CN110327913A - A kind of nano-sheet tungsten oxide/graphene oxide Core-shell structure material and the preparation method and application thereof - Google Patents
A kind of nano-sheet tungsten oxide/graphene oxide Core-shell structure material and the preparation method and application thereof Download PDFInfo
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- CN110327913A CN110327913A CN201910706959.XA CN201910706959A CN110327913A CN 110327913 A CN110327913 A CN 110327913A CN 201910706959 A CN201910706959 A CN 201910706959A CN 110327913 A CN110327913 A CN 110327913A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 58
- 239000011258 core-shell material Substances 0.000 title claims abstract description 42
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910001930 tungsten oxide Inorganic materials 0.000 title claims abstract description 39
- 239000000463 material Substances 0.000 title claims abstract description 37
- 239000002135 nanosheet Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 32
- 239000011259 mixed solution Substances 0.000 claims abstract description 26
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- 239000010410 layer Substances 0.000 claims abstract description 16
- 239000011812 mixed powder Substances 0.000 claims abstract description 16
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims abstract description 16
- 239000002356 single layer Substances 0.000 claims abstract description 12
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 8
- 239000011775 sodium fluoride Substances 0.000 claims abstract description 8
- 235000013024 sodium fluoride Nutrition 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000007146 photocatalysis Methods 0.000 claims abstract description 7
- 230000001699 photocatalysis Effects 0.000 claims abstract description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 6
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 6
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 6
- 239000011734 sodium Substances 0.000 claims abstract description 6
- 238000005253 cladding Methods 0.000 claims abstract description 5
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 7
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 7
- 238000012856 packing Methods 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 abstract 1
- 238000000034 method Methods 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 239000011858 nanopowder Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 229910052721 tungsten Inorganic materials 0.000 description 7
- 239000010937 tungsten Substances 0.000 description 7
- 238000011065 in-situ storage Methods 0.000 description 5
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 5
- 239000011257 shell material Substances 0.000 description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B01J35/30—
-
- B01J35/33—
-
- B01J35/39—
-
- B01J35/397—
-
- B01J35/398—
Abstract
A kind of nano-sheet tungsten oxide/graphene oxide Core-shell structure material and the preparation method and application thereof.Tungsten powder and sodium fluoride are uniformly mixed and obtain mixed powder A；Take H2O2And HNO3It is uniformly mixed to obtain mixed solution B；Graphene oxide water solution is added into mixed solution B and obtains mixed solution C；Mixed powder A is slowly added to obtain solution E in mixed solution C；Solution E is placed in hydrothermal reaction kettle and carries out hydro-thermal reaction, cooling, washing is collected, dried to get nano-sheet tungsten oxide/graphene oxide Core-shell structure material is arrived.The Core-shell structure material is rectangular single thin layer laminated structure, internal layer core be rectangular tungstic oxide nano-sheets, outer layer is graphene oxide, wherein monolayer of tungsten oxide thin slice with a thickness of 10~30nm, length and width are 100~250nm, and the cladding of outer oxide graphene is with a thickness of 5~20nm.Applied to sodium/lithium/Magnesium ion battery, supercapacitor and photocatalysis field, excellent performance is shown.
Description
Technical field
The present invention relates to a kind of preparation methods of nuclear shell structure nano sheet layer material, and in particular to a kind of fabricated in situ
Nano-sheet tungsten oxide/graphene oxide Core-shell structure material preparation method.
Background technique
Tungstic acid is stable n-type semiconductor, is widely used in photocatalysis and electrochemical catalysis etc..Closely
Nian Lai, it is main to make in terms of tungstic acid is also widely used in electrochemical energy storage as lithium/sodium-ion battery research is goed deep into
It is studied for lithium/sodium-ion battery negative electrode material.However, nano tungsten trioxide there are electric charge transfer rates slow, surface reaction
Active sites are few and are easy to happen the defects of photo-generate electron-hole pairs are easily compound, significantly limit its suitable application area.Oxidation
Graphene has a big specific surface area as New Two Dimensional carbon material, superior electric conductivity, good mechanical property and high
Chemical and thermal stability is widely used in electrochemical field.
In recent years, tungstic acid/graphene oxide composite material receives the wide of researchers as cell negative electrode material
General research, but up to the present, about being the report of the two-dimensional nano composite material of shell by core, graphene oxide of tungstic acid
Road almost without.
Summary of the invention
The purpose of the present invention is to provide a kind of easy to operate, and the fabricated in situ that reaction temperature is low, reaction time is short is received
Rice sheet tungsten oxide/graphene oxide Core-shell structure material preparation method, tungsten oxide obtained/graphene oxide core-shell structure
Material structure is single, purity is high.
To achieve the goals above, the present invention adopts the following technical scheme:
1) tungsten powder and sodium fluoride are uniformly mixed by the mass ratio of 10:1~10:3 and obtain mixed powder A；
2) taking 5~15ml mass concentration respectively is 30% H2O2The HNO for being 69% with 5~15ml mass concentration3Mixing is equal
It is even to obtain mixed solution B；
3) graphene oxide water solution that 2~6ml mass concentration is 0.05%~0.15% is added into mixed solution B,
Obtain mixed solution C；
4) 1~8g mixed powder A is taken to be slowly added in mixed solution C, stirring obtains solution E to it after completely dissolution；
5) solution E is placed in hydrothermal reaction kettle in 120~200 DEG C of progress hydro-thermal reactions, it is after reaction, cooling, it washes
It washs, collect, drying to get nano-sheet tungsten oxide/graphene oxide Core-shell structure material is arrived.
2~3 μm of the size of the tungsten powder.
The graphene oxide is micron order single-layer graphene oxide structure.
The stirring is magnetic agitation or ultrasonic disperse.
It is 35~75% that the solution E, which is placed in the packing ratio in hydrothermal reaction kettle,.
The reaction time is 20~35h.
The washing uses dehydrated alcohol centrifuge washing 3~5 times, described to be collected as being collected by centrifugation.
The drying temperature is 50~80 DEG C, and the time is 12~16h.
The Core-shell structure material made of method made above is rectangular single thin layer laminated structure, and internal layer core is rectangular oxidation
Tungsten nanometer sheet, outer layer are graphene oxide, wherein monolayer of tungsten oxide thin slice with a thickness of 10~30nm, length and width are 100~
250nm, the cladding of outer oxide graphene is with a thickness of 5~20nm.
The tungsten oxide of the nano-sheet made of method made above/graphene oxide Core-shell structure material be applied to sodium/lithium/
Magnesium ion battery, supercapacitor and photocatalysis field.
Compared with the existing technology, the present invention at least has the advantages that
The present invention uses in-situ one-step synthesis tungsten oxide/graphene oxide core-shell structure nanopowder body, and this method does not need
Large scale equipment and harsh reaction condition, are not necessarily to pattern controlling agent, and raw material is easy to get, at low cost, and yield is high, are not necessarily to post-processing,
It is environmentally friendly, it can be suitble to be mass produced.
And by this method prepare tungsten oxide/graphene oxide core-shell structure nanopowder body, have using tungsten oxide as core,
Graphene oxide is the core-shell structure of shell.The application of nanopowder of the core-shell structure is in sodium/lithium/Magnesium ion battery and photocatalysis
Field shows excellent performance.
Detailed description of the invention
Fig. 1 is nano-sheet tungsten oxide/graphene oxide Core-shell structure material powder X- prepared by the embodiment of the present invention 1
X ray diffraction (XRD) map；
Fig. 2 and Fig. 3 is nano-sheet tungsten oxide/graphene oxide Core-shell structure material powder prepared by the embodiment of the present invention 1
Scanning electron microscope (SEM) photo and transmission electron microscope (TEM) photo of body.
Specific embodiment
Invention is further described in detail with reference to the accompanying drawings and embodiments.
Embodiment 1:
1) 2~3 μm of tungsten powders and sodium fluoride are uniformly mixed by the mass ratio of 10:1 and obtain mixed powder A；
2) taking 5ml mass concentration respectively is 30% H2O2The HNO for being 69% with 5ml mass concentration3It is uniformly mixed to obtain mixing
Solution B；
3) the graphene oxide water for the micron order single layer structure that 2ml mass concentration is 0.05% is added into mixed solution B
Solution obtains mixed solution C；
4) 1g mixed powder A is taken to be slowly added in mixed solution C, magnetic agitation waits for that it obtains solution E after completely dissolution；
5) solution E is placed in hydrothermal reaction kettle in 160 DEG C of hydro-thermal reaction 22h by 35% packing ratio, after reaction,
It is cooling, using dehydrated alcohol centrifuge washing 3 times, be collected by centrifugation, in 50 DEG C of drying 12h to get arriving nano-sheet tungsten oxide/oxidation
Graphene Core-shell structure material.
Core-shell structure material by this method fabricated in situ is rectangular single thin layer laminated structure, and internal layer core is rectangular oxidation
Tungsten nanometer sheet, outer layer are graphene oxide, wherein monolayer of tungsten oxide thin slice with a thickness of 10~30nm, length and width are 100~
250nm, the cladding of outer oxide graphene is with a thickness of 5~20nm.The core-shell material be applied to sodium/lithium/Magnesium ion battery and
Photocatalysis field.Especially when it is applied to sodium-ion battery, excellent chemical property is shown.
From figure 1 it appears that prepared composite material is the composite material of tungstic acid and graphene oxide.
It can be clearly seen that prepared nano-powder is individual layer laminated structure of uniform size from Fig. 2, having a size of
100-200nm, thickness are about 20-30nm.
It can furthermore be seen that prepared nanocrystal monolayer piece length and width are the tungsten oxide of 100nm or so, outer layer from Fig. 3
The uniformly graphene oxide layer that cladding thickness is about 15nm.Further demonstrating prepared material is core-shell structure.
Embodiment 2:
1) 2~3 μm of tungsten powders and sodium fluoride are uniformly mixed by the mass ratio of 10:1.5 and obtain mixed powder A；
2) taking 8ml mass concentration respectively is 30% H2O2The HNO for being 69% with 8ml mass concentration3It is uniformly mixed to obtain mixing
Solution B；
3) the graphene oxide water for the micron order single layer structure that 2.5ml mass concentration is 0.1% is added into mixed solution B
Solution obtains mixed solution C；
4) 2.5g mixed powder A is taken to be slowly added in mixed solution C, ultrasonic disperse waits for that it obtains solution E after completely dissolution；
5) solution E is placed in hydrothermal reaction kettle in 180 DEG C of hydro-thermal reactions for 24 hours by 75% packing ratio, after reaction,
It is cooling, using dehydrated alcohol centrifuge washing 3 times, be collected by centrifugation, in 60 DEG C of drying 14h to get arriving nano-sheet tungsten oxide/oxidation
Graphene Core-shell structure material.
Embodiment 3:
1) 2~3 μm of tungsten powders and sodium fluoride are uniformly mixed by the mass ratio of 10:3 and obtain mixed powder A；
2) taking 10ml mass concentration respectively is 30% H2O2The HNO for being 69% with 10ml mass concentration3It is uniformly mixed mixed
Close solution B；
3) the graphene oxide water for the micron order single layer structure that 4ml mass concentration is 0.13% is added into mixed solution B
Solution obtains mixed solution C；
4) 5.2g mixed powder A is taken to be slowly added in mixed solution C, magnetic agitation waits for that it obtains solution E after completely dissolution；
5) solution E is placed in hydrothermal reaction kettle in 160 DEG C of hydro-thermal reaction 30h by 35% packing ratio, after reaction,
It is cooling, using dehydrated alcohol centrifuge washing 5 times, be collected by centrifugation, in 80 DEG C of drying 16h to get arriving nano-sheet tungsten oxide/oxidation
Graphene Core-shell structure material.
Implement 41:
1) 2~3 μm of tungsten powders and sodium fluoride are uniformly mixed by the mass ratio of 10:2 and obtain mixed powder A；
2) taking 15ml mass concentration respectively is 30% H2O2The HNO for being 69% with 12ml mass concentration3It is uniformly mixed mixed
Close solution B；
3) the graphene oxide water for the micron order single layer structure that 5ml mass concentration is 0.08% is added into mixed solution B
Solution obtains mixed solution C；
4) 8g mixed powder A is taken to be slowly added in mixed solution C, ultrasonic disperse waits for that it obtains solution E after completely dissolution；
5) solution E is placed in hydrothermal reaction kettle in 120 DEG C of hydro-thermal reaction 35h by 50% packing ratio, after reaction,
It is cooling, using dehydrated alcohol centrifuge washing 4 times, be collected by centrifugation, in 70 DEG C of drying 13h to get arriving nano-sheet tungsten oxide/oxidation
Graphene Core-shell structure material.
Embodiment 5:
1) 2~3 μm of tungsten powders and sodium fluoride are uniformly mixed by the mass ratio of 10:2.5 and obtain mixed powder A；
2) taking 12ml mass concentration respectively is 30% H2O2The HNO for being 69% with 15ml mass concentration3It is uniformly mixed mixed
Close solution B；
3) the graphene oxide water for the micron order single layer structure that 6ml mass concentration is 0.15% is added into mixed solution B
Solution obtains mixed solution C；
4) 6g mixed powder A is taken to be slowly added in mixed solution C, ultrasonic disperse waits for that it obtains solution E after completely dissolution；
5) solution E is placed in hydrothermal reaction kettle in 200 DEG C of hydro-thermal reaction 20h by 60% packing ratio, after reaction,
It is cooling, using dehydrated alcohol centrifuge washing 5 times, be collected by centrifugation, in 80 DEG C of drying 12h to get arriving nano-sheet tungsten oxide/oxidation
Graphene Core-shell structure material.
Compared with the existing technology, the present invention at least has the advantages that
The present invention uses in-situ one-step synthesis tungsten oxide/graphene oxide core-shell structure nanopowder body, and this method does not need
Large scale equipment and harsh reaction condition, are not necessarily to pattern controlling agent, and raw material is easy to get, at low cost, and yield is high, are not necessarily to post-processing,
It is environmentally friendly, it can be suitble to be mass produced.
And by this method prepare tungsten oxide/graphene oxide core-shell structure nanopowder body, have using tungsten oxide as core,
Graphene oxide is the core-shell structure of shell.The application of nanopowder of the core-shell structure is in sodium/lithium/Magnesium ion battery and photocatalysis
Field shows excellent performance.
Claims (10)
1. a kind of preparation method of nano-sheet tungsten oxide/graphene oxide Core-shell structure material, it is characterised in that:
1) tungsten powder and sodium fluoride are uniformly mixed by the mass ratio of 10:1~10:3 and obtain mixed powder A；
2) taking 5~15ml mass concentration respectively is 30% H2O2The HNO for being 69% with 5~15ml mass concentration3It is uniformly mixed
Mixed solution B；
3) graphene oxide water solution that 2~6ml mass concentration is 0.05%~0.15% is added into mixed solution B, obtains mixed
Close solution C；
4) 1~8g mixed powder A is taken to be slowly added in mixed solution C, stirring obtains solution E to it after completely dissolution；
5) solution E is placed in hydrothermal reaction kettle in 120~200 DEG C of progress hydro-thermal reactions, after reaction, cooling, washing is received
Collection is dried to get nano-sheet tungsten oxide/graphene oxide Core-shell structure material is arrived.
2. the preparation method of nano-sheet tungsten oxide/graphene oxide Core-shell structure material according to claim 1, special
Sign is: 2~3 μm of the size of the tungsten powder.
3. the preparation method of nano-sheet tungsten oxide/graphene oxide Core-shell structure material according to claim 1, special
Sign is: the graphene oxide is micron order single-layer graphene oxide structure.
4. the preparation method of nano-sheet tungsten oxide/graphene oxide Core-shell structure material according to claim 1, special
Sign is: the stirring is magnetic agitation or ultrasonic disperse.
5. the preparation method of nano-sheet tungsten oxide/graphene oxide Core-shell structure material according to claim 1, special
Sign is: it is 35~75% that the solution E, which is placed in the packing ratio in hydrothermal reaction kettle,.
6. the preparation method of nano-sheet tungsten oxide/graphene oxide Core-shell structure material according to claim 1, special
Sign is: the reaction time is 20~35h.
7. the preparation method of nano-sheet tungsten oxide/graphene oxide Core-shell structure material according to claim 1, special
Sign is: the washing uses dehydrated alcohol centrifuge washing 3~5 times, described to be collected as being collected by centrifugation.
8. the preparation method of nano-sheet tungsten oxide/graphene oxide Core-shell structure material according to claim 1, special
Sign is: the drying temperature is 50~80 DEG C, and the time is 12~16h.
9. a kind of nano-sheet tungsten oxide made from preparation method as described in claim 1/graphene oxide core-shell structure material
Material, it is characterised in that: the Core-shell structure material is rectangular single thin layer laminated structure, and internal layer core is rectangular tungstic oxide nano-sheets, outside
Layer is graphene oxide, wherein monolayer of tungsten oxide thin slice with a thickness of 10~30nm, length and width are 100~250nm, outer oxide stone
The cladding of black alkene is with a thickness of 5~20nm.
10. a kind of nano-sheet tungsten oxide made from preparation method as described in claim 1/graphene oxide core-shell structure material
Material, it is characterised in that: the nano-sheet tungsten oxide/graphene oxide Core-shell structure material be applied to sodium/lithium/Magnesium ion battery,
Supercapacitor and photocatalysis field.
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| CN111974377A (en) * | 2020-09-01 | 2020-11-24 | 陕西科技大学 | High-activity high-stability tungsten oxide hydrogen production catalyst with carbon-coated defects and preparation method thereof |
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|---|---|---|---|---|
| CN111974377A (en) * | 2020-09-01 | 2020-11-24 | 陕西科技大学 | High-activity high-stability tungsten oxide hydrogen production catalyst with carbon-coated defects and preparation method thereof |
| CN111974377B (en) * | 2020-09-01 | 2022-11-18 | 陕西科技大学 | High-activity high-stability tungsten oxide hydrogen production catalyst with carbon-coated defects and preparation method thereof |
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