WO2012106854A1 - 一种调控金属纳米颗粒在树脂载体内分布的方法 - Google Patents
一种调控金属纳米颗粒在树脂载体内分布的方法 Download PDFInfo
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- WO2012106854A1 WO2012106854A1 PCT/CN2011/073595 CN2011073595W WO2012106854A1 WO 2012106854 A1 WO2012106854 A1 WO 2012106854A1 CN 2011073595 W CN2011073595 W CN 2011073595W WO 2012106854 A1 WO2012106854 A1 WO 2012106854A1
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- Prior art keywords
- resin
- distribution
- metal
- carrier
- regulating
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- 229920005989 resin Polymers 0.000 title claims abstract description 99
- 239000011347 resin Substances 0.000 title claims abstract description 99
- 238000009826 distribution Methods 0.000 title claims abstract description 34
- 239000002082 metal nanoparticle Substances 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000001105 regulatory effect Effects 0.000 title claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 150000001450 anions Chemical class 0.000 claims abstract description 8
- 230000035484 reaction time Effects 0.000 claims abstract description 7
- 238000001179 sorption measurement Methods 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000000524 functional group Chemical group 0.000 claims abstract description 4
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 4
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 32
- 230000008021 deposition Effects 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 12
- 239000002105 nanoparticle Substances 0.000 claims description 8
- 229920001429 chelating resin Polymers 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 101150003085 Pdcl gene Proteins 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- -1 metal complex anion Chemical class 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000005137 deposition process Methods 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 238000011946 reduction process Methods 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 125000001302 tertiary amino group Chemical group 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 abstract description 11
- 239000003513 alkali Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 19
- 238000001878 scanning electron micrograph Methods 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000000151 deposition Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229910021432 inorganic complex Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000003957 anion exchange resin Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 3
- 229940043267 rhodamine b Drugs 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 2
- 229910002668 Pd-Cu Inorganic materials 0.000 description 2
- 238000005349 anion exchange Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910003471 inorganic composite material Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- 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
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
- B01J41/14—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- 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
- B01J45/00—Ion-exchange in which a complex or a chelate is formed; Use of material as complex or chelate forming ion-exchangers; Treatment of material for improving the complex or chelate forming ion-exchange 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
- B01J47/00—Ion-exchange processes in general; Apparatus therefor
- B01J47/016—Modification or after-treatment of ion-exchangers
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1229—Composition of the substrate
- C23C18/1233—Organic substrates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1287—Process of deposition of the inorganic material with flow inducing means, e.g. ultrasonic
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1644—Composition of the substrate porous substrates
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
- C23C18/1658—Process features with two steps starting with metal deposition followed by addition of reducing agent
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
- C23C18/1664—Process features with additional means during the plating process
- C23C18/1666—Ultrasonics
Definitions
- the present invention relates to a method of regulating the distribution of metal nanoparticles in a resin carrier, and more particularly to a method for regulating the distribution of metal nanoparticles in a resin carrier by changing the diffusion properties of a reducing agent or a precipitating agent.
- Metal organic-inorganic composite materials have been widely used in environmental protection, chemical catalysis and other fields. At present, relevant researches mainly focus on the preparation methods, structural characterization and work performance of these new composite materials, but there are few reports on the relationship between structural regulation and performance. Some foreign researchers have studied the anion exchange resin and ⁇ -A1 2 3 immobilized Pd-Cu bimetallic composite catalyst to reduce nitrate. It is found that the lower partial pressure 3 ⁇ 4 reduced metal catalyst is mainly distributed on the periphery of the carrier, but reduced by NaBH 4 . The metal is evenly distributed throughout the carrier.
- the metal catalyst distributed in the periphery has high reactivity, high selectivity to product N 2 and less metal loss; uniform material has low activity, low selectivity to N 2 and high metal loss (Ga ⁇ parovicovd) , D, Krdlik, ⁇ ., Hronec, ⁇ ., et al., Reduction of nitrates dissolved in water over palladium-copper catalysts supported on a strong cationic resin. Journal of Molecular Catalysis A: Chemical 2006, 244, 258-266; GasparoviCovd, D., Krdlik, M., Hronec, M., et al., Supported Pd-Cu catalysts in the water phase reduction of nitrates: Functional resin versus alumina.
- Nanjing University applied for a patent for the preparation of a resin-based arsenic removal sorbent (ZL 200510095177.5), which immobilized hydrated iron oxide particles on the inner surface of an anion exchange resin.
- Nanjing University applied for “a zero-valent iron nanocomposite resin for catalytic degradation of pollutants and its preparation method” (application number: 200910028413.X; publication number: CN101474560), which is to solidify zero-valent iron nanoparticles. It is loaded onto a resin carrier having an anion exchange group.
- Nanjing University applied for an anion resin-based CdS composite material and its preparation method (application number: Instruction manual
- An object of the present invention is to provide a method for regulating the distribution of metal nanoparticles in a resin carrier, i.e., to regulate the distribution of metal nanoparticles in a resin carrier by changing the rate of reduction or deposition of the metal in the resin phase.
- the principle of the invention using a basic anion exchange resin as a carrier, introducing a metal inorganic complex anion such as FeCl 4 _, CdCl 4 2 ⁇ PdCl 4 2 _ by ion exchange, and fixing the nano metal particles with a depositing agent or a reducing agent among them.
- a metal inorganic complex anion such as FeCl 4 _, CdCl 4 2 ⁇ PdCl 4 2 _ by ion exchange
- a metal inorganic complex anion such as FeCl 4 _, CdCl 4 2 ⁇ PdCl 4 2 _ by ion exchange
- the invention intends to change the intensity contrast of the above two effects by controlling the diffusion property of the deposition agent or the reducing agent, thereby realizing the distribution regulation of the metal nanoparticles in the resin phase.
- a method for regulating the distribution of metal nanoparticles in a resin carrier the steps of which are:
- FeCl 4 CdCl 4 2 PdCl 4 2 - complex anion in aqueous solution is ion-exchanged by using an ion exchange resin or an adsorption resin having a basic functional group and a resin skeleton as a styrene or acrylic resin as a carrier. Introduced into the resin;
- the carrier resin in the step (A) is an ion exchange and adsorption resin having a basic functional group
- the resin skeleton is a styrene-based or acrylic-based resin
- the resin skeleton contains a tertiary amino group, a quaternary amino group or a basic heterocyclic group
- the resin The average pore size is between 1 and 100 nm.
- the carrier resin in the step (A) is D-201, D-30U DA-900, Amberlite IRA-900, Amberlite IRA-958, Amberlite I A-96, Purolite C-100, Purolite A500, WBR109, Instruction manual
- the concentration of the metal inorganic complex anion such as FeCl 4 _, CdCl 4 2 _, PdCl 4 2 _ in the step (A) is 0.1 to 2 mol/L in the aqueous solution, and the solid-liquid ratio of the resin carrier to the metal complex anion solution is 0.1 ⁇ 20g/L.
- the deposition agent in the step (B) includes NaOH, Na 2 S, etc.
- the reducing agent includes NaBH 4 , KBH 4 , etc.
- the concentration (% by mass) of the deposition agent and the reducing agent ranges from 0.5% to 10%
- the resin carrier and the content The solid solution ratio of the solution of the deposition agent or the reducing agent is 0.1 to 20 g/L.
- the reaction time in the step (B) is from 0.5 to 30 min, and the deposition or reduction process is carried out under ultrasonic vibration or stirring.
- the metal and its compounds in the step (B) include hydrated iron oxide, CdS, zero-valent iron, zero-valent palladium, and the like.
- the ratio of the thickness of the cyclic distribution of the metal and its compound nanoparticles in the step (B) on the resin carrier to the radius of the carrier resin is 5% to 100%.
- the invention provides a method for regulating the distribution of metal nanoparticles in a resin carrier, wherein the ring-shaped distribution thickness of the metal and its compound nanoparticles on the resin carrier can be artificially regulated, and the thickness and the carrier are The ratio of the radius of the resin may be 5% to 100%.
- This distribution of metal of different thicknesses has an important influence on the properties of the inorganic-organic composite (e.g., reactivity, reaction selectivity, metal stability, etc.).
- Metal composites with thinner thickness distribution are of great significance for the preparation of high performance composite photocatalysts; metal composites with thicker distribution thickness can often exhibit high chemical activity and fast reaction rate during redox reaction and adsorption separation. , metal loss and other advantages.
- Figure 1 is a scanning electron micrograph of the material prepared in Example 1;
- Figure 2 is a scanning electron micrograph of the material prepared in Example 2.
- Figure 3 is a scanning electron micrograph of the material prepared in Example 3.
- Figure 4 is a scanning electron micrograph of the material prepared in Example 4.
- Figure 5 is a scanning electron micrograph of the material prepared in Example 5.
- Figure 6 is a scanning electron micrograph of the material prepared in Example 6;
- Figure 7 is a scanning electron micrograph of the material prepared in Example 7.
- Figure 8 is a scanning electron micrograph of the material prepared in Example 8.
- Figure 9 is a scanning electron micrograph of the material prepared in Example 9. Detailed description of the specification
- This composite is capable of degrading 50 mL of a 20 mg/L Rhodamine B dye solution by 95% in 5 hours.
- This composite is capable of degrading 50 mL of a 20 mg/L Rhodamine B dye solution by 95% in 6 hours.
- the adsorption kinetics of this composite for a solution of As V) at a concentration of 60 mg/L can be balanced within 80 min, and the quasi-secondary rate constant is 0.00189 g/mg ⁇ min.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Description
说 明 书 一种调控金属纳米颗粒在树脂载体内分布的方法 技术领域
本发明涉及一种调控金属纳米颗粒在树脂载体内分布的方法，更具体的说是 一种通过改变还原剂或沉淀剂的扩散性能来调控金属纳米颗粒在树脂载体内分 布的方法。
背景技术
金属有机 -无机复合材料已广泛应用于环境保护、 化工催化等领域。 目前相 关研究主要侧重于这类新型复合材料的制备方法、结构表征与工作性能，而对其 结构调控及与性能之间的关系研究报道较少。国外有学者在研究阴离子交换树脂 和 γ -A1203固载 Pd-Cu双金属复合催化剂还原硝酸根时发现， 较低分压 ¾还原 的金属催化剂主要分布于载体外围， 而用 NaBH4还原的金属则均匀分布于整个 载体。 分布在外围的金属催化剂具有较高反应活性， 对产物 N2的选择性高， 金 属流失少;而均匀分布的材料活性较低， 对 N2的选择性低， 金属流失较多 (Ga§ parovicovd, D , Krdlik, Μ.， Hronec, Μ.， et al., Reduction of nitrates dissolved in water over palladium-copper catalysts supported on a strong cationic resin. Journal of Molecular Catalysis A: Chemical 2006, 244, 258-266; GasparoviCovd, D.， Krdlik, M., Hronec, M.， et al., Supported Pd-Cu catalysts in the water phase reduction of nitrates: Functional resin versus alumina. Journal of Molecular Catalysis A: Chemical 2007， 264, 93-102)。 另有研究者用蒙脱石作为模板和载体制备亚纳米级的 ZVI时也发 现， 随着 NaBH4/Fe(m)摩尔比的增加， ZVI的含量增加， 且硝基苯被还原为苯胺 的效率升高（Gu, C.， Jia, H. Z., Li, H., et al., Synthesis of highly reactive subnano-sized zero-valent iron using smectite clay templates. Environmental Science & Technology 2010, 44, 4258-4263)。
2005 年南京大学申请了 《一种树脂基除砷吸附剂的制备方法》 专利 （ZL 200510095177.5 ), 该专利是将水合氧化铁颗粒固载于阴离子交换树脂内表面。 2009年南京大学申请了 《一种催化降解污染物的载零价铁纳米复合树脂及其制 备方法》 （申请号： 200910028413.X; 公开号： CN101474560 ), 该专利是将零 价铁纳米颗粒固载到具有阴离子交换基团的树脂载体上。 2009年南京大学申请 了 《一种阴离子树脂基负载 CdS 复合材料及其制备方法》 （申请号：
说 明 书
200910232275.7； 公开号： CN101716525A), 该专利是将 CdS纳米颗粒固载到具 有阴离子交换基团的树脂载体上。这些成果均未阐述对无机金属颗粒分布的调控 方法及其对性能的影响。
发明内容
1、 发明要解决的技术问题
本发明的目的是提供一种调控金属纳米颗粒在树脂载体内分布的方法，亦即 通过改变金属在树脂相内的还原或沉积速度来调控金属纳米颗粒在树脂载体内 分布。
2、 技术方案
本发明的原理： 以碱性阴离子交换树脂为载体， 通过离子交换作用导入 FeCl4_、 CdCl4 2\ PdCl4 2_等金属无机络合阴离子， 并用沉积剂或还原剂将纳米金 属颗粒固定于其中。这一固定化过程中有两种作用同时进行。一是 FeC 、 CdCl4 2-、 PdCl4 2_等金属无机络合阴离子遇水水解， 金属易以阳离子的形式从载体上流失； 二是沉积或还原作用，这种作用可将金属及其化合物固定在载体上。本发明拟通 过调控沉积剂或还原剂的扩散性能来改变上述两种作用的强弱对比，从而实现金 属纳米颗粒在树脂相内的分布调控。沉积或还原作用的速度越快， 强度越高， 金 属及其化合物越能在载体树脂上获得较均匀的分布， 也即环状分布的厚度较大。
一种调控金属纳米颗粒在树脂载体内分布的方法， 其步骤为：
(A) 以具有碱性功能基团和树脂骨架为苯乙烯系或丙烯酸系的离子交换树 脂或吸附树脂为载体， 将水溶液中的 FeCl4 CdCl4 2 PdCl4 2—络合阴离子通过离 子交换作用导入树脂内；
(B ) 用沉积剂或者还原剂通过沉积或者还原反应将金属固定在树脂载体 上， 随着沉积剂或还原剂浓度的增加和反应时间的延长， 金属及其化合物纳米颗 粒在树脂载体上呈现由外到内的不同厚度与密度的环状分布。
步骤（A) 中的载体树脂为具有碱性功能基团的离子交换与吸附树脂， 树脂 骨架为苯乙烯系或丙烯酸系， 树脂骨架上含有叔氨基、 季氨基或碱性杂环基团， 树脂的平均孔径在 1-lOOnm之间。
步骤 （A) 中的载体树脂为 D-201、 D-30U DA-900, Amberlite IRA-900、 Amberlite IRA-958, Amberlite I A-96, Purolite C-100、 Purolite A500、 WBR109,
说 明 书
NDA-88或 NDA-99树脂。
步骤 （A) 中的 FeCl4_、 CdCl4 2_、 PdCl4 2_等金属无机络合阴离子在水溶液中 的浓度为 0.1〜2mol/L，树脂载体与金属络合阴离子溶液的固液比为 0.1〜20g/L。
步骤（B)中的沉积剂包括 NaOH、 Na2S等， 还原剂包括 NaBH4、 KBH4等， 沉积剂和还原剂的浓度 (；质量百分比)范围为 0.5%〜10%，树脂载体与含有沉积剂 或还原剂的溶液的固液比为 0.1〜20g/L。
步骤（B) 中的反应时间为 0.5〜30min， 沉积或者还原过程需在超声振荡或 者搅拌的条件下进行。
步骤（B) 中的金属及其化合物包括水合氧化铁、 CdS、 零价铁、 零价钯等。 步骤（B) 中的金属及其化合物纳米颗粒在树脂载体上呈现的环状分布的厚 度与载体树脂半径的比值为 5%〜100%。
3、 有益效果
本发明提供的一种调控金属纳米颗粒在树脂载体内分布的方法所制得复合 材料中，金属及其化合物纳米颗粒在树脂载体上呈现的环状分布厚度可以实现人 为调控， 这一厚度与载体树脂半径的比值可为 5%〜100%。这种不同厚度的金属 分布对于无机-有机复合材料的性能（如反应活性、 反应选择性、 金属稳定性等) 具有重要影响。具有较薄分布厚度的金属复合材料对于制备高性能复合光催化剂 具有重要意义；具有较厚分布厚度的金属复合材料在氧化还原反应及吸附分离等 过程中往往可表现出化学活性高、 反应速率快、 金属流失少等优点。
附图说明
图 1为实施例 1制备得到的材料的扫描电子显微图；
图 2为实施例 2制备得到的材料的扫描电子显微图；
图 3为实施例 3制备得到的材料的扫描电子显微图；
图 4为实施例 4制备得到的材料的扫描电子显微图；
图 5为实施例 5制备得到的材料的扫描电子显微图；
图 6为实施例 6制备得到的材料的扫描电子显微图；
图 7为实施例 7制备得到的材料的扫描电子显微图；
图 8为实施例 8制备得到的材料的扫描电子显微图；
图 9为实施例 9制备得到的材料的扫描电子显微图。
说 明 书 具体实施方式
以下通过实施例进一步说明本发明
实施例 1 :
将 5gD-201树脂加入 2m0l/L的 FeCl4_溶液中， 固液比为 10g/L。 振荡， 使 FeCl4_和树脂发生离子交换反应 4h，过滤。将浓度（重量百分比）为 0.9%的 NaBH4 或 KBH4溶液与之混合， 超声振荡下反应 15min， 然后用无氧水洗涤。 40°C下真 空干燥 24h。 制得的纳米零价铁分布在树脂载体外围， 其厚度占载体剖面半径的 25%左右。 此材料的扫描电子显微图片如图 1所示。
此复合材料在溶液初始 pH=2时还原 50mg/LNO3— -N的转化率为 40%， Fe的 流失率为 90%; pH=6时产物 NH4 +生成速率为 Ο.ΟΙΟηώι·1 。
实施例 2:
将 5gD-201树脂加入 2mol/L的 FeCl4_溶液中， 固液比为 10g/L。 振荡， 使 FeCl4_和树脂发生离子交换反应 4h， 过滤。 将浓度为 1.8%的 NaBH4或 KBH4溶 液与之混合， 超声振荡下反应 15min， 然后用无氧水洗涤。 40°C下真空干燥 24h。 制得的纳米零价铁分布在树脂载体外围，其厚度占载体剖面半径的 50%左右。此 材料的扫描电子显微图片如图 2所示。
此复合材料在溶液初始 pH=2时还原 50mg/LNO3_-N的转化率为 44%， Fe的 流失率为 76%; pH=6时产物 NH4 +生成速率为 0.018min—
实施例 3 :
将 5gD-201树脂加入 2mol/L的 FeCl4_溶液中， 固液比为 10g/L。 振荡， 使 FeCl4_ff树脂发生离子交换反应 4h， 过滤。 将浓度为 3.6%的 NaBH4或 KBH4溶 液与之混合， 超声振荡下反应 15min， 然后用无氧水洗涤。 40°C下真空干燥 24h。 制得的纳米零价铁分布在树脂载体外围，其厚度占载体剖面半径的 80%左右。此 材料的扫描电子显微图片如图 3所示。
此复合材料在溶液初始 pH=2时还原 50mg/LNO3_-N的转化率为 45%， Fe的 流失率为 73%; pH=6时产物 NH4 +生成速率为 O.C^lmin—
实施例 4:
将 5g D-201树脂加入 2mol/L的 FeCl4_溶液中， 固液比为 10g/L。 振荡， 使 FeCl4_和树脂发生离子交换反应 4h， 过滤。 将浓度为 7.2%的 NaBH4或 KBH4溶
说 明 书 液与之混合， 超声振荡下反应 15min， 然后用无氧水洗涤。 40Ό下真空干燥 24h。 制得的纳米零价铁均匀分布在树脂载体整个剖面， 其厚度占载体剖面半径的 100%。 此材料的扫描电子显微图片如图 4所示。
此复合材料在溶液初始 pH=2时还原 50mg/LNO3_-N的转化率为 49%, Fe的 流失率为 70%; pH=6时产物 NH4 +生成速率为 Ο.ί^^ώι·1 »
实施例 5 :
将 5g D201树脂树脂加入 O. lmol/L的 (104 2_溶液中， 固液比为 0.1g/L。 振荡， 使 CdCl4 2—和树脂发生离子交换反应 24h ， 过滤。 将浓度为 1.0%的 Na2S 溶液与之混合， 超声振荡下反应 0.5min， 然后用蒸馏水洗涤。 40Ό下真空干燥 24h。 制得的纳米 CdS分布在树脂载体外围， 其厚度占载体剖面半径的约 10%。 此材料的扫描电子显微图片如图 5所示。
此复合材料能在 5小时内将 50mL浓度为 20mg/L的罗丹明 B染料溶液降解 95%。
实施例 6:
将 5g D201树脂树脂加入 O. lmol/L的 CdCl4 2 液中， 固液比为 0.1g/L。 振 荡， 使 CdCl4 2—和树脂发生离子交换反应 24h， 过滤。 将浓度为 1.0%的 Na2S溶液 与之混合， 超声振荡下反应 lmin， 然后用蒸馏水洗涤。 40°C下真空干燥 24h。 制 得的纳米 CdS分布在树脂载体外围， 其厚度占载体剖面半径的约 40%。 此材料 的扫描电子显微图片如图 6所示。
此复合材料能在 6小时内将 50mL浓度为 20mg/L的罗丹明 B染料溶液降解 95%。
实施例 7:
将 5g D-201树脂树脂加入 O. lmol/L的 0(1 14 2_溶液中， 固液比为 0.1g/L。 振 荡， 使 CdCl4 2_和树脂发生离子交换反应 24h， 过滤。 将浓度为 1%的 Na2S溶液 与之混合， 超声振荡下反应 1.5min， 然后用蒸熘水洗涤。 40°C下真空干燥 24h。 制得的纳米 CdS分布在树脂载体外围， 其厚度占载体剖面半径的约 80%。 此材 料的扫描电子显微图片如图 7所示。
此复合材料能在 6小时内将 50mL浓度为 20mg/L的罗丹明 B染料溶液降解
说 明 书 实施例 8:
将 5g D-201树脂加入 2mol/L的 FeCl4_溶液中， 固液比为 10g/L。 振荡， 使 FeCl4_和树脂发生离子交换反应 4h， 过滤。将浓度为 4%的 NaOH溶液与之混合， 搅拌下反应 30min， 然后用蒸馏水洗涤。 40°C下真空干燥 24h。 制得的纳米水合 氧化铁分布在树脂载体外围，其厚度占载体剖面半径的 30%左右。此材料的扫描 电子显微图片如图 8所示。
此复合材料对浓度为 60mg/L的 As(V)的溶液的吸附动力学在 lOOmin内即 可达到平衡， 准二级速率常数为 0.00293g/mg · min。
实施例 9:
将 5g D-201树脂加入 2mol/L的 FeCl4_溶液中， 固液比为 10g/L。 振荡， 使 FeCl4_和树脂发生离子交换反应 4h， 过滤。将浓度为 8%的 NaOH溶液与之混合， 搅拌下反应 30min， 然后用蒸馏水洗涤。 40°C下真空干燥 24h。 制得的纳米水合 氧化铁分布在树脂载体外围，其厚度占载体剖面半径的 70%左右。此材料的扫描 电子显微图片如图 9所示：
此复合材料对浓度为 60mg/L的 As V)的溶液的吸附动力学在 80min内即可 达到平衡， 准二级速率常数为 0.00189g/mg · min„
实施例 10:
将实施例 1-9中的 D-201树脂换成 D-301或 NDA-900或 Amberlite IRA-900 或 Amberlite IRA-958或 Amberlite IRA-96或 Purolite C-100或 Purolite A500或 WBR109或 NDA-88或 NDA-99树脂； FeCV、 CdCl4 2\ PdCl4 2-等金属无机络合 阴离子在水溶液中的浓度在 0.1〜2mol/L， 固液比为 0.1〜20g/L; 沉积剂包括 NaOH, Na2S等，还原剂包括 NaBH4、 KBH4等，其固液比为 0.1〜20g L，浓度 (质 量百分比；)范围为 0.5%〜10%； 反应时间为 0.5〜30min， 沉积或者还原过程需在 超声振荡或者搅拌的条件下进行； 金属及其化合物包括水合氧化铁、 CdS、 零价 铁、零价钯等； 随着沉积剂或还原剂浓度的增加、 反应时间的延长， 金属及其化 合物纳米颗粒在树脂载体上呈现的环状分布的厚度与载体树脂半径的比值为 5%〜100%。
Claims
1. 一种调控金属纳米颗粒在树脂载体内分布的方法， 其步骤为：
(A) 以具有碱性功能基团和树脂骨架为苯乙烯系或丙烯酸系的离子交换树脂或 吸附树脂为载体， 将水溶液中的 FeCl4 CdCl4 2 ¾ PdCl4 2—络合阴离子通过离子交 换作用导入树脂内；
(B)用沉积剂或者还原剂通过沉积或者还原反应将金属固定在树脂载体上， 随 着沉积剂或还原剂浓度的增加和反应时间的延长，金属及其化合物纳米颗粒在树 脂载体上呈现由外到内的不同厚度与密度的环状分布。
2. 根据权利要求 1所述的一种调控金属纳米颗粒在树脂载体内分布的方法， 其 特征在于步骤 （A) 中的载体树脂骨架上含有叔氨基、 季氨基或碱性杂环基团， 载体树脂的平均孔径在 1-lOOnm之间。
3. 根据权利要求 2所述的一种调控金属纳米颗粒在树脂载体内分布的方法， 其 特征在于步骤（A)中的载体树脂为 D-201、 D-301、 NDA-900、 Amberlite I A-900. Amberlite IRA-958, Amberlite IRA-96、 Purolite C-100、 Purolite A500、 WBR109、 NDA-88或 DA-99树脂。
4. 根据权利要求 3所述的一种调控金属纳米颗粒在树脂载体内分布的方法， 其 特征在于步骤 （A) 中的 FeCl4 CdCl4 2—或 1¾。14 2_金属络合阴离子在水溶液中的 浓度为 0.1〜2 mol/L, 树脂载体与金属络合阴离子溶液的固液比为 0.1〜20 g/L。
5. 根据权利要求 1~4中任一项所述的一种调控金属纳米颗粒在树脂载体内分布 的方法， 其特征在于步骤 （B ) 中的沉积剂为 NaOH或 Na2S， 还原剂为 NaBH4 或 KBH4。
6. 根据权利要求 5所述的一种调控金属纳米颗粒在树脂载体内分布的方法， 其 特征在于步骤（B) 中的沉积剂或还原剂的质量百分比浓度为 0.5%〜10%， 树脂 载体与含有沉积剂或还原剂的溶液的固液比为 0.1〜20g/L。
7. 根据权利要求 6所述的一种调控金属纳米颗粒在树脂载体内分布的方法， 其 特征在于步骤 （B) 中的反应时间为 0.5〜30 min。
8. 根据权利要求 6所述的一种调控金属纳米颗粒在树脂载体内分布的方法， 其 特征在于步骤 （B) 中的金属及其化合物为水合氧化铁、 CdS、 零价铁、 零价钯 或复合金属。
9. 根据权利要求 6所述的一种调控金属纳米颗粒在树脂载体内分布的方法， 其 权 利 要 求 书 特征在于步骤（B ) 中的金属及其化合物纳米颗粒在树脂载体上呈现的环状分布 的厚度为载体树脂半径的 5%〜100%。
10. 根据权利要求 6所述的一种调控金属纳米颗粒在树脂载体内分布的方法，其 特征在于步骤 （B ) 中的沉积或者还原过程需在超声振荡或者搅拌下进行。
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| US10583419B2 (en) * | 2016-07-15 | 2020-03-10 | Nanjing University | Resin nanocomposite, method for preparing the same, and method for treating sewage with the same |
| CN106244831B (zh) * | 2016-07-29 | 2018-12-14 | 中南大学 | 一种从含钪溶液中去除铁离子和锆离子的方法 |
| CN107500396A (zh) * | 2017-09-29 | 2017-12-22 | 厦门理工学院 | 一种阴离子树脂负载纳米铁去除自来水离子的方法 |
| CN112316896B (zh) * | 2020-10-12 | 2022-10-14 | 昆明理工大学 | 一种废弃铜吸附剂资源化利用的方法 |
| CN113233536B (zh) * | 2021-03-31 | 2022-05-17 | 浙江工业大学 | 一种利用乙二胺树脂基零价钯纳米复合材料定向还原水体中亚硝酸根的方法 |
| CN113578401A (zh) * | 2021-09-09 | 2021-11-02 | 江南大学 | 一种去除低浓度氨氮的改性树脂 |
| CN115770573A (zh) * | 2022-11-14 | 2023-03-10 | 中国药科大学 | 一种Fe0/TiO2@D201型复合材料及其制备方法与应用 |
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| CN102102198A (zh) | 2011-06-22 |
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