CN107224983B - A kind of Ag/Cu2O/CeO2One pot of solid phase reaction preparation method of ternary nano compound - Google Patents
A kind of Ag/Cu2O/CeO2One pot of solid phase reaction preparation method of ternary nano compound Download PDFInfo
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- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 50
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000003746 solid phase reaction Methods 0.000 title claims abstract description 15
- 150000001875 compounds Chemical class 0.000 title claims description 16
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 68
- 238000000498 ball milling Methods 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 150000000703 Cerium Chemical class 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 239000002114 nanocomposite Substances 0.000 claims abstract description 7
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000005580 one pot reaction Methods 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver nitrate Substances [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 30
- 239000010949 copper Substances 0.000 claims description 27
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 14
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 13
- 239000012153 distilled water Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims description 2
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims 1
- 239000007800 oxidant agent Substances 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 239000007790 solid phase Substances 0.000 abstract description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 16
- 238000000227 grinding Methods 0.000 description 16
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 16
- 229910001928 zirconium oxide Inorganic materials 0.000 description 16
- 238000002441 X-ray diffraction Methods 0.000 description 12
- 229910052684 Cerium Inorganic materials 0.000 description 7
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 7
- 150000004677 hydrates Chemical class 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CQPFMGBJSMSXLP-ZAGWXBKKSA-M Acid orange 7 Chemical compound OC1=C(C2=CC=CC=C2C=C1)/N=N/C1=CC=C(C=C1)S(=O)(=O)[O-].[Na+] CQPFMGBJSMSXLP-ZAGWXBKKSA-M 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- CQGVSILDZJUINE-UHFFFAOYSA-N cerium;hydrate Chemical compound O.[Ce] CQGVSILDZJUINE-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—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
- B01J23/8933—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of Ag/Cu2O/CeO2One pot of solid phase reaction preparation method of ternary nano composite material mixes Solid raw materials silver salt, mantoquita, cerium salt with alkali, ball milling solid phase reaction in molar ratio, and products therefrom washing is centrifugated and prepares after drying.The present invention is mixed using solid, and the reaction of raw material room temperature solid-phase ball milling, preparation process is simple, reunion that is easily controllable and can largely reducing product particles；It avoids improving product purity using reductant-oxidant, template and solvent, meets the requirement that material green is combined to, be also suitable for being mass produced.
Description
Technical field
The present invention relates to a kind of Ag/Cu2O/CeO2One pot of solid phase reaction preparation method of ternary nano composite material, belongs to
Nanocomposite preparation technical field.
Background technique
Cu2O/CeO2Composite material is a kind of functional material that purposes is very extensive, is had in fields such as catalysis, electrode materials
Important application.Wherein, Cu2O/CeO2Compound shows stronger visible light absorption capacity and light is urged as photochemical catalyst
Change activity, is a kind of outstanding visible-light photocatalysis material.
Currently, Cu2O/CeO2The preparation method of composite material is mainly liquid phase reactor method.
Such as: using glucose as reducing agent, Cu is prepared by soaking and reducing method2O/CeO2Heterojunction photocatalyst
(Shichao Hu, et. al. Preparation of Cu2O/CeO2 heterojunction photocatalyst for
The degradation of Acid Orange 7 under visible light irradiation, Catalysis
Communications, 2011,12:794-797)；
With cube and octahedron Cu2O prepares Cu by template auxiliary law as template is sacrificed2O/CeO2Nanometer is multiple
Close object (Huizhi Bao, et. al. Compositions, structures, and catalytic activities
of CeO2@Cu2O nanocomposites prepared by the template-assisted method,
Langmuir, 30 (22): 6427-6436)；
It is caught up with by Argon Bubble gas pre-treatment except the oxygen in reaction medium, with Ce (OH) in alkaline solution3For template, benefit
The Cu of core-shell structure is prepared with redox assembling2O/CeO2Nanocube (Xiao Wang, et. al. Clean
synthesis of Cu2O@CeO2Core@shell nanocubes with highly active interface, NPG
Asia Materials, 2015,7 (1): 7-19)；
With cube and octahedron Cu2O prepares Cu by template auxiliary law as template is sacrificed2O/CeO2Nanometer is multiple
Close object, subsequent amination Cu2O/CeO2Obtain Cu2O/CeO2-NH2Compound, then pass through reduction of sodium citrate AuCl4 -Ion obtains
Au nanoparticle is obtained, Au nanoparticle and-NH are passed through2Between construct stable chemical bond and obtain Cu2O@CeO2- Au is nano combined
Object (Faying Li, et. al. Ultrasensitive amperometric immunosensor for PSA
detection based on Cu2O@CeO2-Au nanocomposites as integrated triple signal
Amplification strategy, Biosensors and Bioelectronics, 2017,87:630-637).
Although a variety of preparation methods disclosed in the prior art can prepare Cu2O/CeO2Composite material can also use above-mentioned side
Method is produced such as Au/Cu2O/CeO2Ternary complex, but Shortcomings are needed using a large amount of solvents in liquid phase method preparation process,
During the preparation process, some need is used before inert gas using reductant-oxidant, some need using template, some need
Processing, especially the also increasingly complex while ultra-fine product particles of the chemical reaction in solution be easier reunite, need after
Continuous further investigation.
Summary of the invention
For above-mentioned technical problem underlying, the purpose of the present invention is to provide one kind without using solvent, also without
Reductant-oxidant or template, the Ag/Cu that the operation is simple and convenient, environmentally protective need to be added2O/CeO2Ternary nano is compound
One pot of solid phase reaction preparation method of material.
To achieve the above object, technological means adopted by the present invention is: a kind of Ag/Cu2O/CeO2Ternary nano composite wood
Expect one pot of solid phase reaction preparation method, Solid raw materials silver salt, mantoquita, cerium salt mixed in molar ratio with alkali, ball milling solid phase reaction,
Products therefrom washing, is centrifugated and prepares after drying.
Further, during the preparation process, product Ag/ is controlled by adjusting the molar ratio of Ball-milling Time and silver nitrate
Cu2O/CeO2Cu in ternary nano compound2O and CeO2Average grain size and Ag load capacity and its average crystal grain ruler
It is very little.
Further, the silver salt, mantoquita, cerium salt are to be uniformly mixed at x: 1-x: 1: 8 with alkali in molar ratio, wherein x=0~
0.2, but x is not equal to 0.
Further, the silver salt is silver nitrate.
Further, the mantoquita is cupric salt.
Further, the cupric salt be Gerhardite, Salzburg vitriol, Copper dichloride dihydrate one
Kind.
Further, the cerium salt is Ce (NO3)3·6H2O。
Further, the alkali is sodium hydroxide.
Further, the ball milling solid phase reaction refers to: it is put into ball milling zirconium tank, is placed in ball mill after raw material mixing,
480 rpm/min of setting speed, ball-milling reaction 1~5 hour.
Further, the product is washed with distilled water, is centrifugated and true under 60 DEG C and 0.1Mpa vacuum degree
Sky is 2 hours dry.
The beneficial effects of the present invention are: it is mixed using solid, the reaction of raw material room temperature solid-phase ball milling, preparation process is simple,
Reunion easily controllable and that product particles can be largely reduced；It avoids improving product using reductant-oxidant, template and solvent
Purity meets the requirement that material green is combined to, and is also suitable for being mass produced.
Detailed description of the invention
The present invention is further elaborated with embodiment with reference to the accompanying drawing.
Fig. 1 is Ag/Cu prepared by the embodiment of the present invention 1,2,3,4 and 52O/CeO2Ternary nano compound XRD spectrum；
Fig. 2 is Ag/Cu prepared by the embodiment of the present invention 2,6,7 and 82O/CeO2Ternary nano compound XRD spectrum.
Specific embodiment
Embodiment 1
0.0005 mole of analytically pure silver nitrate, 0.0095 mole of analysis are weighed according to 0.05: 0.95: 1: 8 molar ratio
Pure Gerhardite, 0.01 mole of analytically pure six nitric hydrates cerium, 0.08 mole of analytically pure sodium hydroxide addition are matched
In the 50ml zirconia ball grinding jar of standby 50 diameter 6mm zirconium oxide balls and 8 diameter 10mm zirconium oxide balls, in QM-3SP04
In planetary high-energy ball mill under 480 rpm continuously grinding 1 hour, product is washed with distilled water, centrifuge separation simultaneously
It is dried in vacuo 2 hours under 60 DEG C and 0.1Mpa vacuum degree, obtains Ag/Cu2O/CeO2Ternary nano compound.
To Ag/Cu2O/CeO2Ternary product carries out XRD analysis, is calculated according to Scherrer formula, Ag/Cu2O/
CeO2Cu in ternary nano compound2O and CeO2Average grain size is respectively 9.6 nm and 13.2 nm.
Embodiment 2
0.0005 mole of analytically pure silver nitrate, 0.0095 mole of analysis are weighed according to 0.05: 0.95: 1: 8 molar ratio
Pure Gerhardite, 0.01 mole of analytically pure six nitric hydrates cerium, 0.08 mole of analytically pure sodium hydroxide addition are matched
In the 50ml zirconia ball grinding jar of standby 50 diameter 6mm zirconium oxide balls and 8 diameter 10mm zirconium oxide balls, in QM-3SP04
In planetary high-energy ball mill under 480 rpm continuously grinding 2 hours, product is washed with distilled water, centrifuge separation simultaneously
It is dried in vacuo 2 hours under 60 DEG C and 0.1Mpa vacuum degree, obtains Ag/Cu2O/CeO2Ternary nano compound.
To Ag/Cu2O/CeO2Ternary product carries out XRD analysis, is calculated according to Scherrer formula, Ag/Cu2O/
CeO2Cu in ternary nano compound2O and CeO2Average grain size is respectively 11.4 nm and 14.9 nm.
Embodiment 3
0.0005 mole of analytically pure silver nitrate, 0.0095 mole of analysis are weighed according to 0.05: 0.95: 1: 8 molar ratio
Pure Gerhardite, 0.01 mole of analytically pure six nitric hydrates cerium, 0.08 mole of analytically pure sodium hydroxide addition are matched
In the 50ml zirconia ball grinding jar of standby 50 diameter 6mm zirconium oxide balls and 8 diameter 10mm zirconium oxide balls, in QM-3SP04
In planetary high-energy ball mill under 480 rpm continuously grinding 3 hours, product is washed with distilled water, centrifuge separation simultaneously
It is dried in vacuo 2 hours under 60 DEG C and 0.1Mpa vacuum degree, obtains Ag/Cu2O/CeO2Ternary nano compound.
To Ag/Cu2O/CeO2Ternary product carries out XRD analysis, is calculated according to Scherrer formula, Ag/Cu2O/
CeO2Cu in ternary nano compound2O and CeO2Average grain size is respectively 13.0 nm and 16.1 nm.
Embodiment 4
0.0005 mole of analytically pure silver nitrate, 0.0095 mole of analysis are weighed according to 0.05: 0.95: 1: 8 molar ratio
Pure Gerhardite, 0.01 mole of analytically pure six nitric hydrates cerium, 0.08 mole of analytically pure sodium hydroxide addition are matched
In the 50ml zirconia ball grinding jar of standby 50 diameter 6mm zirconium oxide balls and 8 diameter 10mm zirconium oxide balls, in QM-3SP04
In planetary high-energy ball mill under 480 rpm continuously grinding 4 hours, product is washed with distilled water, centrifuge separation simultaneously
It is dried in vacuo 2 hours under 60 DEG C and 0.1Mpa vacuum degree, obtains Ag/Cu2O/CeO2Ternary nano compound.
To Ag/Cu2O/CeO2Ternary product carries out XRD analysis, is calculated according to Scherrer formula, Ag/Cu2O/
CeO2Cu in ternary nano compound2O and CeO2Average grain size is respectively 14.5 nm and 17.4 nm.
Embodiment 5
0.0005 mole of analytically pure silver nitrate, 0.0095 mole of analysis are weighed according to 0.05: 0.95: 1: 8 molar ratio
Pure Gerhardite, 0.01 mole of analytically pure six nitric hydrates cerium, 0.08 mole of analytically pure sodium hydroxide addition are matched
In the 50ml zirconia ball grinding jar of standby 50 diameter 6mm zirconium oxide balls and 8 diameter 10mm zirconium oxide balls, in QM-3SP04
In planetary high-energy ball mill under 480 rpm continuously grinding 5 hours, product is washed with distilled water, centrifuge separation simultaneously
It is dried in vacuo 2 hours under 60 DEG C and 0.1Mpa vacuum degree, obtains Ag/Cu2O/CeO2Ternary nano compound.
To Ag/Cu2O/CeO2Ternary product carries out XRD analysis, is calculated according to Scherrer formula, Ag/Cu2O/
CeO2Cu in ternary nano compound2O and CeO2Average grain size is respectively 15.8 nm and 18.2 nm.
Embodiment 6
0.01 mole of analytically pure Gerhardite, 0.01 mole analytically pure six are weighed according to 1: 1: 8 molar ratio
Nitric hydrate cerium, 0.08 mole of analytically pure sodium hydroxide are added and are equipped with 50 diameter 6mm zirconium oxide balls and 8 diameter 10mm
In the 50ml zirconia ball grinding jar of zirconium oxide balls, continuously ground under 480 rpm in QM-3SP04 planetary high-energy ball mill
Mill 2 hours, washs product with distilled water, is centrifugated and small with vacuum drying 2 under 0.1Mpa vacuum degree at 60 DEG C
When, obtain Cu2O-2CeO2Nano-complex.
To Cu2O-2CeO2Product carries out XRD analysis, is calculated according to Scherrer formula, Cu2O-2CeO2Nanometer is multiple
Close Cu in object2O and CeO2Average grain size is respectively 11.5 nm and 14.9 nm.
Embodiment 7
According to 0.1: 0.9: 1: 8 molar ratio weigh 0.001 mole of analytically pure silver nitrate, 0.009 mole it is analytically pure
Gerhardite, 0.01 mole of analytically pure six nitric hydrates cerium, 0.08 mole of analytically pure sodium hydroxide are added and are equipped with 50
In the 50ml zirconia ball grinding jar of a diameter 6mm zirconium oxide balls and 8 diameter 10mm zirconium oxide balls, in QM-3SP04 planet
In formula high energy ball mill under 480 rpm continuously grinding 5 hours, product is washed with distilled water, be centrifugated and 60
DEG C and 0.1Mpa vacuum degree under be dried in vacuo 2 hours, obtain Ag/Cu2O/CeO2Ternary nano compound.
To Ag/Cu2O/CeO2Ternary product carries out XRD analysis, is calculated according to Scherrer formula, Ag/Cu2O/
CeO2Cu in ternary nano compound2O and CeO2Average grain size is respectively 11.3 nm and 14.9 nm.
Embodiment 8
It is pure that 0.0015 mole of analytically pure silver nitrate, 0.0085 mole of analysis are weighed according to 0.2: 0.8: 1: 8 molar ratio
Gerhardite, 0.01 mole of analytically pure six nitric hydrates cerium, 0.08 mole of analytically pure sodium hydroxide be added and be equipped with
In the 50ml zirconia ball grinding jar of 50 diameter 6mm zirconium oxide balls and 8 diameter 10mm zirconium oxide balls, in QM-3SP04 row
In planetary high energy ball mill under 480 rpm continuously grinding 5 hours, product is washed with distilled water, be centrifugated and
It is dried in vacuo 2 hours under 60 DEG C and 0.1Mpa vacuum degree, obtains Ag/Cu2O/CeO2Ternary nano compound.
To Ag/Cu2O/CeO2Ternary product carries out XRD analysis, is calculated according to Scherrer formula, Ag/Cu2O/
CeO2Ag, Cu in ternary nano compound2O and CeO2Average grain size is respectively 7.7 nm, 10.9 nm and 14.5 nm.
The X-ray diffraction of above-described embodiment analyzes (XRD analysis): respectively by Ag/ made from embodiment 1,2,3,4 and 5
Cu2O/CeO2Ternary nano compound carries out XRD analysis, the result is shown in Figure 1.It is calculated by Scherrer formula: reaction raw materials nitre
Sour silver, Gerhardite, six nitric hydrate ceriums and sodium hydroxide distinguish ball after mixing according to 0.05: 0.95: 1: 8 molar ratio
When grinding solid phase reaction 1h, 2h, 3h, 4h, 5h, products therefrom Ag/Cu2O/CeO2Cu in ternary nano compound2O and CeO2It is average
Crystallite dimension is respectively 9.6 nm, the nm of the nm of 11.4 nm, 13.0,14.5,15.8 and 13.2,14.9,16.1,17.4,18.2,
Show the variation of ball milling solid phase reaction time to Ag/Cu2O/CeO2Cu in ternary nano compound2O and CeO2Average grain size
Size have certain influence, with the extension of ball milling solid phase reaction time, Ag/Cu2O/CeO2Cu in ternary nano compound2O and
CeO2Crystal grain is gradually being grown up.
Meanwhile to Ag/Cu made from embodiment 2,6,7 and 82O/CeO2Ternary nano compound carries out XRD analysis, as a result
See Fig. 2.It is equally calculated by Scherrer formula: when silver nitrate, Gerhardite, six nitric hydrate ceriums and sodium hydroxide
Molar ratio when being increased to 0.2: 0.8: 1: 8 by 0: 1: 1: 8, products therefrom Ag/Cu2O/CeO2Cu in ternary nano compound2O
And CeO2Average grain size is respectively 11.5,11.4,11.3,10.9 nm and 14.9,14.9,14.9,14.8nm, show with
The raising of silver nitrate molar ratio, to Ag/Cu2O/CeO2Cu in ternary nano compound2O average grain size reduces slightly, and
CeO2Average grain size is almost unchanged, and rubbing when silver nitrate, Gerhardite, six nitric hydrate ceriums and sodium hydroxide
When you are than being 0.2: 0.8: 1: 8, calculated according to Scherrer formula, Ag/Cu2O/CeO2The average crystalline substance of Ag in ternary nano compound
Particle size is 7.7 nm.So during the preparation process, can be controlled by suitably changing the molar ratio of Ball-milling Time and silver nitrate
Product Ag/Cu processed2O/CeO2Cu in ternary nano compound2O and CeO2Average grain size and Ag load capacity and Qi Ping
Equal crystallite dimension.
Those of ordinary skill in the art will appreciate that: the above embodiments are only used to illustrate the technical solution of the present invention., and
It is non-that it is limited；Although present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art
It is understood that it is still possible to modify the technical solutions described in the foregoing embodiments, either to part of or
All technical features are equivalently replaced；And these are modified or replaceed, it does not separate the essence of the corresponding technical solution this hair
The range of bright each embodiment technical solution.
Claims (1)
1. a kind of Ag/Cu2O/CeO2One pot of solid phase reaction preparation method of ternary nano composite material, by Solid raw materials silver salt, copper
Salt, cerium salt mix in molar ratio with alkali, ball milling solid phase reaction, and products therefrom washing is centrifugated and prepares after drying；It is preparing
In the process, product Ag/Cu is controlled by adjusting the molar ratio of Ball-milling Time and silver nitrate2O/CeO2In ternary nano compound
Cu2O and CeO2Average grain size and Ag load capacity and its average grain size；The silver salt, mantoquita, cerium salt and alkali
It is uniformly mixed in molar ratio for x: 1-x: 1: 8, wherein x=0~0.2, but x is not equal to 0；The silver salt is silver nitrate；The mantoquita
For cupric salt；The cupric salt is one kind of Gerhardite, Salzburg vitriol, Copper dichloride dihydrate；The cerium
Salt is Ce (NO3)3·6H2O；The alkali is sodium hydroxide；The ball milling solid phase reaction refers to: being put into ball milling zirconium after raw material mixing
It in tank, is placed in ball mill, 480 rpm/min of setting speed, ball-milling reaction 1~5 hour；The product is washed with distilled water
It washs, be centrifugated and be dried in vacuo 2 hours under 60 DEG C and 0.1Mpa vacuum degree.
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| CN101318689A (en) * | 2008-05-16 | 2008-12-10 | 深圳市危险废物处理站 | Method for preparing monoclinic system crystalline state cupric oxide and uses thereof |
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