CN110404537A - CuO@Cu2The preparation method of O@Cu micro-nano ball - Google Patents
CuO@Cu2The preparation method of O@Cu micro-nano ball Download PDFInfo
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- 239000011807 nanoball Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 47
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000013049 sediment Substances 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 9
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 8
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 6
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 150000001879 copper Chemical class 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 1
- 229910001948 sodium oxide Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 24
- 239000010949 copper Substances 0.000 abstract description 12
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052802 copper Inorganic materials 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 abstract description 4
- 230000001276 controlling effect Effects 0.000 abstract description 2
- 229910001431 copper ion Inorganic materials 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000006259 organic additive Substances 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 229910021642 ultra pure water Inorganic materials 0.000 description 5
- 239000012498 ultrapure water Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B01J35/51—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
Abstract
The invention discloses a kind of CuO@Cu2The preparation method of O Cu micro-nano ball, comprising the following steps: by inorganic mantoquita under the conditions of reducing agent one-step synthesis CuO Cu2The micro-nano copper oxygen compound of O@Cu；Mantoquita is reduced directly using reducing agent, so that bivalent cupric ion is reduced into monovalence or copper simple substance, by controlling the amount of reducing agent, so that rapid reaction occurs, univalent copper ion, bivalent cupric ion and copper simple substance coexists as a mixture, at normal temperature one-step synthesis CuO@Cu2O@Cu micro-nano ball, do not use surfactant and organic additive, reaction temperature is low, reaction condition is easily controllable, the morphology and size and compositely proportional of regulatory complex may be implemented by regulation reaction raw materials ratio, mixing and the rate of stirring and reaction time, cost of material is low, and simple process is easy to operate, industrialized production easy to accomplish.
Description
Technical field
The present invention relates to a kind of micro-nano complex copper oxygen compounds, and in particular to a kind of CuO@Cu2O@Cu micro-nano ball
Preparation method.
Background technique
Cu oxide is as typical p-type semiconductor material, difference of the band gap based on Cu valent state and crystal structure
Between 1.7eV to 2.2eV；In addition, a small amount of simple substance Cu in copper oxygen compound surface can be effective due to plasma effect
Absorb the luminous energy of long-wave band.Due to its ideal band gap width and to effective absorption of solar energy, can generate a large amount of
Photo-generate electron-hole pair, therefore all there is potential application in fields such as photocatalytic hydrogen production by water decomposition, photocatalytic degradation of organic matter
Value.Electron hole pair can occurs in some to the photo-generated carrier that semiconductor material generates when material internal migrates
It is compound.The electron hole separation probability of copper oxygen compound photo-generated carrier is higher, and recombination rate is smaller, and the performance of corresponding material is just
It is stronger.Pass through effective composite Cu O, Cu2O, Cu can reduce electron hole pair recombination probability enhancing photo-generated carrier utilization rate.Together
When transiting metal group belonged to due to Cu, the variation of valence state, which generates effective redox reaction, can be used as fake capacitance electrochemistry
The electrode material of energy storage device, the small scale of micro-nano ball and big specific surface are conducive to also increase while redox reaction
The electric double layer effect of electron adsorption desorption, micro-nano complex copper oxygen compound is the ideal candidate of electrochemical energy storage materials.
But in the prior art, CuO, Cu2O, the combination process of Cu is all complex, can not achieve the effect that one-step synthesis, and need
Want raw material more, need by equipment it is huge, cause preparation cost relatively high, operate it is more complicated.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of preparation method of CuO Cu2O Cu micro-nano ball, Neng Gouyi
Step synthesis CuO@Cu2O@Cu micro-nano ball, does not need other auxiliary agents, reaction temperature is low, and reaction condition is easily controllable, cost of material
Low, simple process is easy to operate.
CuO@Cu of the invention2The preparation method of O Cu micro-nano ball, comprising the following steps: by inorganic mantoquita in reducing agent
Under the conditions of one-step synthesis CuO@Cu2The micro-nano copper oxygen compound of O@Cu；
Further, comprising the following steps: inorganic copper salt solution is mixed at normal temperature with reducing agent；
Further, the inorganic mantoquita is at least one of copper chloride, copper acetate, and the reducing agent is hydrazine hydrate or boron
At least one of sodium hydride；
Further, reducing agent is added after inorganic copper salt solution being first mixed with lye to be mixed；
Further, the lye is one of sodium hydroxide and ammonium hydroxide；
Further, it will be washed, filtered after the solution left standstill after reaction, collected sediment, sediment is dried, CuO
Cu2O@Cu micro-nano ball；
Further, the mixing time is 0.5-2h；
Further, the inorganic copper salt solution raw material includes following components by weight: 0~200 part of deionized water, anhydrous
0~200 part of ethyl alcohol, 1~5 part of inorganic mantoquita, the parts by weight of the reducing agent are 0.5~2.5 part；
Further, the inorganic copper salt solution raw material includes following components by weight: 100 parts of deionized water, anhydrous second
100 parts of alcohol, 2 parts of inorganic mantoquita；
Further, by sediment temperature be 50~70 DEG C at dry.
The beneficial effects of the present invention are: CuO@Cu of the invention2The preparation method of O@Cu micro-nano ball is straight using reducing agent
Reduction mantoquita is connect, so that bivalent cupric ion is reduced into monovalence or copper simple substance, by controlling the amount of reducing agent, so that rapid reaction
Occur, univalent copper ion, bivalent cupric ion and copper simple substance coexists as a mixture, at normal temperature one-step synthesis CuO@
Cu2O@Cu micro-nano ball does not use surfactant and organic additive, and reaction temperature is low, and reaction condition is easily controllable, passes through
Regulation reaction raw materials ratio, the rate of mixing and stirring and reaction time may be implemented regulatory complex morphology and size and
Compositely proportional, cost of material is low, and simple process is easy to operate, industrialized production easy to accomplish.The CuO@as made from this method
Cu2O@Cu micro-nano ball, it is different to which this is greatly improved that the compound that three kinds of materials are constituted effectively facilitates the separation of electron hole pair
The photoelectric characteristic of matter knot and redox property when as catalyst, can be widely applied to electrochemical energy storage, photocatalysis Decomposition
The technical fields such as water hydrogen manufacturing, photocatalytic degradation of organic matter.
Detailed description of the invention
The invention will be further described with reference to the accompanying drawings and examples:
Fig. 1 is CuO@Cu prepared by embodiment 12The SEM of O@Cu micro-nano ball schemes；
Fig. 2 is CuO@Cu prepared by embodiment 22The SEM of O@Cu micro-nano ball schemes；
Fig. 3 is CuO@Cu prepared by embodiment 32The SEM of O@Cu micro-nano ball schemes；
Fig. 4 is CuO@Cu prepared by embodiment 32The EDS of O@Cu micro-nano ball is composed；
Fig. 5 is CuO@Cu prepared by embodiment 32The sample under the TEM (transmission electron microscope) of O@Cu micro-nano ball
The Elemental redistribution mapping of appearance and corresponding region；
Fig. 6 is CuO@Cu prepared by embodiment 42The SEM of O@Cu micro-nano ball schemes.
Specific embodiment
Embodiment one
2g copper acetate, 100ml dehydrated alcohol and 100mL ultrapure water are mixed 30 minutes and dispersed, is then added dropwise
It is stirred 30 minutes after 2mL ammonium hydroxide, 0.5ml hydrazine hydrate is finally diluted to 5mL and is added dropwise, drip off sufficiently reaction 30 minutes
Afterwards, by after the solution left standstill 5h after reaction, sediment is collected in washing, filtering, is dried at being 50 DEG C in temperature by the sediment of collection
It does to get micro-nano CuO@Cu2O@Cu。
Embodiment two
2g copper acetate, 100ml dehydrated alcohol and 100mL ultrapure water are stirred 30 minutes and dispersed, 2mL ammonia is then added dropwise
It is stirred 30 minutes after water, 1ml hydrazine hydrate is finally diluted to 5mL and is added dropwise, it, will after dripping off after sufficiently reacting 30 minutes
After solution left standstill 5h after reaction, sediment is collected in washing, filtering, is dried at being 50 DEG C in temperature by the sediment of collection, i.e.,
Obtain micro-nano CuO@Cu2O@Cu。
Embodiment three
2g copper acetate, 100ml dehydrated alcohol and 100mL ultrapure water are mixed 30 minutes and dispersed, is then added dropwise
It is stirred 30 minutes after 2.5mL ammonium hydroxide, 2ml hydrazine hydrate is finally diluted to 5mL and is added dropwise, to sufficiently react 30 points after dripping off
Zhong Hou, after the solution left standstill 5h after reaction, sediment is collected in washing, filtering, by the sediment of collection in the case where temperature is 50 DEG C
Drying is to get micro-nano CuO@Cu2O@Cu。
Example IV
2g copper acetate, 100ml dehydrated alcohol and 100mL ultrapure water are mixed 30 minutes and dispersed, is then added dropwise
It is stirred 30 minutes after 20mLNaOH solution, 2ml hydrazine hydrate is finally diluted to 5mL and is added dropwise, to sufficiently react after dripping off
After 30 minutes, after the solution left standstill 5h after reaction, washing, filtering, collect sediment, by the sediment of collection temperature be 50
Drying is at DEG C to get micro-nano CuO@Cu2O@Cu。
Embodiment five
1g copper chloride, 100ml deionized water are mixed 40 minutes by weight and dispersed, is then added dropwise 1ml parts
It is stirred 30 minutes after ammonium hydroxide, 0.5ml hydrazine hydrate is finally diluted to 5ml and is added dropwise, it, will after dripping off sufficiently reaction 30 minutes
After solution left standstill 5h after reaction, sediment is collected in washing, filtering, is dried at being 60 DEG C in temperature by the sediment of collection, i.e.,
Obtain micro-nano CuO@Cu2O@Cu。
Embodiment six
5g copper chloride, 10ml deionized water are mixed 20 minutes by weight and dispersed, 1.5ml ammonia is then added dropwise
It is stirred 20 minutes after water, finally 2.5ml sodium borohydride is diluted to after 25ml and is added dropwise, drip off sufficiently reaction 20 minutes
Afterwards, by after the solution left standstill 6h after reaction, sediment is collected in washing, filtering, is dried at being 70 DEG C in temperature by the sediment of collection
It does to get micro-nano CuO@Cu2O@Cu。
Embodiment seven
3g copper chloride, 20ml dehydrated alcohol are mixed 35 minutes by weight and dispersed, 2.5ml ammonia is then added dropwise
It is stirred 35 minutes after water, finally 1ml sodium borohydride is diluted to after 10ml and is added dropwise, after dripping off sufficiently reaction 35 minutes,
After the solution left standstill 7h after reaction, sediment is collected in washing, filtering, is dried at being 55 DEG C in temperature by the sediment of collection,
Up to micro-nano CuO@Cu2O@Cu。
Embodiment eight
By weight 2g copper acetate, 20ml dehydrated alcohol are mixed to stir 10 minutes and be dispersed, 20ml ammonium hydroxide is then added dropwise
Afterwards stir 10 minutes, finally by 1ml sodium borohydride dilute 5ml after and be added dropwise, drip off sufficiently reaction after ten minutes, will react
After solution left standstill 7h afterwards, sediment is collected in washing, filtering, and drying is at being 65 DEG C in temperature by the sediment of collection to get micro-
Nanometer CuO@Cu2O@Cu。
Embodiment nine
2g copper acetate, 1g copper chloride, 180ml dehydrated alcohol and 150mL ultrapure water are mixed 40 minutes and dispersed, then
It is stirred 40 minutes after 20mLNaOH solution is added dropwise, 2.5ml hydrazine hydrate is finally diluted to 5mL and is added dropwise, after dripping off
To sufficiently react after forty minutes, after the solution left standstill 5h after reaction, washing, filtering collect sediment, by the sediment of collection
Drying is at being 60 DEG C in temperature to get micro-nano CuO@Cu2O@Cu。
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to compared with
Good embodiment describes the invention in detail, those skilled in the art should understand that, it can be to skill of the invention
Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this
In the scope of the claims of invention.
Claims (10)
1. a kind of CuO@Cu2The preparation method of O Cu micro-nano ball, it is characterised in that: the following steps are included: by inorganic mantoquita also
One-step synthesis CuO@Cu under the conditions of former agent2The micro-nano copper oxygen compound of O@Cu.
2. CuO@Cu according to claim 12The preparation method of O@Cu micro-nano ball, it is characterised in that: including following step
It is rapid: inorganic copper salt solution is mixed at normal temperature with reducing agent.
3. CuO@Cu according to claim 22The preparation method of O Cu micro-nano ball, it is characterised in that: the inorganic mantoquita
For at least one of copper chloride, copper acetate, the reducing agent is at least one of hydrazine hydrate or sodium borohydride.
4. CuO@Cu according to claim 32The preparation method of O Cu micro-nano ball, it is characterised in that: inorganic mantoquita is molten
Liquid adds reducing agent mixing after being first mixed with lye.
5. CuO@Cu according to claim 42The preparation method of O@Cu micro-nano ball, it is characterised in that: the lye is hydrogen
One of sodium oxide molybdena and ammonium hydroxide.
6. CuO@Cu according to claim 42The preparation method of O@Cu micro-nano ball, it is characterised in that: will be molten after reaction
Liquid is washed after standing, is filtered, and is collected sediment, sediment is dried, CuO Cu2O@Cu micro-nano ball.
7. CuO@Cu according to claim 12The preparation method of O@Cu micro-nano ball, it is characterised in that: the mixing time
For 0.5-2h.
8. CuO@Cu according to claim 22The preparation method of O Cu micro-nano ball, it is characterised in that: the inorganic mantoquita
Solution materials include following components by weight: 0~200 part of deionized water, 0~200 part of dehydrated alcohol, inorganic mantoquita 1~5
Part, the parts by weight of the reducing agent are 0.5~2.5 part.
9. CuO@Cu according to claim 82The preparation method of O Cu micro-nano ball, it is characterised in that: the inorganic mantoquita
Solution materials include following components by weight: 100 parts of deionized water, 100 parts of dehydrated alcohol, 2 parts of inorganic mantoquita.
10. CuO@Cu according to claim 42The preparation method of O@Cu micro-nano ball, it is characterised in that: sediment exists
Temperature is to dry at 50~70 DEG C.
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| CN111495365A (en) * | 2020-05-29 | 2020-08-07 | 扬州大学 | Novel n-Cu2Preparation method of O/CuO semiconductor photocatalyst |
| CN111589448A (en) * | 2020-06-08 | 2020-08-28 | 中国石油大学(华东) | Carbon dioxide electro-reduction catalyst with ultrahigh gas phase selectivity |
| CN112536034A (en) * | 2020-11-22 | 2021-03-23 | 重庆交通大学 | CQDS/CuO@Cu2Preparation method of O-micron balls |
| CN112899709A (en) * | 2021-01-19 | 2021-06-04 | 北京化工大学 | Copper-based compound/copper nano electrode with interface synergistic effect and preparation and application thereof |
| CN113394381A (en) * | 2021-06-10 | 2021-09-14 | 肇庆市华师大光电产业研究院 | Preparation method of layered double hydroxide composite material for positive electrode of lithium-sulfur battery |
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| CN112536034A (en) * | 2020-11-22 | 2021-03-23 | 重庆交通大学 | CQDS/CuO@Cu2Preparation method of O-micron balls |
| CN112899709A (en) * | 2021-01-19 | 2021-06-04 | 北京化工大学 | Copper-based compound/copper nano electrode with interface synergistic effect and preparation and application thereof |
| CN113394381A (en) * | 2021-06-10 | 2021-09-14 | 肇庆市华师大光电产业研究院 | Preparation method of layered double hydroxide composite material for positive electrode of lithium-sulfur battery |
| CN113394381B (en) * | 2021-06-10 | 2023-02-10 | 肇庆市华师大光电产业研究院 | Preparation method of layered double hydroxide composite material for positive electrode of lithium-sulfur battery |
| CN113856704A (en) * | 2021-11-16 | 2021-12-31 | 四川轻化工大学 | Photocatalyst for efficiently degrading antibiotics and preparation method and application thereof |
| CN113856704B (en) * | 2021-11-16 | 2023-04-07 | 四川轻化工大学 | Photocatalyst for efficiently degrading antibiotics and preparation method and application thereof |
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