CN105728744B - A kind of preparation method of stabilizing activity charcoal/nanoscale Pd/Fe composite particles - Google Patents
A kind of preparation method of stabilizing activity charcoal/nanoscale Pd/Fe composite particles Download PDFInfo
- Publication number
- CN105728744B CN105728744B CN201610284705.XA CN201610284705A CN105728744B CN 105728744 B CN105728744 B CN 105728744B CN 201610284705 A CN201610284705 A CN 201610284705A CN 105728744 B CN105728744 B CN 105728744B
- Authority
- CN
- China
- Prior art keywords
- nanoscale
- composite particles
- activity charcoal
- preparation
- stabilizing activity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000011246 composite particle Substances 0.000 title claims abstract description 96
- 230000000087 stabilizing effect Effects 0.000 title claims abstract description 40
- 239000003610 charcoal Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 201
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 191
- 239000002245 particle Substances 0.000 claims abstract description 98
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000008187 granular material Substances 0.000 claims abstract description 13
- 230000008859 change Effects 0.000 claims abstract description 10
- 150000002940 palladium Chemical class 0.000 claims abstract description 10
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 10
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 5
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910010277 boron hydride Inorganic materials 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 16
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 7
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- ZLXPLDLEBORRPT-UHFFFAOYSA-M [NH4+].[Fe+].[O-]S([O-])(=O)=O Chemical compound [NH4+].[Fe+].[O-]S([O-])(=O)=O ZLXPLDLEBORRPT-UHFFFAOYSA-M 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 15
- 238000005054 agglomeration Methods 0.000 abstract description 11
- 230000002776 aggregation Effects 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000003911 water pollution Methods 0.000 abstract description 2
- 230000006641 stabilisation Effects 0.000 description 51
- 229910052751 metal Inorganic materials 0.000 description 48
- 239000002184 metal Substances 0.000 description 48
- 239000007864 aqueous solution Substances 0.000 description 32
- 239000000243 solution Substances 0.000 description 25
- 239000013078 crystal Substances 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000008367 deionised water Substances 0.000 description 20
- 229910021641 deionized water Inorganic materials 0.000 description 20
- 238000005406 washing Methods 0.000 description 20
- 229910052603 melanterite Inorganic materials 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 16
- 239000000203 mixture Substances 0.000 description 14
- 229910052763 palladium Inorganic materials 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000002178 crystalline material Substances 0.000 description 12
- 238000010586 diagram Methods 0.000 description 12
- 230000009467 reduction Effects 0.000 description 12
- 238000001228 spectrum Methods 0.000 description 12
- 229910052742 iron Inorganic materials 0.000 description 11
- 239000007791 liquid phase Substances 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 9
- 230000002045 lasting effect Effects 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 239000002585 base Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical class OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- ZHLKXBJTJHRTTE-UHFFFAOYSA-N Chlorobenside Chemical compound C1=CC(Cl)=CC=C1CSC1=CC=C(Cl)C=C1 ZHLKXBJTJHRTTE-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 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
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
Abstract
The present invention relates to a kind of preparation method of stabilizing activity charcoal/nanoscale Pd/Fe composite particles, belong to nano-substance water pollution processing technology field.In order to solve the problem of existing particle diameter and specific surface area for agglomeration and particle easily occur is poor; a kind of preparation method of stabilizing activity charcoal/nanoscale Pd/Fe composite particles is provided; this method is included under inert gas shielding; make soluble ferrite under conditions of the boron hydride and ul-trasonic irradiation of alkali metal and stir to be reacted, make Fe2+Change into nanoscale zero-valent iron particle；Add soluble palladium salt to be reacted, obtain the reaction solution containing nanoscale Pd/Fe particles；Activated carbon granule is added, then stirring carries out load-reaction under ul-trasonic irradiation, obtains stabilizing activity charcoal/nanoscale Pd/Fe composite particles.The present invention has particle diameter small, and specific surface area is big and finely dispersed effect.
Description
Technical field
The present invention relates to a kind of preparation method of stabilizing activity charcoal/nanoscale Pd/Fe composite particles, belong to nano-substance
Water pollution processing technology field.
Background technology
Since 1990s, nano zero valence iron (NZVI) has specific surface area big because of it, and reactivity is strong and valency
Honest and clean the features such as, it is widely used in the removal of the pollutants such as heavy metal in environment, chlorinatedorganic.In recent ten years, people is studied
Member does a lot of work in terms of NZVI degraded environmental contaminants, it was confirmed that NZVI is as reducing agent and catalyst to a variety of common
Pollutant, which has, preferably to be removed or conversion capability, and organic matter such as halide, nitrobenzene and halogenation phenol etc., inorganic matter include a huge sum of money
Belong to ion, nitrate and high chromic acid content root etc..Wherein chlorinated organics include chlorinated aliphatic hydrocarbon, Polychlorinated biphenyls, chlorophenol and containing chlorbenside
Worm agent etc. is the organic matter of current pollution most serious, and quite a few is listed in Environment Priority control pollutant, its to soil and
The pollution of water body environment has obtained the extensive attention of environmental worker.
But, because NZVI particles are common by magnetostatic power (Van der Waals force) and surface tension between magnetic force, little particle etc.
With influence, bigger particle is easily agglomerated into, causes reactivity to decline, and with the progress of reaction, NZVI surfaces can be deposited
Oxides-containing iron or hydroxide, form passivation layer, suppress NZVI corrosion and covering reactivity site.Therefore, it is how right
NZVI stabilizes to prevent it from reuniting, be passivated and being easy to recovery etc. to be recent study hotspot.It is related in order to eliminate above-mentioned influence
The researcher in field has attempted many effective method of modifying, wherein, have to use and bear Nanoscale Iron or iron-based bimetallic
It is loaded in organic or inorganic carrier, such as Chinese patent application (publication number：CN103100721A) disclose a kind of modified Nano palladium/
The preparation method of iron double metal particle, this method includes coordinating polymethyl methacrylate common to nanometer by adding ethanol
Palladium/iron particle is modified to realize, it improves the performance of product to a certain extent, can also make to reach preferably scattered
Property, however, the addition of these polymethyl methacrylates, although, the reunion of Nanoscale Iron can be prevented, but it can also occupy nanometer
The surface of iron, while adding for these materials can increase processing cost, and may cause secondary pollution.
The content of the invention
The present invention is multiple there is provided a kind of stabilizing activity charcoal/nanoscale Pd/Fe for defect present in above prior art
It is that the dispersiveness for how improving nanoscale Pd/Fe composite particles makes with less to close the problem of preparation method of particle, solution
Particle diameter and the specific surface area for improving particle.
The purpose of the present invention technical scheme is that, a kind of stabilizing activity charcoal/nanoscale Pd/Fe
The preparation method of composite particles, this method comprises the following steps：
A, under inert gas shielding, make soluble ferrite in the boron hydride of alkali metal and the condition of ul-trasonic irradiation
Descend and stir to be reacted, make the Fe in reaction system2+Change into nanoscale zero-valent iron particle；Soluble palladium salt is added to continue
Reacted, obtain the reaction solution containing nanoscale Pd/Fe particles；The frequency of the ultrasonic wave is 20KHz~100KHz；
B, add activated carbon granule in the above-mentioned reaction solution containing nanoscale Pd/Fe particles, then frequency be 20KHz~
Stirring carries out load-reaction under 100KHz ul-trasonic irradiation, obtains stabilizing activity charcoal/nanoscale Pd/Fe composite particles.
The preparation method of stabilizing activity charcoal of the present invention/nanoscale Pd/Fe composite particles, by making the frequency of ultrasonic wave exist
20KHz~100KHz, shows as pyrolytic, effect of scattered and shearing-crushing etc. using its frequency characteristic, acts on these
Power puts on solid-liquid surface, so that the influence of the form to the surface of solids, composition, structure and chemical reactivity is shown as,
The nanoscale zero-valent iron particle and palladium particle of generation is set to be respectively provided with preferably dispersiveness and surface-active, meanwhile, by making reaction
During the frequency of control ultrasonic wave also for destroying magnetic force between the particle and particle of nanoscale zero-valent iron particle and palladium particle
Effect, realizes the benefit for reducing agglomeration.Then, add activated carbon granule (GAC) and carried out in the effect of ultrasonic wave, energy
Enough make the nanoscale zero-valent iron particle and palladium of generation are evengranular to be supported on the surface of activated carbon granule, so as to be effectively improved
The mineralogical characteristic of GAC/ nanoscale bimetallic Zero-valent Iron composite particles, also achieves the work that its fully dispersed and reduction is reunited
With making the composite particles prepared have that particle diameter is smaller, specific surface area is bigger, with more high reaction activity and be easy to what is reclaimed
Effect.On the other hand, the present invention by the way that nanoscale Pd/Fe composite particles are first made, add activated carbon and loaded, can
Nanoscale Pd and Fe is sufficiently supported in activated carbon surface and hole, improve the reactivity of composite particles, there is utilization again
Improve dispersiveness.And if being directly added into activated carbon in the course of reaction for preparing nanoscale Pd or Fe, it is easy to make ferrous salt and
The ionic adsorption of palladium salt on the activated carbon, is unfavorable for the progress of reaction, is also easy to destroy the pore structure of activated carbon surface, can shadow
The specific surface area of particle surface is rung, is unfavorable for follow-up nanoscale Pd and Fe and effectively loads.And by making in whole course of reaction
Carried out under the protection of inert gas, in order to prevent the metallic particles of generation to be oxidized and influence the active and whole of product
Body yield.
In the preparation method of above-mentioned stabilizing activity charcoal/nanoscale Pd/Fe composite particles, preferably, institute in step A
State one or more of the soluble ferrite selected from frerrous chloride, ferrous sulfate, ferrous nitrate and ammonium sulfate in ferrous；The palladium
Salt is K2PdCl6.Certainly it can also be palladium bichloride raw material.These raw materials have soluble good, the advantage being readily obtained, and use
Above-mentioned ferrous salt and palladium salt can more effectively be reduced to corresponding nanoscale zero-valent iron particle and palladium particle.
In the preparation method of above-mentioned stabilizing activity charcoal/nanoscale Pd/Fe composite particles, preferably, described solvable
Property palladium salt and soluble ferrite mol ratio be 1：200~4000.Why using so big mol ratio, it is therefore an objective to reach
Using extraction and nanometer iron metal as bulk composition, metal Pd particle can be enable preferably to crystallize in nanoscale zero-valent iron particle
Surface, realizes that Pd/Fe's is effectively compound.It is used as further preferred, the mol ratio of the soluble palladium salt and soluble ferrite
For 1：500~1000.
In the preparation method of above-mentioned stabilizing activity charcoal/nanoscale Pd/Fe composite particles, preferably, institute in step A
The boron hydride for stating alkali metal is selected from potassium borohydride or sodium borohydride.Effect with reproducibility by force, preferably makes ferrous ion
The effect of corresponding Zero-valent Iron and palladium particle is reduced to palladium.
In the preparation method of above-mentioned stabilizing activity charcoal/nanoscale Pd/Fe composite particles, preferably, step A and step
The frequency of ultrasonic wave is 60KHz~80KHz described in rapid B；The power of the ultrasonic wave is 100~150W.By using ultrasound
The frequency characteristic and energy response of ripple, on the one hand, can make the Zero-valent Iron to be formed and palladium particle that there is more preferable dispersion effect, make
Palladium particle forms knot circle on the surface of zero-valent iron particle, so as to form Pd/Fe composite particles；On the other hand, it can make what is formed
The compound surfaces for being more effectively supported on activated carbon granule of Pd/Fe, preferably realize and reach static stabilization, be not easy to by oxygen
Change, and the specific surface area of particle is bigger, particle diameter is also smaller.
In the preparation method of above-mentioned stabilizing activity charcoal/nanoscale Pd/Fe composite particles, preferably, institute in step B
The mol ratio for stating activated carbon granule and soluble ferrite is 1：40~70.The activity in unit grain can more effectively be improved
Ability, improves the activity of unit grain.
In the preparation method of above-mentioned stabilizing activity charcoal/nanoscale Pd/Fe composite particles, preferably, institute in step B
The particle diameter for stating activated carbon granule is 20~30 mesh.By controlling the particle diameter of activated carbon granule, it can preferably make nanoscale Pd/Fe
It is composite particle-loaded on its surface, meanwhile, be also beneficial to ensure absorption validity.
In the preparation method of above-mentioned stabilizing activity charcoal/nanoscale Pd/Fe composite particles, preferably, institute in step A
The temperature for stating reaction is 20 DEG C~30 DEG C；The temperature of load-reaction described in step B is 20 DEG C~30 DEG C.With reaction condition temperature
With, it is easy to the effect of control.
In the preparation method of above-mentioned stabilizing activity charcoal/nanoscale Pd/Fe composite particles, preferably, institute in step B
The composite particles for stating stabilizing activity charcoal/nanoscale Pd/Fe are stored in alcoholic solvent.It ensure that the not oxidized effect of product
Really.As further preferably, the alcoholic solvent is selected from ethanol, propyl alcohol or methanol.
In summary, the present invention compared with prior art, with advantages below：
The preparation method of stabilizing activity charcoal of the present invention/nanoscale Pd/Fe composite particles, is 20KHz by using frequency
~100KHz ul-trasonic irradiation, makes the composite particles to be formed have particle diameter small, the big effect of specific surface area；Meanwhile, by adopting
With activated carbon as support materials and in combination with ul-trasonic irradiation, nanoscale Pd/Fe is set more effectively to disperse to be supported on
The surface of activated carbon particles, with dispersed uniform effect.
Brief description of the drawings
Fig. 1 is the TEM (transmissions of the stabilizing activity charcoal/nanoscale Pd/Fe composite particles obtained in the embodiment of the present invention 1
Electron microscope) test chart.
Fig. 2 is the EDX (X-rays of the stabilizing activity charcoal/nanoscale Pd/Fe composite particles obtained in the embodiment of the present invention 1
Electron spectrometer) test chart.
Embodiment
Below by specific embodiment, technical scheme is described in further detail, but the present invention is simultaneously
It is not limited to these embodiments.
Embodiment 1
It is 0.25molL by concentration under the protection of inert nitrogen gas-1FeSO4·7H2O aqueous solution 200mL is added
In 500mL three-necked flask, then, control temperature is under conditions of 30 DEG C, and in ultrasonic wave, (frequency is 40KHz, and power is
150W) act on lower and carry out lasting stirring, be 0.50molL by 200mL concentration-1NaBH4The aqueous solution is added drop-wise to above-mentioned dropwise
It is 20 DEG C~30 DEG C that temperature is controlled in solution, during dropwise addition, and makes time for adding control in 10min, and completion of dropping is follow-up
Continuous control temperature carries out reaction 10min under conditions of 30 DEG C, makes the Fe in reaction system2+Change into nanoscale zero-valent abrasive grit
Son, obtains nanoscale zero-valent iron particle, and control rate of addition is conducive to the generation of nanoscale zero-valent iron particle；Then, directly exist
It is 0.005molL that 26.8mL concentration is added in above-mentioned reaction solution-1K2PdCl6The aqueous solution is stirred and in ultrasonic wave (frequency
Rate is 40KHz, and power is 150W) in the presence of react, and controlling reaction temperature be 30 DEG C, until making the color of solution by reddish brown
When color is changed into light green completely, reaction terminates, and obtains the reaction solution containing nanoscale Pd/Fe particles；Then, above-mentioned freshly prepared
The reaction solution containing nanoscale Pd/Fe particles in add activated carbon (GAC) particle of a diameter of 20 mesh of 0.1g, and in ultrasonic wave
(frequency is 40KHz, and power is 150W) acts on and continues stirring reaction 120min, after reaction terminates, and obtains stabilizing
GAC/ nanoscale Pd/Fe composite particles, can select obtained compound of stabilisation GAC/ nanoscales Pd/Fe using magnetic method
Grain, is first fully washed with the anaerobic deionized water of certain volume, after then fully being washed using absolute ethyl alcohol, is used in washing process
To anaerobic deionized water and the consumption of absolute ethyl alcohol can be adjusted according to the situation of washing, it is not specific to limit,
Obtained stabilisation GAC/ nanoscale Pd/Fe composite particles are stored in absolute ethyl alcohol, obtained composite particles do not occur
Agglomeration, good dispersion.Obtained stabilisation GAC/ nanoscale Pd/Fe composite particles are carried out to related test, specifically
Test result is as follows：
TEM test results show：Particle is uniformly distributed, and particle size range is in 55nm~80nm or so, average grain diameter 65nm, root
Fe surface compositions are analyzed according to grain boundary structure, TEM spectrograms are amplified step by step, it was observed that metal Pd grain boundary structure is clear at Fe surfaces
Chu Mingxian, using Gatan Digitalmicrograph software processings, obtains crystal boundary spacing for 0.02261nm, with metal Pd
(1110) crystal face (0.2249nm) diffraction is corresponding, and it is metal Pd to illustrate the crystalline material at Fe surfaces.
EDX test result shows to occur in energy spectrum diagram the diffraction maximum of corresponding C and metal Pd.
BET test results show that it is 45m to stabilize GAC/ nanoscale Pd/Fe composite particles specific surface area2/g。
Embodiment 2
It is 0.25molL by concentration under the protection of inert gas argon gas-1Ferrous chloride aqueous solution 200mL is added
In 500mL three-necked flask, then, control temperature is under conditions of 30 DEG C, and in ultrasonic wave, (frequency is 20KHz, and power is
100W) act on lower and carry out lasting stirring, be 1.0molL by 200mL concentration-1KBH4The aqueous solution is added drop-wise to above-mentioned molten dropwise
It is 20 DEG C~30 DEG C that temperature is controlled in liquid, during dropwise addition, and makes time for adding control in 10min, is continued after completion of dropping
Control temperature carries out reaction 10min under conditions of 25 DEG C, makes the Fe in reaction system2+Nanoscale zero-valent iron particle is changed into,
Nanoscale zero-valent iron particle is obtained, control rate of addition is conducive to the generation of nanoscale zero-valent iron particle；Then, directly above-mentioned
It is 0.005molL that 50mL concentration is added in reaction solution-1K2PdCl6The aqueous solution is stirred and (frequency is in ultrasonic wave
60KHz, power is 100W) in the presence of react, and controlling reaction temperature be 25 DEG C, until making the color of solution complete by rufous
When being changed into light green entirely, reaction terminates, and obtains the reaction solution containing nanoscale Pd/Fe particles；Then, freshly prepd contain above-mentioned
There is activated carbon (GAC) particle that a diameter of 30 mesh of 0.1g is added in the reaction solution of nanoscale Pd/Fe particles, and in ultrasonic wave (frequency
Rate is 20KHz, and power is 150W) act on and continue stirring reaction 120min, after reaction terminates, obtain stabilizing GAC/
Nanoscale Pd/Fe composite particles, can select obtained stabilisation GAC/ nanoscale Pd/Fe composite particles, first using magnetic method
Fully washed, after then fully being washed using absolute ethyl alcohol, used in washing process with the anaerobic deionized water of certain volume
The consumption of anaerobic deionized water and absolute ethyl alcohol can be adjusted according to the situation of washing, not specific to limit, will
To stabilisation GAC/ nanoscale Pd/Fe composite particles be stored in anhydrous propyl alcohol, obtained composite particles are not reunited
Phenomenon, good dispersion.Obtained stabilisation GAC/ nanoscale Pd/Fe composite particles are carried out to related test, specific test
As a result it is as follows：
TEM test results show：Particle is uniformly distributed, particle size range in 58~85nm or so, average grain diameter 68nm, according to
Grain boundary structure analyzes Fe surface compositions, TEM spectrograms is amplified step by step, it was observed that metal Pd grain boundary structure understands at Fe surfaces
Substantially, using Gatan Digitalmicrograph software processings, crystal boundary spacing is obtained for 0.02261nm, with metal Pd
(1110) crystal face (0.2249nm) diffraction is corresponding, and crystalline material is metal Pd.
EDX test result shows：The corresponding C of energy spectrum diagram appearance and metal Pd diffraction maximum.
BET test results show：Nanoscale Pd/Fe specific grain surfaces prepared by intensified by ultrasonic wave liquid phase reduction are accumulated
41m2/g。
Embodiment 3
It is 0.25molL by concentration under the protection of inert nitrogen gas-1Ferrous sulfate aqueous ammonium 200mL is added
In 500mL three-necked flask, then, control temperature is under conditions of 30 DEG C, and in ultrasonic wave, (frequency is 80KHz, and power is
150W) act on lower and carry out lasting stirring, be 0.75molL by 200mL concentration-1NaBH4The aqueous solution is added drop-wise to above-mentioned dropwise
It is 20 DEG C~30 DEG C that temperature is controlled in solution, during dropwise addition, and makes time for adding control in 10min, and completion of dropping is follow-up
Continuous control temperature carries out reaction 10min under conditions of 30 DEG C, makes the Fe in reaction system2+Change into nanoscale zero-valent abrasive grit
Son, obtains nanoscale zero-valent iron particle, and control rate of addition is conducive to the generation of nanoscale zero-valent iron particle；Then, directly exist
It is 0.005molL that 10mL concentration is added in above-mentioned reaction solution-1K2PdCl6The aqueous solution is stirred and in ultrasonic wave (frequency
For 80KHz, power is 150W) in the presence of react, and controlling reaction temperature be 30 DEG C, until making the color of solution by rufous
When being changed into light green completely, reaction terminates, and obtains the reaction solution containing nanoscale Pd/Fe particles；Then, above-mentioned freshly prepd
Activated carbon (GAC) particle of a diameter of 25 mesh of 0.1g is added in reaction solution containing nanoscale Pd/Fe particles, and in ultrasonic wave
(frequency is 80KHz, and power is 150W) acts on and continues stirring reaction 120min, after reaction terminates, and obtains stabilizing
GAC/ nanoscale Pd/Fe composite particles, can select obtained compound of stabilisation GAC/ nanoscales Pd/Fe using magnetic method
Grain, is first fully washed with the anaerobic deionized water of certain volume, after then fully being washed using absolute ethyl alcohol, is used in washing process
To anaerobic deionized water and the consumption of absolute ethyl alcohol can be adjusted according to the situation of washing, it is not specific to limit,
Obtained stabilisation GAC/ nanoscale Pd/Fe composite particles are stored in absolute ethyl alcohol, obtained composite particles do not occur
Agglomeration, good dispersion.Obtained stabilisation GAC/ nanoscale Pd/Fe composite particles are carried out to related test, specifically
Test result is as follows：
TEM test results show：Pd/Fe composite particles are uniformly distributed, and particle size range is in 20~35nm or so, average grain diameter
28nm, analyzes Fe surface compositions according to grain boundary structure, TEM spectrograms is amplified step by step, it was observed that metal Pd is brilliant at Fe surfaces
Boundary's structure becomes apparent from, using Gatan Digitalmicrograph software processings, obtains crystal boundary spacing for 0.02261nm, with
Metal Pd (1110) crystal face (0.2249nm) diffraction is corresponding, and crystalline material is metal Pd.
EDX test result shows：The corresponding C of energy spectrum diagram appearance and metal Pd diffraction maximum.
BET test results show：Compound of stabilisation GAC/ nanoscales Pd/Fe prepared by intensified by ultrasonic wave liquid phase reduction
Grain specific surface area is 103m2/g。
Embodiment 4
It is 0.25molL by concentration under the protection of inert nitrogen gas-1FeSO4·7H2O aqueous solution 200mL is added
In 500mL three-necked flask, then, control temperature is under conditions of 28 DEG C, and in ultrasonic wave, (frequency is 100KHz, and power is
250W) act on lower and carry out lasting stirring, be 0.5molL by 200mL concentration-1KBH4The aqueous solution is added drop-wise to above-mentioned molten dropwise
It is 25 DEG C~30 DEG C that temperature is controlled in liquid, during dropwise addition, and makes time for adding control in 10min, is continued after completion of dropping
Control temperature carries out reaction 10min under conditions of 28 DEG C, makes the Fe in reaction system2+Nanoscale zero-valent iron particle is changed into,
Nanoscale zero-valent iron particle is obtained, control rate of addition is conducive to the generation of nanoscale zero-valent iron particle；Then, directly above-mentioned
It is 0.005molL that 37.5mL concentration is added in reaction solution-1K2PdCl6The aqueous solution is stirred and (frequency is in ultrasonic wave
100KHz, power is 250W) in the presence of react, and controlling reaction temperature be 25 DEG C, until making the color of solution by rufous
When being changed into light green completely, reaction terminates, and obtains the reaction solution containing nanoscale Pd/Fe particles；Then, above-mentioned freshly prepd
Activated carbon (GAC) particle of a diameter of 30 mesh of 0.1g is added in reaction solution containing nanoscale Pd/Fe particles, and in ultrasonic wave
(frequency is 100KHz, and power is 250W) acts on and continues stirring reaction 100min, after reaction terminates, and obtains stabilizing
GAC/ nanoscale Pd/Fe composite particles, can select obtained compound of stabilisation GAC/ nanoscales Pd/Fe using magnetic method
Grain, is first fully washed with the anaerobic deionized water of certain volume, after then fully being washed using absolute ethyl alcohol, is used in washing process
To anaerobic deionized water and the consumption of absolute ethyl alcohol can be adjusted according to the situation of washing, it is not specific to limit,
Obtained stabilisation GAC/ nanoscale Pd/Fe composite particles are stored in anhydrous propyl alcohol, obtained composite particles do not occur
Agglomeration, good dispersion.Obtained stabilisation GAC/ nanoscale Pd/Fe composite particles are carried out to related test, specifically
Test result is as follows：
TEM test results show：Pd/Fe composite particles are uniformly distributed, and particle size range is in 63~100nm or so, average grain
Footpath 87nm, analyzes Fe surface compositions according to grain boundary structure, TEM spectrograms is amplified step by step, it was observed that metal Pd at Fe surfaces
Grain boundary structure becomes apparent from, using Gatan Digitalmicrograph software processings, obtains crystal boundary spacing for 0.02261nm,
Corresponding with metal Pd (1110) crystal face (0.2249nm) diffraction, crystalline material is metal Pd.
EDX test result shows：The corresponding C of energy spectrum diagram appearance and metal Pd diffraction maximum.
BET test results show：Compound of stabilisation GAC/ nanoscales Pd/Fe prepared by intensified by ultrasonic wave liquid phase reduction
Grain specific surface area is 51.2m2/g。
Embodiment 5
It is 0.25molL by concentration under the protection of inert nitrogen gas-1FeSO4·7H2O aqueous solution 200mL is added
In 500mL three-necked flask, then, control temperature is under conditions of 22 DEG C, and in ultrasonic wave, (frequency is 90KHz, and power is
200W) act on lower and carry out lasting stirring, be 0.5molL by 200mL concentration-1NaBH4The aqueous solution is added drop-wise to above-mentioned dropwise
It is 20 DEG C~25 DEG C that temperature is controlled in solution, during dropwise addition, and makes time for adding control in 10min, and completion of dropping is follow-up
Continuous control temperature carries out reaction 10min under conditions of 25 DEG C, makes the Fe in reaction system2+Change into nanoscale zero-valent abrasive grit
Son, obtains nanoscale zero-valent iron particle, and control rate of addition is conducive to the generation of nanoscale zero-valent iron particle；Then, directly exist
It is 0.005molL that 5.0mL concentration is added in above-mentioned reaction solution-1K2PdCl6The aqueous solution is stirred and in ultrasonic wave (frequency
For 90KHz, power is 200W) in the presence of react, and controlling reaction temperature be 25 DEG C, until making the color of solution by rufous
When being changed into light green completely, reaction terminates, and obtains the reaction solution containing nanoscale Pd/Fe particles；Then, above-mentioned freshly prepd
Activated carbon (GAC) particle of a diameter of 20 mesh of 0.1g is added in reaction solution containing nanoscale Pd/Fe particles, and in ultrasonic wave
(frequency is 90KHz, and power is 200W) acts on and continues stirring reaction 100min, after reaction terminates, and obtains stabilizing
GAC/ nanoscale Pd/Fe composite particles, can select obtained compound of stabilisation GAC/ nanoscales Pd/Fe using magnetic method
Grain, is first fully washed with the anaerobic deionized water of certain volume, after then fully being washed using absolute ethyl alcohol, is used in washing process
To anaerobic deionized water and the consumption of absolute ethyl alcohol can be adjusted according to the situation of washing, it is not specific to limit,
Obtained stabilisation GAC/ nanoscale Pd/Fe composite particles are stored in anhydrous propyl alcohol, obtained composite particles do not occur
Agglomeration, good dispersion.Obtained stabilisation GAC/ nanoscale Pd/Fe composite particles are carried out to related test, specifically
Test result is as follows：
TEM test results show：Particle is uniformly distributed, particle size range in 25~35nm or so, average grain diameter 30nm, according to
Grain boundary structure analyzes Fe surface compositions, TEM spectrograms is amplified step by step, it was observed that metal Pd grain boundary structure understands at Fe surfaces
Substantially, using Gatan Digitalmicrograph software processings, crystal boundary spacing is obtained for 0.02261nm, with metal Pd
(1110) crystal face (0.2249nm) diffraction is corresponding, and crystalline material is metal Pd.
EDX test result shows：The corresponding C of energy spectrum diagram appearance and metal Pd diffraction maximum.
BET test results show：Compound of stabilisation GAC/ nanoscales Pd/Fe prepared by intensified by ultrasonic wave liquid phase reduction
Grain specific surface area is 104.3m2/g。
Embodiment 6
The specific preparation method be the same as Example 5 of the stabilisation GAC/ nanoscale Pd/Fe composite particles of the present embodiment is consistent, area
It is not only that, with raw material FeSO4·7H2It is 0.25molL by concentration on the basis of O-1FeSO4·7H2O aqueous solution 200mL is added
500mL three-necked flask, adds K2PdCl6The amount of the aqueous solution is with FeSO4·7H2O is defined, and makes FeSO4·7H2O and K2PdCl6's
Mol ratio is 4000：1, meanwhile, the frequency for making ultrasonic wave is 80KHz, and power is 200W, makes the activated carbon and FeSO of addition4·
7H2O mol ratio is 1：40, finally give stabilisation and stabilize GAC/ nanoscale Pd/Fe composite particles, magnetic method can be used
Obtained stabilisation GAC/ nanoscale Pd/Fe composite particles are selected, are first fully washed with the anaerobic deionized water of certain volume, so
After fully being washed using absolute ethyl alcohol afterwards, the anaerobic deionized water and the consumption of absolute ethyl alcohol used in washing process can bases
The situation of washing is adjusted, not specific to limit, and obtained stabilisation GAC/ nanoscale Pd/Fe composite particles are preserved
In anhydrous propyl alcohol, there is not agglomeration, good dispersion in obtained composite particles.By obtained stabilisation GAC/ nanoscales
Pd/Fe composite particles carry out related test, and specific test result is as follows：
TEM test results show：Particle is uniformly distributed, particle size range in 21~37nm or so, average grain diameter 31nm, according to
Grain boundary structure analyzes Fe surface compositions, TEM spectrograms is amplified step by step, it was observed that metal Pd grain boundary structure understands at Fe surfaces
Substantially, using Gatan Digitalmicrograph software processings, crystal boundary spacing is obtained for 0.02261nm, with metal Pd
(1110) crystal face (0.2249nm) diffraction is corresponding, and crystalline material is metal Pd.
EDX test result shows：The corresponding C of energy spectrum diagram appearance and metal Pd diffraction maximum.
BET test results show：Compound of stabilisation GAC/ nanoscales Pd/Fe prepared by intensified by ultrasonic wave liquid phase reduction
Grain specific surface area is 95.6m2/g。
Embodiment 7
The specific preparation method be the same as Example 5 of the stabilisation GAC/ nanoscale Pd/Fe composite particles of the present embodiment is consistent, area
It is not only that, with raw material FeSO4·7H2It is 0.25molL by concentration on the basis of O-1FeSO4·7H2O aqueous solution 200mL is added
500mL three-necked flask, adds K2PdCl6The amount of the aqueous solution is with FeSO4·7H2O is defined, and makes FeSO4·7H2O and K2PdCl6's
Mol ratio is 2000：1, meanwhile, the frequency for making ultrasonic wave is 80KHz, and power is 200W, makes the activated carbon and FeSO of addition4·
7H2O mol ratio is 1：70, finally give stabilisation and stabilize GAC/ nanoscale Pd/Fe composite particles, magnetic method can be used
Obtained stabilisation GAC/ nanoscale Pd/Fe composite particles are selected, are first fully washed with the anaerobic deionized water of certain volume, so
After fully being washed using absolute ethyl alcohol afterwards, the anaerobic deionized water and the consumption of absolute ethyl alcohol used in washing process can bases
The situation of washing is adjusted, not specific to limit, and obtained stabilisation GAC/ nanoscale Pd/Fe composite particles are preserved
In anhydrous propyl alcohol, there is not agglomeration, good dispersion in obtained composite particles.By obtained stabilisation GAC/ nanoscales
Pd/Fe composite particles carry out related test, and specific test result is as follows：
TEM test results show：Particle is uniformly distributed, particle size range in 28~40nm or so, average grain diameter 34nm, according to
Grain boundary structure analyzes Fe surface compositions, TEM spectrograms is amplified step by step, it was observed that metal Pd grain boundary structure understands at Fe surfaces
Substantially, using Gatan Digitalmicrograph software processings, crystal boundary spacing is obtained for 0.02261nm, with metal Pd
(1110) crystal face (0.2249nm) diffraction is corresponding, and crystalline material is metal Pd.
EDX test result shows：The corresponding C of energy spectrum diagram appearance and metal Pd diffraction maximum.
BET test results show：Compound of stabilisation GAC/ nanoscales Pd/Fe prepared by intensified by ultrasonic wave liquid phase reduction
Grain specific surface area is 98.5m2/g。
Embodiment 8
The specific preparation method be the same as Example 5 of the stabilisation GAC/ nanoscale Pd/Fe composite particles of the present embodiment is consistent, area
It is not only that, with raw material FeSO4·7H2It is 0.25molL by concentration on the basis of O-1FeSO4·7H2O aqueous solution 200mL is added
500mL three-necked flask, adds K2PdCl6The amount of the aqueous solution is with FeSO4·7H2O is defined, and makes FeSO4·7H2O and K2PdCl6's
Mol ratio is 2000：1, meanwhile, the frequency for making ultrasonic wave is 100KHz, and power is 200W, makes the activated carbon and FeSO of addition4·
7H2O mol ratio is 1：50, finally give stabilisation and stabilize GAC/ nanoscale Pd/Fe composite particles, magnetic method can be used
Obtained stabilisation GAC/ nanoscale Pd/Fe composite particles are selected, are first fully washed with the anaerobic deionized water of certain volume, so
After fully being washed using absolute ethyl alcohol afterwards, the anaerobic deionized water and the consumption of absolute ethyl alcohol used in washing process can bases
The situation of washing is adjusted, not specific to limit, and obtained stabilisation GAC/ nanoscale Pd/Fe composite particles are preserved
In anhydrous propyl alcohol, there is not agglomeration, good dispersion in obtained composite particles.By obtained stabilisation GAC/ nanoscales
Pd/Fe composite particles carry out related test, and specific test result is as follows：
TEM test results show：Particle is uniformly distributed, and particle size range is in 80~155nm or so, average grain diameter 120nm, root
Fe surface compositions are analyzed according to grain boundary structure, TEM spectrograms are amplified step by step, it was observed that metal Pd grain boundary structure is clear at Fe surfaces
Chu Mingxian, using Gatan Digitalmicrograph software processings, obtains crystal boundary spacing for 0.02261nm, with metal Pd
(1110) crystal face (0.2249nm) diffraction is corresponding, and crystalline material is metal Pd.
EDX test result shows：The corresponding C of energy spectrum diagram appearance and metal Pd diffraction maximum.
BET test results show：Compound of stabilisation GAC/ nanoscales Pd/Fe prepared by intensified by ultrasonic wave liquid phase reduction
Grain specific surface area is 18m2/g。
Embodiment 9
The specific preparation method be the same as Example 8 of the stabilisation GAC/ nanoscale Pd/Fe composite particles of the present embodiment is consistent, area
It is not only that, is 0.25molL by concentration-1FeSO4·7H2O aqueous solution 200mL is substituted for 200mL FeSO4·7H2O and chlorine
Change ferrous mixed aqueous solution, and make FeSO in mixed aqueous solution4·7H2O concentration is 0.15molL-1, frerrous chloride it is dense
Spend for 0.1molL-1.Obtained stabilisation GAC/ nanoscale Pd/Fe composite particles.By obtained stabilisation GAC/ nanoscales
Pd/Fe composite particles carry out related test, and specific test result is as follows：
TEM test results show：Particle is uniformly distributed, and particle size range is in 86~148nm or so, average grain diameter 118nm, root
Fe surface compositions are analyzed according to grain boundary structure, TEM spectrograms are amplified step by step, it was observed that metal Pd grain boundary structure is clear at Fe surfaces
Chu Mingxian, using Gatan Digitalmicrograph software processings, obtains crystal boundary spacing for 0.02261nm, with metal Pd
(1110) crystal face (0.2249nm) diffraction is corresponding, and crystalline material is metal Pd.
EDX test result shows：The corresponding C of energy spectrum diagram appearance and metal Pd diffraction maximum.
BET test results show：Compound of stabilisation GAC/ nanoscales Pd/Fe prepared by intensified by ultrasonic wave liquid phase reduction
Grain specific surface area is 19m2/g。
Embodiment 10
The specific preparation method be the same as Example 5 of the stabilisation GAC/ nanoscale Pd/Fe composite particles of the present embodiment is consistent, area
It is not only that, is 0.25molL by concentration-1FeSO4·7H2O aqueous solution 200mL is substituted for 200mL ferrous nitrate and sulfuric acid
The mixed aqueous solution of ferrous ammonium, and make the concentration of ferrous nitrate in mixed aqueous solution for 0.12molL-1, iron ammonium sulfate it is dense
Spend for 0.13molL-1.Obtained stabilisation GAC/ nanoscale Pd/Fe composite particles.By obtained stabilisation GAC/ nanoscales
Pd/Fe composite particles carry out related test, and specific test result is as follows：
TEM test results show：Particle is uniformly distributed, particle size range in 24~36nm or so, average grain diameter 31nm, according to
Grain boundary structure analyzes Fe surface compositions, TEM spectrograms is amplified step by step, it was observed that metal Pd grain boundary structure understands at Fe surfaces
Substantially, using Gatan Digitalmicrograph software processings, crystal boundary spacing is obtained for 0.02261nm, with metal Pd
(1110) crystal face (0.2249nm) diffraction is corresponding, and crystalline material is metal Pd.
EDX test result shows：The corresponding C of energy spectrum diagram appearance and metal Pd diffraction maximum.
BET test results show：Compound of stabilisation GAC/ nanoscales Pd/Fe prepared by intensified by ultrasonic wave liquid phase reduction
Grain specific surface area is 105.1m2/g。
Comparative example 1
It is 0.25molL by concentration under the protection of inert nitrogen gas-1FeSO4·7H2O aqueous solution 200mL is added
In 500mL three-necked flask, then the activated carbon granule 0.1g of a diameter of 20 mesh is first added, then, bar of the control temperature at 30 DEG C
Under part, act on lower in ultrasonic wave (frequency is 40KHz, and power is 150W) and carry out lasting stirring, be by 200mL concentration
0.50mol·L-1NaBH4The aqueous solution is added drop-wise in above-mentioned solution dropwise, and it is 20 DEG C~30 DEG C that temperature is controlled during dropwise addition,
And make time for adding control continue to control temperature to carry out reaction 10min under conditions of 30 DEG C in 10min, after completion of dropping,
Make the Fe in reaction system2+Nanoscale zero-valent iron particle is changed into, nanoscale zero-valent iron particle is obtained, control rate of addition is favourable
In the generation of nanoscale zero-valent iron particle；Then, it is 0.005molL that 26.8mL concentration is added directly in above-mentioned reaction solution-1
K2PdCl6The aqueous solution is stirred and reacted in the presence of ultrasonic wave (frequency is 40KHz, and power is 150W), and controls anti-
It is 30 DEG C to answer temperature, and when the color for making solution is changed into light green completely from rufous, reaction terminates, and obtains being stabilized
GAC/ nanoscale Pd/Fe composite particles are stabilized, the obtained GAC/ nanoscales Pd/Fe that stabilizes can be selected using magnetic method and is answered
Particle is closed, is first fully washed with the anaerobic deionized water of certain volume, after then fully being washed using absolute ethyl alcohol, washing process
In the consumption of the anaerobic deionized water used and absolute ethyl alcohol can be adjusted according to the situation of washing, not specific limit
It is fixed, obtained stabilisation GAC/ nanoscale Pd/Fe composite particles are stored in absolute ethyl alcohol, obtained composite particles are occurred in that
A small amount of agglomeration, dispersiveness is general.Obtained stabilisation GAC/ nanoscale Pd/Fe composite particles are carried out to related survey
Examination, specific test result is as follows：
TEM test results show：Particle is uniformly distributed, particle size range in 100~164nm or so, average grain diameter 135nm,
Fe surface compositions are analyzed according to grain boundary structure, TEM spectrograms amplified step by step, it was observed that metal Pd grain boundary structure at Fe surfaces
Become apparent from, using Gatan Digitalmicrograph software processings, crystal boundary spacing is obtained for 0.02261nm, with metal Pd
(1110) crystal face (0.2249nm) diffraction is corresponding, and crystalline material is metal Pd.
EDX test result shows：The corresponding C of energy spectrum diagram appearance and metal Pd diffraction maximum.
BET test results show：Compound of stabilisation GAC/ nanoscales Pd/Fe prepared by intensified by ultrasonic wave liquid phase reduction
Grain specific surface area is 20m2/g。
Comparative example 2
It is 0.25molL by concentration under the protection of inert nitrogen gas-1FeSO4·7H2O aqueous solution 200mL is added
In 500mL three-necked flask, then, control temperature is under conditions of 30 DEG C, and in ultrasonic wave, (frequency is 40KHz, and power is
150W) act on lower and carry out lasting stirring, be 0.50molL by 200mL concentration-1NaBH4The aqueous solution is added drop-wise to above-mentioned dropwise
It is 20 DEG C~30 DEG C that temperature is controlled in solution, during dropwise addition, and makes time for adding control in 10min, and completion of dropping is follow-up
Continuous control temperature carries out reaction 10min under conditions of 30 DEG C, makes the Fe in reaction system2+Change into nanoscale zero-valent abrasive grit
Son, obtains nanoscale zero-valent iron particle, and control rate of addition is conducive to the generation of nanoscale zero-valent iron particle；Then, then first add
It is 0.005molL to enter the activated carbon granule 0.1g of a diameter of 20 mesh and 26.8mL concentration is added in above-mentioned reaction solution-1's
K2PdCl6The aqueous solution is stirred and reacted in the presence of ultrasonic wave (frequency is 40KHz, and power is 150W), and controls reaction
Temperature is 30 DEG C, and when the color for making solution is changed into light green completely from rufous, reaction terminates, and obtains stabilizing surely
Surely change GAC/ nanoscale Pd/Fe composite particles, the obtained GAC/ nanoscales Pd/Fe that stabilizes can be selected using magnetic method and is combined
Particle, is first fully washed with the anaerobic deionized water of certain volume, after then fully being washed using absolute ethyl alcohol, in washing process
The anaerobic deionized water and the consumption of absolute ethyl alcohol used can be adjusted according to the situation of washing, not specific limit
It is fixed, obtained stabilisation GAC/ nanoscale Pd/Fe composite particles are stored in absolute ethyl alcohol, obtained composite particles are occurred in that
A small amount of agglomeration, dispersiveness is general.Obtained stabilisation GAC/ nanoscale Pd/Fe composite particles are carried out to related survey
Examination, specific test result is as follows：
TEM test results show：Particle is uniformly distributed, and particle size range is in 95~136nm or so, average grain diameter 114nm, root
Fe surface compositions are analyzed according to grain boundary structure, TEM spectrograms are amplified step by step, it was observed that metal Pd grain boundary structure is clear at Fe surfaces
Chu Mingxian, using Gatan Digitalmicrograph software processings, obtains crystal boundary spacing for 0.02261nm, with metal Pd
(1110) crystal face (0.2249nm) diffraction is corresponding, and crystalline material is metal Pd.
EDX test result shows：The corresponding C of energy spectrum diagram appearance and metal Pd diffraction maximum.
BET test results show：Compound of stabilisation GAC/ nanoscales Pd/Fe prepared by intensified by ultrasonic wave liquid phase reduction
Grain specific surface area is 22m2/g。
Specific embodiment described in the present invention is only to spirit explanation for example of the invention.Technology neck belonging to of the invention
The technical staff in domain can be made various modifications or supplement to described specific embodiment or be replaced using similar mode
Generation, but without departing from the spiritual of the present invention or surmount scope defined in appended claims.
It is skilled to this area although having been made a detailed description to the present invention and being cited some specific embodiments
For technical staff, as long as it is obvious that can make various changes or correct without departing from the spirit and scope of the present invention.
Claims (10)
1. a kind of preparation method of stabilizing activity charcoal/nanoscale Pd/Fe composite particles, it is characterised in that this method include with
Lower step：
A, under inert gas shielding, make soluble ferrite under conditions of the boron hydride and ul-trasonic irradiation of alkali metal simultaneously
Stirring is reacted, and makes the Fe in reaction system2+Change into nanoscale zero-valent iron particle；Soluble palladium salt is added to proceed
Reaction, obtains the reaction solution containing nanoscale Pd/Fe particles；The frequency of the ultrasonic wave is 20KHz~100KHz；
B, add activated carbon granule in the above-mentioned reaction solution containing nanoscale Pd/Fe particles, then frequency be 20KHz~
Stirring carries out load-reaction under 100KHz ul-trasonic irradiation, obtains stabilizing activity charcoal/nanoscale Pd/Fe composite particles.
2. the preparation method of stabilizing activity charcoal/nanoscale Pd/Fe composite particles according to claim 1, it is characterised in that
The one kind or several of soluble ferrite described in step A in frerrous chloride, ferrous sulfate, ferrous nitrate and iron ammonium sulfate
Kind；The palladium salt is K2PdCl6。
3. the preparation method of stabilizing activity charcoal according to claim 1 or claim 2/nanoscale Pd/Fe composite particles, its feature exists
In the mol ratio of soluble palladium salt and soluble ferrite is 1 described in step A：200~4000.
4. the preparation method of stabilizing activity charcoal according to claim 1 or claim 2/nanoscale Pd/Fe composite particles, its feature exists
In the boron hydride of alkali metal described in step A is selected from potassium borohydride or sodium borohydride.
5. the preparation method of stabilizing activity charcoal/nanoscale Pd/Fe composite particles according to claim 1, it is characterised in that
The frequency of ultrasonic wave described in step A and step B is 60KHz~90KHz；The power of the ultrasonic wave is 100~250W.
6. the preparation method of stabilizing activity charcoal/nanoscale Pd/Fe composite particles according to claim 1 or 2 or 5, it is special
Levy and be, the mol ratio of activated carbon granule and soluble ferrite described in step B is 1：40~70.
7. the preparation method of stabilizing activity charcoal/nanoscale Pd/Fe composite particles according to claim 1, it is characterised in that
The particle diameter of activated carbon granule described in step B is 20~30 mesh.
8. the preparation method of stabilizing activity charcoal/nanoscale Pd/Fe composite particles according to claim 1, it is characterised in that
The temperature reacted described in step A is 20 DEG C~30 DEG C；The temperature of load-reaction described in step B is 20 DEG C~30 DEG C.
9. the preparation method of stabilizing activity charcoal/nanoscale Pd/Fe composite particles according to claim 1, it is characterised in that
Stabilizing activity charcoal described in step B/nanoscale Pd/Fe composite is stored in alcoholic solvent.
10. the preparation method of stabilizing activity charcoal/nanoscale Pd/Fe composite particles according to claim 9, its feature exists
In the alcoholic solvent is selected from ethanol, propyl alcohol or methanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610284705.XA CN105728744B (en) | 2016-04-29 | 2016-04-29 | A kind of preparation method of stabilizing activity charcoal/nanoscale Pd/Fe composite particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610284705.XA CN105728744B (en) | 2016-04-29 | 2016-04-29 | A kind of preparation method of stabilizing activity charcoal/nanoscale Pd/Fe composite particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105728744A CN105728744A (en) | 2016-07-06 |
| CN105728744B true CN105728744B (en) | 2017-11-07 |
Family
ID=56287943
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610284705.XA Expired - Fee Related CN105728744B (en) | 2016-04-29 | 2016-04-29 | A kind of preparation method of stabilizing activity charcoal/nanoscale Pd/Fe composite particles |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105728744B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106180747B (en) * | 2016-07-07 | 2019-01-22 | 王荔 | A kind of palladium copper binary alloy nano material, preparation method and its CO is restored as catalyst electro-catalysis2Application |
| CN107008919A (en) * | 2017-03-07 | 2017-08-04 | 沈阳化工大学 | A kind of manganese dioxide load nano nickel iron double metal functional material preparation method |
| CN106964197B (en) * | 2017-04-26 | 2019-11-19 | 吉林师范大学 | A kind of Supported On Granular Activated Carbon Nanoscale Iron composite filter element material and preparation method thereof |
| CN110605385B (en) * | 2019-10-29 | 2021-08-24 | 广东银纳科技有限公司 | Preparation method of tungsten-based micro-nano composite powder and tungsten-based micro-nano composite powder |
| CN113909472A (en) * | 2020-06-22 | 2022-01-11 | 中国石油化工股份有限公司 | Nano composite particle, preparation method and application thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101708457B (en) * | 2009-08-31 | 2012-02-08 | 清华大学 | Preparation method and application of activated carbon loaded nano-iron material |
| KR101190283B1 (en) * | 2012-03-22 | 2012-10-12 | 한국과학기술원 | Cu-promoter and pd-noble metal doping nzvi bimetallic catalyst and method of manufacturing the same |
| CN103100721A (en) * | 2013-01-23 | 2013-05-15 | 昆明理工大学 | Method for preparing modified nanometer-palladium/iron duplex-metal particles |
| CN103111306A (en) * | 2013-02-07 | 2013-05-22 | 浙江工业大学 | Magnetic load type nanometer palladium/iron grain catalyst and preparation method and application thereof |
| CN103084585A (en) * | 2013-02-19 | 2013-05-08 | 南开大学 | Preparation method of active carbon / vermiculite supported zero valent nano iron |
| CN104308181B (en) * | 2014-10-17 | 2017-01-11 | 浙江工业大学 | Method for preparing nanoscale zero-valent iron and nanoscale duplex metal Cu/Fe |
-
2016
- 2016-04-29 CN CN201610284705.XA patent/CN105728744B/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| Synthesis of Reactive Nano-Fe/Pd Bimetallic System-Impregnated Activated Carbon for the Simultaneous Adsorption and Dechlorination of PCBs;Hyeok Choi等;《Materials Chemistry》;20080705;第20卷(第11期);第3649-3655页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105728744A (en) | 2016-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105728744B (en) | A kind of preparation method of stabilizing activity charcoal/nanoscale Pd/Fe composite particles | |
| Wang et al. | Synergistic effect of PMS activation by Fe0@ Fe3O4 anchored on N, S, O co-doped carbon composite for degradation of sulfamethoxazole | |
| Liu et al. | A novel step-scheme BiVO4/Ag3VO4 photocatalyst for enhanced photocatalytic degradation activity under visible light irradiation | |
| Xu et al. | Heterogeneous activation of peroxymonosulfate by a biochar-supported Co3O4 composite for efficient degradation of chloramphenicols | |
| Tang et al. | Novel Z‐scheme In2S3/BiVO4 composites with improved visible-light photocatalytic performance and stability for glyphosate degradation | |
| Ji et al. | Catalytic activity of core–shell structured Cu/Fe3O4@ SiO2 microsphere catalysts | |
| Ren et al. | Boosting the activation of Peroxymonosulfate and the degradation of metronidazole over FeCo2O4 quantum dots anchored on β-FeOOH Nanosheets: Inspired from octahedral Co (II) with missing angle | |
| Dong et al. | Synthesis of g-C3N4/BiVO4 heterojunction composites for photocatalytic degradation of nonylphenol ethoxylate | |
| Boudjemaa et al. | Fe2O3/carbon spheres for efficient photo-catalytic hydrogen production from water and under visible light irradiation | |
| Wan et al. | Fenton-like degradation of sulfamethazine using Fe 3 O 4/Mn 3 O 4 nanocomposite catalyst: kinetics and catalytic mechanism | |
| Salari et al. | Fabrication of novel Fe2O3/MoO3/AgBr nanocomposites with enhanced photocatalytic activity under visible light irradiation for organic pollutant degradation | |
| Liu et al. | In-situ fabrication of ultrafine Pd supported on nitrogen-doped reduced graphene oxide via nitrogen glow discharge plasma for catalytic reduction of 4-Nitrophenol | |
| Sun et al. | Ag/g-C3N4 photocatalysts: microwave-assisted synthesis and enhanced visible-light photocatalytic activity | |
| Chen et al. | Magnetic recyclable lanthanum-nitrogen co-doped titania/strontium ferrite/diatomite heterojunction composite for enhanced visible-light-driven photocatalytic activity and recyclability | |
| CN107930629A (en) | The preparation method of support type charcoal catalysis material | |
| CN103706327B (en) | Three-dimensional graphite thiazolinyl nano metal composite, its preparation method and application | |
| Ma et al. | BiVO4 ternary photocatalyst co-modified with N-doped graphene nanodots and Ag nanoparticles for improved photocatalytic oxidation: A significant enhancement in photoinduced carrier separation and broad-spectrum light absorption | |
| Gupta et al. | Ag and CuO impregnated on Fe doped ZnO for bacterial inactivation under visible light | |
| Navadeepthy et al. | N-doped Graphene/ZnFe2O4: A novel nanocomposite for intrinsic peroxidase based sensing of H2O2 | |
| CN105338799A (en) | Nanocomposite made of magnetic-metal-doped multiwalled carbon nanotubes/tin dioxide | |
| Zhang et al. | Oxalated zero valent iron enables highly efficient heterogeneous Fenton reaction by self-adapting pH and accelerating proton cycle | |
| Wang et al. | Dechlorination of chloroacetic acids by Pd/Fe nanoparticles: Effect of drying method on metallic activity and the parameter optimization | |
| Gao et al. | Enhanced reductive degradation of tetrabromobisphenol A by biochar supported sulfidated nanoscale zero-valent iron: Selectivity and core reactivity | |
| CN106824195A (en) | Porous Fe3Co7The application of@C nanos ball and catalytic degradation organic pollution | |
| CN108816235A (en) | It is a kind of can magnetic recycling porous Ni@GCC composite material and preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171107 |