CN116355220B - Selenium functionalized porous material and preparation method and application thereof - Google Patents
Selenium functionalized porous material and preparation method and application thereof Download PDFInfo
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- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000011669 selenium Substances 0.000 title claims abstract description 53
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 52
- 239000011148 porous material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- -1 gold ions Chemical class 0.000 claims abstract description 62
- 239000010931 gold Substances 0.000 claims abstract description 55
- 229910052737 gold Inorganic materials 0.000 claims abstract description 54
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 230000004048 modification Effects 0.000 claims abstract description 6
- 238000012986 modification Methods 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 39
- 239000000741 silica gel Substances 0.000 claims description 35
- 229910002027 silica gel Inorganic materials 0.000 claims description 35
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 150000003346 selenoethers Chemical class 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 55
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 13
- 239000000126 substance Substances 0.000 abstract description 10
- 239000002351 wastewater Substances 0.000 abstract description 10
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000003607 modifier Substances 0.000 abstract description 2
- 229920001296 polysiloxane Polymers 0.000 abstract description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 238000012512 characterization method Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- YWWZCHLUQSHMCL-UHFFFAOYSA-N diphenyl diselenide Chemical compound C=1C=CC=CC=1[Se][Se]C1=CC=CC=C1 YWWZCHLUQSHMCL-UHFFFAOYSA-N 0.000 description 8
- 239000003463 adsorbent Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000003068 static effect Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000001255 X-ray photoelectron diffraction Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- ZUKYESOJWBQOFL-UHFFFAOYSA-N 1-(pentyldiselanyl)pentane Chemical compound CCCCC[Se][Se]CCCCC ZUKYESOJWBQOFL-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical group CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- WCLHNDXRIBKVEI-UHFFFAOYSA-N bromobenzene;oxolane Chemical compound C1CCOC1.BrC1=CC=CC=C1 WCLHNDXRIBKVEI-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 1
- VTOQFOCYBTVOJZ-UHFFFAOYSA-N 3-bromopentane Chemical compound CCC(Br)CC VTOQFOCYBTVOJZ-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013310 covalent-organic framework Substances 0.000 description 1
- ALVPFGSHPUPROW-UHFFFAOYSA-N di-n-propyl disulfide Natural products CCCSSCCC ALVPFGSHPUPROW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000013312 porous aromatic framework Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/398—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing boron or metal atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a selenium functionalized porous material, a preparation method and application thereof. The invention constructs a class of silicone ether surface modifier, and carries out modification treatment on the porous material by a chemical grafting method to obtain the selenium functionalized porous material. The preparation method is simple to operate and low in cost, and is suitable for batch mass production of selenium functionalized porous materials; the prepared selenium functionalized porous material has high adsorption capacity, high adsorption rate, high selectivity and reducibility on gold ions, can be used for statically or dynamically adsorbing free gold elements in wastewater and reducing gold ions in situ to obtain gold simple substances, and has good application prospect in the aspect of gold ion adsorption materials.
Description
Technical Field
The invention relates to the technical field of adsorption material preparation, in particular to a selenium functionalized porous material, and a preparation method and application thereof.
Background
Gold, one of the noble metals, is widely used in the fields of chemical industry, metallurgy, electronics, catalysis, etc., due to its good stability, excellent electron transfer capability, and many other unique physical and chemical properties. Although gold is widely used, its reserves are limited and not renewable. Therefore, the separation and enrichment of noble metals are of great importance for sustainable development and environmental protection. The separation and enrichment of noble metals from leachate are commonly used methods such as ion exchange (JIndEng chem.2019,69, 255-262), solvent extraction (acsustain. Chem. En. 2019,7, 19975-19983), membrane separation (Small 2020,16,1907282), etc., wherein adsorption is considered to be the most effective method for separating noble metals from wastewater due to low cost, high efficiency and simple operation.
Conventional adsorbents such as resins (J.ColidInterface Sci.2020,561, 449-458), carbon materials (ACSAppl. Mater. Interface.2019, 11, 24560-24570) and ion imprinting (ACSAppl. Nano Mater.2020,3, 4102-4113) adsorbents have been studied for recovery of gold ions from filtrate. However, most of the conventional adsorption materials still exist in ionic form after adsorption, and further reduction is required to become gold. Thus, reduction in combination with adsorption is the most desirable recovery method. In recent years, many functional adsorbents such as metal organic frameworks (chem.eng.j.2020, 384), covalent organic frameworks (angel.chem.int.ed.2020, 59, 1767-17683), porous aromatic frameworks (chem.commun.2019, 55, 14271-14274), porous organic polymers (acsapp.mate.interfaces.2020, 12, 30274-3082) and the like have been receiving attention for their functional designability. However, these materials cannot be widely used due to the expensive manufacturing costs and high technical equipment requirements. Thus, the current state of the art requires the development of a more efficient gold recovery process combining reduction and adsorption.
CN110643822B discloses a method for refining and enriching gold element by using selenoether, which comprises preparing selenium-containing porous material by one-pot method by using small molecular compound with selenoether structure and isocyanate, and the material can realize enrichment and reduction of free gold element in waste water under the condition of soaking at room temperature. However, the selenium-containing porous material has a slower enrichment rate of gold elements, the selenium-containing porous material is placed in chloroauric acid solution and placed in a shaking table for reaction for 10 hours, the gold elements in the wastewater are removed only by about 60 percent, the time is prolonged to 24 hours, 20 percent of gold elements still remain in the wastewater, the gold extraction capacity is relatively low and is 189.2mg/g, the total adsorption efficiency is low, and the selenium-containing porous material is not suitable for dynamic adsorption of gold ion-containing wastewater.
Disclosure of Invention
The invention aims to solve the technical problem of providing a selenium functionalized porous material, a preparation method and application thereof. The material has high adsorption capacity, high adsorption rate and high selectivity to gold ions, and can be used for dynamically adsorbing free gold elements in wastewater.
In order to solve the technical problems, the invention provides the following technical scheme:
the first aspect of the invention provides a preparation method of a selenium functionalized porous material, which comprises the steps of grafting and modifying the porous material by using a selenium ether silane coupling agent in the presence of a solvent to obtain the selenium functionalized porous material; the selenoether silane coupling agent has the following structural general formula:
wherein n is selected from any integer from 1 to 10; r is a C1-C10 alkyl group or a (substituted) aryl group, and the (substituted) aryl group refers to a substituted or unsubstituted aryl group.
Further, the preparation method of the selenium ether silane coupling agent comprises the following steps:
reacting the silane coupling agent with selenolactone in the presence of a solvent to obtain the selenoethyl silane coupling agent.
Further, the selenolactone is gamma-butylselenolactone.
Further, the silane coupling agent has the following structural general formula:
wherein n is selected from any integer from 1 to 10; r is a C1-C10 alkyl group or a (substituted) aryl group, more preferably a C1-C5 alkyl group.
In some preferred embodiments, the silane coupling agent is (3-aminopropyl) trimethoxysilane or (3-aminopropyl) triethoxysilane.
Further, the temperature of the reaction is 0 to 100 ℃, more preferably 20 to 30 ℃, and the reaction time is 1 to 10 hours, for example, 1.5 hours, 3 hours, 5 hours, 8 hours, etc.; more preferably, the reaction is carried out under stirring conditions, for example 1000rpm.
In some preferred embodiments, the molar ratio of the silane coupling agent to selenolactone is 1:1; the solvent is anhydrous tetrahydrofuran.
In some preferred embodiments, the seleno-ether silane coupling agent is butyramide propyl trimethoxy silane diselenide or butyramide propyl triethoxy silane diselenide.
Further, the porous material is silica gel powder, mesoporous silica or activated carbon.
Further, the porous material is more preferably silica gel powder. The silica gel has excellent thermal stability and mechanical stability, and unique large surface area, is poor in selectivity as an inorganic solid adsorbent, and has poor interaction capability with other species although the surface contains rich silanol groups, so that the silica gel is subjected to surface modification by a single electron method for fixing atoms, and the adsorption capability of substance ions of the silica gel is improved.
Further, the porous material is added into the mixed solution containing the selenium ether silane coupling agent, and the selenium functionalized porous material is obtained through heating reaction.
Further, the mixed solution is obtained by dissolving a seleno-ether silane coupling agent in toluene, wherein the volume ratio of the seleno-ether silane coupling agent to toluene is 1:10-100, and more preferably 1:30-60.
Further, the temperature of the heating reaction is 40 to 150 ℃, more preferably 60 to 90 ℃, and the time of the heating reaction is 1 to 16 hours.
In a second aspect, the invention provides a selenium functionalized porous material prepared by the preparation method in the first aspect.
The third aspect of the invention provides an application of the selenoether silane coupling agent in the aspect of adsorbing and reducing gold ions.
Further, the adsorption may be static adsorption or dynamic adsorption.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention constructs a class of silicone ether surface modifier and carries out modification treatment on the porous material by a chemical grafting method, combines the excellent characteristics of simple operation, large specific surface area and the like of the porous material with the excellent redox activity of selenium element by utilizing the mode of loading selenium-containing compounds on the porous material, and prepares the selenium functionalized porous material integrating adsorption and reduction.
2. The selenium functionalized porous material prepared by the invention has the characteristics of high adsorption capacity, high adsorption rate, high selectivity and the like for gold ions in a wastewater treatment test, and can be used for treating wastewater containing gold ions through static adsorption or dynamic adsorption; compared with the selenium-containing porous material synthesized in situ in the prior art, the selenium-functionalized porous material prepared by the method has higher adsorption capacity and extremely fast adsorption kinetics, the adsorption-desorption balance can be achieved by stirring for 10min at room temperature, the adsorption capacity of gold ions can reach 280mg/g (the adsorption capacity of selenium element to gold ions is 11.6 g/g), the waste CPU treatment solution with the gold ion concentration of 7mg/L is filtered by a filter column filled with the selenium-functionalized porous material (1 g/root), and the gold ion concentration of effluent liquid is only 0.1mg/L (equivalent to 1 ppm).
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of butyramide propyl trimethoxy silane diselenide prepared in example 1;
FIG. 2 is a nuclear magnetic resonance spectrum of diphenyl diselenide prepared in example 1;
FIG. 3 is a synthetic route for preparing butyramide propyl trimethoxysilane diselenide loaded silica gel of example 2;
FIG. 4 is a SEM-EDS-Mapping selenium element spectrum of butyramide propyl trimethoxy silane diselenide loaded silica gel prepared in example 2;
FIG. 5 is a selenium spectrum of X-ray photoelectron diffraction analysis of butyramide propyl trimethoxy silane diselenide loaded silica gel prepared in example 2;
FIG. 6 is a Fourier transform infrared spectrum of butyramide propyl trimethoxysilane diselenide loaded silica gel prepared in example 2;
FIG. 7 is an adsorption capacity of different adsorption materials in wastewater of different gold ion concentrations;
FIG. 8 shows the concentration change of different metal ions in the aqueous phase before and after adsorption in static adsorption of butyramide propyl trimethoxy silane diselenide loaded silica gel;
FIG. 9 is an SEM image of butyramide propyl trimethoxysilane diselenide loaded silica gel prepared in example 2 after adsorbing gold ions;
FIG. 10 XPS chart of butyramide propyl trimethoxysilane diselenide loaded silica gel after gold ion adsorption was prepared in example 2.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items. The term "comprising" or "comprises" as used herein means that it may include or comprise other components in addition to the components described. The term "comprising" or "comprising" as used herein may also be replaced by "being" or "consisting of" closed.
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
The specific operation of the test characterization referred to in the examples below is as follows:
1. nuclear magnetic hydrogen spectrum @ 1 H NMR) is performed by using Bruker 300MHz nuclear magnetic resonance apparatus to measure the sample in CDCl 3 As a solvent, tetramethylsilane (TMS) is used as an internal standard to be dissolved and then tested;
2. uniformly coating the obtained sample on a conductive adhesive and adhering the conductive adhesive on a sample table, spraying metal at 30mA for 60 seconds, and observing the sample under a working voltage of 5kV by using an SU8010 HITICHI cold field emission scanning electron microscope;
3. adhering a sample to a 5X 5mm double-sided adhesive tape, tabletting, adhering to a sample table, and characterizing the surface element composition of the sample by XPS;
4. sample chemistry was analyzed on a bruker Tensor330 FT-IR using KBr pellet method;
5. the aqueous phase solution was analyzed for noble metal ion content using ICP-OES.
Example 1
The embodiment relates to the preparation of different selenoether surface modifying agents, which comprises the following specific operations:
(1) Synthesis of butyramide propyl trimethoxy silane diselenide
3.6g of (3-aminopropyl) trimethoxysilane and 3g of gamma-butylselenolactone are weighed into a 250mL round bottom flask, 50mL of anhydrous tetrahydrofuran is added as a solvent, and the reaction is stirred at room temperature and 1000rpm for 1.5h to complete the reaction. Suction filtering, rotary steaming to remove redundant solvent, washing with petroleum ether for three times, and drying to obtain the target product. The reaction route is as follows:
fig. 1 is a nuclear magnetic characterization diagram of the product, and it can be seen from the diagram that butyramide propyl trimethoxy silane diselenide, abbreviated as MPBADSe, is successfully prepared in this example.
(2) Synthesis of diphenyl diselenide
80g of bromobenzene is taken and dissolved in 280mL of tetrahydrofuran, poured into a constant pressure dropping funnel, 12g of magnesium turnings and two simple substance iodides are weighed and added into a 500mL three-necked flask, and argon is introduced for protection. Dropwise adding bromobenzene tetrahydrofuran solution, stirring until magnesium chips are removed, regulating the rotating speed to 1000rpm, thermally triggering by using a high-temperature spray gun under the condition of ice water bath, adding ice cubes into a water tank for cooling after white foam appears, and simultaneously continuously dropwise adding bromobenzene tetrahydrofuran mixed solution, wherein the reaction is stable until the dropwise addition is complete. The three-necked flask was transferred to an oil bath at 40℃for 1h until the magnesium turnings were substantially fully reacted. 38g of selenium powder is added, and the mixture is condensed and refluxed for 1 hour until the reaction liquid turns to be earthy yellow. Heating was stopped, 30g of liquid bromine was weighed and slowly added dropwise (about 1 h). After the completion of the dropwise addition, 40mL of a saturated ammonium chloride solution was added to complete the reaction. Pouring the reaction solution into a beaker, adding dichloromethane, stirring to separate layers, filtering, washing with tetrahydrofuran, removing more solvent by rotary evaporation, and recrystallizing to obtain the target product. The reaction route is as follows:
fig. 2 is a nuclear magnetic characterization diagram of the product, and it can be seen from the diagram that diphenyl diselenide, abbreviated as DPDS, is successfully prepared in this example.
(3) Synthesis of dipentyldiselenide
The preparation method is the same as the synthesis of diphenyl diselenide, and only monobromopentane is used for replacing bromobenzene, so that the dipentyl diselenide is prepared and is called DPSe for short.
Example 2
The embodiment relates to the preparation of different selenium functionalized porous materials, which comprises the following specific operations:
(1) Butyramide propyl trimethoxy silane diselenide to carry out chemical grafting modification on silica gel (SG, 200-300 meshes)
1g of silica gel powder was weighed and put into a 250mL round bottom flask, 1mL of butyramidopropyl trimethoxysilane diselenide prepared in example 1 was dissolved in 50mL of anhydrous toluene, and the mixture was added into the flask and reacted at 70℃and 1000rpm for 16 hours to complete the loading. And (3) carrying out suction filtration, washing for multiple times by using tetrahydrofuran and anhydrous toluene, and drying to obtain a target product. The reaction scheme is shown in FIG. 3.
FIGS. 4 and 5 are, respectively, SEM-EDS-Mapping-Se diagrams of butyramide propyl trimethoxy silane diselenide loaded silica gel (SG-MPBADSe) and X-ray photoelectron diffraction analysis selenium spectra, and it can be seen that selenium element is successfully and uniformly loaded on silica gel; fig. 6 is a fourier transform infrared spectrum of the material, further confirming the successful loading of elemental selenium.
(2) Silica gel (SG, 200-300 meshes) is modified by diphenyl diselenide
1g of silica gel powder was weighed and put into a 250mL sullenk bottle, 50mg of diphenyldiselenide prepared in example 1 was dissolved in 50mL absolute ethanol, and the mixture was added into the flask and reacted at 70℃and 1000rpm for 16 hours to complete the loading. Drying by using a rotary evaporator (as diphenyl diselenide is loaded on silica gel through physical adsorption and cannot be washed by adopting an organic solvent), and drying to obtain a target product.
And carrying out scanning electron microscopy, X-ray photoelectron diffraction analysis and Fourier transform infrared characterization on a product of diphenyl diselenide loaded silica gel (SG-DPDS), wherein the characterization result shows that selenium element is successfully loaded on the silica gel.
(3) Silica gel (SG, 200-300 meshes) is modified by dipentyldiselenide
1g of silica gel powder was weighed and put into a 250mL Schlenk bottle, 50mg of dipentyldiselener prepared in example 1 was dissolved in 50mL absolute ethanol, and the mixture was added into the flask and reacted at 70℃and 1000rpm for 16 hours to complete the loading. Drying by using a rotary evaporator, and drying to obtain a target product.
Scanning electron microscopy, X-ray photoelectron diffraction analysis and Fourier transformation infrared characterization are carried out on the product of dipentyldiselener loaded silica gel (SG-DPDSe), and the characterization result shows that the selenium element is successfully loaded on the silica gel.
Application of
The different selenium functionalized porous materials prepared in example 2 are used for adsorbing gold ions in the water phase by adopting a static adsorption method or a dynamic adsorption method.
(1) Static adsorption
Taking 0.01g of selenium functionalized porous material, respectively adding 5mL of chloroauric acid aqueous solutions with different concentrations (500, 1000, 1500, 2000, 2500 and 3000 mg/L) into a 10mL glass bottle, stirring at 660rpm at 25 ℃ for 10min, filtering the supernatant after adsorption-desorption balance is achieved, and detecting the concentration of gold ions in the aqueous phase by ICP, thereby calculating the mass of gold ions which can be adsorbed by the selenium-containing loaded silica gel per unit mass.
FIG. 7 shows the adsorption capacity of different selenium functionalized porous materials to gold ions in water phases with different gold ion concentrations, and the adsorption capacity of butyramide propyl trimethoxy silane diselenide loaded silica gel to gold ions is far higher than that of other two selenium functionalized porous materials; the maximum adsorption amount of gold ions by different selenium functionalized porous materials and the maximum adsorption amount of gold ions by corresponding selenium element in the adsorption material in the concentration range are shown in the following table 1:
TABLE 1
Wherein, the maximum adsorption quantity of the corresponding selenium element = the maximum adsorption quantity of the selenium functionalized porous material to gold ions/the ratio of the selenium element in the selenium functionalized material. As can be seen from Table 1, butyramide propyl trimethoxy silane diselenide loaded silica gel is used as an adsorption material, the adsorption amount of gold ions is highest, and the maximum adsorption amount of corresponding selenium element in the adsorption material is far higher than that of other adsorption materials.
(2) Dynamic adsorption
Filling butyramide propyl trimethoxy silane diselenide loaded silica gel into a filter column with the filling amount of 1 g/root, and filling absorbent cotton at the bottom of the filter column to fix the adsorbent and prevent the adsorbent from flowing out of the filter column. Waste CPU treatment liquid with gold ion concentration of 7mg/L is added from the upper end of the filtering column, effluent liquid at the bottom is collected, the concentration of gold ions in the water phase is detected by ICP, and the concentration of gold ions in the water phase after adsorption is about 0.1mg/L.
The concentration changes of each metal ion of the waste gas CPU treatment liquid before and after treatment are shown in the following table 2:
TABLE 2
| Metal ion | Concentration before treatment (mg/L) | Concentration after treatment (mg/L) |
| Au | 12 | 0.1 |
| Al | 18 | 18 |
| Ba | 80 | 80 |
| Ca | 10 | 10 |
| Cu | 929 | 929 |
| Fe | 40 | 40 |
| Na | 50 | 50 |
| Ni | 100 | 100 |
| Pb | 200 | 199 |
| Sb | 33 | 32 |
| Sn | 88 | 88 |
| Ti | 16 | 16 |
| Zn | 5 | 5 |
As can be seen from Table 2 and FIG. 8, the selenium functionalized porous material prepared by the invention has high selectivity to gold ions, and can rapidly adsorb gold ions in wastewater by a dynamic adsorption mode, the removal rate is as high as 98.57%, and extremely rapid adsorption kinetics are shown.
(3) Reducibility of
And (3) carrying out characterization treatment on the butyramide propyl trimethoxy silane diselenide loaded silica gel subjected to static adsorption treatment by adopting a scanning electron microscope and an X-ray photoelectron spectrum analyzer, wherein the characterization result is as follows:
fig. 9 is an SEM image of butyramide propyl trimethoxy silane diselenide loaded silica gel after adsorbing gold ions, and it can be seen that the gold simple substance can be observed on the surface of the silica gel powder after adsorbing gold ions.
Fig. 10 is a graph xps of butyramide propyl trimethoxy silane diselenide loaded silica gel after adsorbing gold ions, which shows that trivalent gold ions adsorbed on the surface of silica gel powder are reduced to zero-valent gold simple substance.
In conclusion, the selenium functionalized porous material prepared by the invention has high adsorption rate and adsorption capacity on gold ions, and the dynamic adsorption treatment of CPU waste liquid shows high selectivity on gold ions, and gold ions adsorbed on the surface can be reduced to Jin Shanzhi in situ.
The above-described embodiments are merely preferred embodiments for fully explaining the present invention, and the scope of the present invention is not limited thereto. Equivalent substitutions and modifications will occur to those skilled in the art based on the present invention, and are intended to be within the scope of the present invention. The protection scope of the invention is subject to the claims.
Claims (10)
1. The preparation method of the selenium functionalized porous material is characterized in that a selenium ether silane coupling agent is used for grafting modification on the porous material in the presence of a solvent to obtain the selenium functionalized porous material;
the selenoether silane coupling agent has the following structural general formula:
wherein n is selected from any integer from 1 to 10; r is C1-C10 alkyl or aryl.
2. The preparation method of claim 1, wherein the preparation method of the selenoether silane coupling agent is as follows: reacting a silane coupling agent with selenolactone in the presence of a solvent to obtain a selenoether silane coupling agent; the selenolactone is gamma-butyl selenolactone, and the structure of the selenolactone is shown as a formula I; the silane coupling agent has a structural general formula shown in a formula II:
3. the preparation method according to claim 2, wherein the reaction temperature is 0 to 100 ℃ and the reaction time is 1 to 10 hours.
4. The preparation method according to claim 1, wherein the selenoether silane coupling agent is butyramide propyl trimethoxy silane diselener or butyramide propyl triethoxy silane diselener.
5. The method of claim 1, wherein the porous material is silica gel powder, mesoporous silica, or activated carbon.
6. The preparation method according to claim 1, wherein the porous material is added to the mixed solution of the selenium ether-containing silane coupling agent to perform a heating reaction; the mixed solution is obtained by dissolving a selenoether silane coupling agent in toluene.
7. The method according to claim 6, wherein the heating reaction is carried out at a temperature of 40 to 150℃for a period of 1 to 16 hours.
8. The preparation method of claim 6, wherein the volume ratio of the selenoether silane coupling agent to toluene in the mixed solution is 1:10-100.
9. A selenium functionalized porous material prepared by the method of any of claims 1-8.
10. Use of the selenium functionalized porous material of claim 9 for selectively adsorbing and reducing gold ions.
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| CN104130421A (en) * | 2014-07-23 | 2014-11-05 | 苏州大学 | Method for preparing diselenide polymer |
| CN106861631A (en) * | 2017-02-27 | 2017-06-20 | 苏州大学 | Hollow mesoporous silicon dioxide nano microballoon of functionalization and preparation method thereof and the application in Adsorption of Heavy Metals ion |
| CN111592658A (en) * | 2020-06-12 | 2020-08-28 | 天津大学 | Selenium or tellurium functionalized covalent organic framework material, and preparation method and application thereof |
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| CN103521186A (en) * | 2013-09-27 | 2014-01-22 | 湖南中烟工业有限责任公司 | Silica gel with ionic liquid and mercaptan loaded on surface as well as preparation method and application |
| CN104130421A (en) * | 2014-07-23 | 2014-11-05 | 苏州大学 | Method for preparing diselenide polymer |
| CN106861631A (en) * | 2017-02-27 | 2017-06-20 | 苏州大学 | Hollow mesoporous silicon dioxide nano microballoon of functionalization and preparation method thereof and the application in Adsorption of Heavy Metals ion |
| CN111592658A (en) * | 2020-06-12 | 2020-08-28 | 天津大学 | Selenium or tellurium functionalized covalent organic framework material, and preparation method and application thereof |
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