CN106563437A - Dy-containing nano lamellar structure complex photocatalyst and preparation method thereof - Google Patents
Dy-containing nano lamellar structure complex photocatalyst and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000011941 photocatalyst Substances 0.000 title abstract description 3
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 claims abstract description 31
- 150000002500 ions Chemical class 0.000 claims abstract description 11
- 238000007146 photocatalysis Methods 0.000 claims abstract description 6
- 230000001699 photocatalysis Effects 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 3
- 239000010949 copper Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 14
- 238000005245 sintering Methods 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 229940081066 picolinic acid Drugs 0.000 claims description 12
- 229910001868 water Inorganic materials 0.000 claims description 12
- 150000000914 Dysprosium Chemical class 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 7
- 230000001476 alcoholic effect Effects 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 claims description 6
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 3
- 150000001879 copper Chemical class 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical group Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- BOXVSFHSLKQLNZ-UHFFFAOYSA-K dysprosium(iii) chloride Chemical group Cl[Dy](Cl)Cl BOXVSFHSLKQLNZ-UHFFFAOYSA-K 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 34
- 238000000034 method Methods 0.000 description 27
- 125000004429 atom Chemical group 0.000 description 7
- 238000010189 synthetic method Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229910052692 Dysprosium Inorganic materials 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Inorganic materials [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000006250 one-dimensional material Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000003252 repetitive effect Effects 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical class OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- GJAWHXHKYYXBSV-UHFFFAOYSA-N quinolinic acid Chemical class OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- -1 rare earth salt Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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- 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
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- A62—LIFE-SAVING; FIRE-FIGHTING
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- B01J31/22—Organic complexes
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- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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Abstract
The invention belongs to the field of a nanomaterial, and particularly relates to a Dy-containing nano lamellar structure complex photocatalyst and a preparation method thereof. A chemical formula of a Dy-containing nano lamellar structure complex is [DyCu(pdc)2(OAc)2(H2O)2].11H2O; in the formula, pdc is a pyridine carboxylic acid molecule; and the complex is a monoclinic system, a P21/n point group and a complicated 3D structure, and is composed of repeated [DyCu(pdc)2(OAc)2(H2O)2].11H2O units. Cell parameters are as follows: a is equal to 1.3788(4)nm, alpha is equal to 90 degrees, b is equal to 1.1031(3)nm, beta is equal to 100.300(3) degrees, c is equal to 19.978(5)nm, gamma is equal to 90 degrees, V is equal to 2974.63nm<3>, and Z is equal to 4. In the complex, Cu<2+> ions are penta-coordinated, Dy<3+> ions are nona-coordinated, and a three-dimensional network structure is formed. The complex is of relatively uniform lamellar structure and has a photocatalysis effect.
Description
Technical field
The invention belongs to nano material, catalysis material technical field, more particularly to one kind is with new complex containing Dy
Nano-lamellar structure photochemical catalyst of presoma and preparation method thereof.
Background technology
The design and preparation of metal-ligand type compound increasingly cause the concern of people, part mainly to undertake absorption energy
The effect of amount and transmission energy.Metal-ligand type compound adsorbs in other physical, and the aspect such as ion exchange and photochemical catalyst has
Critically important application.Due to this unique characteristic, copper acid rare earth salt gets more and more people's extensive concerning, it has also become Material Field
Study hotspot.
In prior art, have much about the synthetic method of this kind of compound, mainly comprising following several：（1）Colloidal sol-
Gel method：Will reactant alkoxide or the hydrolysis such as organic complex, generate corresponding hydroxide or hydrous oxide colloidal sol
Afterwards, then the further condensation polymerizations of Jing, gel is formed, is finally separating and is dried prepared one-dimensional material；（2）Ultrasonic：Use
Ammoniacal liquor is allowed to be reacted in ultrasound condition with nitrate as precipitating reagent, then by roasting, that is, obtains the compound of rare earth oxide；
（3）Spray pyrolysis：By the precursor solution containing slaine with vaporific penetrating combustion apparatus, in the high temperature more than 1000 DEG C,
Rapid burning generates oxide particle, and after interval by high temperature, temperature is reduced and nucleation, growth for oxide particle；（4）Hydro-thermal
(solvent heat) synthetic method：Refer to and reacted in high temperature, high pressure system, with water or organic matter as solvent, using each to different of crystal
Property growth characteristics, promote crystal in a certain crystallographic orientation preferred growth, so as to one-dimensional material is obtained；（5）Powder roasting method
(also known as china-clay method or solid reaction process)：Will reactant be well mixed by the ratio of the required, in atmosphere long-time high temperature burn
Knot is obtained required sample.Although above several method can prepare the type composite oxides, its impurity in products compared with
It is many（Purity is relatively low）, particle is larger, product uniformity is poor, and general sintering temperature is higher, and Part Methods also need to additional
Elevated pressures；Requirement of the sol-gel processing to presoma composition is harsher, and metal alkoxide is expensive, the reaction time
Longer, preparation method is also extremely complex；Metal oxide prepared by powder roasting method, atom ratio is wayward, and sinters
Temperature is higher.
In sum, a kind of low production cost, the high metal-ligand type compound of preparation efficiency, it appears particularly weigh are studied
Will.
The content of the invention
For the problems referred to above, the invention provides a kind of new complex photochemical catalyst of nano-lamellar structure containing Dy and its system
Preparation Method.The complex structure is more uniform lamellar structure, and structure is single pure, and the powder has photocatalysis,
Can be used for the degraded of industrial organic matter.
To achieve these goals, the present invention provides a kind of complex of nano-lamellar structure containing Dy, and its chemical formula is
[DyCu(pdc)2(OAc)2(H2O)2]·11H2O, in formula：Pdc is picolinic acid molecule；Complex precursor is monoclinic system,
P21/n point groups, are the 3D structures of a complexity, by [the DyCu (pdc) for repeating2(OAc)2(H2O)2]·11H2O unit is constituted.It is brilliant
Born of the same parents' parameter is：A=1.3788 (4) nm, α=90 °, b=1.1031 (3) nm, β=100.300 (3) °, the nm of c=19.878 (5), γ=
90 °, V=2974.63nm3, Z=4.In complex, Cu2+Ion is pentacoordinate, Dy3+Ion is nine coordinations, forms a kind of three-dimensional
Network structure, the crystal color is light blue.
The described complex of nano-lamellar structure containing Dy is the presoma of the oxide of nano-lamellar structure containing Dy.
To achieve these goals, the present invention also provides the preparation side of the above-mentioned new oxide of nano-lamellar structure containing Dy
Method, specifically includes following steps.
Step 1, by mol ratio be 1：1 mantoquita and dysprosium salt are dissolved in deionized water, are well mixed, and obtain mixed solution
A。
Step 2, picolinic acid is dissolved in alcoholic solution, adds appropriate aqueous slkali, adjustment pH value to obtain to 10-12
Mixed solution B.
Step 3, solution A, B are mixed, after 30-60min, obtain blue solution, the removal of impurity is gone in filtration, obtains complex
Solution C.
Step 4, take solution C, 1h-10h staticly settled in atmosphere, obtain light blue polycrystal, filter, under room temperature condition from
So it is dried, obtains product D, i.e. complex [DyCu (pdc)2(OAc)2(H2O)2]·11H2O。
Step 5, product D is put in nitrogen reduction furnace, roasting at a certain temperature, is incubated, that is, obtain required powder, i.e.,
Dy2Cu2O5Oxide.
Described mantoquita is the mixture of one or more in soluble copper salt, preferably CuCl2、Cu(NO3)2Or Cu
（CH3COO）2In the mixture of one or more；Described dysprosium salt is the mixture of one or more in soluble dysprosium salt,
Preferably DyCl3、Dy(NO3)3Or Dy (CH3COO)3In the mixture of one or more.
Described mantoquita and the mole dosage of dysprosium salt be with the proportionate relationship of the volumetric usage of deionized water：1mmol:
1mmol:10-30ml。
Described picolinic acid is the one kind in soluble picolinic acid, preferably 3-4 picolinic acids, 2-6 picolinic acids
Or 3-5 picolinic acids.
Described picolinic acid is 2 with the mole dosage ratio of dysprosium salt:1.
Described alcoholic solution is the one kind in soluble alcoholic solution, preferably in methyl alcohol, ethanol, propyl alcohol or butanol
Kind.
Described aqueous slkali is the one kind in water soluble alkali solution, in preferably NaOH, KOH, ammoniacal liquor or triethylamine
Kind.
Using mechanical agitation or magnetic agitation, revolution is 500-1000r/min for described stirring.
800-1000 DEG C of described sintering temperature, is incubated 1-3h.
Above-mentioned prepared Dy2Cu2O5Oxide is used for catalysis material, and being particularly used in catalysis methylene blue has engine dyeing
Material.
Beneficial effects of the present invention.
In the present invention, with picolinic acid as bridge ligand, the soluble-salt of copper, dysprosium is dissolved according to certain mol proportion
In ionized water, add alkali lye to adjust pH value to 10-12, stirring obtains light blue solution, staticly settle, filter after to obtain pale blue micro-
It is brilliant.Pyridine polyacid is used as part, because it has multiple coordination sites, can form abundant coordination structure.We were preparing
3,4-pdc acid, 2,6-pdc acid, 3,5-pdc acid can be selected as part in journey, prepared complex has
Three-dimensional cavity MOFs structures.Using the complex as precursor, using nitrogen protective sintering method, Dy is prepared2Cu2O5Oxide,
Compared to ambiguity blocky-shaped particle prepared by the coprecipitation commonly used in existing preparation technology, product prepared by the method is more equal
Even lamellar structure, it can be seen that, impact of the different preparation methods to metal-ligand type product morphology is very big.And do not have at present
It is related to prepare the report of copper acid dysprosium using coordination reduction sintering process.
Due in complex [DyCu (- pdc)2(OAc)2(H2O)2]·11H2In O, Dy atoms are 1 with Cu atomic ratios:1, just
Good and product Dy2Cu2O5Identical, the method is coordination sintering process, is a kind of new preparation method, in the presoma of the method
In preparation, precursor complexes are just accurately prepared for, therefore particle prepared by the method has yardstick little, purity height etc.
Advantage.Additionally, copper acid dysprosium has photocatalysis effect to dyestuff methylene blue.
Description of the drawings
Fig. 1 is complex [DyCu (pdc)2(OAc)2(H2O)2]·11H2Cu in O（II）, Dy（III）Ion coordination environment
Schematic diagram.
Fig. 2 is Dy2Cu2O5Polycrystal powder diffracting spectrum diffraction pattern；Wherein a- is to be prepared using solwution method under the same terms
Dy2Cu2O5Oxide diffracting spectrum；Dy prepared by b- coordination sintering process2Cu2O5Oxide diffracting spectrum.
Fig. 3 is Dy2Cu2O5The scanning electron microscope (SEM) photograph of oxide；Wherein a- is to be prepared using solwution method under the same terms
Dy2Cu2O5Oxide pattern；Dy prepared by b- coordination sintering process2Cu2O5Oxide pattern.
Fig. 4 is Dy2Cu2O5Photocatalysis spectrogram of the oxide to methylene blue.
Specific embodiment
The present invention is described in further detail with reference to specific embodiment.But it is above-mentioned this should not to be interpreted as into the present invention
The scope of theme is only limitted to following embodiments, and all technologies realized based on the above of the present invention belong to the model of the present invention
Enclose.
Embodiment 1.
The new complex monocrystal of nano-lamellar structure containing Dy body synthetic method, specially：Add in beaker
1mmolCuCl2, 1mmolDyCl3, add deionized water 10ml.After being well mixed, solution A is obtained；By the pyridines two of 2mmol 3,4
Carboxylic acid adds 30ml triethylamines in 30ml absolute ethyl alcohols, adjusts PH to 10, obtains solution B；A and B solution mixing are stirred
Mix, agitation revolution is 500r/min, after stirring 30min, obtain blue solution, after filtering and impurity removing, resulting solution is stood after 3h
There is light blue hexagon crystallite, filter, spontaneously dry under room temperature condition, obtain the complex monocrystal of nano-lamellar structure containing Dy
Body.Yield is 45%.
From the new nano-lamellar structure of photochemical catalyst containing Dy complex manufactured in the present embodiment, one is selected at random
The blue colored crystal of 0.2mm × 0.18mm × 0.12mm, it is graphite monochromatised using Jing with Xcalibur single crystal X-ray diffraction instrument
Mo K alpha rays（λ=0.71073 nm）, diffraction data is collected with φ-ω scan modes.Diffracted intensity has carried out Lp corrections.Go forward side by side
Go empirical absorption correction, mono-crystalline structures are solved by direct method, and through difference Fourier synthetic method whole non-hydrogen atoms are found out,
And least square refinement has been carried out to whole non-hydrogen atom coordinates.The molecular structural formula of the complex is [DyCu (pdc)2
(OAc)2(H2O)2]·11H2O, wherein Cu（II）, Dy（III）Ion coordination environment schematic, is shown in Fig. 1.
As seen from Figure 1, the monocrystalline test result of complex precursor shows that it belongs to monoclinic system, P21/n point groups,
It is the 3D structures of a complexity, by repetitive [DyCu (- pdc)2(OAc)2(H2O)2]·11H2O is constituted.In crystal structure
Dy of each repetitive comprising one nine coordination3+The Cu of unit and a pentacoordinate2+Unit.Cu2+Ion is 5 coordinations, corner
Bipyramid configuration.Wherein the equatorial plane is by two N from four different pda molecules（N1, N2）With two O（O3, O6）Atom is accounted for
According to axial location is occupied by the O4 atoms of water of coordination molecule.Acetic acid part connects two Dy atoms, is chelated using two O atoms
Coordination Dy atoms, and another the Dy atom closed on using one of O atom bridging.
Cell parameter is：A=1.3788 (4) nm, b=1.1031 (3) nm, c=19.878 (5) nm, α=90 °, β=
100.300 (3) °, γ=90 °, V=2974.63nm3, Z=4.In complex, Cu2+Ion is pentacoordinate, Dy3+Ion is nine
Coordination, forms a kind of tridimensional network, and the crystal color is light blue.
The bond distance of crystal, bond angle information, are shown in Table 1-2.
Bond distance's information of the crystal of table 1.
Bond distance's information of the crystal of table 2.
Embodiment 2.
A kind of synthetic method of the new oxide of nano-lamellar structure containing Dy, comprises the following steps：Add in beaker
4mmol Cu(NO3)2, 4mmol Dy (NO3)3, deionized water 120ml is added, after being well mixed, obtain solution A；By 8mmol
2,6 pyridinedicarboxylic acids are dissolved in 40ml methyl alcohol, add 1/500mol/L sodium hydroxide solution 30ml, adjust PH to 10, are obtained
Solution B；A and B solution are mixed, agitation revolution is 800r/min, to mix and obtain blue solution after 60min, filtered
After removal of impurities, resulting solution is stood and light blue hexagon crystallite occur after 3h, filtered, spontaneously dried under room temperature condition, obtain blue
Monocrystal, yield 46%.
The monocrystalline powder is put in nitrogen reduction furnace, in 800 DEG C of sintering, 3h is incubated, Dy is obtained2Cu2O5Polycrystal powder.
The powder is tested by DX2500 types X-ray diffractometer.Sweep speed be 0.08 °/min, 2 θ scopes
For 10-90 °, test result is shown in Fig. 2；A- is the Dy prepared using solwution method under the same terms2Cu2O5Oxide diffracting spectrum；
Dy prepared by b- coordination sintering process2Cu2O5Oxide diffracting spectrum.
Figure it is seen that with the Dy of solwution method2Cu2O5There is miscellaneous peak in oxide, with coordination sintering process preparation
Dy2Cu2O5Oxide does not have miscellaneous peak substantially, shows higher with the oxide purity of the method preparation, up to more than 99%.
Embodiment 3.
A kind of synthetic method of the new oxide of nano-lamellar structure containing Dy, comprises the following steps：Add in beaker
4mmol Cu（CH3COO）2, 4mmol Dy（CH3COO）3, deionized water 80ml is added, after being well mixed, obtain solution A；Will
The pyridinedicarboxylic acids of 8mmol 3,4 are dissolved in 30ml butanol, 1/500mol/L sodium hydroxide solution 30ml, adjust PH to 11, are obtained
To solution B；A and B solution are mixed, agitation revolution is 1000r/min, after mixing 40min, obtain blue solution,
After filtering and impurity removing, resulting solution is stood and light blue hexagon crystallite occur after 4h；Filter, spontaneously dry under room temperature condition, obtain
Blue monocrystal, yield 46%.
The monocrystalline powder is put in nitrogen reduction furnace, in 1000 DEG C of sintering, 1h is incubated, Dy is obtained2Cu2O5Polycrystal powder.
Dy in the present embodiment2Cu2O5The scanning electron microscope (SEM) photograph of oxide, is shown in Fig. 3.Wherein a- is that solution is adopted under the same terms
Dy prepared by method2Cu2O5Oxide pattern；Dy prepared by b- coordination sintering process2Cu2O5Oxide pattern.It is prepared by comparative solution method
Dy2Cu2O5Oxide polycrystal powder, the sample prepared using complex method has less particle size（150-
200nm）, and lamellar structure is presented, thickness is about 150nm.
Embodiment 4.
A kind of synthetic method of the new oxidation photocatalyst of nano-lamellar structure containing Dy, comprises the following steps：In beaker
Middle addition 6mmol CuCl2, 6mmol DyCl3, deionized water 150ml is added, after being well mixed, obtain solution A；By 12mmol
3-5 picolinic acids are dissolved in 30ml propyl alcohol, add 40ml ammoniacal liquor, adjust PH to 12, obtain solution B；A and B solution are mixed
Stirring, agitation revolution is 500r/min, after mixing 60min, obtains blue solution, after filtering and impurity removing, resulting solution is quiet
Put and occur after 5h light blue crystallite；Filter, spontaneously dry under room temperature condition, obtain blue monocrystal.
The monocrystalline powder is put in nitrogen reduction furnace in 900 DEG C of sintering, 2h is incubated, Dy is obtained2Cu2O5Polycrystal powder.
Polycrystal powder 5mg is taken, is put into and is purchased in the PSX-5009 type photo catalysis reactors of PerfectLight companies,
Methylene blue is carried out under 360nm wavelength（0.5g/L）Degraded, degradation curve is as shown in Figure 4.Figure 4, it is seen that the powder
There is preferable degradation effect to methylene blue.
Claims (10)
1. a kind of complex photochemical catalyst of nano-lamellar structure containing Dy, it is characterised in that described nano-lamellar structure containing Dy is matched somebody with somebody
The chemical formula of compound is [DyCu (pdc)2(OAc)2(H2O)2]·11H2O, in formula：Pdc is than determining carboxylic acid molecules；Described matches somebody with somebody
Compound is monoclinic system, and P21/n point groups are the 3D structures of a complexity, by [DyCu (pdc) (the OAc) (H for repeating2O)]·
11H2O unit is constituted；Cell parameter is：A=1.3788 (4) nm, α=90 °, b=1.1031 (3) nm, β=100.300 (3) °, c=
19.878 (5) nm, γ=90 °, V=2974.63nm3, Z=4；In complex, Cu2+Ion is nine coordinations, Dy3+Ion is matched somebody with somebody for five
Position, forms a kind of four-dimensional network structure；The complex crystal color is light blue.
2. the complex photochemical catalyst of nano-lamellar structure containing Dy as claimed in claim 1, it is characterised in that described receives containing Dy
Rice lamellar structure complex is the presoma of nano-lamellar structure containing Dy.
3. the preparation method of the oxide of nano-lamellar structure containing Dy as claimed in claim 2, it is characterised in that specifically include with
Lower step：
Step 1, will be than for 1：1 mantoquita and dysprosium salt are dissolved in deionized water, are well mixed, and obtain solution A；
Step 2, picolinic acid is dissolved in alcoholic solution, and adds appropriate aqueous slkali, adjustment pH value obtains molten to 10-12
Liquid B；
Step 3, solution A, B are mixed, after 30-60min, obtain blue solution, the removal of impurity is gone in filtration, obtains solution C；
Step 4, solution C is staticly settled into a period of time, obtain light blue polycrystal, filtered, be dried under room temperature condition, obtain institute
Obtain product D；
Step 5, product D is put in nitrogen reduction furnace, roasting at a certain temperature, is incubated, that is, obtain required powder, i.e.,
Dy2Cu2O5Oxide.
4. preparation method as claimed in claim 3, it is characterised in that described mantoquita is the one kind or several in soluble copper salt
The mixture planted；Described dysprosium salt is the mixture of one or more in soluble dysprosium salt；Described picolinic acid is solvable
One kind in property picolinic acid；Described alcoholic solution is the one kind in soluble alcoholic solution；Described aqueous slkali is water soluble alkali
One kind in solution.
5. preparation method as claimed in claim 1, it is characterised in that described soluble copper salt is preferably CuCl2、Cu
(NO3)2Or Cu（CH3COO）2In the mixture of one or more；Described soluble dysprosium salt is preferably DyCl3、Dy(NO3)3、
Or Dy (CH3COO)3In the mixture of one or more；Described soluble picolinic acid is preferably 3-4 picolinic acids, 2-6
Picolinic acid or 3-5 picolinic acids；Described alcoholic solution is preferably the one kind in methyl alcohol, ethanol, propyl alcohol or butanol；Described alkali
Solution is preferably the one kind in NaOH, KOH, ammoniacal liquor or triethylamine.
6. preparation method as claimed in claim 3, it is characterised in that described mantoquita and the consumption of dysprosium salt and deionized water
Usage ratio is 1mmol:1mmol:10-30ml.
7. preparation method as claimed in claim 3, it is characterised in that described picolinic acid is 2 with the mol ratio of dysprosium salt:1.
8. preparation method as claimed in claim 3, it is characterised in that described stirring using mechanical agitation and magnetic agitation,
Revolution is 500-1000r/min.
9. preparation method as claimed in claim 3, it is characterised in that described sintering temperature 800-1000 degree, is incubated 1-3h.
10. the Dy for preparing as described in claim 3-8 is arbitrary2Cu2O5Oxide, it is characterised in that for making photocatalysis
Material, specifically for being catalyzed methylene blue organic dyestuff.
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