CN108273563A - A kind of embedded precious metals pd/BiVO4@RuIIIThe preparation method of-TA nuclear-shell structured nano-composite materials - Google Patents
A kind of embedded precious metals pd/BiVO4@RuIIIThe preparation method of-TA nuclear-shell structured nano-composite materials Download PDFInfo
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- CN108273563A CN108273563A CN201810105532.XA CN201810105532A CN108273563A CN 108273563 A CN108273563 A CN 108273563A CN 201810105532 A CN201810105532 A CN 201810105532A CN 108273563 A CN108273563 A CN 108273563A
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- bivo
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- precious metals
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- 229910002915 BiVO4 Inorganic materials 0.000 title claims abstract description 69
- 239000000463 material Substances 0.000 title claims abstract description 33
- 239000010970 precious metal Substances 0.000 title claims abstract description 30
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910002666 PdCl2 Inorganic materials 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 229910019891 RuCl3 Inorganic materials 0.000 claims abstract description 11
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003643 water by type Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 150000001621 bismuth Chemical class 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910003206 NH4VO3 Inorganic materials 0.000 claims description 3
- 229910020700 Na3VO4 Inorganic materials 0.000 claims description 3
- 241000549556 Nanos Species 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 3
- 239000012456 homogeneous solution Substances 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- IHIXIJGXTJIKRB-UHFFFAOYSA-N trisodium vanadate Chemical compound [Na+].[Na+].[Na+].[O-][V]([O-])([O-])=O IHIXIJGXTJIKRB-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- UXAMZEYKWGPDBI-UHFFFAOYSA-N C(CCCCCCCCCCCCCCC)Br(C)(C)C Chemical class C(CCCCCCCCCCCCCCC)Br(C)(C)C UXAMZEYKWGPDBI-UHFFFAOYSA-N 0.000 claims 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims 1
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 abstract description 34
- 239000001263 FEMA 3042 Substances 0.000 abstract description 34
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 abstract description 34
- 229940033123 tannic acid Drugs 0.000 abstract description 34
- 235000015523 tannic acid Nutrition 0.000 abstract description 34
- 229920002258 tannic acid Polymers 0.000 abstract description 34
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 abstract description 21
- 239000002105 nanoparticle Substances 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 5
- 230000009467 reduction Effects 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 229910001385 heavy metal Inorganic materials 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 abstract 1
- 239000002957 persistent organic pollutant Substances 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 abstract 1
- 239000011257 shell material Substances 0.000 description 22
- 239000000047 product Substances 0.000 description 15
- 229910000510 noble metal Inorganic materials 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920003228 poly(4-vinyl pyridine) Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/36—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of vanadium, niobium or tantalum
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- 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
- B01J35/396—Distribution of the active metal ingredient
- B01J35/398—Egg yolk like
-
- 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)
- Inorganic Chemistry (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention belongs to new material technology fields, are related to a kind of embedded precious metals pd/BiVO4@RuIIIThe preparation method of TA nuclear-shell structured nano-composite materials.By disposably combining BiVO4、RuCl3、PdCl2And tannic acid solution, the ingenious double action using tannic acid, can and Ru3+Pd can be restored again by forming complex compound shell2+Pd nano particle is obtained, directly one-step synthesis precious metals pd/BiVO can be embedded under normal temperature and pressure stirring4@RuIIITA nuclear-shell structured nano-composite materials, substantially increase BiVO4With the application range of tannic acid.The present invention has many advantages, such as environmental-friendly, simple and easy to get.Nanocomposite stability height, the absorption degradation synthesized is had excellent performance, and can be widely used for the fields such as biological medicine, biosensor, catalysis, the removal of Organic Pollutants in Wastewater, heavy metal ion reduction.
Description
Technical field
The invention belongs to new material technology fields, are related to a kind of embedded precious metals pd/BiVO4@RuIII- TA nucleocapsids are received
The preparation method of nano composite material.
Background technology
Pucherite (BiVO4) it is used as a kind of novel semiconductor material, because its narrow energy gap (2.4eV) can be directly by can
Light-exposed excitation has become current catalysis material research so as to more effectively utilize solar energy to realize the degradation of pollutant
One of the hot spot in field.But due to its small specific surface area and high electron-hole recombination rate, limit BiVO4It is further
Using.How the BiVO of high electron-hole transport efficiency and high activity is prepared4Catalysis material is still current research
Key points and difficulties.It is well known that by depositing noble metal, Schottky potential barriers are formed on metal-semiconductor interface, in light
Light induced electron, the compound of hole is prevented to provide effective capture trap in catalytic process, to change the surface nature of semiconductor,
This is a kind of common approach for improving photocatalysis quantum efficiency.However noble metal nano particles are since its grain size is small, specific surface area
Greatly, surface energy is high, and easy coalescence is blocking between particle, causes its surface plasma bulk effect to weaken or lose, reduces it
Activity simultaneously limits and further recycles ability.
Along this thinking, first in BiVO4Surface forms close shell, then that noble metal is embedding from nano-particle Inner
In hud typed BiVO4Shell in, the embedding noble metal BiVO of Inner of formation4Core/shell structure nano material is than single noble metal nano grain
Son load is more stable, and has both the physicochemical properties of noble metal and Core-shell structure material, ingenious using between multi-stage interface
Coupling, more effective active units, higher quantum efficiency and better stability are obtained, to realize single urge
Agent is difficult the bigger serface taken into account, high-quantum efficiency and high solar utilization rate.Zhang et al. is by precious metals pd nanoparticle
In the embedded hud typed PS-co-P4VP microballoons of son [Chem.Mater.2008,20,2144-2150], for Suzuki reactions and table
High catalytic efficiency is revealed.Patent CN107096530A is disclosed during a kind of noble metal gold is embedded in inside titanium dioxide
The preparation method of hollow structure photochemical catalyst.Gold colloid particle is loaded to pre-synthesis silica surface by the technology first,
It is hydrolyzed in its outer layer by adding butyl titanate, finally highly basic etching silicon dioxide template is used to be inlayed to obtain noble metal gold
Hollow structure photochemical catalyst inside titanium dioxide.
It is not difficult to find out, the existing technical step for preparing noble metal-core-shell material is relatively complicated, it usually needs highly basic or height
Temperature removes removing template, this increases energy consumption to practical application.Therefore, tannic acid (TA) is utilized under a kind of normal temperature and pressure of present invention offer
And Ru3+Form complex compound shell and reduction Pd2+The direct one-step synthesis of Pd nano-particles is made and embeds precious metals pd/BiVO4@
RuIIIThe method of-TA nuclear-shell structured nano-composite materials has easy to operate, low energy consumption, of low cost, environmental-friendly etc. excellent
Point, there is presently no the reports about such technology, go out a new road for the development exploration of new material.
Invention content
The purpose of the present invention is to provide a kind of environmental-friendly, simple and easy to get method prepare embed precious metals pd/
BiVO4@RuIII- TA nuclear-shell structured nano-composite materials utilize tannic acid (TA) and Ru at normal temperatures and pressures3+Form complex compound shell
Layer and reduction Pd2+The direct one-step synthesis of Pd nano-particles is made and embeds precious metals pd/BiVO4@RuIII- TA nuclear shell structure nanos
Composite material has easy to operate, low energy consumption, of low cost, advantages of environment protection.
What the object of the invention was realized in：A kind of embedded precious metals pd/BiVO4@RuIII- TA nuclear shell structure nanos are compound
The preparation method of material, it is critical that by TA and BiVO4Sample is according to molar ratio：TA:BiVO4=0.61~1:1 is added
Into beaker, and 15mL deionized waters are added, then according to RuCl3：PdCl2：BiVO4The molar ratio of sample is 0.02~0.2:
0.04~0.2:1, RuCl is successively added3And PdCl2, 24~48h is stirred at room temperature, and products obtained therefrom separation, washing and drying obtain
Precious metals pd/BiVO is embedded to target product4@RuIII- TA nuclear-shell structured nano-composite materials.
More particularly, it is as follows：
Step 1：Weigh 1.23mmol BiVO4(0.4g) sample, according to n (TA:BiVO4)=0.61~1:1 is added 0.75
~1.23mmol TA (1.28~2.09g) are added 15mL deionized waters and are uniformly mixed, then according to RuCl3：PdCl2：BiVO4
The molar ratio of sample is 0.02~0.2:0.04~0.08:1,0.025~0.25mmol RuCl are successively added3(0.005~
0.052g) and 0.05~0.1mmol PdCl2(0.009~0.018g) stirs 24~48h at room temperature；
Step 2：The separation of step 1 products obtained therefrom, washing and drying are embedded into precious metals pd/BiVO to get target product4@
RuIII- TA nuclear-shell structured nano-composite materials.
More particularly, BiVO4The preparation process of sample is as follows：
Step A：It takes the bismuth salt of 0.02mol to be dissolved in 20mL concentrated nitric acids and obtains homogeneous solution, stir 2h；
Step B：The vanadium-containing compound of 0.02mol is dissolved in the NaOH aqueous solutions of the 6M of 20mL；
Step C：Step B acquired solutions are added in step A acquired solutions, then by 0.1~0.5g cetyl front threes
Base ammonium bromide (CTAB) is added in acquired solution, stirs 2h, is then slowly added into the NaOH aqueous solutions of 30mL 6M, obtains uniformly
Suspension stirs 2h；
Step D：The liner that step C acquired solutions are added to 100mL is in the stainless steel cauldron of polytetrafluoroethylene (PTFE) 180
48h is kept at DEG C, products therefrom deionized water is centrifuged multiple, and then dry 8h at 60 DEG C, obtains BiVO4Sample.
Bismuth salt described in above-mentioned steps A is Bi (NO3)3·5H2O or BiCl3。
Vanadium-containing compound described in above-mentioned steps A is NH4VO3Or Na3VO4。
The purity of drug used is pure not less than analyzing in above-mentioned steps D.
In above-mentioned steps 2 after solid matter separation, alternately washed using deionized water, absolute ethyl alcohol, it is to obtain the final product interior after dry
Embedding precious metals pd/BiVO4@RuIII- TA nuclear-shell structured nano-composite materials.
In above-mentioned steps 2, use deionized water washing times for 4~6 times；The drying temperature is 60~80 DEG C, dry
Time is 6~12h.
The beneficial effects of the present invention are：
1, the present invention, which realizes, utilizes TA and Ru under normal temperature and pressure3+Form complex compound shell and reduction Pd2+Obtained Pd receives
The direct one-step synthesis of rice corpuscles embeds precious metals pd/BiVO4@RuIII- TA nuclear-shell structured nano-composite materials, the composite material table
Abundant hydroxyl and carboxylic group are contained in face, and Pd nano-particles have preferably dispersibility and stability.
2, synthetic method provided by the invention is easy to operate, low energy consumption, and material itself has environmental-friendly, degradable harmful
The advantages that pollutant.
3, products therefrom post-processing of the present invention is simple, and recycling is convenient, can be recycled, by-product is few.
Description of the drawings
Fig. 1 show Pd/BiVO4@RuIIIThe synthesis schematic diagram of-TA nuclear-shell structured nano-composite materials.
Fig. 2 show the embodiment of the present invention 4 and the TEM of 5 gained samples schemes, in figure：(a)BiVO4；(b)22Pd/BiVO4@
RuIII-TA；(c)51Pd/BiVO4@RuIII-TA.。
Fig. 3 show the TEM-mapping figures of 4 gained sample of the embodiment of the present invention.
Fig. 4 is the EDX elemental analysis collection of illustrative plates of 4 gained sample of the embodiment of the present invention.
Fig. 5 show the infrared spectrogram of 4 gained sample of the embodiment of the present invention.
Fig. 6 show the XRD spectra of gained sample：(a)BiVO4；(b)22Pd/BiVO4@RuⅢ-TA。
Specific implementation mode
The present invention is further clarified with reference to embodiment.
Embodiment 1：
BiVO4The preparation process of sample is as follows：
Step A：It takes the bismuth salt of 0.02mol to be dissolved in 20mL concentrated nitric acids and obtains homogeneous solution, stir 2h；The bismuth salt is Bi
(NO3)3·5H2O or BiCl3；The vanadium-containing compound is NH4VO3Or Na3VO4；
Step B：The vanadium-containing compound of 0.02mol is dissolved in the NaOH aqueous solutions of the 6M of 20mL；
Step C：Step B acquired solutions are added in step A acquired solutions, then by 0.1~0.5g cetyl front threes
Base ammonium bromide (CTAB) is added in acquired solution, stirs 2h, is then slowly added into the NaOH aqueous solutions of 30mL 6M, obtains uniformly
Suspension stirs 2h；
Step D：The liner that step 3 acquired solution is added to 100mL is in the stainless steel cauldron of polytetrafluoroethylene (PTFE) 180
48h is kept at DEG C, products therefrom deionized water is centrifuged multiple, and then dry 8h at 60 DEG C, obtains BiVO4Sample.Step D
In drug used purity not less than analyze it is pure, ensure cleaning separation process in does not bring impurity into.
Fig. 2 a1 and a2 are synthesized pure phase BiVO4Transmission electron microscope picture and high-resolution-ration transmission electric-lens figure, interplanar distance be
0.31nm corresponds to monocline scheelite phase BiVO4(- 121) crystal face.Fig. 5 a are synthesized pure phase BiVO4XRD spectra, correspond to
Monocline scheelite phase BiVO4(JCPDS No.14-0688)。
Embodiment 2：
Weigh the 1.23mmol BiVO that embodiment 1 obtains4(0.4g) sample, according to n (TA:BiVO4)=0.61:1 is added
0.75mmol TA (1.28g) are added 15mL deionized waters and are uniformly mixed, then according to RuCl3：PdCl2：BiVO4Sample rubs
You are than being 0.02:0.04:1,0.025mmol RuCl are successively added3(0.005g) and 0.05mmol PdCl2(0.009g), room temperature
Lower stirring is for 24 hours.Products obtained therefrom separation, washing and drying embed precious metals pd/BiVO to get target product4@RuIII- TA nucleocapsids
Structure nanometer composite material (is labeled as 051Pd/BiVO4@RuIII-TA)。
Embodiment 3:
Weigh the 1.23mmol BiVO that embodiment 1 obtains4(0.4g) sample, according to n (TA:BiVO4)=0.61:1 is added
0.75mmol TA (1.28g) are added 15mL deionized waters and are uniformly mixed, then according to RuCl3：PdCl2：BiVO4Sample rubs
You are than being 0.02:0.08:1,0.025mmol RuCl are successively added3(0.005g) and 0.1mmol PdCl2(0.018g), room temperature
Lower stirring is for 24 hours.Products obtained therefrom separation, washing and drying embed precious metals pd/BiVO to get target product4@RuIII- TA nucleocapsids
Structure nanometer composite material (is labeled as 052Pd/BiVO4@RuIII-TA)。
Embodiment 4:
Weigh the 1.23mmol BiVO that embodiment 1 obtains4(0.4g) sample, according to n (TA:BiVO4)=0.61:1 is added
0.75mmol TA (1.28g) are added 15mL deionized waters and are uniformly mixed, then according to RuCl3：PdCl2：BiVO4Sample rubs
You are than being 0.08:0.08:1,0.1mmol RuCl are successively added3(0.02g) and 0.1mmol PdCl2(0.018g), is stirred at room temperature
It mixes for 24 hours.Products obtained therefrom separation, washing and drying embed precious metals pd/BiVO to get target product4@RuIII- TA nucleocapsids
Nanocomposite (is labeled as 22Pd/BiVO4@RuIII-TA)。
Fig. 2 b1, b2, b3 and b4 are synthesized 22Pd/BiVO4@RuIIIThe transmission electron microscope picture and high-resolution of-TA samples transmit
Electron microscope, it can be seen that Pd nano-particles are wrapped in amorphous complex compound shell, and shell thickness is about 25nm, Pd nanoparticles
Seed diameter is about 30nm.Interplanar distance is (111) crystal face that 0.225nm corresponds to Pd (0) in b4, and interplanar distance is 0.467nm
Corresponding monocline scheelite phase BiVO4(011) crystal face.Fig. 3 is synthesized 22Pd/BiVO4@RuIIIThe TEM- of-TA samples
Mapping schemes, and Fig. 4 is synthesized 22Pd/BiVO4@RuIIIThe EDX elemental analysis collection of illustrative plates of-TA samples, it can be seen that Ru, Pd member
Element is implicitly present in, and is evenly distributed in sample.Fig. 5 is synthesized 22Pd/BiVO4@RuIIIThe infrared spectrum of-TA samples
Scheme, in addition in 747cm in infrared spectrogram-1,828cm-1And 476cm-1Belong to BiVO4In V-O stretching vibration peaks outside, separately
External 1718,1610,1444,1329,1205,1088and 1030cm-1There is apparent characteristic peak, wherein in 1444cm-1,1205cm-1,1088cm-1,1030cm-1It is respectively belonging to the O-H deformation vibrations peak in tannic acid, C-O stretching vibration peaks, OH
Out-of-plane bending peak, epoxy group C-O stretching vibration peaks further demonstrate in Ru3+In the presence of success in BiVO4Surface is formed
Complex compound shell.B is synthesized 22Pd/BiVO in Fig. 64@RuIIIThe XRD spectra of-TA samples corresponds to monocline scheelite phase
BiVO4(JCPDS No.14-0688)。
Embodiment 5：
Weigh the 1.23mmol BiVO that embodiment 1 obtains4(0.4g) sample, according to n (TA:BiVO4)=1:1 is added
1.23mmol TA (2.09g) are added 15mL deionized waters and are uniformly mixed, then according to RuCl3：PdCl2：BiVO4Sample rubs
You are than being 0.2:0.04:1,0.25mmol RuCl are successively added3(0.052g) and 0.05mmol PdCl2(0.009g), at room temperature
Stir 48h.Products obtained therefrom separation, washing and drying embed precious metals pd/BiVO to get target product4@RuIII- TA nucleocapsid knots
Structure nanocomposite (is labeled as 51Pd/BiVO4@RuIII-TA)。
Fig. 2 c1 and c2 are synthesized 51Pd/BiVO4@RuIIIThe transmission electron microscope picture and high-resolution-ration transmission electric-lens of-TA samples
Figure is learnt from figure as addition 0.25mmol RuCl3When, complex compound shell obviously thickens, and shell thickness is about 60nm, and Pd receives
Rice corpuscles is embedded in shell.
Although the embodiment of the present invention is had been presented for herein, it will be appreciated by those of skill in the art that not taking off
In the case of from spirit of that invention, the embodiments herein can be changed.Above-described embodiment is only exemplary, should not be with
Restriction of the embodiments herein as interest field of the present invention.
Claims (8)
1. a kind of embedded precious metals pd/BiVO4@RuIIIThe preparation method of-TA nuclear-shell structured nano-composite materials, feature exist
In：：By TA and BiVO4Sample is added in beaker, and deionized water is added, and adds RuCl3And PdCl2, it stirs at room temperature,
Products obtained therefrom separation, washing and drying obtain target product and embed precious metals pd/BiVO4@RuIII- TA nuclear shell structure nanos are multiple
Condensation material.
2. a kind of embedded precious metals pd/BiVO according to claim 14@RuIII- TA nuclear-shell structured nano-composite materials
Preparation method, it is characterised in that：By TA and BiVO4Sample is according to molar ratio：TA:BiVO4=0.61~1:1 is added to beaker
In, and deionized water dissolving is added, then according to RuCl3：PdCl2：BiVO4The molar ratio of sample is 0.02~0.2:0.04~
0.2:1, RuCl is successively added3And PdCl2, 24~48h is stirred at room temperature, and products obtained therefrom separation, washing and drying obtain target
Product embeds precious metals pd/BiVO4@RuIII- TA nuclear-shell structured nano-composite materials.
3. a kind of embedded precious metals pd/BiVO according to claim 24@RuIII- TA nuclear-shell structured nano-composite materials
Preparation method, it is characterised in that：
Step 1：Weigh 1.23mmol BiVO4Sample, according to n (TA:BiVO4)=0.61~1:1 is added 0.75~1.23mmol
TA is added 15mL deionized waters and is uniformly mixed, then according to RuCl3：PdCl2：BiVO4The molar ratio of sample is 0.02~0.2:
0.04~0.08:1,0.025~0.25mmol RuCl are successively added3With 0.05~0.1mmol PdCl2, at room temperature stir 24~
48h；
Step 2：The separation of step 1 products obtained therefrom, washing and drying are embedded into precious metals pd/BiVO to get target product4@RuIII-
TA nuclear-shell structured nano-composite materials.
4. a kind of embedded precious metals pd/BiVO according to claim 24@RuIII- TA nuclear-shell structured nano-composite materials
Preparation method, it is characterised in that：The BiVO4The preparation process of sample is as follows：
Step A：It takes the bismuth salt of 0.02mol to be dissolved in 20mL concentrated nitric acids and obtains homogeneous solution, stir 2h；
Step B：The vanadium-containing compound of 0.02mol is dissolved in the NaOH aqueous solutions of the 6M of 20mL；
Step C：Step B acquired solutions are added in step A acquired solutions, then by 0.1~0.5g cetyl trimethyl bromines
Change ammonium (CTAB) to be added in acquired solution, stirs 2h, be then slowly added into the NaOH aqueous solutions of 30mL 6M, obtain even suspension
Liquid stirs 2h；
Step D：The liner that step C acquired solutions are added to 100mL is in the stainless steel cauldron of polytetrafluoroethylene (PTFE), at 180 DEG C
48h is kept, products therefrom deionized water is centrifuged multiple, then dry 8h at 60 DEG C, obtains BiVO4Sample.
5. a kind of embedded precious metals pd/BiVO according to claim 44@RuIII- TA nuclear-shell structured nano-composite materials
Preparation method, it is characterised in that：Bismuth salt described in above-mentioned steps A is Bi (NO3)3·5H2O or BiCl3。
6. a kind of embedded precious metals pd/BiVO according to claim 44@RuIII- TA nuclear-shell structured nano-composite materials
Preparation method, it is characterised in that：Vanadium-containing compound described in above-mentioned steps A is NH4VO3Or Na3VO4。
7. a kind of embedded precious metals pd/BiVO according to claim 44@RuIII- TA nuclear-shell structured nano-composite materials
Preparation method, it is characterised in that：In above-mentioned steps 2 after solid matter separation, alternately washed using deionized water, absolute ethyl alcohol,
Up to embedded precious metals pd/BiVO after drying4@RuIII- TA nuclear-shell structured nano-composite materials.
8. a kind of embedded precious metals pd/BiVO according to claim 44@RuIII- TA nuclear-shell structured nano-composite materials
Preparation method, it is characterised in that：In above-mentioned steps 2, use deionized water washing times for 4~6 times；The drying temperature is 60
~80 DEG C, drying time is 6~12h.
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| CN103933972A (en) * | 2014-04-21 | 2014-07-23 | 国家纳米科学中心 | Method for preparing precious metal titanium dioxide core-shell structure |
| CN105332050A (en) * | 2015-11-30 | 2016-02-17 | 中国科学技术大学 | Palladium nanocrystals and synthesis method thereof |
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| CN103933972A (en) * | 2014-04-21 | 2014-07-23 | 国家纳米科学中心 | Method for preparing precious metal titanium dioxide core-shell structure |
| CN105332050A (en) * | 2015-11-30 | 2016-02-17 | 中国科学技术大学 | Palladium nanocrystals and synthesis method thereof |
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| CN110983362A (en) * | 2019-12-19 | 2020-04-10 | 湖南大学 | MOFs-coated OV-BiVO4Composite photo-anode and preparation method and application thereof |
| CN110983362B (en) * | 2019-12-19 | 2021-05-28 | 湖南大学 | MOFs-coated OV-BiVO4Composite photo-anode and preparation method and application thereof |
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