include: 50 μ L 5%Nafion solution, water/ethyl alcohol volume ratio is 4:
1), ultrasonic disperse 1 hour, forming concentration is 5mg mL-1Uniform dispersion.It is on 3mm rotating disk electrode (r.d.e) (RDE) to diameter
Instilling 10 μ L dispersion liquids, (electrode surface catalytic amount is 0.0.337mg cm-2), electro-chemical test can be carried out after to be dried.?
In electrocatalytic hydrogen evolution test, carbon-point is made to electrode, and saturated calomel electrode is reference electrode, and glass-carbon electrode is working electrode, electrolysis
Liquid is 1M KOH.It is 5mV s that speed is swept in the test of Linear Circulation voltammetric scan-1, scanning range -1V~0V.Rotating disk electrode (r.d.e) revolving speed
For 1600rpm.Cyclic voltammetry curve test sweeps speed and is respectively set to 20-200mV s-1.All potentials use reversible hydrogen electrode
(RHE) it is corrected.Curve 1 is phosphating sludge/graphitized carbon catalyst liberation of hydrogen performance curve in figure, and curve 2 is purchase
Business Pt/C (Johnson Matthey company) catalyst catalytic activity.The phosphating sludge/graphitized carbon composite material conduct
Electrocatalytic hydrogen evolution catalyst is under alkaline condition, it is shown that and excellent catalytic activity has lower take-off potential 5mV,
10mA cm-2Current density under, required overpotential is only 96mV, and with good stability, illustrates small size, high score
Phosphating sludge is dissipated to play a significant role the promotion of catalytic activity, and the coating function of graphitized carbon significantly improves it in alkalinity
Under the conditions of stability.
Claims (7)
1. a kind of prepare phosphating sludge/graphitized carbon composite material method, which is characterized in that be to follow these steps to realize:
One, by egg yolk and egg white separate, a certain amount of egg white is placed in a beaker；
Two, in deionized water by polyacid dissolution, polyacid aqueous solution is obtained, polyacid aqueous solution is added to egg white under stirring
In, obtain reaction suspension；
Three, the reaction suspension that step 2 obtains is transferred to hydro-thermal process in the water heating kettle with polytetrafluoroethyllining lining, taken out
Solid formation is collected in filter, obtains composite material after drying；
Four, the composite material for obtaining step 3 is put into Muffle furnace, is calcined under air atmosphere, is obtained calcined compound
Body；
Five, calcined complex and sodium hypophosphite are respectively put into tube furnace, sodium hypophosphite is placed in front end, and rear end is put
Calcined complex is set, phosphorating treatment is carried out then with furnace natural cooling and obtains phosphating sludge/graphitized carbon composite material.
2. a kind of phosphating sludge/graphitized carbon composite material method is prepared according to claim 1, which is characterized in that step
Mixing speed described in rapid two is 400~2000rpm, and mixing time is 2~10 hours.
3. a kind of phosphating sludge/graphitized carbon composite material method is prepared according to claim 1, which is characterized in that step
Polyacid described in rapid two is ammonium molybdate, silicomolybdic acid or phosphomolybdic acid.
4. a kind of phosphating sludge/graphitized carbon composite material method is prepared according to claim 1, which is characterized in that step
Rapid two be 1:(8~42 in mass ratio) polyacid solution is added in egg white, obtain the polyacid organic-inorganic of egg white modification
Hybrid.
5. a kind of phosphating sludge/graphitized carbon composite material method is prepared according to claim 1, which is characterized in that step
The temperature of rapid three hydro-thermal process is 160~200 DEG C, and the hydro-thermal time is 8~24 hours.
6. a kind of phosphating sludge/graphitized carbon composite material method is prepared according to claim 1, which is characterized in that step
The temperature of rapid four calcining is 250~350 DEG C, and calcination time is 2~8 hours.
7. a kind of phosphating sludge/graphitized carbon composite material method is prepared according to claim 1, which is characterized in that step
Rapid five parkerized temperature is 400~800 DEG C, and phosphating time is 3~6 hours.
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| CN110479332A (en) * | 2019-07-04 | 2019-11-22 | 南方科技大学 | Porous flake phosphating sludge/carbon composite material and preparation method |
| CN111659430A (en) * | 2020-05-07 | 2020-09-15 | 黑龙江大学 | Preparation method of low-platinum composite material for hydrogen production by acidic electrolyzed water |
| CN112125289A (en) * | 2020-09-07 | 2020-12-25 | 广州大学 | Metal phosphide and preparation method and application thereof |
| CN112830469A (en) * | 2020-12-31 | 2021-05-25 | 西安理工大学 | Preparation method of biomass carbon quantum dot compounded porous carbon electrode material |
| CN113842936A (en) * | 2021-10-22 | 2021-12-28 | 四川大学华西医院 | Platinum-based single-atom electro-catalytic material and preparation method and application thereof |
| CN114232021A (en) * | 2021-11-24 | 2022-03-25 | 黑龙江大学 | Preparation method of molybdenum phosphide nano microsphere composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110479332A (en) * | 2019-07-04 | 2019-11-22 | 南方科技大学 | Porous flake phosphating sludge/carbon composite material and preparation method |
| CN111659430A (en) * | 2020-05-07 | 2020-09-15 | 黑龙江大学 | Preparation method of low-platinum composite material for hydrogen production by acidic electrolyzed water |
| CN112125289A (en) * | 2020-09-07 | 2020-12-25 | 广州大学 | Metal phosphide and preparation method and application thereof |
| CN112830469A (en) * | 2020-12-31 | 2021-05-25 | 西安理工大学 | Preparation method of biomass carbon quantum dot compounded porous carbon electrode material |
| CN112830469B (en) * | 2020-12-31 | 2022-07-15 | 西安理工大学 | Preparation method of biomass carbon quantum dot compounded porous carbon electrode material |
| CN113842936A (en) * | 2021-10-22 | 2021-12-28 | 四川大学华西医院 | Platinum-based single-atom electro-catalytic material and preparation method and application thereof |
| CN113842936B (en) * | 2021-10-22 | 2023-06-23 | 四川大学华西医院 | Platinum-based monoatomic electrocatalytic material and preparation method and application thereof |
| CN114232021A (en) * | 2021-11-24 | 2022-03-25 | 黑龙江大学 | Preparation method of molybdenum phosphide nano microsphere composite material |
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