CN109692666A - With three teeth chelating adsorption site lead stamp mark silicon materials and its preparation method and application - Google Patents

With three teeth chelating adsorption site lead stamp mark silicon materials and its preparation method and application Download PDF

Info

Publication number
CN109692666A
CN109692666A CN201910001565.4A CN201910001565A CN109692666A CN 109692666 A CN109692666 A CN 109692666A CN 201910001565 A CN201910001565 A CN 201910001565A CN 109692666 A CN109692666 A CN 109692666A
Authority
CN
China
Prior art keywords
lead
bpma
dipa
preparation
ion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201910001565.4A
Other languages
Chinese (zh)
Other versions
CN109692666B (en
Inventor
侯秀峰
詹兵
仪莹
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fudan University
Original Assignee
Fudan University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fudan University filed Critical Fudan University
Priority to CN201910001565.4A priority Critical patent/CN109692666B/en
Publication of CN109692666A publication Critical patent/CN109692666A/en
Application granted granted Critical
Publication of CN109692666B publication Critical patent/CN109692666B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • 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
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • 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
    • 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
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • 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
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention belongs to heavy metal ion adsorbed technical fields, specially have three teeth chelating adsorption site lead stamp mark silicon materials and its preparation method and application.Preparation method of the present invention includes:, respectively by BPMA, DIPA and lead compound hybrid reaction, to obtain BPMA and DIPA lead source in methanol and/or ethyl alcohol；It is steaming in toluene again, mesoporous silicon material and CPTES after activation is added, heating reaction, and treated product, BPMA or DIPA lead source, alkali are heated to reflux in toluene, then with acid elution removal lead to get two kinds it is novel have three teeth chelate site lead ion imprinted material.Three tooth functionalization lead stamp mark MCM-41 materials of the invention have fast large amount of adsorption, adsorption rate, good selectivity, stronger anti-interference ability to lead ion and ability are recycled, and can be used for adsorbing and/or detecting lead ion.

Description

With three teeth chelating adsorption site lead stamp mark silicon materials and its preparation method and application
Technical field
The invention belongs to heavy metal ion adsorbed technical fields, and in particular to there are three teeth to chelate adsorption site lead stamp mark silicon The application of material and preparation method thereof and absorption heavy metal ion.
Background technique
Lead is a kind of heavy metal element for seriously threatening Human Physiology health, is especially had to human liver and urinary system It seriously endangers.Lead in industrial wastewater can be enriched with by the aquatic products and crop of pollution in food chain.Therefore, it is enriched with and removes The trace lead element of water body, receives significant attention, and compared to the methods of traditional chemical deposition, ion exchange, film filtering, inhales Attached method has many advantages, such as that selectivity is strong, high-efficient, at low cost.
Ionic imprinting technique (ion imprinted technique, IIT) is with it with specific specific recognition ability, system The advantages that standby simple process, stability are high, selectivity is strong, is usually used in the absorption of Heavy Metals in Water Environment ion.Hou et al. (Microchemical Journal, 2017,131,130-136) reports a kind of modified SBA-15 mesoporous material of double pyrazole Material absorption Cr (III) ion.The common synthetic method of IIP is as follows: (1) preparation of Monomer-Metal Complex；(2) to above-mentioned network It closes object and carries out polymerization reaction；(3) template ion is removed using proper method, obtains three-dimensional recognition site.Currently, chitosan, 4- The function monomers such as vinylpyridine, imidazoles, amine are used for the preparation of lead ion imprinted polymer.Wherein, the lead of amino functionalization Ion imprinted polymer has extraordinary enrichment and separation effect, but its chemical stability is poor.Therefore, a kind of stabilization is developed Property height, large amount of adsorption, the lead ion trace system in selectivity high three tooth of nitrogenous type chelating site, there is important practical meaning.
The advantages that Metaporous silicon dioxide material is easily modified with its high-specific surface area, orderly uniform pore-size distribution, surface, makees It is widely used in the enrichment and separation of heavy metal for solid phase extraction material, studies have shown that Metaporous silicon dioxide material is function modified The separative efficiency of heavy metal can be improved.S.Ravi et al.(Microporous and Mesoporous Materials, 2018,258,62-71) the SBA-15 type Metaporous silicon dioxide material for reporting a kind of phosphoramidic acid modification, inhales for selectivity Lead ion in attached water environment. Hou,et al.(Microporous and Mesoporous Materials 2017,241, 165-177) report a kind of modified lead ion trace mesoporous silicon material of double pyrazole, the selection applied to lead ion in water environment Property absorption.Therefore, it by the lead ion trace point on optimization design Metaporous silicon dioxide material surface, realizes to lead ion Selective absorption and separation, the detection to trace lead ion in complicated substrate is applied to, are of great significance.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the adsorbance of the adsorbent material in existing lead ion adsorption technology The defects of small, selective weak, not strong to the anti-interference ability of coexisting ion, material circulation is poor using ability, providing one kind has Three teeth chelate the application of adsorption site lead stamp mark silicon materials and preparation method thereof and absorption heavy metal ion
The preparation method with three teeth chelating adsorption site lead stamp mark silicon materials provided by the invention, the specific steps are as follows:
(1) in methanol and/or ethyl alcohol, BPMA, DIPA are mixed with lead compound respectively, reaction obtains BPMA and DIPA Lead source；
(2) then, it is steaming in toluene again, the MCM-41 and CPTES after activation is added are heated to reflux, and by treated Product and BPMA or DIPA lead source, alkali, are heated to reflux in toluene, then with acid elution removal lead to get two kinds It is novel that there are three teeth to chelate site lead ion imprinted material.
The BPMA is bis- (pyridine -2- ylmethyl) amine, chemical structural formula are as follows:
The DIPA is two (pyridine -2- base) methylamines, chemical structural formula are as follows:
The CPTES is 3- chloropropyl triethoxysilane, chemical structural formula are as follows:
The MCM-41 refers to a kind of mesoporous material commonly used in the art.
In the present invention, the alkali, preferably K2CO3, triethylamine and Na2CO3One of or it is a variety of, more preferably for Triethylamine.
In the present invention, the molar ratio of the lead complex and alkali is 1:(1~1.2)；The MCM-41's and CPTES Molal weight ratio are as follows: 5mmol:(0.95g~1.00g)；The molal weight ratio of the lead complex and mesoporous material is 1mmol:(0.95g~1.00g).
In the present invention, the temperature being heated to reflux is 100~110 DEG C, and the time being heated to reflux is 20~24 hours.
In the present invention, before the mesoporous material grafting function monomer, the post-processing is preferably filtered, gained Solid is washed with methylene chloride, dry；Before the mesoporous material removes lead with acid elution, post-processing is preferably For filtering, obtained solid is dried with successively being washed with methylene chloride, distilled water, ethyl alcohol and ethyl acetate；Wherein, institute It states acid and is preferably hydrochloric acid；The molar concentration of the acid is preferably 3mol/L.
In the present invention, the BPMA lead complex the preparation method is as follows: in methanol and/or ethyl alcohol, by BPMA and lead Compound hybrid reaction；Wherein, the lead compound is preferably plumbi nitras；The temperature of the reaction is preferably It is 10~30 DEG C；The time of the reaction is preferably 4~6 hours；The molar ratio of the BPMA and lead compound is preferably For 2:1~1.2.
In the present invention, the DIPA lead complex the preparation method is as follows: in methanol and/or ethyl alcohol, by DIPA and lead Compound hybrid reaction；Wherein, the lead compound is preferably plumbi nitras；The temperature of the reaction is preferably 10~30 DEG C；The time of the reaction is preferably 4~6 hours；The molar ratio of the DIPA and lead compound is preferably 2:1~1.2.
It is prepared by the present invention that there are three teeth to chelate adsorption site lead stamp mark silicon materials, it is three tooth functionalization lead stamp mark MCM-41 Material, high to the selective absorption of lead ion, to the strong antijamming capability of coexisting ion, the renewable ability of material is strong, And have many advantages, such as that detection sensitivity is high, precision is high, detection efficiency is high.Therefore, which can be used for adsorbing and/or examining Sounding lead ion.Wherein, the lead is preferably divalent lead.
Detailed description of the invention
Fig. 1 is the crystal structure figure of two kinds of lead sources.Wherein, (a) is the crystal structure figure of BPMA-Pb-IIMS, (b) The crystal structure figure of DIPA-Pb-IIMS.
Fig. 2 is the FTIR spectrum figure of two kinds of lead imprinted materials.
Fig. 3 is the SEM micrograph of two kinds of lead imprinted materials.Wherein, (a) is BPMA-Pb-IIMS (a), (b) is DIPA-Pb-IIMS。
Fig. 4 is the TEM microphoto of two kinds of lead imprinted materials.Wherein, [(a1) and (b1)] it is BPMA-Pb-IIMS, [(a2) With (b2)] it is DIPA-Pb-IIMS.
Fig. 5 is the low-angle XRD diagram of two kinds of lead imprinted materials.
Fig. 6 is the N of two kinds of lead imprinted materials2Absorption-desorption thermoisopleth and graph of pore diameter distribution.
Fig. 7 is two kinds of lead imprinted materials to the relational graph between the adsorbance of Pb (II) and the pH value of solution.
Fig. 8 is the adsorption isotherm of two kinds of lead imprinted materials of the Pb (II) of different original concentrations.
Fig. 9 is influence of the time of contact to two kinds of lead imprinted materials BPMA-Pb-IIMS, DIPA-Pb-IIMS.
Figure 10 is lead imprinted material BPMA-Pb-IIMS reusability figure.
Figure 11 is present invention preparation diagram.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but example is only a part of the embodiment of the present invention. Based on the embodiments of the present invention, those of ordinary skill in the art are obtained under the premise of not doing creative work Every other embodiment, shall fall within the protection scope of the present invention.
It is as follows that the present invention detects used instrument:
X-ray intensity DATA REASONING is in 300K Bruker SMART 1000CCD x-ray diffraction instrument system support Mo- It is carried out under the electric power of target x ray tube (λ=0.71073) 2000W.Using Bruker spectrometer in CDCl3In 400MHz(1H) and 100MHz (13C it is operated under) to measure NMR spectra.It is analyzed on Nicolet AVATAR-360IR Fourier transform infrared (FT-IR) spectrum in KBr.Cu K α radiation is used using the scattering of Bruker D4 X-ray powder (45kV, 650mA) measures small angle X ray scattering (SAXS) measurement.Using 2010 electron microscope of JEOL JEM at 200kV Carry out transmission electron microscope (TEM) image measurement.Electricity is scanned under the acceleration voltage of 4.8kV to 15kV using Phenom Prox Mirror (SEM).Whole night after degasification, N2 adsorption is measured at 77K at 383K on 4000 analyzer of Quantachrome Nova Thermoisopleth.Pore-size distribution and specific surface area (SBET) are calculated separately using BJH model and BET method.
Embodiment 1
Synthesize BPMA
Pyridine carboxaldehyde (1.07g, 10mmol), 2- aminomethyl-pyridine (1.08g, 10mmol) are dissolved in ethanol solution In, brown mixed solution stirs 3h.Reaction flask is placed in ice-water bath, by NaBH4(0.76g, 10mmol) is added three times, after Continuous stirring 16h.It is adjusted to pH=4 with concentrated hydrochloric acid, filters NaCl solid.Vacuum drains solvent, and 15mL water is added, and solution is used The CH of 20mL2Cl25 times (removing unreacted 2- pyridine carboxaldehyde) are washed, water phase Na2CO3It is adjusted to pH=10, solution CH2Cl2 Extraction 3 times merges organic phase, uses anhydrous Na2SO4After drying, filtering, it is spin-dried for solvent, obtains pale tan oil.It reflects through nuclear-magnetism It surely is target product BPMA (yield 76%).
Nuclear magnetic data is as follows:
1H NMR(400MHz,CDCl3) δ 8.55 (d, J=4.3Hz, 1H), 7.94-7.51 (m, 1H), 7.33 (t, J= 18.3Hz,1H),7.19–7.07(m,1H),3.98(s,2H).
13C NMR(101MHz,CDCl3) δ 159.55 (s), 149.28 (s), 136.45 (s), 122.11 (d, J=33.2 Hz),79.13–74.85(m)。
Embodiment 2
Synthesize DIPA
NH2OHHCl (750mg, 10.8mmol), NaAc (886mg, 10.8mmol) are blended in the water of 10mL and are heated to 60 DEG C, 1h is stirred, after methanol (2mL) solution of pyridone (1g, 5.43mmol) is added, mixed solution continues to be stirred overnight (60 DEG C), reactant is cooled to room temperature (0 DEG C) of rear ice-water bath filtering, and is washed with a small amount of cold water, vacuum drying.It obtains pink Color solid powder (yield 90%).
By above-mentioned pink solid powder oxime (1g, 5mmol), NH4Ac(665mg,8.5mmol)、NH3·H2O (25%, 15ml), CH3CH2OH (20ml) and H2O (10ml) is mixed and heated to 80 DEG C, and Zn powder (1.47g, 22.5mmol) divides in 30min 3 additions, mixed solution flow back 3h at 80 DEG C, are stirred at room temperature overnight, and mixed solution filtering removal solid is used respectively Methanol and water washing, are spin-dried for methanol, and remaining aqueous solution is modulated into strong base solution with the NaOH solution of 10M.With the CH of 30mL2Cl2 Repeatedly extraction strong base solution, organic phase extracted continue to be extracted with saturation NaCl solution, and a small amount of saturation NH is added4Cl is molten Liquid washing.Organic phase anhydrous Na extracted2SO4It is dry, it is spin-dried for CH2Cl2, obtain pale tan oil (yield 90%).
Nuclear magnetic data is as follows:
1H NMR(400MHz,CDCl3) δ 8.57 (d, J=4.3Hz, 2H), 7.64 (td, J=7.7,1.7Hz, 2H), 7.40 (d, J=7.8Hz, 2H), 7.16 (dd, J=6.6,5.0Hz, 2H), 5.32 (d, J=12.6Hz, 1H)
13C NMR(101MHz,CDCl3)δ162.74(s),149.17(s),136.63(s),122.08(s),121.75 (s),77.30(s),76.98(s),76.66(s),62.33(s)。
Embodiment 3
Synthesize BPMA lead complex
The three tooth BPMA function monomers and 1mmol plumbi nitras of 1mmol are dissolved in together in 20mL methanol, stirring is straight at room temperature Buff powder (yield 76%) is obtained until solution is bright, after filtration drying.
Nuclear magnetic data is as follows:
1H NMR (400MHz, DMSO) δ 8.75 (d, J=4.5Hz, 1H), 8.27-7.72 (m, 2H), 7.48 (t, J= 5.9Hz,1H),6.95(s,1H),4.54(s,1H).
13C NMR(101MHz,CDCl3)δ158.72,148.76,139.45,123.90,54.41。
Embodiment 4
Synthesize DIPA lead complex
Double pyrazole function monomer DIPA and the 0.5mmol plumbi nitras of 1mmol is dissolved in together in 20mL methanol, is stirred at room temperature It mixes until solution is bright, buff powder (yield 72%) is obtained after filtration drying.
Nuclear magnetic data is as follows:
1H NMR (400MHz, DMSO) δ 8.76 (s, 1H), 7.97 (t, J=7.4Hz, 1H), 7.60 (t, J=14.8Hz, 1H),7.56–7.41(m,1H),4.51(s,2H).
13C NMR (101MHz, DMSO) δ 158.72 (s), 148.76 (s), 139.45 (s), 123.90 (d, J=13.1 Hz),54.41(s)。
Embodiment 5
Synthesize the bis- pyridine functional lead stamp mark MCM-41 materials (i.e. BPMA-Pb-IIMS) of BPMA
Activated MCM-41 mesoporous silicon material (1g) is dissolved in 20mL to steam in toluene solvant again, after stirring 1h, dropwise It is added 3- chloropropyl triethoxysilane (5mmol), in N2Protection under flow back for 24 hours, after suction filtration, obtained solid dichloromethane After alkane washing, drain to obtain light tan solid powder under vacuum.By the bis- pyridine lead of the BPMA of obtained solid powder, 1mmol The triethylamine for closing object and 1mmol is dissolved in 20mL and steams in toluene solvant again, and flow back 18h, and after suction filtration, obtained solid is with two After chloromethanes, water, 95% ethyl alcohol and ethyl acetate wash repeatedly, drain to obtain light green solid powder under vacuum, with 3M's Lead ion in HCl eluting material continues to be eluted to neutrality with distilled water, and 60 DEG C in vacuum oven after elution for several times Lower drying, obtains lead ion imprinted material.
Embodiment 6
It synthesizes the bis- pyrrole pyridine functional MCM-41 materials of BPMA (i.e. BPMA-NIMS material)
Activated MCM-41 mesoporous silicon material (1g) is dissolved in 20mL to steam in toluene solvant again, after stirring 1h, dropwise It is added chloropropyl triethoxysilane (5mmol), in N2Protection under flow back for 24 hours, after suction filtration, obtained solid methylene chloride After washing, drain to obtain light tan solid powder under vacuum.By obtained solid powder, 1mmol BPMA ligand and The triethylamine of 1mmol is dissolved in 20mL and steams in toluene solvant again, and flow back 18h, after suction filtration, obtained solid methylene chloride, After water, 95% ethyl alcohol and ethyl acetate wash repeatedly, drain to obtain light yellow solid powder BPMA-NIMS under vacuum.
Embodiment 7
Synthesize the bis- pyridine functional lead imprinted materials (i.e. DIPA-Pb-IIMS) of DIPA
Activated MCM-41 mesoporous silicon material (1g) is dissolved in 20mL to steam in toluene solvant again, after stirring 1h, dropwise It is added 3- chloropropyl triethoxysilane (5mmol), in N2Protection under flow back for 24 hours, after suction filtration, obtained solid dichloromethane After alkane washing, drain to obtain light tan solid powder under vacuum.By the bis- pyridine lead of the DIPA of obtained solid powder, 1mmol The triethylamine for closing object and 1mmol is dissolved in 20mL and steams in toluene solvant again, and flow back 18h, and after suction filtration, obtained solid is with two After chloromethanes, water, 95% ethyl alcohol and ethyl acetate wash repeatedly, drain to obtain light green solid powder under vacuum, with 3M's Lead ion in HCl eluting material continues to be eluted to neutrality with distilled water, and 60 DEG C in vacuum oven after elution for several times Lower drying, obtains lead ion marking material.
Embodiment 8
It synthesizes the bis- pyrrole pyridine functional MCM-41 materials of DIPA (i.e. DIPA-NIMS material)
Activated MCM-41 mesoporous silicon material (1g) is dissolved in 20mL to steam in toluene solvant again, after stirring 1h, dropwise It is added chloropropyl triethoxysilane (5mmol), in N2Protection under flow back for 24 hours, after suction filtration, obtained solid methylene chloride After washing, drain to obtain light tan solid powder under vacuum.By obtained solid powder, 1mmol DIPA ligand and The triethylamine of 1mmol is dissolved in 20mL and steams in toluene solvant again, and flow back 18h, after suction filtration, obtained solid methylene chloride, After water, 95% ethyl alcohol and ethyl acetate wash repeatedly, drain to obtain light yellow solid powder DIPA-NIMS under vacuum.
Effect example 1
Product analysis is carried out to BPMA-Pb-IIMS, DIPA-Pb-IIMS of synthesis, as a result as follows:
Fig. 1 shows the structure of Pb-BPMA and Pb-DIPA.Lead source Pb-BPMA and Pb-DIPA is by Pb (NO3)2And list Body 1:2 reaction preparation.In order to further inquire into the mode of action of monomer and lead ion, by slow evaporation obtain Pb-BPMA and Pb-DIPA monocrystalline.Pb-BPMA complex forms (Fig. 1 is left) by a BPMA function monomer and 2 nitrate anions. Pb-DIPA complex compound is coordinated by DIPA and 3 nitrate anion, and two of them nitrate anion is two metallic leads Share (Fig. 1 is right).
Fig. 2 is shown in 3440cm-1And 1632cm-1Neighbouring width and strong absorption band belongs to Si-OH.Si-O-Si group In 1080 cm-1,824cm-1,442cm-1Nearby there is characteristic peak.Meanwhile the absorption peak of function monomer is respectively in 1630cm-1(C= N near), 1380cm-1(C-N), 2920cm-1(aliphatic C-H) and 3230cm-1Near (aromatic series C-H).
Fig. 3 SEM image shows that BPMA-Pb-IIMS, DIPA-Pb-IIMS have the laminated structure of opposite ordered morphologies.
Fig. 4 TEM image shows that PBPMA-Pb-IIMS, DIPA-Pb-IIMS are original hexagonal hole structures, and corresponding Channel longitudinal section is parallel lines structure, and MCM-41 still keeps the meso-hole structure of high-sequential after showing improvement.
Fig. 5 low-angle XRD is the result shows that the range of BPMA-Pb-IIMS, DIPA-Pb-IIMS in (2 θ=2.2 °) has record Intact peak value, this is can be traceable to MCM-41 (100), (110) and (200) reflection.This illustrates the structure structure of MCM-41 It saves well, this supports the result of SEM and TEM well.
Fig. 6 is BPMA-Pb-IIMS, nitrogen adsorption-desorption isotherm of DIPA-Pb-IIMS, with DIPA-Pb-IIMS phase Than BPMA-Pb-IIMS has higher nitrogen percentage, shows the grafting of more multifunctional monomer on MCM-41.This shows BPMA- Pb-IIMS has highest N content, and the adsorption capacity to Pb (II) can be enhanced.
Effect example 2
The influence that pH adsorbs lead ion
For the influence for studying pH, BPMA-Pb-IIMS and DIPA-Pb-IIMS are added separately to different pH (2~7) and contained 30mg·L-1Pb (II) ion samples solution in, pH value pass through NaAc_HAc buffer solution adjust.By mixture at 25 DEG C Lower continuous water-bath vibrates 30 minutes, then stable to place 30 minutes, and centrifugation, filtering are sent out by inductively coupled plasma atom Penetrate the concentration of Pb (II) in spectroscopic methodology (ICP-AES) measurement upper solution.
Adsorbance is calculated by following equation:
Wherein qe(adsorbance, mgg-1) be Pb-IIMS absorption Pb (II) amount, CoAnd CeIt is Pb in solution (II) Original and equilibrium concentration, m (g) are the weight of Pb-IIMS, and V (L) is the volume of metal ion solution.
As shown in fig. 7, pH value of solution has a significant impact lead ion absorption, and when pH is greater than 7, Pb2+It can generally be precipitated.Cause This, we have studied absorption BPMA-Pb-IIMS and DIPA-Pb-IIMS with pH value from 2 to 7.When initial pH value is low, inhale The low reason of attached capacity may be the protonation of N atom, and which reduce the sequestering powers of the lead ion on pyridine ring.Cause This, determines that the optimal pH of lead ion imprinted material is 7.0.
Effect example 3
The influence that eluant strength recycles lead ion
With acidic elution agent such as HCl, HNO of various concentration3And its it is eluted with the mixture of thiocarbamide as auxiliary additive Pb in these imprinted materials2+.As shown in Table 1,3mol L-1HCl solution can complete Pb2+Quantitative elution.Therefore, we Select 3mol L-1Eluent of the HCl (V=10ml) as research metal ion.
The influence of the eluant, eluent of 1 different type of table and concentration
The volume of eluant, eluent is 10mL.
Effect example 4
The determination of adsorption saturation concentration
In order to preferably probe into absorption behavior, adsorption isotherm such as Fig. 8 institute of BPMA-Pb-IIMS and DIPA-Pb-IIMS Show.With Pb2+Initial concentration gradually increases, and the equilibrium adsorption ability of two kinds of Pb-IIMS also increases sharply, in Pb2+Concentration When close to 70ppm, adsorption process reaches saturation state.The adsorption capacity of BPMA-Pb-IIMS is slightly above DIPA-Pb-IIMS, this It may be since BPMA-Pb-IIMS has been loaded caused by more function monomers.
Effect example 5
The determination of the rate of adsorption
The rate of adsorption of Pb in water sample (II) is determined to Pb (II) progress dynamics research, it is as follows: by every kind of suction of 5mg Attached dose is dispersed in 20mL and contains in the solution of identical initial p b (II) concentration of 70ppm.By every kind of mixture at 25 DEG C continuous water Bath oscillation 10,20,30,40,50 or 60 minutes.After each period, filtering solution is simultaneously analyzed by ICP-AES with determination The concentration of Pb (II) in final solution.As shown in figure 9, the BPMA-Pb-IIMS rate of adsorption is very fast, 20min reaches adsorption equilibrium, The rate of adsorption is 8.75mgg-1·min-1.The DIPA-Pb-IIMS rate of adsorption is slower, and 30min reaches adsorption equilibrium.Absorption Rate is 4.83mgg-1·min-1。
Effect example 6
Adsorptive selectivity experiment
To study specificity and selective absorption to Pb (II), containing Cd2+,Cu2+,Cr3+,Ni2+,Zn2+,Mg2+With Fe3+As the adsorptivity in the mixed solution of competing ions, carrying out two kinds of ion blotting materials and its corresponding non-imprinted material It can test.Breadth coefficient K is calculated based on following equationd(mL·g-1), selectivity factor (α), relative selectivity coefficient (β):
Wherein Co(mL·g-1) and Ce(mL·g-1) indicate Pb (II) original and equilibrium concentration；M (g) is the weight of IIMS Amount, V (L) is the volume of metal ion solution；KdPbAnd KdMIt is the breadth coefficient of Pb (II) and competing ions respectively；α and β difference Indicate the selectivity factor and relative selectivity coefficient of ion blotting material and nonionic imprinted material.
Table 2 clearly illustrates that BPMA-Pb-IIMS is higher than the selectivity factor of Pb (II) contained in competitive metal ion DIPA-Pb-IIMS and non-imprinted material, it can be deduced that the BPMA-Pb-IIMS of a conclusion, synthesis has superior Pb (II) selectivity.
The adsorption selectivity of table 2 Pb-IIMS and NIMS
A possibility that in order to assess adsorbent application, study the influence of various ions in water, such as Li+, Na+, K+, Mg2 +, Cd2+, Cu2+, Mn2+, Ni2+, Fe3+, Hg2+, SO4 2-, CH3COO-, Cl-.We defined with tolerance may cause be less than ± The maximum concentration of the foreign ion of 5% error is indicated permissible concentration ratio using X/Pb (II), uses adsorbent pair The recovery rate of Pb (II) illustrates under conditions of having interfering ion, the anti-interference of our adsorbent.It the results are shown in Table 3. As can be seen from the table, foreign ion does not have obvious shadow to Pb (II) ion detection of DIPA-Pb-IIMS at optimum conditions It rings.
Various ion pair Pb (II) ion measurements of table 3 allow to compare
Effect example 7
Reusability experiment
For the reusability for evaluating BPMA-Pb-IIMS, We conducted circulation experiments, and Pb is desorbed from adsorbent (II).Use 10mL, 3molL-1Hydrochloric acid is as eluant, eluent, and by solution, continuous water-bath vibrates 30 minutes at 25 DEG C.From solution Middle removing Pb (II) ion and after being washed with deionized, passes through ICP-AES and measures lead ion content in solution.It carries out following Adsorption experiment.
By using 3molL-1HCl is re-used for as stripping medium, the stability and reusability of BPMA-Pb-IIMS Eight adsorption-desorption cycles, the results are shown in Figure 10.Other than adsorbance has slight decrease during eight circulations, ion Trace mesoporous silicon oxide is still maintained at very high level to the adsorbance of Pb (II).Therefore, it was demonstrated that obtaining has height The BPMA-Pb-IIMS of adsorbance can be reused.
Effect example 8
BPMA-Pb-IIMS is used to measure the Pb (II) in industrial wastewater
20mL prepares water sample and mixes Pb (II) standard items (5ugL of three kinds of concentration of 5mg BPMA-Pb-IIMS-1、 10ug·L-1And 50ugL-1), gained mixture is adjusted to pH 7.0 using buffer solution, mixture solution connects at 25 DEG C Continuous stirring 30 minutes.After filtering, 10mL, 3molL are used-1Hydrochloric acid elution absorption Pb (II) ion, and pass through ICP- AES measurement.Three repeated experiments are carried out respectively for every kind of concentration.
Pass through Pb (II) concentration of standard addition method analysis absorption.As shown in table 4, the gained rate of recovery is in 98% or more, RSD In 1.36%~2.2% range.It is inferred that BPMA-Pb-IIMS is the ideal for adsorbing and going Pb (II) in water removal Candidate.The rate of recovery (%) and relative standard deviation of the BPMA-Pb-IIMS for the Pb (II) that table 4 is obtained from water sample (RSD, %)

Claims (9)

1. a kind of preparation method with three teeth chelating adsorption site lead stamp mark silicon materials, which is characterized in that specific step is as follows:
(1) in methanol and/or ethyl alcohol, BPMA, DIPA are mixed with lead compound respectively, reaction obtains BPMA and DIPA lead and matches Close object；
(2) then, steaming in toluene again, the MCM-41 and CPTES after activation is added are heated to reflux, and will treated product, And BPMA or DIPA lead source, alkali, it is heated to reflux in toluene, then with acid elution removal lead to get two kinds of novel tools There are three teeth to chelate site lead ion imprinted material；
Wherein, the BPMA is bis- (pyridine -2- ylmethyl) amine, and the DIPA is two (pyridine -2- base) methylamines, the CPTES It is 3- chloropropyl triethoxysilane, the MCM-41 is a kind of mesoporous material.
2. preparation method according to claim 1, which is characterized in that the alkali is K2CO3, triethylamine and Na2CO3In It is one or more.
3. preparation method according to claim 1, which is characterized in that the molar ratio of the lead complex and alkali is 1:(1 ~ 1.2)；The molal weight ratio of the MCM-41 and CPTES are as follows: 5mmol: (0.95g ~ 1.00g)；The lead network The molal weight ratio for closing object and mesoporous material is 1mmol:(0.95g ~ 1.00g).
4. preparation method according to claim 1, which is characterized in that the temperature being heated to reflux is 100 ~ 110 DEG C, being heated to reflux the time is 20 ~ 24 hours.
5. preparation method according to claim 1, which is characterized in that the described mesoporous material grafting function monomer it Before, through filtration treatment, obtained solid is washed with methylene chloride, dry；Before the mesoporous material removes lead with acid elution, Through filtration treatment, obtained solid is dried with successively being washed with methylene chloride, distilled water, ethyl alcohol and ethyl acetate.
6. preparation method according to claim 1, which is characterized in that the preparation flow of the BPMA lead complex is such as Under: in methanol and/or ethyl alcohol, by BPMA and lead compound hybrid reaction；Wherein, the lead compound is nitric acid Lead；Reaction temperature is 10 ~ 30 DEG C；Reaction time is 4 ~ 6 hours；The molar ratio of the BPMA and lead compound is 2:1 ~ 1.2.
7. preparation method according to claim 1, which is characterized in that the preparation flow of the DIPA lead complex is such as Under: in methanol and/or ethyl alcohol, by DIPA and lead compound hybrid reaction；Wherein, the lead compound is nitric acid Lead；Reaction temperature is 10 ~ 30 DEG C, and the reaction time is 4 ~ 6 hours；The molar ratio of the DIPA and lead compound is 2:1 ~ 1.2.
8. one kind preparation method as described in one of claim 1 ~ 7 is obtained there are three teeth to chelate adsorption site lead stamp mark silicon material Material.
9. a kind of as claimed in claim 8 there are three teeth to chelate adsorption site lead stamp mark silicon materials, lead is being adsorbed and/or detected Application in ion.
CN201910001565.4A 2019-01-02 2019-01-02 Lead imprinted silicon material with tridentate chelating adsorption sites and preparation method and application thereof Active CN109692666B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910001565.4A CN109692666B (en) 2019-01-02 2019-01-02 Lead imprinted silicon material with tridentate chelating adsorption sites and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910001565.4A CN109692666B (en) 2019-01-02 2019-01-02 Lead imprinted silicon material with tridentate chelating adsorption sites and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN109692666A true CN109692666A (en) 2019-04-30
CN109692666B CN109692666B (en) 2021-09-17

Family

ID=66232477

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910001565.4A Active CN109692666B (en) 2019-01-02 2019-01-02 Lead imprinted silicon material with tridentate chelating adsorption sites and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN109692666B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111514861A (en) * 2020-05-13 2020-08-11 天津工业大学 Preparation method and application of tridentate ligand heavy metal ion imprinting material
CN115677734A (en) * 2022-10-28 2023-02-03 福州大学 Metal complex, preparation method and application thereof in photocatalysis antibiosis

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101968445A (en) * 2010-03-11 2011-02-09 大连理工大学 Mesoporous silicon material immobilized by 1, 8-naphthalimide fluorescent dye and application thereof
CN102441367A (en) * 2011-09-08 2012-05-09 中南大学 Preparation method for silica gel-loaded aminomethylpyridine chelating resin for deep copper removal
KR101871636B1 (en) * 2017-10-24 2018-06-26 서울대학교산학협력단 Method for preparing heavy metal ions imprinted absorbent for the selective separation of heavy metal ions
CN108236923A (en) * 2016-12-23 2018-07-03 上海出入境检验检疫局工业品与原材料检测技术中心 Double pyrazole functionalization lead stamp mark MCM-41 materials and preparation method and application
CN108339535A (en) * 2018-03-14 2018-07-31 济南大学 A kind of preparation method of lead ion trace adsorbent

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101968445A (en) * 2010-03-11 2011-02-09 大连理工大学 Mesoporous silicon material immobilized by 1, 8-naphthalimide fluorescent dye and application thereof
CN102441367A (en) * 2011-09-08 2012-05-09 中南大学 Preparation method for silica gel-loaded aminomethylpyridine chelating resin for deep copper removal
CN108236923A (en) * 2016-12-23 2018-07-03 上海出入境检验检疫局工业品与原材料检测技术中心 Double pyrazole functionalization lead stamp mark MCM-41 materials and preparation method and application
KR101871636B1 (en) * 2017-10-24 2018-06-26 서울대학교산학협력단 Method for preparing heavy metal ions imprinted absorbent for the selective separation of heavy metal ions
CN108339535A (en) * 2018-03-14 2018-07-31 济南大学 A kind of preparation method of lead ion trace adsorbent

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
XIANFEI ZENG ETAL.: "Selective Zn (II) chemosensor based on di(2-picolyl)amine functionalized inorganic/organic hybrid magnetic network", 《 CHEMICAL ENGINEERING JOURNAL》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111514861A (en) * 2020-05-13 2020-08-11 天津工业大学 Preparation method and application of tridentate ligand heavy metal ion imprinting material
CN111514861B (en) * 2020-05-13 2022-07-05 天津工业大学 Preparation method and application of tridentate ligand heavy metal ion imprinting material
CN115677734A (en) * 2022-10-28 2023-02-03 福州大学 Metal complex, preparation method and application thereof in photocatalysis antibiosis

Also Published As

Publication number Publication date
CN109692666B (en) 2021-09-17

Similar Documents

Publication Publication Date Title
Jeong et al. Removal of Cu (II) from water by tetrakis (4-carboxyphenyl) porphyrin-functionalized mesoporous silica
Wang et al. Simultaneous adsorption of Cu (II) and SO42− ions by a novel silica gel functionalized with a ditopic zwitterionic Schiff base ligand
Hajiaghababaei et al. Highly efficient removal and preconcentration of lead and cadmium cations from water and wastewater samples using ethylenediamine functionalized SBA-15
Rapti et al. Rapid, green and inexpensive synthesis of high quality UiO-66 amino-functionalized materials with exceptional capability for removal of hexavalent chromium from industrial waste
Huang et al. Fabrication of an efficient surface ion-imprinted polymer based on sandwich-like graphene oxide composite materials for fast and selective removal of lead ions
El-Safty et al. Mesoporous aluminosilica sensors for the visual removal and detection of Pd (II) and Cu (II) ions
Jamshidi et al. New ion-imprinted polymer-functionalized mesoporous SBA-15 for selective separation and preconcentration of Cr (iii) ions: modeling and optimization
Awual et al. pH dependent Cu (II) and Pd (II) ions detection and removal from aqueous media by an efficient mesoporous adsorbent
Wu et al. Adsorption of Cu (II)–EDTA chelates on tri-ammonium-functionalized mesoporous silica from aqueous solution
Huang et al. Pb (II) removal from aqueous media by EDTA-modified mesoporous silica SBA-15
Wang et al. Removal of uranium (VI) from aqueous solution using iminodiacetic acid derivative functionalized SBA-15 as adsorbents
Matusik et al. Enhanced heavy metal adsorption on functionalized nanotubular halloysite interlayer grafted with aminoalcohols
Fu et al. Synthesis of multi-ion imprinted polymers based on dithizone chelation for simultaneous removal of Hg 2+, Cd 2+, Ni 2+ and Cu 2+ from aqueous solutions
Wang et al. Preparation of a functionalized magnetic metal–organic framework sorbent for the extraction of lead prior to electrothermal atomic absorption spectrometer analysis
Zhang et al. Synthesis and characterization of ferric tannate as a novel porous adsorptive-catalyst for nitrogen removal from wastewater
Ebrahimzadeh et al. Novel magnetic ion imprinted polymer as a highly selective sorbent for extraction of gold ions in aqueous samples
Fu et al. Pyridine-based covalent organic framework for efficient and selective removal of Hg (II) from water: Adsorption behavior and adsorption mechanism investigations
El-Safty et al. Visual detection and revisable supermicrostructure sensor systems of Cu (II) analytes
Zare-Dorabei et al. Synthesis, characterization and application of cyclam-modified magnetic SBA-15 as a novel sorbent and its optimization by central composite design for adsorption and determination of trace amounts of lead ions
Li et al. Efficient separation and high selectivity for nickel from cobalt-solution by a novel chelating resin: Batch, column and competition investigation
Hu et al. Efficient adsorption toward precious metal from aqueous solution by zeolitic imidazolate framework-8
Guo et al. Investigation of antimony adsorption on a zirconium-porphyrin-based metal–organic framework
CN115490879B (en) EDTA modified UIO-66 (Zr) metal organic framework material and preparation method and application thereof
CN109692666A (en) With three teeth chelating adsorption site lead stamp mark silicon materials and its preparation method and application
CN109806844A (en) A kind of magnetic metal organic framework materials of dephosphorization and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant