CN109317151A - A kind of preparation method of the catalyst for ultraviolet catalytic wet oxidation - Google Patents
A kind of preparation method of the catalyst for ultraviolet catalytic wet oxidation Download PDFInfo
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- CN109317151A CN109317151A CN201811296135.1A CN201811296135A CN109317151A CN 109317151 A CN109317151 A CN 109317151A CN 201811296135 A CN201811296135 A CN 201811296135A CN 109317151 A CN109317151 A CN 109317151A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 15
- 238000009279 wet oxidation reaction Methods 0.000 title claims abstract description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000001354 calcination Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 239000003245 coal Substances 0.000 abstract description 11
- 239000012141 concentrate Substances 0.000 abstract description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 8
- 230000001590 oxidative effect Effects 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 239000010842 industrial wastewater Substances 0.000 abstract description 4
- 238000003980 solgel method Methods 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 239000008139 complexing agent Substances 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 23
- 230000003647 oxidation Effects 0.000 description 14
- 238000007254 oxidation reaction Methods 0.000 description 14
- 239000002351 wastewater Substances 0.000 description 13
- 229910002254 LaCoO3 Inorganic materials 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 238000002309 gasification Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 150000002978 peroxides Chemical class 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 235000013399 edible fruits Nutrition 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910002248 LaBO3 Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/39—
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
Abstract
The present invention relates to a kind of preparation methods of catalyst that can be used for ultraviolet catalytic wet oxidation.The catalyst is with La (NO3)3With Co (NO3)2For presoma, citric acid is complexing agent, the LaCoO formed after calcination at high temperature by sol-gel processing3Perovskite type catalyst.The catalyst can sufficiently cooperate with ultraviolet light, in acid condition, using hydrogen peroxide as oxidant, efficiently catalyzing and oxidizing coal chemical industrial waste water film concentrate at relatively low temperatures and pressures, and the catalyst structure is controllable, thermal stability is good, can be reused, and has great environment and economic benefit.
Description
Technical field
The present invention relates to a kind of preparation method of catalyst for ultraviolet catalytic wet oxidation, more particularly to one kind are available
In the preparation method of the catalyst of ultraviolet catalytic wet oxidation coal chemical industrial waste water film concentrate.
Background technique
For the requirement for meeting coal chemical industry " zero-emission ", coal chemical industrial waste water advanced treatment unit frequently with UF membrane
Technology.Membrane separation technique can carry out Selective Separation, but film point to impurity in coal gasification waste water on molecule or ion concentration
Essential from technology is separation pollutant, can not be degraded to pollutant, therefore can still generate during processing
A certain amount of film concentrate.Film concentrate has the characteristics that organic concentration is high, coloration is big, biodegradability is poor.How effectively
Process film concentrate is the significant challenge faced in coal chemical industrial waste water advanced treating.
Ultraviolet-catalytic wet peroxide oxidation (UV-CWPO) is in catalytic wet hydrogen peroxide oxidation system
(CWPO) ultraviolet light (UV) is introduced in, assists to promote using the effect direct photolysis organic pollutant of ultraviolet light and by ultraviolet light
Into catalysed oxidn degradable organic pollutant, organic and part inorganic pollution difficult to degrade in waste water is completely decomposed into
CO2, the harmless composition such as water, while can realize the harmless treatment of toxic wastewater with deodorization, decoloration and sterilizing, compared to
Catalysis wet-type oxidation technology reduces the temperature and pressure of conventional catalyst wet oxidation due to the introducing of ultraviolet light (UV).Catalysis
Agent is the key that ultraviolet-catalytic wet peroxide oxidation, and the active component in catalyst can reduce reaction condition, mention
High reaction efficiency, how to find a kind of catalyst of efficient stable is the key that promote this technology.Perovskite type catalyst is one
Kind crystal structure is the metal composite oxide of cubic system, has good structure-controllable, thermal stability, high catalytic efficiency and oxygen
Change the advantages that reducing power is strong, is with a wide range of applications in catalytic field.Gao Wenwen etc. has studied LaCoO3Ca-Ti ore type
Catalyst heterogeneous Fenton handles semi-coke wastewater, and under optimum process condition, the COD removal rate of semi-coke wastewater reaches
72.7%.Zou Wen waits quietly having studied LaBO3(B=Cr, Mn, Fe, Co, Ni) perofskite type oxide Surfactant dodecane
Base benzene sulfonic acid sodium salt (SDS) photolytic efficiency, wherein LaCoO3There is preferable degradation effect to SDS solution, degradation rate reaches
85.19%.
Summary of the invention
It is provided a kind of for ultraviolet catalytic wet oxidation the purpose of the invention is to improve the deficiencies in the prior art
The preparation method of catalyst, the catalyst can sufficiently cooperate as a kind of novel photochemical catalyst with the ultraviolet light in system,
And due to its structure-controllable, the feature that thermal stability is good, high catalytic efficiency, redox ability are strong, can be suitable for
Wet oxidation system, provides new approaches in order to overcome the deficiencies of the prior art.
The technical solution of the present invention is as follows: a kind of preparation method of the catalyst for ultraviolet catalytic wet oxidation of, specific
Steps are as follows:
(1) La (NO is stoichiometrically accurately measured3)3With Co (NO3)2It is dissolved in distilled water and forms mixed solution；
(2) citric acid is added into mixed solution to stir to being completely dissolved to form colloidal sol；
(3) drying forms gel at a certain temperature；
(4) by gel abrasive sieving for standby；
(5) LaCoO is obtained after heating calcining3Perovskite type catalyst.
La (NO described in preferred steps (1)3)3With Co (NO3)2Stoichiometric ratio be 1:(1~2)；In mixed solution
The mass concentration of solute is 10%~20%.
The citric acid and metal ion molar ratio added in preferred steps (2) is 3:(1~2), colloidal sol is thick shape.
The temperature of drying described in preferred steps (3) is 90 DEG C~110 DEG C；Gel form is bread-like.
Grinding sieves with 100 mesh sieve in preferred steps (3).
Calcination temperature described in preferred steps (5) is 700 DEG C~900 DEG C, and calcination time is 5~7h；Gained catalyst
For grey powder.
Beneficial effects of the present invention:
(1) catalyst of the invention is prepared using sol-gel method, and synthesis technology is simple；
(2) catalyst of the invention is high-efficient, thermal stability is strong, redox ability is strong；
(3) catalyst of the invention, can be with ultraviolet-catalytic wet hydrogen peroxide as a kind of novel photochemical catalyst
Ultraviolet light in oxidation technology sufficiently cooperates, the catalytic efficiency in raising system；
(4) reaction condition needed for catalyst of the invention can reduce conventional catalyst wet oxidation, in the shape of low-temperature atmosphere-pressure
The oxidation to coal gasification film concentrate is realized under state, reduces operating cost；
(5) catalyst of the invention can realize recycling, good economy performance.
Detailed description of the invention
Fig. 1 is LaCoO3The X-ray diffractogram of perovskite type catalyst.
Fig. 2 is LaCoO3The scanning electron microscope (SEM) photograph of perovskite type catalyst.
Fig. 3 is LaCoO3The nonexpondable catalytic effect of perovskite type catalyst compares histogram.
Specific embodiment
Embodiment 1:
The preparation of the catalyst of the present embodiment carries out as follows:
(1) stoichiometrically 1:1 accurately measures La (NO3)3·nH2O and Co (NO3)2·6H2O is dissolved in a certain amount of steaming
The mixed solution that Solute mass concentration is 10% is formed in distilled water；
(2) citric acid (citric acid and metal ion molar ratio be 3:1) is added into mixed solution to stir to being completely dissolved
Form colloidal sol；
(3) drying forms gel at 90 DEG C；
(4) gel abrasive is sieved with 100 mesh sieve spare；
(5) 5h is calcined at 700 DEG C obtain LaCoO3Perovskite type catalyst；The X-ray diffractogram of gained catalyst and
Scanning electron microscope (SEM) photograph difference is as depicted in figs. 1 and 2.
Using catalyst manufactured in the present embodiment, using certain coal gasification film concentrate as process object, using it is ultraviolet-urge
Change wet-type peroxide oxidizing to be handled.Experiment carries out in photochemistry autoclave, takes 250ml waste water in reaction kettle
In, reaction condition: H is set2O2Dosage 1.2ml/L, catalyst amounts 0.8g/L, 120 DEG C of reaction temperature, reaction pressure
0.5MPa, pH=3, reaction time 60min.It is analyzed after reaction in sample tap sampling, the oxidation effect of 1 waste water of embodiment
Fruit is as shown in table 1.
Table 1
| Detection project | COD | TOC | UV254 |
| Raw water | 1510 | 658 | 1.562 |
| Oxidation water outlet | 184 | 114 | 0.05 |
| Removal rate | 87.8% | 82.7% | 96.8% |
Embodiment 2:
The preparation of the catalyst of the present embodiment carries out as follows:
(1) stoichiometrically 2:3 accurately measures La (NO3)3·nH2O and Co (NO3)2·6H2O is dissolved in a certain amount of steaming
The mixed solution that Solute mass concentration is 15% is formed in distilled water；
(2) citric acid (citric acid and metal ion molar ratio be 2:1) is added into mixed solution to stir to being completely dissolved
Form colloidal sol；
(3) drying forms gel at 100 DEG C；
(4) gel abrasive is sieved with 100 mesh sieve spare；
(5) 6h is calcined at 800 DEG C obtain LaCoO3Perovskite type catalyst.
Catalyst prepared by Application Example 2, using certain coal gasification film concentrate as process object, using ultraviolet-catalysis
Wet-type peroxide oxidizing is handled.Experiment carries out in photochemistry autoclave, takes 250ml waste water in reaction kettle,
Reaction condition: H is set2O2Dosage 1.2ml/L, catalyst amounts 0.8g/L, 120 DEG C of reaction temperature, reaction pressure
0.5MPa, pH=3, reaction time 60min.It is analyzed after reaction in sample tap sampling, the oxidation effect of 2 waste water of embodiment
Fruit is as shown in table 2.
Table 2
| Detection project | COD | TOC | UV254 |
| Raw water | 1510 | 658 | 1.562 |
| Oxidation water outlet | 146 | 101 | 0.044 |
| Removal rate | 90.3% | 84.6% | 97.2% |
Embodiment 3:
The preparation of the catalyst of the present embodiment carries out as follows:
(1) stoichiometrically 1:2 accurately measures La (NO3)3·nH2O and Co (NO3)2·6H2O is dissolved in a certain amount of steaming
The mixed solution that Solute mass concentration is 20% is formed in distilled water；
(2) citric acid (citric acid and metal ion molar ratio be 3:2) is added into mixed solution to stir to being completely dissolved
Form colloidal sol；
(3) drying forms gel at 110 DEG C；
(4) gel abrasive is sieved with 100 mesh sieve spare；
(5) 7h is calcined at 900 DEG C obtain LaCoO3Perovskite type catalyst.
Catalyst prepared by Application Example 3, using certain coal gasification film concentrate as process object, using ultraviolet-catalysis
Wet-type peroxide oxidizing is handled.Experiment carries out in photochemistry autoclave, takes 250ml waste water in reaction kettle,
Reaction condition: H is set2O2Dosage 1.2ml/L, catalyst amounts 0.8g/L, 120 DEG C of reaction temperature, reaction pressure
0.5MPa, pH=3, reaction time 60min.It is analyzed after reaction in sample tap sampling, the oxidation effect of 3 waste water of embodiment
Fruit is as shown in table 3.
Table 3
| Detection project | COD | TOC | UV254 |
| Raw water | 1510 | 658 | 1.562 |
| Oxidation water outlet | 177 | 109 | 0.05 |
| Removal rate | 88.3% | 83.4% | 96.8% |
Embodiment 4:
By catalyst prepared by the embodiment 2 after first use after centrifugation, deionized water washing and being dried,
It repeatedly uses under the same conditions.Using certain coal gasification film concentrate as process object, using ultraviolet-catalytic wet
Hydrogen peroxide oxidation is handled.Experiment carries out in photochemistry autoclave, takes 250ml waste water in reaction kettle, is arranged
Reaction condition: H2O2Dosage 1.2ml/L, catalyst amounts 0.8g/L, 120 DEG C of reaction temperature, reaction pressure 0.5MPa, pH
=3, reaction time 60min.It is analyzed after reaction in sample tap sampling, the oxidation effectiveness of 4 waste water of embodiment such as 4 institute of table
Show, it can be seen that the catalyst catalytic performance for reusing 5 times shows that catalyst stability is good, such as Fig. 3 there is no significant change
It is shown.
Table 4
| Detection project | COD | TOC | UV254 |
| Raw water | 1510 | 658 | 1.562 |
| For the first time using water outlet | 147 | 101 | 0.044 |
| For the second time using water outlet | 149 | 103 | 0.045 |
| Third time uses water outlet | 154 | 105 | 0.047 |
| 4th use water outlet | 162 | 109 | 0.049 |
| 5th use water outlet | 168 | 112 | 0.052 |
Claims (6)
1. a kind of preparation method of the catalyst for ultraviolet catalytic wet oxidation, the specific steps of which are as follows:
(1) La (NO is stoichiometrically accurately measured3)3With Co (NO3)2It is dissolved in distilled water and forms mixed solution；
(2) citric acid is added into mixed solution to stir to being completely dissolved to form colloidal sol；
(3) drying forms gel at a certain temperature；
(4) by gel abrasive sieving for standby；
(5) LaCoO is obtained after heating calcining3Perovskite type catalyst.
2. preparation method according to claim 1, it is characterised in that La (NO described in step (1)3)3With Co (NO3)2's
Stoichiometric ratio is 1:(1~2)；The mass concentration of solute is 10%~20% in mixed solution.
3. preparation method according to claim 1, it is characterised in that the citric acid added in step (2) rubs with metal ion
You are than being 3:(1~2).
4. preparation method according to claim 1, it is characterised in that the temperature of drying described in step (3) be 90 DEG C~
110℃。
5. preparation method according to claim 1, it is characterised in that grinding sieves with 100 mesh sieve in step (3).
6. preparation method according to claim 1, it is characterised in that calcination temperature described in step (5) be 700 DEG C~
900 DEG C, calcination time is 5~7h.
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| CN110075856A (en) * | 2019-05-21 | 2019-08-02 | 南京工业大学 | A kind of catalyst and preparation method thereof for catalytic wet oxidation nitro-chlorobenzene waste water |
| CN111533234A (en) * | 2020-04-29 | 2020-08-14 | 南京中微纳米功能材料研究院有限公司 | Method for degrading antibiotic wastewater by catalyzing persulfate through perovskite |
| CN111686755A (en) * | 2019-03-14 | 2020-09-22 | 天津大学 | Surface modified perovskite catalyst and preparation method and application thereof |
| CN112110497A (en) * | 2020-09-28 | 2020-12-22 | 中国科学技术大学 | Lanthanide metal-doped lanthanum cobaltate type nanotube material, preparation method thereof and method for producing hydrogen by electrolyzing water |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110075856A (en) * | 2019-05-21 | 2019-08-02 | 南京工业大学 | A kind of catalyst and preparation method thereof for catalytic wet oxidation nitro-chlorobenzene waste water |
| CN111533234A (en) * | 2020-04-29 | 2020-08-14 | 南京中微纳米功能材料研究院有限公司 | Method for degrading antibiotic wastewater by catalyzing persulfate through perovskite |
| CN112110497A (en) * | 2020-09-28 | 2020-12-22 | 中国科学技术大学 | Lanthanide metal-doped lanthanum cobaltate type nanotube material, preparation method thereof and method for producing hydrogen by electrolyzing water |
| CN112110497B (en) * | 2020-09-28 | 2022-04-19 | 中国科学技术大学 | Lanthanide metal-doped lanthanum cobaltate type nanotube material, preparation method thereof and method for producing hydrogen by electrolyzing water |
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