CN117563612A - Preparation method and application of cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst - Google Patents
Preparation method and application of cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst Download PDFInfo
- Publication number
- CN117563612A CN117563612A CN202410051052.5A CN202410051052A CN117563612A CN 117563612 A CN117563612 A CN 117563612A CN 202410051052 A CN202410051052 A CN 202410051052A CN 117563612 A CN117563612 A CN 117563612A
- Authority
- CN
- China
- Prior art keywords
- aluminum hydrotalcite
- cerium oxide
- nickel
- deionized water
- precipitate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 title claims abstract description 92
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 85
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 85
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 54
- -1 cerium oxide-nickel aluminum Chemical compound 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 46
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 46
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- 239000008367 deionised water Substances 0.000 claims description 42
- 229910021641 deionized water Inorganic materials 0.000 claims description 42
- 239000002244 precipitate Substances 0.000 claims description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- 239000006228 supernatant Substances 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 6
- 229910003297 Ni(NO3)3·6H2O Inorganic materials 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 3
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 239000007791 liquid phase Substances 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract description 2
- 238000003746 solid phase reaction Methods 0.000 abstract description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract 1
- 229910052759 nickel Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 30
- 238000001878 scanning electron micrograph Methods 0.000 description 9
- 239000004809 Teflon Substances 0.000 description 7
- 229920006362 Teflon® Polymers 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000233866 Fungi Species 0.000 description 1
- 241000700605 Viruses Species 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
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- 108700012359 toxins Proteins 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 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
- B01J23/007—Mixed salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/007—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by irradiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
-
- 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
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
Abstract
The invention discloses a preparation method of a cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst, which specifically comprises the following steps: (1) preparation of cubic cerium oxide; (2) preparation of nickel aluminum hydrotalcite; (3) And (3) preparing the cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst. The invention combines cerium oxide and nickel with good appearanceThe cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst obtained by compounding aluminum hydrotalcite realizes better photocatalytic performance, and the photocatalyst has wide application, not only can be applied to gas-liquid phase, but also can be directly applied to gas-solid phase reaction and CO 2 Photocatalytic high value conversion of (c), etc.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a preparation method and application of a cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst.
Background
The photocatalyst is a generic term for a semiconductor material having a photocatalytic function, typified by nano-scale titanium dioxide. A representative photocatalyst is titanium dioxide, which is capable of generating a substance having a strong oxidizing property (e.g., hydroxyl radical, oxygen, etc.) upon irradiation with light, and is useful for decomposing organic compounds, part of inorganic compounds, bacteria, viruses, etc. In daily life, the photocatalyst can effectively degrade toxic and harmful gases in the air, such as formaldehyde and the like, and can efficiently purify the air; meanwhile, the method can effectively kill various bacteria, and can decompose and harmlessly treat toxins released by the bacteria or fungi.
At present, the problems of low conversion rate, low quantum efficiency, energy supplementation and the like of the traditional semiconductor photocatalyst are solved, and the efficient, stable and low-cost photocatalyst is sought to become a research hot spot in the field of photocatalysis. Among these, layered double hydroxides (layered double hydroxides, LDHs) are metal hydroxides composed of one or more metal elements, and LDHs are widely used in the fields of catalysis and the like due to the advantages that the composition of the layered double hydroxides is easy to be combined with other materials to realize functionalization. Among these, nickel aluminum hydrotalcite is a type of hydrotalcite material that is widely used. Based on this, hydrotalcite-like compounds are also considered as a promising alternative material in conventional semiconductors.
However, the excessive high photo-generated carrier recombination rate is still a main factor for restricting the photocatalytic activity of hydrotalcite-like compounds, so that the hydrotalcite-like compounds are regulated to obtain more proper band gaps and energy levels so as to realize higher light energy utilization rate, and the current difficulty is realized.
Cerium oxide has a narrower band gap than conventional titanium dioxide, and is also widely used in the field of photocatalysis.
Therefore, the development of a cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst is a problem that needs to be solved by a person skilled in the art.
Disclosure of Invention
In view of the above, the present invention aims to provide a preparation method and application of a cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst, so as to solve the defects in the prior art.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst specifically comprises the following steps:
(1) Preparation of cubic cerium oxide
Ce (NO) 3 ) 3 ·6H 2 Adding O into the first part of deionized water, stirring and dissolving to obtain a solution A; adding NaOH into the second deionized water, and stirring and dissolving to obtain a solution B; then dropwise adding the solution A into the solution B under the condition of continuous magnetic stirring, and continuously stirring to obtain a solution C; then preserving the temperature of the solution C, cooling, centrifuging, and removing the supernatant to obtain a precipitate; finally, washing and centrifuging the precipitate, and drying overnight to obtain cubic cerium oxide;
(2) Preparation of nickel-aluminum hydrotalcite
1) Preparation of nickel-aluminum hydrotalcite by A method
Ni (NO) 3 ) 3 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 Adding O into deionized water, then dropwise adding formamide solution and NaOH solution at the same time under the condition of continuous stirring until the pH value of the system is 9.5-10.5, centrifuging, and removing supernatant to obtain precipitate; finally, washing the precipitate, and freeze-drying the precipitate in a wet state to obtain nickel-aluminum hydrotalcite;
2) Preparation of nickel-aluminum hydrotalcite by B method
Ni (NO) 3 ) 3 ·6H 2 O、Al(NO 3 ) 3 ·9H 2 Adding O and hexamethylenetetramine into deionized water, continuously stirring, performing hydrothermal reaction, centrifuging, and removing supernatant to obtain precipitate; finally, washing the precipitate with water and drying to obtain nickel-aluminum hydrotalcite;
3) Preparation of nickel-aluminum hydrotalcite by C method
Ni (NO) 3 ) 3 ·6H 2 O、Al(NO 3 ) 3 ·9H 2 Adding O and urea into deionized water, continuously stirring, performing hydrothermal reaction, centrifuging, and removing supernatant to obtain precipitate; finally, washing the precipitate with water and drying to obtain nickel-aluminum hydrotalcite;
(3) Preparation of cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst
Firstly, adding cubic cerium oxide and nickel aluminum hydrotalcite into a solvent for thermal synthesis, then centrifuging to remove supernatant fluid to obtain precipitate, and finally drying the precipitate to obtain the cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst.
Further, in the above step (1), ce (NO) 3 ) 3 ·6H 2 The mol volume ratio of O, the first deionized water, naOH and the second deionized water is 0.006-0.008 mol:20 mL:0.90-0.96 mol:140 mL; continuously stirring for 30 min; the temperature of the heat preservation is 180 ℃ and the time is 24 hours; the reagent for cleaning and centrifuging is deionized water and ethanol, and the times are 3-5 times; the temperature of drying was 80 ℃.
Further, in the above step 1), ni (NO) 3 ) 3 ·6H 2 O、Al（NO 3 ) 3 ·9H 2 The mol volume ratio of O to deionized water is 37-38mM, 12-13mM, 20-30 and mL; the mass fraction of the formamide solution is 21% -24%; the concentration of the NaOH solution is 0.22-0.26M; the washed reagent is ethanol for 2-3 times.
Further, in the above step 2), ni (NO) 3 ) 3 ·6H 2 O、Al(NO 3 ) 3 ·9H 2 The molar ratio of O to hexamethyltetramine is 90-92 mM, 10-12 mM, 130-132 mM, ni (NO 3 ) 3 ·6H 2 O、Al(NO 3 ) 3 ·9H 2 The sum of the volumes of O hexamethyltetramine and deionized water is 240mL; the stirring time is 20 min; the temperature of the hydrothermal reaction is 130-150 ℃ and the time is 20-25 h; washing with water to neutrality; the temperature of drying was 60℃and the time was 8 h.
Further, in the above step 3), ni (NO) 3 ) 3 ·6H 2 O、Al(NO 3 ) 3 ·9H 2 The molar volume ratio of O, urea and deionized water is 30 mM:9-11 mM:40-42 mM:300 mL; the stirring time is 30 min; the temperature of the hydrothermal reaction is 150-180 ℃ and the time is 30-36 h; the reagent for water washing is deionized water to be neutral; the temperature of drying was 60℃and the time was 8 h.
Further, in the step (3), the mass volume ratio of the cubic cerium oxide, the nickel aluminum hydrotalcite and the solvent is (5-20) g, namely 100 g to 100 mL; the solvent is prepared by mixing deionized water, ethanol and N, N-dimethylformamide; the temperature of the thermal synthesis is 130-150 ℃ and the time is 12-18 h; the temperature of drying was 60℃and the time was 8 h.
The invention also claims a cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst prepared by the preparation method in CO 2 Application in photocatalytic high value conversion.
Furthermore, the reactor for the photocatalytic reaction can realize gas-liquid and gas-solid reactions and can also realize pressure regulation, and meanwhile, the reactor is provided with a temperature sensor and a pressure regulating device to realize temperature control and pressure control; the sampling port is convenient, and gas-liquid phase substances can be conveniently sampled and detected; has the magnetic stirring function, and can realize CO to a greater extent in a gas-liquid reaction system 2 Is fully contacted with the photocatalyst; in the gas-solid reaction process, the photocatalyst is loaded by utilizing the glass slide, so that the experiment operation is facilitated.
Compared with the prior art, the invention has the following beneficial effects:
the invention combines cerium oxide with better appearance with nickel aluminum hydrotalcite, thus the obtained cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst realizes better photocatalytic performance, and the photocatalyst has wide application, not only can be applied to gas-liquid phase, but also can be directly applied to gas-solid phase reaction, and also can be applied to CO 2 Photocatalytic high value conversion of (c), etc.
Drawings
FIG. 1 is a block diagram of a cubic cerium oxide (CeO) prepared in example 1 2 ) SEM images of (a);
FIG. 2 is a SEM image of nickel aluminum hydrotalcite (A-NiAl-LDHs) obtained in example 1;
FIG. 3 is a view showing a cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst (5% CeO) obtained in example 1 2 SEM image of/A-NiAl-LDHs);
FIG. 4 is a SEM image of nickel aluminum hydrotalcite (B-NiAl-LDHs) obtained in example 2;
FIG. 5 is a schematic illustration of a cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst (5% CeO) prepared in example 2 2 B-NiAl-LDHs);
FIG. 6 is a SEM image of nickel aluminum hydrotalcite (C-NiAl-LDHs) obtained in example 3;
FIG. 7 is a view showing a cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst (5% CeO) obtained in example 3 2 C-NiAl-LDHs);
FIG. 8 shows a cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst (5% CeO) prepared in examples 3 to 6 2 /C-NiAl-LDHs、10%CeO 2 /C-NiAl-LDHs、15%CeO 2 C-NiAl-LDHs and 20% CeO 2 C-NiAl-LDHs) and CO of a blank group 2 Transformation performance diagram.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst specifically comprises the following steps:
(1) Preparation of cubic cerium oxide
First, 0.006 mol of Ce (NO) 3 ) 3 ·6H 2 Adding O into 20 mL deionized water, stirring and dissolving to obtain solution A; adding 0.90 mol of NaOH into 140 mL deionized water, stirring and dissolving to obtain a solution B; then stirring under continuous magnetic forceDropwise adding the solution A into the solution B under the condition of (1) and continuously stirring for 30min to obtain a solution C; transferring the solution C into a Teflon tank of 250 mL, placing the Teflon tank into an oven, preserving heat for 24 hours at 180 ℃, cooling, centrifuging, and removing supernatant to obtain a precipitate; finally, washing and centrifuging the precipitate with deionized water and ethanol for 3 times respectively, and drying overnight in an oven at 80 ℃ to obtain cubic cerium oxide;
(2) Method for preparing nickel-aluminum hydrotalcite by A method
At a constant temperature of 80℃37mM Ni (NO 3 ) 3 ·6H 2 O and 12mM Al (NO) 3 ) 3 ·9H 2 Adding O into 20 mL deionized water, then adding 21% formamide solution and 0.22M NaOH solution dropwise to a system pH value of 9.5 under the condition of continuous stirring, controlling the whole process to be completed within 12 min, centrifuging, and removing supernatant to obtain precipitate; finally, washing the precipitate for 2 times by using ethanol, and keeping a wet sample state for freeze drying to obtain nickel-aluminum hydrotalcite;
(3) Preparation of cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst
Firstly, adding 5 g cubic blocks of cerium oxide and 100 g nickel aluminum hydrotalcite into a solvent prepared by mixing 100mL deionized water, ethanol and N, N-dimethylformamide, thermally synthesizing 18 h at 130 ℃, centrifuging to remove supernatant fluid to obtain precipitate, and finally drying the precipitate at 60 ℃ to obtain 8 h, thereby obtaining the cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst.
Example 2
The preparation method of the cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst specifically comprises the following steps:
(1) Preparation of cubic cerium oxide
0.008 mol Ce (NO) 3 ) 3 ·6H 2 Adding O into 20 mL deionized water, stirring and dissolving to obtain solution A; adding 0.96 mol of NaOH into 140 mL deionized water, stirring and dissolving to obtain a solution B; then dropwise adding the solution A into the solution B under the condition of continuous magnetic stirring, and continuously stirring for 30min to obtain a solution C; transfer solution C to 250 mLPlacing the mixture into a Teflon tank, placing the Teflon tank into an oven, preserving heat for 24 hours at 180 ℃, cooling, centrifuging, and removing supernatant to obtain a precipitate; finally, washing and centrifuging the precipitate with deionized water and ethanol for 5 times respectively, and drying overnight in an oven at 80 ℃ to obtain cubic cerium oxide;
(2) Method for preparing nickel-aluminum hydrotalcite by B method
92 mM Ni (NO) 3 ) 3 ·6H 2 O、12 mM Al(NO 3 ) 3 ·9H 2 Adding O and 32 mM hexamethyltetramine into deionized water to form 240mL mixed solution, continuously stirring for 20 min, performing hydrothermal reaction at 150 ℃ for 20 h, centrifuging, and removing supernatant to obtain precipitate; finally, washing the precipitate to be neutral, and drying 8 h at 60 ℃ to obtain nickel-aluminum hydrotalcite;
(3) Preparation of cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst
Firstly, adding 5 g cubic blocks of cerium oxide and 100 g nickel aluminum hydrotalcite into a solvent prepared by mixing 100mL deionized water, ethanol and N, N-dimethylformamide, thermally synthesizing 12 h at 150 ℃, centrifuging to remove supernatant to obtain precipitate, and finally drying the precipitate at 60 ℃ to obtain 8 h, thereby obtaining the cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst.
Example 3
The preparation method of the cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst specifically comprises the following steps:
(1) Preparation of cubic cerium oxide
0.008 mol Ce (NO) 3 ) 3 ·6H 2 Adding O into 20 mL deionized water, stirring and dissolving to obtain solution A; adding 0.92 mol of NaOH into 140 mL deionized water, stirring and dissolving to obtain a solution B; then dropwise adding the solution A into the solution B under the condition of continuous magnetic stirring, and continuously stirring for 30min to obtain a solution C; transferring the solution C into a Teflon tank of 250 mL, placing the Teflon tank into an oven, preserving heat for 24 hours at 180 ℃, cooling, centrifuging, and removing supernatant to obtain a precipitate; finally, the sediment is washed and centrifuged for 4 times by deionized water and ethanol respectively, and is put into an oven to be dried overnight at 80 ℃,obtaining cubic cerium oxide;
(2) Method for preparing nickel-aluminum hydrotalcite by C method
30 mM Ni (NO) 3 ) 3 ·6H 2 O、10 mM Al(NO 3 ) 3 ·9H 2 Adding O and 42 mM urea into 300 mL deionized water, continuously stirring for 30min, transferring to a Teflon tank, performing hydrothermal reaction at 160 ℃ for 32 h, cooling to room temperature, centrifuging, and removing supernatant to obtain precipitate; finally, washing the precipitate with deionized water to be neutral, and drying 8 h at 60 ℃ to obtain nickel-aluminum hydrotalcite;
(3) Preparation of cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst
Firstly, adding 5 g cubic cerium oxide and 100 g nickel aluminum hydrotalcite into a solvent prepared by mixing 100mL deionized water, ethanol and N, N-dimethylformamide, thermally synthesizing 16 h at 140 ℃, centrifuging to remove supernatant fluid to obtain precipitate, and finally drying the precipitate at 60 ℃ for 8 h to obtain the cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst.
Example 4
The preparation method of the cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst is different from example 3 only in that in the step (3), the mass of the cubic cerium oxide is 10 g.
Example 5
The preparation method of the cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst is different from example 3 only in that in the step (3), the mass of the cubic cerium oxide is 15 g.
Example 6
The preparation method of the cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst is different from example 3 only in that in the step (3), the mass of the cubic cerium oxide is 20 g.
Performance testing
1. SEM characterization
1. Cubic cerium oxide (CeO) prepared in example 1 2 ) An SEM image of (2) is shown in figure 1.
As can be seen from fig. 1, the cerium oxide synthesized in example 1 by the simple hydrothermal method has a better cube structure, and the size of these cubes is concentrated between 20 and 150 and nm.
2. Nickel aluminum hydrotalcite (A-NiAl-LDHs) and cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst (5% CeO) prepared in example 1 2 SEM images of/a-NiAl-LDHs) are shown in fig. 2 and 3, respectively.
As can be seen from fig. 2 and 3, the nickel aluminum hydrotalcite prepared by the method a in example 1 is mainly in a block shape, and maintains the original morphology in the subsequent compounding process with cubic cerium oxide.
3. Nickel-aluminum hydrotalcite (B-NiAl-LDHs) and cerium oxide-nickel-aluminum hydrotalcite composite heterojunction photocatalyst (5% CeO) prepared in example 2 2 SEM images of/B-NiAl-LDHs) are shown in fig. 4 and 5, respectively.
As can be seen from fig. 4 and 5, the nickel aluminum hydrotalcite prepared in the B method in example 2 is mainly in the shape of self-assembled nano-sheets, and is well combined with cubic cerium oxide after being compounded.
4. Nickel-aluminum hydrotalcite (C-NiAl-LDHs) and cerium oxide-nickel-aluminum hydrotalcite composite heterojunction photocatalyst (5% CeO) prepared in example 3 2 SEM images of/C-NiAl-LDHs) are shown in fig. 6 and 7, respectively.
As can be seen from fig. 6 and 7, the nickel aluminum hydrotalcite prepared in example 3C is an ultrathin nano-sheet, and is well connected with cubic cerium oxide to form a heterojunction.
2. Catalytic test
The cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst (5% CeO) prepared in each of examples 3-6 was taken 2 /C-NiAl-LDHs、10%CeO 2 /C-NiAl-LDHs、15%CeO 2 C-NiAl-LDHs and 20% CeO 2 Respectively placing/C-NiAl-LDHs and nickel-aluminum hydrotalcite (C-NiAl-LDHs) prepared in example 3 into 100mL high-pressure reaction kettle, setting blank control group (without placing any photocatalyst), and injecting high-purity CO 2 +H 2 O gas reaches 0.1MPa, after being absorbed in dark for 30min, the lamp is turned on to carry out photoreaction, one sample is taken every 1h, the products are detected and analyzed by gas chromatography, and the CO of each treatment group is respectively tested 2 Converted to CO production.
The results are shown in FIG. 8.
As can be seen from FIG. 8, example 3 Nickel aluminum hydrotalcite CO 2 Conversion to CO with a CO yield of 22.63. Mu. Mol/g (6 h), examples 3-6 cerium oxide-Nickel aluminum hydrotalcite composite heterojunction photocatalyst 2 The yields of CO converted to 36.33, 89.05, 130.30 and 87.33. Mu. Mol/g (6 h), respectively, were compared to CO in a control group without any photocatalyst 2 Is not converting, i.e. it has been demonstrated that the overall reactivity is achieved by the addition of the photocatalyst according to the invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (6)
1. The preparation method of the cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst is characterized by comprising the following steps of:
(1) Preparation of cubic cerium oxide
Ce (NO) 3 ) 3 ·6H 2 Adding O into the first part of deionized water, stirring and dissolving to obtain a solution A; adding NaOH into the second deionized water, and stirring and dissolving to obtain a solution B; then dropwise adding the solution A into the solution B under the condition of continuous magnetic stirring, and continuously stirring to obtain a solution C; then preserving the temperature of the solution C, cooling, centrifuging, and removing the supernatant to obtain a precipitate; finally, washing and centrifuging the precipitate, and drying overnight to obtain cubic cerium oxide;
(2) Preparation of nickel-aluminum hydrotalcite
1) Preparation of nickel-aluminum hydrotalcite by A method
Ni (NO) 3 ) 3 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 Adding O into deionized water, then dropwise adding formamide solution and NaOH solution at the same time under the condition of continuous stirring until the pH value of the system is 9.5-10.5, centrifuging, and removing supernatant to obtain precipitate; finally, washing the precipitate, and freeze-drying the precipitate in a wet state to obtain nickel-aluminum hydrotalcite;
2) Preparation of nickel-aluminum hydrotalcite by B method
Ni (NO) 3 ) 3 ·6H 2 O、Al(NO 3 ) 3 ·9H 2 Adding O and hexamethylenetetramine into deionized water, continuously stirring, performing hydrothermal reaction, centrifuging, and removing supernatant to obtain precipitate; finally, washing the precipitate with water and drying to obtain nickel-aluminum hydrotalcite;
3) Preparation of nickel-aluminum hydrotalcite by C method
Ni (NO) 3 ) 3 ·6H 2 O、Al(NO 3 ) 3 ·9H 2 Adding O and urea into deionized water, continuously stirring, performing hydrothermal reaction, centrifuging, and removing supernatant to obtain precipitate; finally, washing the precipitate with water and drying to obtain nickel-aluminum hydrotalcite;
(3) Preparation of cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst
Firstly, adding cubic cerium oxide and nickel aluminum hydrotalcite into a solvent for thermal synthesis, then centrifuging to remove supernatant fluid to obtain precipitate, and finally drying the precipitate to obtain the cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst.
2. The method for preparing a cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst according to claim 1, wherein in step (1), the Ce (NO 3 ) 3 ·6H 2 The mol volume ratio of O, the first deionized water, naOH and the second deionized water is 0.006-0.008 mol:20 mL:0.90-0.96 mol:140 mL; the stirring time is 30 min; the temperature of the heat preservation is 180 ℃ and the time is 24 hours; the cleaning and centrifuging reagent is deionized water and ethanol, and the times are 3-5 times; the temperature of the drying was 80 ℃.
3. The method for preparing a cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst according to claim 1, wherein in step 1), the Ni (NO 3 ) 3 ·6H 2 O、Al（NO 3 ) 3 ·9H 2 The mol volume ratio of O to deionized water is 37-38mM, 12-13mM, 20-30 and mL; the mass fraction of the formamide solution is 21% -24%; the concentration of the NaOH solution is 0.22-0.26M; the washing reagent is ethanol, and the times are 2-3 times.
4. The method for preparing a cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst according to claim 1, wherein in step 2), the Ni (NO 3 ) 3 ·6H 2 O、Al(NO 3 ) 3 ·9H 2 The mol ratio of O to hexamethylenetetramine is 90-92 mM, 10-12 mM, 130-132 and mM; the Ni (NO) 3 ) 3 ·6H 2 O、Al(NO 3 ) 3 ·9H 2 The sum of the volumes of O hexamethyltetramine and deionized water is 240mL; the duration of the continuous stirring is 20 min; the temperature of the hydrothermal reaction is 130-150 ℃ and the time is 20-25 h; washing with water to neutrality; the drying temperature was 60℃and the time was 8 h.
5. The method for preparing a cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst according to claim 1, wherein in step 3), the Ni (NO 3 ) 3 ·6H 2 O、Al(NO 3 ) 3 ·9H 2 The molar volume ratio of O, urea and deionized water is 30 mM:9-11 mM:40-42 mM:300 mL; the duration of the continuous stirring is 30 min; the temperature of the hydrothermal reaction is 150-180 ℃ and the time is 30-36 h; the water-washed reagent is deionized water to be neutral; the drying temperature was 60℃and the time was 8 h.
6. The preparation method of the cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst according to claim 1, wherein in the step (3), the mass-volume ratio of the cubic cerium oxide, the nickel aluminum hydrotalcite and the solvent is (5-20) g to 100 mL; the solvent is prepared by mixing deionized water, ethanol and N, N-dimethylformamide; the temperature of the thermal synthesis is 130-150 ℃ and the time is 12-18 h; the drying temperature was 60℃and the time was 8 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410051052.5A CN117563612A (en) | 2024-01-15 | 2024-01-15 | Preparation method and application of cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410051052.5A CN117563612A (en) | 2024-01-15 | 2024-01-15 | Preparation method and application of cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117563612A true CN117563612A (en) | 2024-02-20 |
Family
ID=89892039
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410051052.5A Pending CN117563612A (en) | 2024-01-15 | 2024-01-15 | Preparation method and application of cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117563612A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140090972A1 (en) * | 2011-06-08 | 2014-04-03 | Antecy B.V. | Direct photoconversion of carbon dioxide to liquid products |
| CN113716529A (en) * | 2021-09-15 | 2021-11-30 | 昆明理工大学 | Method for recovering sulfur by low-temperature photocatalysis Claus and photocatalyst |
| CN117244563A (en) * | 2023-11-15 | 2023-12-19 | 内蒙古鄂尔多斯电力冶金集团股份有限公司 | Coated Ni-based photo-thermal catalyst and preparation method and application thereof |
-
2024
- 2024-01-15 CN CN202410051052.5A patent/CN117563612A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140090972A1 (en) * | 2011-06-08 | 2014-04-03 | Antecy B.V. | Direct photoconversion of carbon dioxide to liquid products |
| CN113716529A (en) * | 2021-09-15 | 2021-11-30 | 昆明理工大学 | Method for recovering sulfur by low-temperature photocatalysis Claus and photocatalyst |
| CN117244563A (en) * | 2023-11-15 | 2023-12-19 | 内蒙古鄂尔多斯电力冶金集团股份有限公司 | Coated Ni-based photo-thermal catalyst and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| YANG, M等: "Atomic activation triggering selective photoreduction of CO2 to CH4 over NiAl-LDH/CeO2 heterojunction", 《CHEMICAL ENGINEERING JOURNAL》, 31 August 2023 (2023-08-31), pages 145071 * |
| 宋赞: "CeO2@NiAl-LDHs 对萘酚蓝黑的吸附-光催化降解特性及其作用机理 研究", 《万方数据》, 1 November 2023 (2023-11-01) * |
| 阳敏: "LDH 基多孔复合材料的制备及光催化CO2还原性能研究", 《万方数据》, 16 December 2022 (2022-12-16) * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11224866B2 (en) | Tricobalt tetraoxide dodecahedron/carbon nitride nanosheet composite and application thereof in exhaust gas treatment | |
| CN108097255B (en) | Porous carbon frame nickel-based catalyst for carbon dioxide reforming reaction and preparation method and use method thereof | |
| CN105195197A (en) | TiO2 catalyst with large specific surface area and visible-light response function and method for preparing TiO2 catalyst | |
| CN105170173B (en) | A kind of perovskite material/organic polymer composite photo-catalyst, preparation and application | |
| CN111450820B (en) | Chromium oxide-loaded titanium dioxide photocatalyst, and preparation method and application thereof | |
| CN110075854B (en) | Preparation and application method of monolithic catalyst | |
| CN111821966A (en) | Black TiO2Preparation method of nanosheet photocatalyst | |
| CN113952986A (en) | WO (WO)3TpPa-1-COF composite material and preparation method and application thereof | |
| CN113731503A (en) | Preparation method of metal phthalocyanine complex-titanium dioxide composite photocatalyst | |
| CN107308973B (en) | Basic cobalt phosphate nanoneedle composite LTON photocatalyst and preparation method and application thereof | |
| CN111974436B (en) | Graphite-phase carbon nitride and preparation method thereof, and method for producing hydrogen by photocatalytic water | |
| CN106732587B (en) | A kind of preparation method of the ZnO polycrystal nanobelt package assembly of high H2-producing capacity atomic state Ag modification | |
| CN112604691A (en) | Reverse water gas shift catalyst and preparation method and application thereof | |
| CN109647373B (en) | Black indium oxide ultrathin nanosheet and preparation method and photo-thermal catalysis application thereof | |
| CN117563612A (en) | Preparation method and application of cerium oxide-nickel aluminum hydrotalcite composite heterojunction photocatalyst | |
| CN114849789B (en) | Preparation method and application of MIL-125 supported 1T-phase molybdenum sulfide composite photocatalyst | |
| CN114452996B (en) | g-C 3 N 4 /WO 3 ·H 2 O/Pd ternary composite photocatalyst and preparation method and application thereof | |
| CN114308132B (en) | Protonated CdS-COF-366-M composite photocatalyst and preparation method thereof | |
| CN112844375B (en) | MnO for removing nitrogen oxide 2 /Bi 2 WO 6 Heterojunction photocatalyst and preparation method thereof | |
| CN114100633B (en) | Catalyst for preparing hydrogen by catalyzing and decomposing hydrogen sulfide by visible light and preparation method thereof | |
| CN113522273B (en) | Preparation method of oxygen vacancy-rich tungsten trioxide and application of oxygen vacancy-rich tungsten trioxide in photocatalytic reaction | |
| CN110756189B (en) | Co with full solar spectrum response3O4/rGO composite catalyst, preparation method and photo-thermal catalysis application thereof | |
| CN115779939B (en) | Rare earth doped copper bismuthate/MXene composite material, preparation method and application thereof in photocatalytic nitrogen fixation | |
| CN114405548B (en) | Composite photocatalyst metal phthalocyanine/lanthanum titanate and preparation method and application thereof | |
| CN113731397B (en) | Photocatalytic composite material ZnO-KTaO3/K2Ta2O6And preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |