CN106179281A - A kind of gold ion solid extracting agent and its preparation method and application - Google Patents

A kind of gold ion solid extracting agent and its preparation method and application Download PDF

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Publication number
CN106179281A
CN106179281A CN201610667034.5A CN201610667034A CN106179281A CN 106179281 A CN106179281 A CN 106179281A CN 201610667034 A CN201610667034 A CN 201610667034A CN 106179281 A CN106179281 A CN 106179281A
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China
Prior art keywords
extracting agent
gold ion
solid
mwcnts
gold
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Pending
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CN201610667034.5A
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Chinese (zh)
Inventor
叶存玲
刘畅
王慎
王全坤
王治科
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Henan Normal University
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Henan Normal University
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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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • 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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/46—Materials comprising a mixture of inorganic and organic materials

Abstract

The invention discloses a kind of gold ion solid extracting agent and its preparation method and application.Its preparation process is that first mesoporous silicon oxide is coated with multi-walled carbon nano-tubes and reacts prepared gold ion solid extracting agent further with silane coupler 3 mercaptopropyl trimethoxysilane, and this gold ion solid extracting agent can be used in selective separation enrichment gold ion.Preparation process of the present invention is controlled and easy and simple to handle, and the solid extracting agent prepared has that selectivity is strong, big to gold ion absorption amount, easily regeneration and the plurality of advantages such as reusable.

Description

A kind of gold ion solid extracting agent and its preparation method and application
Technical field
The invention belongs to the synthesis technical field of solid extracting agent in sample pre-treatments, be specifically related to a kind of gold ion solid phase Extractant and its preparation method and application.
Background technology
Gold content in the sample is the lowest, and sample matrices is the most extremely complex.The mensuration of gold generally includes the separation and concentration of gold With measure two aspects.At present, the detection method of gold reaches its maturity, and separation and concentration is the committed step of Accurate Determining gold.Separate richness The method of collection gold has: ensaying method, coprecipitation, active carbon adsorption, earth Using Adsorption of Polyurethane Foam method, ion exchange resin concentration and separation Method, solvent extraction and solid phase extraction etc..Wherein solid phase extraction have that enrichment times is high, organic solvent consumes less and easily from The advantages such as dynamicization control, the most all conduct in-depth research this method for separating and concentrating.CNT is because of the most modified, property The features such as matter is stable and specific surface area is big, have obtained common concern as Solid-Phase Extraction agent material.
Summary of the invention
Present invention solves the technical problem that there is provided that a kind of selectivity is strong, adsorbance big, easily regeneration and reusable Gold ion solid extracting agent and preparation method thereof, the solid extracting agent that the method prepares is filled in solid-phase extraction column and can use In the separation and concentration containing gold ion water sample, lay a good foundation for its popularization and application.
The present invention solves that above-mentioned technical problem adopts the following technical scheme that, the preparation side of a kind of gold ion solid extracting agent Method, it is characterised in that concretely comprise the following steps:
Step (1), by 2g cetyl trimethylammonium bromide ultrasonic dissolution in 30mL water, add 100mg multi-walled carbon nano-tubes, Ultrasonic 1h, adds 80mL dehydrated alcohol, continues ultrasonic 0.5h, then dropping 2mL ammonia spirit, under magnetic stirring, 20min The ethanol solution of interior dropping 41mL positive silicic acid tetraacethyl, wherein positive silicic acid tetraacethyl is 1 with the volume ratio of dehydrated alcohol: 40, then magnetic agitation 12h, centrifugation and with ethanol cyclic washing until washing liquid is neutrality, be subsequently adding 60mL dehydrated alcohol With 2mL concentrated hydrochloric acid, magnetic agitation 10h removes cetyl trimethylammonium bromide, repeatedly with absolute ethanol washing and use deionization Water cleans, and obtains mesoporous SiO in 80 DEG C of vacuum drying 24h subsequently2Cladding multi-walled carbon nano-tubes, is labeled as mSiO2@MWCNTs；
Step (2), the mSiO that 0.5g step (1) is prepared2@MWCNTs joins ultrasonic 10min in the toluene that 50mL is dried, then Add 0.5mL 3-mercaptopropyl trimethoxysilane, be heated to reflux 24h, reacted product first the most under nitrogen atmosphere Benzene, methanol and ether cyclic washing, place in vacuum drying oven and dry prepared gold ion solid extracting agent mSiO in 60 DEG C2@ MWCNTs-MPTS。
Gold ion solid extracting agent of the present invention, it is characterised in that prepared by said method.
The gold ion solid extracting agent of the present invention application in selective separation enrichment gold ion, it is characterised in that Detailed process is: by gold ion solid extracting agent mSiO2@MWCNTs-MPTS loads the solid phase extraction tube being pre-loaded with lower sieve plate In, load onto sieve plate after tamping and obtain the solid-phase extraction column of separation and concentration gold ion, then this solid-phase extraction column is put into leaching in methanol Bubble 24h, the most successively with 10mL methanol and 10mL distilled water wash, will contain gold sample solution and add solid above solid-phase extraction column Phase extraction column, relies on gravity sample solution containing gold by solid-phase extraction column, and gold ion is enriched in solid extracting agent mSiO2@ On MWCNTs-MPTS, then reclaim gold ion, this acid thiourea solution with 10mL acid thiourea solution eluting under gravity The mass concentration of middle thiourea is 1%, and in acid thiourea solution, the molar concentration of HCl is 1mol/L.
Preparation process of the present invention is controlled and easy and simple to handle, and it is strong, to gold ion suction that the solid extracting agent prepared has selectivity Attached amount is big, easily regeneration and the plurality of advantages such as reusable.
Accompanying drawing explanation
Fig. 1 is the solid extracting agent mSiO that embodiment 1 prepares2The thermogravimetric curve of@MWCNTs-MPTS；
Fig. 2 is the scanning electron microscope (SEM) photograph of multi-walled carbon nano-tubes；
Fig. 3 is the solid extracting agent mSiO that embodiment 1 prepares2The scanning electron microscope (SEM) photograph of@MWCNTs-MPTS；
Fig. 4 is solid extracting agent mSiO in embodiment 22@MWCNTs-MPTS selective absorption great hit line；
Fig. 5 be in embodiment 3 adsorption time to solid extracting agent mSiO2The influence curve of@MWCNTs-MPTS ADSORPTION OF GOLD；
Fig. 6 is that embodiment 4 pH value of solution is to solid extracting agent mSiO2The influence curve of@MWCNTs-MPTS ADSORPTION OF GOLD.
Detailed description of the invention
By the following examples the foregoing of the present invention is described in further details, but this should be interpreted as this The scope inventing above-mentioned theme is only limitted to below example, and all technology realized based on foregoing of the present invention belong to this Bright scope.
Embodiment 1
Gold ion solid extracting agent mSiO2The synthesis of@MWCNTs-MPTS
Step (1), by 2g cetyl trimethylammonium bromide (CTAB) ultrasonic dissolution in 30mL water, add 100mg many walls carbon Nanotube (MWCNTs), ultrasonic 1h, add 80mL dehydrated alcohol, continue ultrasonic 0.5h, then dropping 2mL ammonia spirit, Under magnetic agitation, the ethanol solution of dropping 41mL positive silicic acid tetraacethyl in 20min, wherein positive silicic acid tetraacethyl and anhydrous second The volume ratio of alcohol is 1:40, then magnetic agitation 12h, centrifugation and with ethanol cyclic washing until washing liquid is neutrality, then add Entering 60mL dehydrated alcohol and 2mL concentrated hydrochloric acid, magnetic agitation 10h removes cetyl trimethylammonium bromide, repeatedly uses dehydrated alcohol Washing is also cleaned with deionized water, obtains mesoporous SiO in 80 DEG C of vacuum drying 24h subsequently2Cladding multi-walled carbon nano-tubes, is labeled as mSiO2@MWCNTs；
Step (2), the mSiO that 0.5g step (1) is prepared2@MWCNTs joins ultrasonic 10min in the toluene that 50mL is dried, then Add 0.5mL 3-mercaptopropyl trimethoxysilane (MPTS), be heated to reflux 24h, reacted product the most under nitrogen atmosphere With toluene, methanol and ether cyclic washing, place in vacuum drying oven and dry prepared gold ion solid extracting agent in 60 DEG C mSiO2@MWCNTs-MPTS。
As it is shown in figure 1, the solid extracting agent mSiO that the present embodiment prepares2The thermogravimetric curve of@MWCNTs-MPTS have two bright Aobvious mass loss peak, the wherein water of 200 DEG C of front mass loss peak solid extracting agent surface adsorption due to, 200-600 DEG C Mass loss peak cause mainly due to organic principle thermal decomposition in solid extracting agent, solid extracting agent as seen from the figure mSiO2@MWCNTs-MPTS is successfully prepared.
As Figure 2-3, the solid extracting agent mSiO that the present embodiment prepares2@MWCNTs-MPTS and multi-walled carbon nano-tubes phase Ratio, pattern there occurs substantially change.
Embodiment 2
Solid extracting agent mSiO2The selective absorption experiment of@MWCNTs-MPTS
Gold, copper, lead and cadmium ion initial concentration are 50 μ g/mL, volume 50mL, 20mg solid extracting agent mSiO2@MWCNTs- MPTS, duration of oscillation 6h, temperature 30 DEG C, under conditions of oscillation rate 160rpm/min, result of the test is shown in Fig. 4, makes as seen from the figure Standby solid extracting agent mSiO2The adsorbance of gold is far longer than copper, lead, the adsorbance of cadmium by@MWCNTs-MPTS, shows solid Phase extractant mSiO2@MWCNTs-MPTS presents the characteristic of high-selectivity adsorption gold ion.
Embodiment 3
Adsorption time is to solid extracting agent mSiO2The impact of@MWCNTs-MPTS ADSORPTION OF GOLD
Gold initial concentration 50 μ g/mL, volume 50mL, 20mg solid extracting agent mSiO2@MWCNTs-MPTS, temperature 30 DEG C, vibration Speed 160rpm/min, as it is shown in figure 5, solid extracting agent mSiO2@MWCNTs-MPTS is fast to the rate of adsorption of gold ion, 5min Adsorbance has reached the 48.5% of equilibrium adsorption capacity.
Embodiment 4
PH value of solution is to solid extracting agent mSiO2The impact of@MWCNTs-MPTS ADSORPTION OF GOLD
As shown in Figure 6, in the range of wider solution ph, solid extracting agent mSiO2The@MWCNTs-MPTS suction to gold ion Attached amount the most substantially reduces.
Embodiment 5
Gold ion solid extracting agent mSiO2@MWCNTs-MPTS Solid-Phase Extraction is tested
Weigh 200mg solid extracting agent mSiO2@MWCNTs-MPTS, loads the solid phase extraction column pipe being pre-loaded with lower sieve plate In (12.7mm × 66mm), load onto sieve plate after tamping and i.e. obtain the solid phase extraction column of separation and concentration gold ion.The side of pretreatment Method is that this solid phase extraction column is put into immersion 24h in methanol, successively with 10mL methanol and 10mL distilled water wash, will contain gold The sample solution of 100 μ g adds above solid phase extraction column, relies on gravity containing gold sample solution by solid phase extraction column, gold Ion is enriched in solid extracting agent mSiO2On@MWCNTs-MPTS, then with 10mL acid thiourea solution (1wt% thiourea+1M Hydrochloric acid) carry out eluting under gravity, the concentration atomic absorption detecting of gold in eluent, the response rate of gold ion reaches 98%.
Embodiment above describes the ultimate principle of the present invention, principal character and advantage, the technical staff of the industry should Understanding, the present invention is not restricted to the described embodiments, and the simply explanation present invention's described in above-described embodiment and description is former Reason, under the scope without departing from the principle of the invention, the present invention also has various changes and modifications, and these changes and improvements each fall within In the scope of protection of the invention.

Claims (3)

1. the preparation method of a gold ion solid extracting agent, it is characterised in that concretely comprise the following steps:
Step (1), by 2g cetyl trimethylammonium bromide ultrasonic dissolution in 30mL water, add 100mg multi-walled carbon nano-tubes, Ultrasonic 1h, adds 80mL dehydrated alcohol, continues ultrasonic 0.5h, then dropping 2mL ammonia spirit, under magnetic stirring, 20min The ethanol solution of interior dropping 41mL positive silicic acid tetraacethyl, wherein positive silicic acid tetraacethyl is 1 with the volume ratio of dehydrated alcohol: 40, then magnetic agitation 12h, centrifugation and with ethanol cyclic washing until washing liquid is neutrality, be subsequently adding 60mL dehydrated alcohol With 2mL concentrated hydrochloric acid, magnetic agitation 10h removes cetyl trimethylammonium bromide, repeatedly with absolute ethanol washing and use deionization Water cleans, and obtains mesoporous SiO in 80 DEG C of vacuum drying 24h subsequently2Cladding multi-walled carbon nano-tubes, is labeled as mSiO2@MWCNTs；
Step (2), the mSiO that 0.5g step (1) is prepared2@MWCNTs joins ultrasonic 10min in the toluene that 50mL is dried, then Add 0.5mL 3-mercaptopropyl trimethoxysilane, be heated to reflux 24h, reacted product first the most under nitrogen atmosphere Benzene, methanol and ether cyclic washing, place in vacuum drying oven and dry prepared gold ion solid extracting agent mSiO in 60 DEG C2@ MWCNTs-MPTS。
2. a gold ion solid extracting agent, it is characterised in that be to be prepared by the method described in claim 1.
3. the application in selective separation enrichment gold ion of the gold ion solid extracting agent described in claim 2, its feature exists In detailed process it is: by gold ion solid extracting agent mSiO2@MWCNTs-MPTS loads the Solid-Phase Extraction being pre-loaded with lower sieve plate Guan Zhong, loads onto sieve plate and obtains the solid-phase extraction column of separation and concentration gold ion, then put in methanol by this solid-phase extraction column after tamping Soak 24h, the most successively with 10mL methanol and 10mL distilled water wash, gold sample solution will be contained and add above solid-phase extraction column Solid-phase extraction column, relies on gravity sample solution containing gold by solid-phase extraction column, and gold ion is enriched in solid extracting agent mSiO2@ On MWCNTs-MPTS, then reclaim gold ion, this acid thiourea solution with 10mL acid thiourea solution eluting under gravity The mass concentration of middle thiourea is 1%, and in acid thiourea solution, the molar concentration of HCl is 1mol/L.
CN201610667034.5A 2016-08-15 2016-08-15 A kind of gold ion solid extracting agent and its preparation method and application Pending CN106179281A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107253873A (en) * 2017-06-12 2017-10-17 安徽省颍上县正泰电器有限责任公司 A kind of preparation method of Thermo-sensitive graphite fiber alkene composite water conservation coated fertilizer
CN114733495A (en) * 2022-04-08 2022-07-12 华北水利水电大学 Preparation method and application of solvent-free extracting agent for recycling Au (III)
CN114832800A (en) * 2022-06-06 2022-08-02 宁波大学 Solid phase micro-extraction probe, preparation method and application thereof in biogenic amine detection

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CN101130157A (en) * 2007-07-19 2008-02-27 中国科学院生态环境研究中心 Preparation of mixed glue nucleus solitarius shell-type fe3o4 nano solid phase extractive agent and application of the same
CN101810939A (en) * 2010-04-02 2010-08-25 同济大学 Preparation and application method of solid phase extractant capable of simultaneously accumulating multiple heavy metal ions
CN105709690A (en) * 2016-03-07 2016-06-29 河南师范大学 Adsorbent capable of preferentially adsorbing gold and preparing method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5651883A (en) * 1995-06-06 1997-07-29 Argonne National Laboratory/University Of Chicago Development Corp. Method for the chromatographic separation of cations from aqueous samples
CN101130157A (en) * 2007-07-19 2008-02-27 中国科学院生态环境研究中心 Preparation of mixed glue nucleus solitarius shell-type fe3o4 nano solid phase extractive agent and application of the same
CN101810939A (en) * 2010-04-02 2010-08-25 同济大学 Preparation and application method of solid phase extractant capable of simultaneously accumulating multiple heavy metal ions
CN105709690A (en) * 2016-03-07 2016-06-29 河南师范大学 Adsorbent capable of preferentially adsorbing gold and preparing method and application thereof

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XIAOSHENG TANGDENG等: "Adsorption of Hg II Ions by 3 Mercaptopropyltriethoxysilane Modified Mesoporous Silica Based on Multiwalled Carbon Nanotubes: Equilibrium Kinetic and Thermodynamic Studies", 《SEPARATION SCIENCE AND TECHNOLOGY》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107253873A (en) * 2017-06-12 2017-10-17 安徽省颍上县正泰电器有限责任公司 A kind of preparation method of Thermo-sensitive graphite fiber alkene composite water conservation coated fertilizer
CN114733495A (en) * 2022-04-08 2022-07-12 华北水利水电大学 Preparation method and application of solvent-free extracting agent for recycling Au (III)
CN114733495B (en) * 2022-04-08 2023-09-12 华北水利水电大学 Preparation method and application of solvent-free extractant for recovering Au (III)
CN114832800A (en) * 2022-06-06 2022-08-02 宁波大学 Solid phase micro-extraction probe, preparation method and application thereof in biogenic amine detection
CN114832800B (en) * 2022-06-06 2023-08-01 宁波大学 Solid-phase microextraction probe, preparation method and application thereof in biogenic amine detection

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