CN114054042A - Preparation method of Ag-doped nickel oxide nano-microsphere with mesopores and product thereof - Google Patents
Preparation method of Ag-doped nickel oxide nano-microsphere with mesopores and product thereof Download PDFInfo
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- 229910000480 nickel oxide Inorganic materials 0.000 title claims abstract description 126
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000004005 microsphere Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000839 emulsion Substances 0.000 claims abstract description 22
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 9
- 150000002815 nickel Chemical class 0.000 claims abstract description 8
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 5
- 238000004321 preservation Methods 0.000 claims abstract description 5
- 239000002077 nanosphere Substances 0.000 claims description 50
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000012265 solid product Substances 0.000 claims description 9
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- 101710134784 Agnoprotein Proteins 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000004945 emulsification Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000000969 carrier Substances 0.000 claims 1
- 230000008859 change Effects 0.000 abstract description 21
- 239000013078 crystal Substances 0.000 abstract description 15
- 238000012986 modification Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 238000013032 photocatalytic reaction Methods 0.000 abstract description 4
- 238000011160 research Methods 0.000 abstract description 4
- 238000005119 centrifugation Methods 0.000 abstract description 3
- 238000005036 potential barrier Methods 0.000 abstract 1
- 239000011148 porous material Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 235000002639 sodium chloride Nutrition 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- NTJMGOWFGQXUDY-UHFFFAOYSA-N 2H-azirine Chemical class C1C=N1 NTJMGOWFGQXUDY-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 238000006254 arylation reaction Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000006352 cycloaddition reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- B01J35/23—
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- B01J35/39—
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- B01J35/64—
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
Abstract
The invention relates to a preparation method of Ag-doped nickel oxide nano microspheres with mesopores and a product thereof, belonging to the technical field of modification of nickel oxide nano microspheres. According to the method, firstly, nickel salt and a mixed solution formed by adding nitrate and triethanolamine are stirred to form emulsion in an argon atmosphere, then the emulsion is reacted at 50-90 ℃, heat preservation treatment is carried out at 160-200 ℃, then centrifugation is carried out, Ag-doped nickel oxide nano microspheres (Ag/NiO nano microspheres) with mesopores are obtained after drying, meanwhile, high-pressure phase change research is carried out on pure nickel oxide and Ag-doped nickel oxide nano microspheres, the phase change pressure is reduced, the stability of the crystal structure is reduced, the reason is that Ag is doped to cause NiO lattice expansion, the crystal structure is relaxed, and the relative volume change of two phases is increased, so that the phase change potential barrier is reduced, and the phase change of a sample is caused under lower pressure. In addition, the invention also discloses Ag-doped nickel oxide nano microspheres with mesopores, which can greatly improve the photocatalytic reaction efficiency.
Description
Technical Field
The invention belongs to the technical field of nickel oxide nanoparticle modification, and relates to a preparation method of Ag-doped nickel oxide nanoparticles with mesopores and a product thereof.
Background
NiO is a typical wide-bandgap direct band-gap semiconductor oxide, and has higher exciton confinement energy and excellent physicochemical properties such as optical property, electrical property, magnetic property, gas sensitivity and the like. NiO has the same crystal structure as NaCl in nature. The properties of the NiO nano material are closely related to the structure of the NiO nano material, the element doping can change the crystal structure and the band gap width of NiO, the internal defects of NiO crystals are influenced, and the NiO nano material is an effective means for improving the performance of the NiO material.
Therefore, it is necessary to prepare a new NiO nanomaterial by performing morphology and structure controllable design, element doping, a heterogeneous composite structure and the like on NiO, modify the NiO nanomaterial, and try to realize the crystal morphology and size control of the NiO nanomaterial and the synthesis application research of the metal-doped heterogeneous composite structure.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a method for preparing Ag-doped nickel oxide nanospheres with mesopores; the second purpose of the invention is to provide Ag-doped nickel oxide nano microspheres with mesopores.
In order to achieve the purpose, the invention provides the following technical scheme:
1. the preparation method of the Ag-doped nickel oxide nano-microsphere with the mesopores comprises the following steps:
(1) preparing an emulsion: under the argon atmosphere, adding water into nickel salt for fully dissolving, continuously adding a mixed solution formed by nitrate and triethanolamine, and fully stirring until emulsification is carried out to form emulsion;
(2) preparing nano microspheres: heating the emulsion to 50-90 ℃ for reaction, then carrying out heat preservation treatment at 160-200 ℃ for 10-14 h, centrifuging at 10000-11500 rpm, collecting a solid product, repeatedly washing with water and ethanol, and drying overnight to obtain the Ag-doped nickel oxide nanospheres (Ag/NiO nanospheres) with mesopores.
Preferably, in step (1), the nickel salt is Ni (NO)3)2.6H2O、Ni(Cl)2.6H2O、NiF2.4H2O or Ni (CO)4Any one or more of them;
the nitrate is AgNO3、KNO3Or NaNO3Any one or more of them.
Preferably, in step (1), AgNO is contained in the mixed solution3The molar volume ratio of the triethanolamine to the triethanolamine is 0.033-0.1: 15, and the mol is L.
Further preferably, in the step (1), nickel and AgNO in the nickel salt3The molar ratio of (A) to (B) is 4-8: 0.033.
Preferably, in the step (2), the reaction time is 20-28 h.
Preferably, in step (2), the heat-insulating treatment is performed in a stainless steel autoclave lined with polytetrafluoroethylene.
Preferably, in the step (2), the drying temperature is 70-90 ℃.
2. The Ag-doped nickel oxide nano-microsphere with mesopores prepared by the preparation method.
Preferably, the molar ratio of silver (Ag) to nickel oxide (NiO) in the Ag-doped nickel oxide nanospheres with mesopores is 1: 60-480.
3. According to the application of the Ag-doped nickel oxide nano-microsphere with the mesopores in the aspect of preparing the catalyst carrier.
The invention has the beneficial effects that:
1. the invention discloses a preparation method of Ag-doped nickel oxide nano microspheres with mesopores, which mainly comprises the following steps: firstly, stirring nickel salt and a mixed solution formed by adding nitrate and triethanolamine in an argon atmosphere to form an emulsion, then reacting at 50-90 ℃, carrying out heat preservation treatment at 160-200 ℃, then carrying out summary centrifugation, and drying to obtain the Ag-doped nickel oxide nano microspheres (Ag/NiO nano microspheres) with mesopores. The preparation method of the invention simultaneously carries out high-pressure phase change research on two kinds of nano-microspheres of pure nickel oxide and Ag-doped nickel oxide, the phase change pressure is reduced, the stability of the crystal structure is reduced, because the Ag doping causes NiO lattice expansion, the crystal structure is relaxed, and the relative volume change of two phases is increased, thereby causing the phase change barrier to be reduced, and causing the phase change of the sample under lower pressure.
2. The invention also discloses Ag-doped nickel oxide nano microspheres with mesopores, which can greatly improve the photocatalytic reaction efficiency.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention may be realized and attained by the means of the instrumentalities and combinations particularly pointed out hereinafter.
Drawings
For the purposes of promoting a better understanding of the objects, aspects and advantages of the invention, reference will now be made to the following detailed description taken in conjunction with the accompanying drawings in which:
FIG. 1 is a TEM image of Ag-doped nickel oxide nanospheres (Ag/NiO nanospheres) with mesopores prepared in example 1;
FIG. 2 is SEM images of Ag-doped nickel oxide nanospheres (Ag/NiO nanospheres) with mesopores prepared in examples 1 and 2, wherein Ni (NO) is added in a, b, c and d3)2.6H2The amount of O is 2mmol, 4mmol, 8mmol and 16mmol respectively;
FIG. 3 is a distribution diagram of pore diameters of Ag-doped nickel oxide nanospheres (Ag/NiO nanospheres) with mesopores prepared in examples 1 and 2, wherein Ni (NO) is added in a, b, c and d3)2.6H2The amount of O is 2mmol, 4mmol, 8mmol and 16mmol respectively;
FIG. 4 is an XRD diffractogram of 0-70 ℃ for the Ag-doped NiO sample in example 1;
FIG. 5 is a Raman spectrum of Ag-doped nickel oxide nanospheres (Ag/NiO nanospheres) with mesopores prepared in example 1 with increased system pressure;
FIG. 6 shows Ag/NiO nanospheres and SiO prepared in example 12Carrier load Mes-Acr + ClO4 -Catalysis of 2H-azirines and aldehydes to [3+2 ]]Cycloaddition/oxidative arylation to synthesize the 2,4, 5-trisubstituted oxazole.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It should be noted that the drawings provided in the following embodiments are only for illustrating the basic idea of the present invention in a schematic way, and the features in the following embodiments and examples may be combined with each other without conflict.
Example 1
The preparation method of the Ag-doped nickel oxide nano microsphere with mesopores comprises the following steps:
(1) preparing an emulsion: a50 ml three-necked flask was charged with 8mmol of Ni (NO)3)2.6H2O, vacuumizing, introducing argon, and replacing for three times; adding 60ml of pre-ultrasonic deionized water, stirring and dissolving; 0.33mL of 0.1mol/mL AgNO is taken3The solution and 15ml triethanolamine were mixed well and added to the above aqueous solution with a syringe and stirred well until complete emulsification. Forming an emulsion;
(2) preparing nano microspheres: heating the emulsion prepared in the step (1) to 70 ℃ firstly, then reacting for 24h, then transferring the emulsion into a 100ml stainless steel autoclave with a polytetrafluoroethylene lining, and preserving heat for 12h at 180 ℃; after the completion, a high-speed centrifuge is used for centrifuging at the rotating speed of 10000rpm, the obtained solid product is collected, washed with water and ethanol for three times respectively, and then dried at 80 ℃ overnight, and the Ag-doped nickel oxide nano microsphere (Ag/NiO nano microsphere, wherein the molar ratio of Ag to NiO is 1:60(ICP test)) with the product having mesopores is obtained.
Example 2
The procedure and synthesis conditions were the same as in example 1, except that: mixing Ni (NO) in example 13)2.6H2The amount of O is respectively changed from 8mmol to 2mmol, 4mmol and 16mmol, and Ag-doped nickel oxide nano microspheres (Ag/NiO nano microspheres) with different Ag and NiO proportions and mesopores are prepared.
Example 3
The procedure and synthesis conditions were the same as in example 1, except that: 0.33mL of 0.1mol/mL AgNO added in example 13The solutions were replaced with 0.33ml of 0.1mol/L KNO, respectively3And 0.33ml of 0.1mol/L NaNO3And preparing Ag-doped nickel oxide nano microspheres (Ag/NiO nano microspheres) with mesopores, wherein the Ag-doped nickel oxide nano microspheres are obtained under the participation of different nitrates in the reaction.
Example 4
The procedure and synthesis conditions were the same as in example 1, except that: adding Ni (NO) from example 13)2.6H2O is replaced by Ni (Cl)2.6H2O、NiF2.4H2O or Ni (CO)4Preparing the belt obtained under the reaction of different nickel saltsAg-doped nickel oxide nano-microspheres (Ag/NiO nano-microspheres) with mesopores.
Example 5
The preparation method of the Ag-doped nickel oxide nano microsphere with mesopores comprises the following steps:
(1) preparing an emulsion: a50 ml three-necked flask was charged with 4mmol of Ni (NO)3)2.6H2O, vacuumizing, introducing argon, and replacing for three times; adding 60ml of pre-ultrasonic deionized water, stirring and dissolving; 0.33mL of 0.1mol/mL AgNO is taken3The solution and 5ml triethanolamine were mixed well and added to the above aqueous solution with a syringe and stirred well until complete emulsification. Forming an emulsion;
(2) preparing nano microspheres: heating the emulsion prepared in the step (1) to 90 ℃ firstly, then reacting for 20h, then transferring the emulsion into a 100ml stainless steel autoclave with a polytetrafluoroethylene lining, and preserving heat for 14h at 160 ℃; and after the reaction is finished, centrifuging at 10000rpm by using a high-speed centrifuge, collecting the obtained solid product, washing the solid product with water and ethanol for three times respectively, and then drying the solid product at 90 ℃ overnight to obtain the Ag-doped nickel oxide nanospheres (Ag/NiO nanospheres, wherein the molar ratio of Ag to NiO is 1:240(ICP detection)) with the mesoporous products.
Example 6
The preparation method of the Ag-doped nickel oxide nano microsphere with mesopores comprises the following steps:
(1) preparing an emulsion: a50 ml three-necked flask was charged with 8mmol of Ni (NO)3)2.6H2O, vacuumizing, introducing argon, and replacing for three times; adding 60ml of pre-ultrasonic deionized water, stirring and dissolving; 0.33mL of 0.1mol/mL AgNO is taken3The solution and 15ml triethanolamine were mixed well and added to the above aqueous solution with a syringe and stirred well until complete emulsification. Forming an emulsion;
(2) preparing nano microspheres: heating the emulsion prepared in the step (1) to 50 ℃ firstly, then reacting for 28h, then transferring the emulsion into a 100ml stainless steel autoclave with a polytetrafluoroethylene lining, and preserving heat for 10h at 200 ℃; and after the reaction is finished, centrifuging at the rotating speed of 11500rpm by using a high-speed centrifuge, collecting obtained solid products, washing the solid products with water and ethanol for three times respectively, and then drying the solid products at 70 ℃ overnight to obtain Ag-doped nickel oxide nano microspheres (Ag/NiO nano microspheres, wherein the molar ratio of Ag to NiO is 1:240(ICP detection)) with mesoporous products.
FIG. 1 is a TEM image of Ag-doped nickel oxide nanospheres (Ag/NiO nanospheres) with mesopores prepared in example 1. As can be seen from figure 1, the crystal lattices of the silver-doped nickel oxide sample are expanded compared with pure nickel oxide, but the crystal lattices are all hexagonal nickel-bearing ore crystal structures, and the appearance is microspheres formed by stacking dozens of nanometer-sized small particles.
FIG. 2 is SEM images of Ag-doped nickel oxide nanospheres (Ag/NiO nanospheres) with mesopores prepared in examples 1 and 2, wherein Ni (NO) is added in a, b, c and d3)2.6H2The amounts of O were 2mmol, 4mmol, 8mmol and 16mmol, respectively. As can be seen from FIG. 2, Ni (NO) was added in accordance with the preparation method in example 23)2.6H2The Ag-doped nickel oxide nanospheres (Ag/NiO nanospheres) with mesopores prepared by the amount of O have uneven surfaces and a large number of different small holes; while Ni (NO) was added in accordance with the preparation method in example 13)2.6H2The Ag-doped nickel oxide nanospheres (Ag/NiO nanospheres) with mesopores prepared by the amount of O have flat and smooth surfaces and uniform mesopore size distribution.
FIG. 3 is a distribution diagram of pore diameters of Ag-doped nickel oxide nanospheres (Ag/NiO nanospheres) with mesopores prepared in examples 1 and 2, wherein Ni (NO) is added in a, b, c and d3)2.6H2The amounts of O were 2mmol, 4mmol, 8mmol and 16mmol, respectively. As can be seen from FIG. 3, the Ag-doped nickel oxide nanospheres (Ag/NiO nanospheres) with mesopores in a have non-uniform pore size distribution and large deviation between pore sizes; b, the pore size distribution is also uneven and is relatively discrete; the pore diameters are uniformly distributed and are concentrated to 2-6 nm; d the pore size distribution is similar to that in a, and the distribution is not uniform while there is a large deviation between pore sizes.
FIG. 4 is an XRD diffraction pattern of 0-70 ℃ for the Ag-doped NiO sample in example 1. The result shows that the XRD pattern of the Ag-doped NiO sample with mesopores is basically consistent with the absorption peak position of the standard card.
Fig. 5 is a raman spectrum of the Ag-doped nickel oxide nanospheres (Ag/NiO nanospheres) with mesopores prepared in example 1 with increasing system pressure. The high-pressure structure phase change law of the Ag-doped nickel oxide nanospheres (Ag/NiO nanospheres) with mesopores is similar to that of pure nickel oxide (NiO), and before the system pressure is increased to 5.3GPa, the Ag-doped nickel oxide nanospheres (Ag/NiO nanospheres) with mesopores prepared in the embodiment 1 always keep the mesopore structure; when the system pressure is increased to 5.3GPa, the Raman characteristic peak of nickel oxide with the wurtzite structure completely disappears, and meanwhile, the spectrogram is positioned at 595cm-1A new Raman peak appears, which shows that the Ag-doped nickel oxide nanospheres (Ag/NiO nanospheres) with mesopores have structural phase change at about 5.3 GPa; the system is continuously pressurized, the Raman characteristic peak belonging to the rock-salt mine structure NiO is gradually intensified, and meanwhile, the Raman peak slowly moves towards high frequency until the highest pressure of the experiment reaches 16.2GPa, and the Ag-doped nickel oxide nano microspheres (Ag/NiO nano microspheres) with mesopores in the example 1 keep the cubic rock-salt mine type. Therefore, the Ag-doped nickel oxide nanospheres (Ag/NiO nanospheres) with mesopores prepared by the method disclosed by the invention have the phase change pressure of about 7.2GPa when the nickel sulfide ores are changed into rock salt structures. Compared with pure NiO crystal, the Ag-doped NiO crystal has structural phase change under lower pressure, and the phase change process lasts for a short time.
FIG. 6 is a graph showing Ag/NiO nanosphere support and SiO in the presence of light2Carrier load Mes-Acr + ClO4 -Catalysis of 2H-azirines and aldehydes to [3+2 ]]Cycloaddition/oxidative arylation to synthesize the 2,4, 5-trisubstituted oxazole. As can be seen from FIG. 6, the conversion rate of the Ag/NiO nanosphere catalyst reaches more than 95% in about 16h, while the conversion rate of SiO nanosphere catalyst reaches more than 95%2The conversion rate of the catalyst reaches 90% in about 70h, so that the Ag doped nickel oxide nano microspheres can greatly improve the photocatalytic reaction efficiency under the same condition.
Similarly, the Ag-doped nickel oxide nanospheres (Ag/NiO nanospheres) with mesopores prepared in examples 3 to 6 were subjected to a performance test according to the test method for testing the Ag-doped nickel oxide nanospheres (Ag/NiO nanospheres) with mesopores prepared in example 1, and the results thereof were not significantly different from the results in example 1, which indicates that the changes in the conditions during the preparation process in examples 3 to 6 do not affect the performance of the finally prepared Ag-doped nickel oxide nanospheres (Ag/NiO nanospheres) with mesopores.
In summary, the invention discloses a preparation method of Ag-doped nickel oxide nano-microspheres with mesopores, which mainly comprises the following steps: firstly, stirring nickel salt and a mixed solution formed by adding nitrate and triethanolamine in an argon atmosphere to form an emulsion, then reacting at 50-90 ℃, carrying out heat preservation treatment at 160-200 ℃, then carrying out summary centrifugation, and drying to obtain the Ag-doped nickel oxide nano microspheres (Ag/NiO nano microspheres) with mesopores. The preparation method of the invention simultaneously carries out high-pressure phase change research on two kinds of nano-microspheres of pure nickel oxide and Ag-doped nickel oxide, the phase change pressure is reduced, the stability of the crystal structure is reduced, because the Ag doping causes NiO lattice expansion, the crystal structure is relaxed, and the relative volume change of two phases is increased, thereby causing the phase change barrier to be reduced, and causing the phase change of the sample under lower pressure. In addition, the invention also discloses Ag-doped nickel oxide nano microspheres with mesopores, which can greatly improve the photocatalytic reaction efficiency.
Finally, the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all of them should be covered by the claims of the present invention.
Claims (10)
1. The preparation method of the Ag-doped nickel oxide nano-microsphere with the mesopores is characterized by comprising the following steps of:
(1) preparing an emulsion: under the argon atmosphere, adding water into nickel salt for fully dissolving, continuously adding a mixed solution formed by nitrate and triethanolamine, and fully stirring until emulsification is carried out to form emulsion;
(2) preparing nano microspheres: heating the emulsion to 50-90 ℃ for reaction, then carrying out heat preservation treatment at 160-200 ℃ for 10-14 h, centrifuging at 10000-11500 rpm, collecting a solid product, repeatedly washing with water and ethanol, and drying overnight to obtain the Ag-doped nickel oxide nanospheres with mesopores.
2. The method according to claim 1, wherein in the step (1), the nickel salt is Ni (NO)3)2.6H2O、Ni(Cl)2.6H2O、NiF2.4H2O or Ni (CO)4Any one or more of them;
the nitrate is AgNO3、KNO3Or NaNO3Any one or more of them.
3. The method according to claim 1, wherein AgNO is contained in the mixed solution in the step (1)3The molar volume ratio of the triethanolamine to the triethanolamine is 0.033-0.1: 15, and the mol is L.
4. The method according to claim 2, wherein in the step (1), the nickel salt contains nickel and AgNO3The molar ratio of (A) to (B) is 4-8: 0.033.
5. The preparation method according to claim 1, wherein in the step (2), the reaction time is 20-28 h.
6. The method according to claim 1, wherein in the step (2), the heat-retaining treatment is performed in a stainless steel autoclave lined with polytetrafluoroethylene.
7. The method according to claim 1, wherein the drying temperature in the step (2) is 70 to 90 ℃.
8. The Ag-doped nickel oxide nano-microsphere with mesopores, which is prepared by the preparation method according to any one of claims 1 to 7.
9. The Ag-doped nickel oxide nanosphere with mesopores according to claim 8, wherein the molar ratio of silver to nickel oxide in the Ag-doped nickel oxide nanosphere with mesopores is 1: 60-480.
10. The Ag-doped nickel oxide nanospheres with mesopores according to any one of claims 8 to 9, and the application thereof in the preparation of catalyst carriers.
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