CN110102306A - A kind of Ni-Nd is co-doped with ordered mesoporous aluminium oxide material and its preparation method and application - Google Patents
A kind of Ni-Nd is co-doped with ordered mesoporous aluminium oxide material and its preparation method and application Download PDFInfo
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- CN110102306A CN110102306A CN201910313777.6A CN201910313777A CN110102306A CN 110102306 A CN110102306 A CN 110102306A CN 201910313777 A CN201910313777 A CN 201910313777A CN 110102306 A CN110102306 A CN 110102306A
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000000463 material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 11
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims abstract description 4
- USJZIUVMYSUNGB-UHFFFAOYSA-N neodymium;hydrate Chemical compound O.[Nd] USJZIUVMYSUNGB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 22
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000003755 preservative agent Substances 0.000 claims description 7
- 230000002335 preservative effect Effects 0.000 claims description 7
- 229920000428 triblock copolymer Polymers 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 15
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 8
- 239000013335 mesoporous material Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 18
- 238000009826 distribution Methods 0.000 description 7
- 229960004756 ethanol Drugs 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 229910003205 Nd(NO3)3·6H2O Inorganic materials 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000005352 clarification Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 2
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 238000001988 small-angle X-ray diffraction Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 210000003850 cellular structure Anatomy 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000802 evaporation-induced self-assembly Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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Abstract
The invention discloses a kind of Ni-Nd to be co-doped with ordered mesoporous aluminium oxide material and its preparation method and application.The preparation method is that: by P123, concentrated nitric acid, aluminium isopropoxide, Nickelous nitrate hexahydrate, six nitric hydrate neodymium co-dissolves in dehydrated alcohol, it is further continued for stirring after stirring to clarify at room temperature to be sufficiently mixed, obtains uniform clear solution A；Solution A drying is volatilized completely to solvent, obtains xerogel solid B；Xerogel solid B is roasted 4~6 hours at 400~800 DEG C, obtains the orderly mesoporous aluminum oxide material C of Ni-Nd codope after naturally cool to room temperature.The OMA mesoporous material that the present invention passes through change Nickelous nitrate hexahydrate and the available different proportion Ni/Nd of additional amount of six nitric hydrate neodymiums.The method of the present invention simple process, environmentally protective, synthesis cycle is short, yield is high, has application value difficult to the appraisal in catalytic field especially pyroreaction.
Description
Technical field
The invention belongs to mesoporous materials fields, and in particular to a kind of Ni-Nd is co-doped with ordered mesoporous aluminium oxide material and its system
Preparation Method and application.
Background technique
Ordered mesoporous material has the characteristics that the uniform thermal stability that reconciles of large specific surface area, aperture is good, comes in recent years
Extensive concern by catalysis circle's researcher.Ordered mesoporous aluminium oxide (Ordered mesoporous alumina,
OMA), have many advantages, such as that intensity is big, surface acidity is strong, strong with metal interaction, in chemical field always by favor.So
And since used aluminium isopropoxide (as silicon source) has stronger hydrolysis tendency to OMA during the preparation process, so that the conjunction of OMA
Difficulty is had more at than order mesoporous silica-base material.It had been synthesized in succession by solvent volatilization self assembly (EISA) method in recent years numerous
The serial OMA for having metallic site to adulterate, is greatly enlarged application range of the material in catalytic field.
In all multivalent transition metals, the nickel element (Ni) of period 4 VIII group has the catalysis to compare favourably with noble metal
Ability has been widely studied and has been applied in various important Industrial Catalysis reactions.Rare-earth oxide (such as Y2O3、CeO2、
Nd2O3) it can be used as metal promoter, improve the surface nature of catalysis material, and then improve its stability in pyroreaction.It is special
Not, correlative study proves Nd2O3With stronger oxygen storage capacity, catalysis material surface acidic-basic property can be improved, being that modification is Ni-based urges
The ideal material of agent.
The preparation method of catalyst has great influence to the performance and realization industrial-scale application etc. that improve material.
Currently, the preparation method of common OMA metal supported catalyst has: infusion process and one-step synthesis.Though traditional infusion process technique
The stoichiometric ratio of each component is simply and readily controlled, but the catalyst metal particles prepared through this method are larger and are unevenly distributed
Even, Support-metal strong interaction is weaker.Not only time-consuming short, synthetic raw material not easily runs off one-step synthesis, and prepared
Catalyst metal particles are small and dispersion degree is high, and Metal-Support interaction is strong, have better structure thermal stability, are suitble to answer
For industrial pyroreaction.Therefore, seek a kind of simple process, the bimetallic that the period is short, easy to operate and high yield
Adulterate research hotspot and significant challenge that orderly mesoporous aluminum oxide material preparation method has become the field.
Summary of the invention
For insufficient in the prior art, purpose of the present invention primary and foremost purpose is to provide a kind of cellular structure ordering
The orderly mesoporous aluminum oxide material of Ni-Nd codope.
Another object of the present invention is to disclose the preparation method of the above-mentioned orderly mesoporous aluminum oxide material of Ni-Nd codope.
This method not only simplifies operating process using one-step synthesis, and can reduce the loss of material in synthesis process so as to save
Cost-saving.
Another object of the present invention is to disclose the application of the above-mentioned orderly mesoporous aluminum oxide material of Ni-Nd codope.
To achieve the above object, the invention adopts the following technical scheme:
A kind of Ni-Nd is co-doped with the preparation method of ordered mesoporous aluminium oxide material, comprising the following steps:
(1) by triblock copolymer P123 (EO20PO70EO20), concentrated nitric acid, aluminium isopropoxide (Al (OPri)3), six hydration nitre
Sour nickel (Ni (NO3)2·6H2) and six nitric hydrate neodymium (Nd (NO O3)3·6H2O) co-dissolve is stirred at room temperature in dehydrated alcohol
Continue stirring after mixing to clarification to be sufficiently mixed, obtains uniform clear solution A；
(2) by solution A be dried until solvent volatilize completely, obtain xerogel solid B；
(3) by after xerogel solid B roasting, cooled to room temperature obtains the Ni-Nd and is co-doped with order mesoporous oxidation
Aluminum material.
Preferably, step (1) triblock copolymer P123: the molar ratio of aluminium isopropoxide is 0.014~0.017:1.
Preferably, the volume mass ratio of step (1) concentrated nitric acid and triblock copolymer P123 is 1.6~1.8mL/g.
Preferably, the volume ratio of step (1) dehydrated alcohol and concentrated nitric acid is 12~15:1.
Preferably, step (1) Ni (NO3)2·6H20.02~0.06:1 of molar ratio of O and aluminium isopropoxide.
Preferably, step (1) Ni (NO3)2·6H2O and Nd (NO3)3·6H2The molar ratio of O is 1~8.5:1.
Preferably, step (1) room temperature is 25~30 DEG C.
Preferably, step (1) time for continuing stirring is 4~8h.
Preferably, step (2) is described, and solution A is dried specifically: 48~60h, temperature are carried out in air dry oven
The drying that degree is 65~75 DEG C, and cover the container equipped with solution A using the preservative film for pricking hole in the drying process and carry out
It is dry.
Preferably, the atmosphere of step (3) described roasting is still air, and noncurrent air stream.
Preferably, the temperature of step (3) described roasting is 400~800 DEG C, and the time of the roasting is 4~6h.
The Ni-Nd that the preparation method that a kind of above-mentioned Ni-Nd is co-doped with ordered mesoporous aluminium oxide material is prepared is co-doped with orderly
Mesoporous aluminum oxide material.
The Ni-Nd is co-doped with 0.16~0.30cm of Kong Rongwei of ordered mesoporous aluminium oxide material3/ g, aperture be 9.22~
12.04nm, specific surface area are 80~120m2/g。
The Ni-Nd is co-doped with application of the ordered mesoporous aluminium oxide material in CH4 production.
Compared with prior art, the present invention has the following advantages and beneficial effects:
(1) it is regular and have Gao Bibiao that the solvent volatilization self-assembly method that the present invention uses can synthesize high-sequential, duct
The uniform orderly mesoporous aluminum oxide material of Ni-Nd codope in area, aperture；
(2) present invention is mainly low using raw materials, prices such as aluminium isopropoxide, Nickelous nitrate hexahydrate, six nitric hydrate neodymiums, ethyl alcohol
It is honest and clean, be conveniently easy to get, and it is non-toxic to humans, environmentally harmful intermediate product will not be generated；
(3) synthesis process of the present invention is simple and clear, and not will cause the significant loss of intermediate synthesis process；
(4) present invention by one-step synthesis by Ni-Nd codope to ordered mesoporous aluminium oxide material, can be in certain model
Enclose the interior flexible molar ratio for changing Ni/Nd.
Detailed description of the invention
Fig. 1 is the small angle XRD diffraction spectrogram of Examples 1 to 5 products therefrom.
Fig. 2 be Examples 1 to 5 products therefrom nitrogen adsorption desorption isotherm and pore size distribution curve spectrogram, wherein A pairs
Nitrogen adsorption desorption isotherm spectrogram is answered, B corresponds to pore size distribution curve spectrogram.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
The mass fraction of concentrated nitric acid described in the embodiment of the present invention is 67wt%.The molecular formula of the P123 is PEO-PPO-
PEO, molecular weight 5800.
Embodiment 1
A kind of Ni-Nd is co-doped with ordered mesoporous aluminium oxide material and (is denoted as NiNd (8.4:1)-OMA, indicates Ni in bracket
(NO3)2·6H2O and Nd (NO3)3·6H2The molar ratio of O) preparation method, specifically include the following steps:
Weigh 4.0g P123,9.39g Al (OPri)3(molal quantity 46mmol), 6.8mL concentrated nitric acid, 0.2674g Ni
(NO3)2·6H2O (molal quantity 0.92mmol) and 0.0482g Nd (NO3)3·6H2O (molal quantity 0.11mmol) is common molten
Solution at 30 DEG C of room temperature after magnetic agitation to solution clarification, is further continued for stirring 8 hours, obtains in 82mL ethanol solution
Mixed solution；Then above-mentioned mixed solution is placed in air dry oven, covers beaker mouth using the preservative film for there are small holes is pricked,
60 hours dry at 75 DEG C, cooled to room temperature obtains light green color xerogel, transfers them in crucible, is placed in box resistance
800 DEG C are risen to from room temperature with the heating rate of 1 DEG C/min in furnace, is roasted 4 hours under air atmosphere, cooled to room temperature,
Obtain light green solid, i.e. described NiNd (the 8.4:1)-OMA.
The Kong Rongwei 0.28cm of NiNd synthesized by this example (8.4:1)-OMA3/ g, aperture 9.81nm, specific surface area are
110m2/g。
Embodiment 2
A kind of Ni-Nd is co-doped with ordered mesoporous aluminium oxide material and (is denoted as NiNd (4.0:1)-OMA, indicates Ni in bracket
(NO3)2·6H2O and Nd (NO3)3·6H2The molar ratio of O) preparation method, specifically include the following steps:
Weigh 5.0g P123,12.58g Al (OPri)3(molal quantity 62mmol), 8.0mL concentrated nitric acid, 1.0744g Ni
(NO3)2·6H2O (molal quantity 3.69mmol) and 0.4032g Nd (NO3)3·6H2O (molal quantity 0.92mmol) is common molten
Solution at 25 DEG C of room temperature after magnetic agitation to solution clarification, is further continued for stirring 4 hours, obtains in 96mL ethanol solution
Above-mentioned mixed liquor is then placed in air dry oven by mixed liquor, covers beaker mouth using the preservative film for having small holes is pricked, and 65 DEG C
Lower drying 48 hours, cooled to room temperature obtains light green color xerogel, transfers them in crucible, is placed in chamber type electric resistance furnace
400 DEG C are risen to from room temperature with the heating rate of 1 DEG C/min, is roasted 6 hours under air atmosphere, cooled to room temperature obtains
Light green solid, i.e., described NiNd (the 4.0:1)-OMA.
The Kong Rongwei 0.16cm of NiNd synthesized by this example (4.0:1)-OMA3/ g, aperture 12.04nm, specific surface area are
82m2/g。
Embodiment 3
A kind of Ni-Nd is co-doped with ordered mesoporous aluminium oxide material and (is denoted as NiNd (2.0:1)-OMA, indicates Ni in bracket
(NO3)2·6H2O and Nd (NO3)3·6H2The molar ratio of O) preparation method, specifically include the following steps:
Weigh 3.0g P123,6.60g Al (OPri)3(molal quantity 32mmol), 5.1mL concentrated nitric acid, 0.2820g Ni
(NO3)2·6H2O (molal quantity 0.97mmol) and 0.2104g Nd (NO3)3·6H2O (molal quantity 0.48mmol) is common molten
Solution at 29 DEG C of room temperature after magnetic agitation to solution clarification, is further continued for stirring 6 hours, obtains in 71mL ethanol solution
Above-mentioned mixed liquor is then placed in air dry oven by mixed liquor, covers beaker mouth using the preservative film for having small holes is pricked, and 70 DEG C
Lower drying 55 hours, cooled to room temperature obtains light green color xerogel, transfers them in crucible, is placed in chamber type electric resistance furnace
600 DEG C are risen to from room temperature with the heating rate of 1 DEG C/min, is roasted 5 hours under air atmosphere, cooled to room temperature obtains
Light green solid, i.e., described NiNd (the 2.0:1)-OMA.
The Kong Rongwei 0.25cm of NiNd synthesized by this example (2.0:1)-OMA3/ g, aperture 9.92nm, specific surface area are
106m2/g。
Embodiment 4
A kind of Ni-Nd is co-doped with ordered mesoporous aluminium oxide material and (is denoted as NiNd (1.3:1)-OMA, indicates Ni in bracket
(NO3)2·6H2O and Nd (NO3)3·6H2The molar ratio of O) preparation method, specifically include the following steps:
Weigh 1.0g P123,2.07g Al (OPri)3(molal quantity 10mmol), 1.6mL concentrated nitric acid, 0.1180g Ni
(NO3)2·6H2O (molal quantity 0.41mmol) and 0.1359g Nd (NO3)3·6H2O (molal quantity 0.31mmol) is common molten
Solution is in 21mL ethanol solution, at 27 DEG C of room temperature after magnetic agitation to clear solution, is further continued for stirring 5 hours, obtains
Above-mentioned mixed liquor is then placed in air dry oven by mixed liquor, covers beaker mouth using the preservative film for having small holes is pricked, and 68 DEG C
Lower drying 50 hours, cooled to room temperature obtains light green color xerogel, transfers them in crucible, is placed in chamber type electric resistance furnace
500 DEG C are risen to from room temperature with the heating rate of 1 DEG C/min, is roasted 6 hours under air atmosphere, cooled to room temperature obtains
Light green solid, i.e. described NiNd (the 1.3:1)-OMA.
The Kong Rongwei 0.30cm of NiNd synthesized by this example (1.3:1)-OMA3/ g, aperture 9.22nm, specific surface area are
118m2/g。
Embodiment 5
A kind of Ni-Nd is co-doped with ordered mesoporous aluminium oxide material and (is denoted as NiNd (1.0:1)-OMA, indicates Ni in bracket
(NO3)2·6H2O and Nd (NO3)3·6H2The molar ratio of O) preparation method, specifically include the following steps:
Weigh 2.0g P123,4.14g Al (OPri)3(20mmol), 3.6mL concentrated nitric acid, 0.3540g Ni (NO3)2·
6H2O (1.22mmol) and 0.5348g Nd (NO3)3·6H2O (1.22mmol) co-dissolve in 54mL ethanol solution,
At 30 DEG C of room temperature after magnetic agitation to solution clarification, it is further continued for stirring 7 hours, mixed liquor is obtained, then by above-mentioned mixed liquor
It is placed in air dry oven, covers beaker mouth using the preservative film for having small holes is pricked, drying 58 hours, naturally cools at 72 DEG C
Room temperature obtains light green color xerogel, transfers them in crucible, is placed in chamber type electric resistance furnace from room temperature with the heating speed of 1 DEG C/min
Rate rises to 700 DEG C, roasts 5 hours under air atmosphere, cooled to room temperature, obtained light green solid, i.e., described
NiNd(1.0:1)-OMA。
The Kong Rongwei 0.22cm of NiNd synthesized by this example (1.0:1)-OMA3/ g, aperture 10.69nm, specific surface area are
98m2/g。
Small angle X-ray diffraction analysis is carried out to the resulting product of Examples 1 to 5, using Rigaku Co., Ltd.
Smartlab type X-ray diffractometer is analyzed, result as shown in Figure 1 (wherein a, b, c, d and e respectively correspond embodiment 1~
5)。
The mesoporous aluminum oxide material of all embodiments is 0.7 ° of one apparent diffraction of appearance nearby in 2 θ as can be seen from Figure 1
Peak, and nearby there is a faint diffraction maximum at 1.3 °, illustrate that the mesoporous aluminum oxide material of synthesis has the mesoporous of high-sequential
Structure.However, the trend slightly reduced is presented in corresponding diffraction peak intensity as the doping of Ni and Nd increase, illustrate to be situated between
Pore structure is by slight destruction, but overall structure still keeps orderly.The above results explanation is in suitable doping when metal
When measuring in range, ordered mesopore structure can be maintained.
N is carried out to the resulting product of Examples 1 to 52Physical absorption-desorption characterization and pore-size distribution characterization, using the U.S.
The full-automatic specific surface area of 3020 type of Micromeritics company's T riStar II and pore analysis instrument are analyzed, and result is such as
Shown in Fig. 2, the A in Fig. 2 corresponds to N2Physical absorption-desorption characterization, B correspond to aperture distribution table sign.
From the A in Fig. 2 this it appears that all samples show typical IV type adsorption isotherm and H1 type hysteresis
Ring, further demonstrating sample, there are mesopore orbit structures.In addition, the adsorption isotherm of sample relative pressure be 0.65~
There is hysteretic loop because capillary condensation occurs in 0.85 range, shows that sample mesopore orbit height is uniform.In addition, NiNd (1.0:
1) the hysteretic loop slope of-OMA material more tends to gently, illustrate the increase with Nd content, the corresponding duct of material in contrast
Structure is by slight destruction.According to pore-size distribution result (B in such as Fig. 2) it is found that sample is uniform within the scope of 8-12nm
Distribution, and the pore-size distribution intensity of NiNd (1.0:1)-OMA slightly reduces, and further illustrates that Nd content increases and duct is tied
Structure tool has a certain impact.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. the preparation method that a kind of Ni-Nd is co-doped with ordered mesoporous aluminium oxide material, which comprises the following steps:
(1) by triblock copolymer P123, concentrated nitric acid, aluminium isopropoxide, Nickelous nitrate hexahydrate and six nitric hydrate neodymium co-dissolves
In dehydrated alcohol, continues stirring after stirring to clarify at room temperature to be sufficiently mixed, obtain uniform clear solution A；
(2) by solution A be dried until solvent volatilize completely, obtain xerogel solid B；
(3) by after xerogel solid B roasting, cooled to room temperature obtains the Ni-Nd and is co-doped with ordered mesoporous aluminium oxide material
Material.
2. Ni-Nd is co-doped with the preparation method of ordered mesoporous aluminium oxide material according to claim 1, which is characterized in that step
(1) triblock copolymer P123: the molar ratio of aluminium isopropoxide is 0.014~0.017:1.
3. Ni-Nd is co-doped with the preparation method of ordered mesoporous aluminium oxide material according to claim 2, which is characterized in that step
(1) volume mass of the concentrated nitric acid and triblock copolymer P123 ratio is 1.6~1.8mL/g.
4. the preparation method that Ni-Nd according to claim 1 or claim 2 is co-doped with ordered mesoporous aluminium oxide material, which is characterized in that step
Suddenly the volume ratio of (1) described dehydrated alcohol and concentrated nitric acid is 12~15:1.
5. the preparation method that Ni-Nd according to claim 1 or claim 2 is co-doped with ordered mesoporous aluminium oxide material, which is characterized in that step
Suddenly (1) Ni (NO3)2·6H20.02~0.06:1 of molar ratio of O and aluminium isopropoxide.
6. the preparation method that Ni-Nd according to claim 1 or claim 2 is co-doped with ordered mesoporous aluminium oxide material, which is characterized in that step
Suddenly (1) Ni (NO3)2·6H2O and Nd (NO3)3·6H2The molar ratio of O is 1~8.5:1.
7. Ni-Nd is co-doped with the preparation method of ordered mesoporous aluminium oxide material according to claim 1, which is characterized in that step
(1) room temperature is 25~30 DEG C；
Step (1) time for continuing stirring is 4~8h；
The temperature of step (3) described roasting is 400~800 DEG C, and the time of the roasting is 4~6h.
8. Ni-Nd is co-doped with the preparation method of ordered mesoporous aluminium oxide material according to claim 1, which is characterized in that step
(2) described that solution A is dried specifically: 48~60h of progress in air dry oven, the drying that temperature is 65~75 DEG C,
And the container equipped with solution A is covered using the preservative film for pricking hole in the drying process and is dried；
The atmosphere of step (3) described roasting is still air, and noncurrent air stream.
9. a kind of any one of claim 1~8 preparation method that Ni-Nd is co-doped with ordered mesoporous aluminium oxide material is prepared
Ni-Nd be co-doped with ordered mesoporous aluminium oxide material.
10. Ni-Nd described in claim 9 is co-doped with ordered mesoporous aluminium oxide material answering in CH4 production
With.
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