CN109759020A - A kind of Nd-MOFs gas adsorption material and its preparation method and application - Google Patents
A kind of Nd-MOFs gas adsorption material and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of Nd-MOFs gas adsorption material, including ligand AGE synthesis, materials synthesis, it measures ligand solution respectively and neodymium chloride solution is added in conical flask, it is uniformly mixed, under the conditions of magnetic agitation, N, N- diisopropylethylamine (DIEA) is added dropwise and adjusts the pH value of solution to pH 7-8, it is stirred to react under room temperature, then it is filtered with vacuum pump, obtained solid is first washed with distilled water 2-4 times with acetone washing 2-5 times, again, is subsequently placed in dry in baking oven to constant weight and obtains Nd-MOFs gas adsorption material.The present invention prepares the absorption of Nd-MOFs gas adsorption material overcome when active carbon easily desorbs under high temperature environment, zeolite molecular sieve cannot be used for strong inorganic acid and basic conditions, montmorillonite surface carries out the variation that chemical modification needs the pH value of strict control solution in the process and easily causes many factors, lead to the decline of montmorillonite absorption property, adsorption effect is excellent.
Description
Technical field
The present invention relates to technical field of composite materials, a kind of Nd-MOFs gas adsorption material and preparation method thereof is referred specifically to
And application.
Background technique
In recent years, with the fast development of China's economy and society, problem of environmental pollution increasingly sharpens, it has also become current society
The hot spot that can be paid close attention to.It is shown according to statistics, after particulate matter, sulfur dioxide, it was found that the third-largest gaseous pollutant
That is volatile organic compounds (VOCs).Most VOCs have toxicity, and Long Term Contact can seriously endanger human health, damage people
Somatic nerves maincenter and immune system；Even some VOCs have strong carcinogenic effect, threaten the health of resident.In addition,
VOCs and nitrogen oxides can generate photochemical reaction under light action, form photochemical fog, cause animal breath difficulty and
Plant is withered.Therefore, effectively preventing for VOCs gas pollutant causes government and the public greatly pays close attention to.
Currently, the processing technique of VOCs is roughly divided into two classes: recovery technology and destruction technology, recovery technology includes: condensation
Absorption method, membrane separation process, absorption method and solution absorption method etc.；Destruction technology include: Production by Catalytic Combustion Process, flame combustion method, etc. from
Daughter technology and biodegrade etc..These processing methods all achieve good adsorption effect to a certain extent, but respectively
There are certain drawbacks.Wherein condensation method is suitble to the organic exhaust gas of high concentration, and for industrial, it is generally and at other technologies combination
Manage the oil gas of high concentration；Membrane separation process needs to combine other technologies, and seperation film and VOCs have very strong interaction, need
The tolerance of film is very high, reduces manufacture and operating cost is the key that technology further genralrlization application；Solution absorption method is main
For field of waste water treatment；Combustion method has very high requirement to temperature, and at 1100 DEG C or so, temperature increases such as direct ignition temperature
Mean the increase of security risk；The efficiency of plasma technique is lower, there are a large amount of by-products；The degradation class of biological degradation method
There is certain application limitation in type；In order to overcome prior art problem this project to have developed a kind of novel Nd-MOFs gas suction
Enclosure material, and the drying of wood is administered for adsorbing, have many advantages, such as that simple process, operation energy consumption are low, purification efficiency is high.
Summary of the invention
It is an object of the invention to provide a kind of Nd-MOFs gas adsorption material in place of overcome the deficiencies in the prior art, gram
It has taken active carbon easily to desorb under high temperature environment, recycling rate of waterused is low, and use cost height etc., zeolite molecular sieve cannot be used for strong nothing
Absorption when machine acid and basic conditions, montmorillonite surface carry out the pH value that strict control solution is needed during chemical modification and easy
The variation for causing many factors leads to the decline of montmorillonite absorption property；For handling domestic pinus sylvestris var. mongolica material high/low temperature
The VOCs gas (aldehydes, aromatic hydrocarbon, firpene, carbon tetrachloride and alkane etc.) discharged in drying process, adsorption effect is excellent.This hair
It is bright to have developed a kind of novel Nd-MOFs gas adsorption material, the drying of wood is administered for adsorbing, there is simple process, operation
The advantages that low energy consumption, purification efficiency is high.
The technical proposal for solving the technical problem of the invention is:
A kind of preparation method of Nd-MOFs gas adsorption material, including ligand AGE synthesis, materials synthesis,
Ligand AGE synthesis specifically includes the following steps:
It accurately weighs 10.5-12.5 g phthalic anhydride to pour into boiling flask, 40 mL-55mL acetone solns, magnetic force is added
Stirring, dissolves it sufficiently, adds 4.5-5.5 g methyl-α-D- galactopyranoside, be warming up to
After 60-80 DEG C, 2-8mL catalyst n, N- diisopropylethylamine (DIEA) is added, is uniformly mixed, heating stirring, back flow reaction 8-9
Resulting liquid is cooled to room temperature by h, and the anhydrous magnesium sulfate that 1-3 g is added dries, filters, by gained filtrate at 58-62 DEG C
Acetone solvent is boiled off using Rotary Evaporators, obtains sticky colourless liquid i.e. ligand AGE；
The materials synthesis specifically includes the following steps:
Ligand solution preparation: the above-mentioned ligand AGE of 5.5-7.0 g that accurately weighs is placed in conical flask, and 25-35mL third is added
Ketone sufficiently dissolves it；
Neodymium chloride solution preparation: it weighs 2.6-2.9 g neodymium chloride and is dissolved in 10-12 mL distilled water；
Material preparation: measuring 10-12mL ligand solution respectively and neodymium chloride solution be added in conical flask, is uniformly mixed, magnetic force
Under stirring condition, N, N- diisopropylethylamine (DIEA) is added dropwise and adjusts the pH value of solution to pH 7-8, under room temperature
Be stirred to react 2.5-5.5 h, then filtered with vacuum pump, by obtained solid first with acetone washing 2-5 times, use distilled water again
Washing 2-4 times is subsequently placed in drying to constant weight in 60 DEG C -70 DEG C of baking oven and obtains Nd-MOFs gas adsorption material.
Preferably, the preparation method of a kind of Nd-MOFs gas adsorption material, including ligand AGE synthesis, material are closed
At, it is characterised in that:
The ligand AGE synthesis is poured into boiling flask specifically includes the following steps: accurately weighing 11.5 g phthalic anhydrides,
50 mL acetone solns are added, magnetic agitation dissolves it sufficiently under the conditions of 40 DEG C, adds 5 g methyl-α-D- pyrans half
Lactoside after being warming up to 75 DEG C, is added 4 mL catalyst ns, N- diisopropylethylamine (DIEA), is uniformly mixed, heating stirring, returns
Stream 9 h of reaction, resulting liquid are cooled to room temperature, the anhydrous magnesium sulfate that appropriate 2g is added dries, filters, and gained filtrate is existed
Acetone solvent is boiled off using Rotary Evaporators at 60 DEG C, obtains sticky colourless liquid i.e. ligand AGE；
The materials synthesis specifically includes the following steps:
Ligand solution preparation: the above-mentioned ligand AGE of 6.25 g that accurately weighs is placed in conical flask, be added 30 mL acetone by its
Sufficiently dissolution；
Neodymium chloride solution preparation: 2.77 g neodymium chlorides are weighed and are dissolved in 10 mL distilled water；
Material preparation；10 mL ligand solutions are measured respectively and neodymium chloride solution is added in conical flask, are uniformly mixed, magnetic force stirs
Under the conditions of mixing, the pH value of N, N- diisopropylethylamine (DIEA) adjusting solution is added dropwise to pH 7-8, stirs under room temperature
4 h of reaction are mixed, is then filtered with vacuum pump, obtained solid is first used acetone washing 3 times, then be washed with distilled water 3 times, so
It is placed on to dry in 60 DEG C of baking oven to constant weight and obtains Nd-MOFs gas adsorption material.
A kind of Nd-MOFs gas adsorption material, using above-mentioned Nd-MOFs gas-adsorbing material preparation method for material preparation
At.
Preferably, above-mentioned Nd-MOFs gas adsorption material is used for VOCs gas absorption.
Preferably, the VOCs includes aldehydes, aromatic hydrocarbon, firpene, carbon tetrachloride and alkane.
Preferably, the VOCs includes carbon tetrachloride, nopinene, benzene and australene.
The advantages and positive effects of the present invention are:
1, for the first time using ion centered on rare earth ion, environmental-friendly biological material -- glucosides is used as matches the present invention
Body obtains rare earth metal-aryl glycoside acid esters Nd-MOFs material by the rearrangement and self assembly of molecule, and for administering VOCs
Gas (australene, nopinene, benzene and CCl4), adsorption effect is excellent.
2, Nd-MOFs gas adsorption material of the present invention overcomes active carbon and easily desorbs under high temperature environment, recycling rate of waterused
It is low, absorption, montmorillonite surface when use cost height etc., zeolite molecular sieve cannot be used for strong inorganic acid and basic conditions
The variation for needing the pH value of strict control solution in modifying process and easily causing many factors is learned, montmorillonite absorption property is caused
The problems such as decline, has unique structural advantage and becomes the excellent VOCs adsorbent of a kind of Green performance.
3, Inner Mongolia Autonomous Region is the township of rare earth, and the rare earth metal neodymium that the present invention selects embodies the initiative and advantages of the localities；The present invention
Ligand first is that methyl-α-D- galactopyranoside, belongs to polyhydroxy glucosides, be a kind of environmentally friendly biomass material,
It is also one of the main chemical compositions of timber, can extracts to obtain from timber, the application has raw material sources in timber,
And it finally administers in the exhaust emission of timber industry the characteristics of；The present invention is used to prepare the original of Nd-MOFs gas adsorption material
Material source is extensive, nontoxic, cost recovery is low, can recycled for multiple times.The Nd- obtained through molecular rearrangement and self assembly
MOFs gas adsorption material has many advantages, such as easy to operate, stable structure, without secondary environmental pollution.
4, the present invention select phthalic anhydride and methyl-α-D- galactopyranoside synthesis the aryl containing ester carbonyl group/
Methyl-α-D- galactopyranoside acid esters, the lone pair electrons in ester carbonyl group, to match between the empty d track of rare earth ion
The effects of mode of position key and weaker electrostatic attraction, it is combined with each other into hinge type hole type skeleton structure, phthalic anhydride
In contain phenyl ring, methyl-α-D- galactopyranoside contains polyhydroxy saccharide ring, and the two is combined together the length for increasing ligand
Degree, it is bigger with the hole type framework material hole that is formed after rare earth metal Nd ion self assembly；1 is tested from microscopic particulate structure
Angle verifying can the method for the present invention preparation Nd-MOFs gas adsorption material aperture and hole hold size be just conducive to inhale
Attached molal volume range is in 90 cm3/moL-160 cm3Gas molecule within the scope of/moL can adsorb australene, β-pinane simultaneously
Alkene, benzene and CCl4Four kinds of substances, and adsorption effect is better than other materials in the prior art.
5, the present invention carries out air drying and high temperature drying to domestic pinus sylvestris var. mongolica material first respectively, and analysis determines two kinds and does
It is dry during discharge VOCs gaseous species and content, result of study show release VOCs gaseous species mainly include aldehyde,
The organic pollutants such as aromatic hydrocarbon, firpene, carbon tetrachloride and alkane.Nd-MOFs gas adsorption material is applied to adsorb domestic camphor tree
The specific four kinds of VOCs pollutants (carbon tetrachloride, nopinene, benzene and australene) discharged in sub- pine high/low temperature drying process.
Table is carried out using structure of the analytical technologies such as FTIR, XRD, TGA, TEM, SEM, EDS, BET to Nd-MOFs gas adsorption material
Sign.It is wanted the result shows that the structure of Nd-MOFs gas adsorption material complies fully with release VOCs gas absorption in specific industrial process
It asks, adsorption effect is excellent, for specific VOCs gas (carbon tetrachloride, nopinene, benzene and the australene discharged in timber drying
Alkene) four kinds of gas have excellent adsorption effect, and can be recycled repeatedly.
6, the present invention carries out chemical modification to methyl-α-D- galactopyranoside using phthalic anhydride, prepares new
Biological friendly organic ligand ɑ-aryl glycoside acid esters (AGE) of type, the organic ligand and rare earth metal neodymium chloride solution, pass through
Molecular rearrangement and the Nd-MOFs rare earth metal-for being self-assembly of the specific VOCs discharged in adsorbable timber drying are organic
Glucosides acid esters skeleton adsorbent material has modified ester group, carboxyl, carbonyl etc. on the material ligand, increases active function groups
Type and effective adsorption site, significantly improve the adsorption effect to several VOCs gases.
7, large amount of adsorption of the present invention, adsorption effect are good: the MOFs material that rare earth metal Nd is self-assembly of to carbon tetrachloride,
Nopinene, benzene and australene all show excellent adsorption effect, illustrate center rare earth metal Nd-MOFs gas-adsorbing material
Expect that the specific VOCs gas pollutant discharged in dry to domestic pinus sylvestris var. mongolica material high/low temperature has stronger adsorption capacity, it is dry in timber
It has a good application prospect in dry industrial process.
8, have the function of adjusting pH value and catalytic action using solvent N, N- diisopropylethylamine (DIEA) in the present invention,
It is found in experimentation, DIEA spatial volume is big compared with triethylamine compared with triethylamine, avoidable and central ion when as solvent
Nd3+It is combined, and leaves more sky d tracks for ligand, to form stable skeleton structure, enhancing Nd-MOFs gas is inhaled
The stability of enclosure material.
Detailed description of the invention
Fig. 1 is the infrared spectrum of (a) ligand AGE and (b) Nd-MOFs gas adsorption material；
Fig. 2 is that the EDS of Nd-MOFs gas adsorption material schemes；
Fig. 3 is Nd-MOFs gas adsorption material nitrogen adsorption-desorption curve；
Fig. 4 is Nd-MOFs gas adsorption material pore size distribution curve；
Fig. 5 is that the SEM of Nd-MOFs gas adsorption material schemes；
Fig. 6 Nd3+Influence with the molar ratio of AGE to carbon tetrachloride adsorbance；
Fig. 7 Nd3+Influence with the molar ratio of AGE to nopinene adsorbance.
Specific embodiment
For that can further appreciate that the contents of the present invention, feature and effect, following embodiment is enumerated, and cooperate attached drawing specifically
It is bright as follows.It should be noted that the present embodiment be it is descriptive, be not restrictive, cannot thus limit protection of the invention
Range.
Experimental method used in following embodiments is conventional method unless otherwise specified；Used material,
Reagent etc., is commercially available unless otherwise specified.
It describes and prepares for convenience in claims of the present invention, the unit of each raw material is write to the form of g as, actually
As needed, expansion dosage that can be proportional, proportional expansion dosage also belong to protection scope of the present invention.
Embodiment 1
A kind of preparation method of Nd-MOFs gas adsorption material, including ligand AGE synthesis, materials synthesis,
Ligand AGE synthesis specifically includes the following steps:
It accurately weighs 10.5 g phthalic anhydrides to pour into boiling flask, 40 mLmL acetone solns of addition, magnetic agitation,
It is dissolved sufficiently under the conditions of 30 DEG C, adds 4.5 g methyl-α-D- galactopyranosides, and after being warming up to 60 DEG C, 2mL is added
Catalyst n, N- diisopropylethylamine (DIEA) are uniformly mixed, and resulting liquid is cooled to by heating stirring, 8 h of back flow reaction
Room temperature, the anhydrous magnesium sulfate that 1g is added dry, filter, and it is molten that gained filtrate using Rotary Evaporators is boiled off acetone at 58 DEG C
Agent obtains sticky colourless liquid i.e. ligand AGE；
The materials synthesis specifically includes the following steps:
Ligand solution preparation: the above-mentioned ligand AGE of 5.5g that accurately weighs is placed in conical flask, and 25mL acetone is added and is filled
Divide dissolution；
Neodymium chloride solution preparation: 2.6 g neodymium chlorides are weighed and are dissolved in 10 mL distilled water；
Material preparation: measuring 10mL ligand solution respectively and neodymium chloride solution be added in conical flask, is uniformly mixed, magnetic agitation
Under the conditions of, the pH value of N, N- diisopropylethylamine (DIEA) adjusting solution is added dropwise to pH 7-8, stirs under room temperature
React 2.5 h, then filtered with vacuum pump, by obtained solid first with acetone washing 2 times, be washed with distilled water 2 times again, so
It is placed on to dry in 60 DEG C of baking oven to constant weight and obtains Nd-MOFs gas adsorption material.
A kind of Nd-MOFs gas adsorption material prepared using 1 method of embodiment is used for VOCs gas absorption.
Preferably, a kind of Nd-MOFs gas adsorption material prepared using 1 method of embodiment, for adsorbing the VOCs
Gas includes aldehydes, aromatic hydrocarbon, firpene, carbon tetrachloride and alkane.
Preferably, a kind of Nd-MOFs gas adsorption material prepared using 1 method of embodiment, for adsorbing the VOCs
Gas includes carbon tetrachloride, nopinene, benzene and australene.
Embodiment 2
A kind of preparation method of Nd-MOFs gas adsorption material, including ligand AGE synthesis, materials synthesis,
Ligand AGE synthesis specifically includes the following steps:
It accurately weighs 12.5 g phthalic anhydrides to pour into boiling flask, 55mL acetone soln, magnetic agitation, at 50 DEG C is added
Under the conditions of dissolve it sufficiently, add 5.5 g methyl-α-D- galactopyranosides, after being warming up to 80 DEG C, be added 8mL catalysis
Agent N, N- diisopropylethylamine (DIEA) are uniformly mixed, and resulting liquid is cooled to room by heating stirring, 8.5 h of back flow reaction
Temperature, the anhydrous magnesium sulfate that 3 g are added dry, filter, and gained filtrate is boiled off acetone solvent using Rotary Evaporators at 62 DEG C,
Obtain sticky colourless liquid i.e. ligand AGE；
The materials synthesis specifically includes the following steps:
Ligand solution preparation: the above-mentioned ligand AGE of 7.0 g that accurately weighs is placed in conical flask, and 35mL acetone is added and is filled
Divide dissolution；
Neodymium chloride solution preparation: 2.9 g neodymium chlorides are weighed and are dissolved in 12 mL distilled water；
Material preparation: measuring 12mL ligand solution respectively and neodymium chloride solution be added in conical flask, is uniformly mixed, magnetic agitation
Under the conditions of, the pH value of N, N- diisopropylethylamine (DIEA) adjusting solution is added dropwise to pH 7-8, stirs under room temperature
React 5.5 h, then filtered with vacuum pump, by obtained solid first with acetone washing 5 times, be washed with distilled water 4 times again, so
It is placed on to dry in 70 DEG C of baking oven to constant weight and obtains Nd-MOFs gas adsorption material.
A kind of Nd-MOFs gas adsorption material prepared using 2 method of embodiment is used for VOCs gas absorption.
Preferably, a kind of Nd-MOFs gas adsorption material prepared using 2 method of embodiment, for adsorbing the VOCs
Gas includes aldehydes, aromatic hydrocarbon, firpene, carbon tetrachloride and alkane.
Preferably, a kind of Nd-MOFs gas adsorption material prepared using 2 method of embodiment, for adsorbing the VOCs
Gas includes carbon tetrachloride, nopinene, benzene and australene.
Embodiment 3
A kind of preparation method of Nd-MOFs gas adsorption material, including ligand AGE synthesis, materials synthesis,
The ligand AGE synthesis is poured into boiling flask specifically includes the following steps: accurately weighing 11.5 g phthalic anhydrides,
50 mL acetone solns are added, magnetic agitation dissolves it sufficiently under the conditions of 40 DEG C, adds 5 g methyl-α-D- pyrans half
Lactoside after being warming up to 75 DEG C, is added 4 mL catalyst ns, N- diisopropylethylamine (DIEA), is uniformly mixed, heating stirring, returns
Stream 9 h of reaction, resulting liquid are cooled to room temperature, the anhydrous magnesium sulfate that appropriate 2g is added dries, filters, and gained filtrate is existed
Acetone solvent is boiled off using Rotary Evaporators at 60 DEG C, obtains sticky colourless liquid i.e. ligand AGE；
The materials synthesis specifically includes the following steps:
Ligand solution preparation: the above-mentioned ligand AGE of 6.25 g that accurately weighs is placed in conical flask, be added 30 mL acetone by its
Sufficiently dissolution；
Neodymium chloride solution preparation: 2.77 g neodymium chlorides are weighed and are dissolved in 10 mL distilled water；
Material preparation；10 mL ligand solutions are measured respectively and neodymium chloride solution is added in conical flask, are uniformly mixed, magnetic force stirs
Under the conditions of mixing, the pH value of N, N- diisopropylethylamine (DIEA) adjusting solution is added dropwise to pH 7-8, stirs under room temperature
4 h of reaction are mixed, is then filtered with vacuum pump, obtained solid is first used acetone washing 3 times, then be washed with distilled water 3 times, so
It is placed on to dry in 60 DEG C of baking oven to constant weight and obtains Nd-MOFs gas adsorption material.
A kind of Nd-MOFs gas adsorption material prepared using 3 method of embodiment is used for VOCs gas absorption.
Preferably, a kind of Nd-MOFs gas adsorption material prepared using 3 method of embodiment, for adsorbing the VOCs
Gas includes aldehydes, aromatic hydrocarbon, firpene, carbon tetrachloride and alkane.
Preferably, a kind of Nd-MOFs gas adsorption material prepared using 3 method of embodiment, for adsorbing the VOCs
Gas includes carbon tetrachloride, nopinene, benzene and australene.
In order to verify Nd-MOFs gas adsorption material adsorption effect, the present invention has also carried out Nd-MOFs gas adsorption material
Structural characterization experiment and adsorption effect experiment, experimentation and data are as follows:
In order to guarantee the accuracy of experimental result, below in experiment, tests done 10 parallel laboratory tests each time, and take 10
The average value of secondary parallel laboratory test data.
Test 1:Nd-MOFs gas adsorption material structural characterization
Nd-MOFs gas adsorption material structure prepared by embodiment 3 is analyzed, experimental result is as follows:
1.1 FTIR and EDS analysis
Fig. 1 is the infared spectrum (FTIR) of ligand AGE and Nd-MOFs.AGE is in 3360 cm-1Nearby there is a wide and strong suction
Peak is received, due to the characteristic absorption peak of hydroxyl and hydrogen bond, i.e., the hydroxyl not reacted completely on methyl-α-D- galactopyranoside molecule
The absorption peak of base or free hydroxyl；2976 cm-1The absorption peak at place is methyl-CH3Or-CH2On C-H absorption peak；1710
cm-1The absorption peak at place is the characteristic absorption peak of carbonyl；1590 cm-1、1551 cm-1、1486 cm-1With 1445 cm-1It is respectively
The characteristic absorption peak of aromatic ring；1280 cm-1It is-C=O absorption peak；In 1000 cm-1With 1200 cm-1Between both shoulders peak be sugar
The characteristic absorption peak of ring.Compared with the infrared spectrum of ligand AGE, Nd-MOFs is in 1710 cm-1The absorption peak at place obviously almost disappears
It loses, shows that carbonyl takes part in reaction in complexation process, illustrate to have occurred between rare earth ion Nd and ligand AGE and be bonded work
With coordination forms Nd-MOFs gas adsorption material.
Fig. 2 is the EDS figure of Nd-MOFs gas adsorption material.As seen from the figure, it can be seen that in Nd-MOFs material containing C,
H, eight kinds of elements of O, N, Nd, Zr, Al and Cl, wherein Cl and Nd is the element contained in metallic compound, can further prove-
C=O and Nd3+Coordinate self-assembly is carried out, C, H and O are the elements contained originally in ligand structure, and N, Zr and AL are test sample and system
Impurity during sample.
1.2 surface areas and average pore size analysis
Such as Fig. 3, Fig. 4 and table 1 are it is found that N2There is obvious hysteresis loop in adsorption-desorption isothermal curve, shows Nd-MOFs
There are meso-hole structure in gas adsorption material, curve meets IV type of adsorption/desorption isothermal curve, is conducive to the absorption to gas.
When relative pressure reaches 0.6 or so, capillary condensation occurs in mesoporous for adsorbate, so adsorbance suddenly rises.In low pressure
Area's gas illustrates that material and nitrogen have stronger adsorption capacity, illustrates with the presence of partial pore there is also partial adsorbates effect.
1.3 sem analysis
Scanning electron microscope (SEM) picture of Nd-MOFs gas adsorption material is as shown in Figure 5.As seen from the figure, Nd-MOFs gas absorption
Material be by it is a large amount of it is irregular it is laminar structured accumulate, and surface greatly increases Nd-MOFs there are porous pattern
Specific surface area, be conducive to respective aperture size gas molecule absorption.
By FTIR and EDS atlas analysis it is found that organic ligand AGE and Nd3+Between have occurred that molecule rearrangement and from
Assembling；It learns that Nd-MOFs gas adsorption material principally falls into mesoporous profile material by specific surface area and average pore analysis, also contains
There is partial pore hole；By SEM spectrum analysis result can obtain, Nd-MOFs gas adsorption material rough surface, specific surface area compared with
Greatly, aperture and hole appearance size are just conducive to adsorb molal volume range in 90 cm3/moL-160 cm3Within the scope of/moL
Gas molecule (australene, nopinene, benzene and CCl4).In summary characterization result can learn Nd-MOFs gas-adsorbing material
Material has reached requirement.
Experiment 1 from microscopic particulate structure angle verifying can the method for the present invention prepare Nd-MOFs gas adsorption material hole
Diameter and hole hold size and are just conducive to adsorb molal volume range in 90 cm3/moL-160 cm3Gas within the scope of/moL
Molecule can adsorb australene, nopinene, benzene and CCl simultaneously4Four kinds of substances, and adsorption effect is better than in the prior art
Other materials.
2:Nd-MOFs gas adsorption material is tested to the adsorption experiment of drying of wood VOCs
2.1 adsorption experiment principles
A certain amount of Nd-MOFs gas adsorption material is accurately weighed, is placed on mounted in instrument (3H-2000P, the steaming of multistation gravimetric method
Vapour adsorption instrument, Bei Shide instrument Science and Technology Ltd., Beijing) test position, Nd-MOFs gas adsorption material is true by heating
After sky degassing, sample room is in vacuum environment, and by the liquid in Reagent Tube, be evaporated to sample room becomes steaming adsorbate
Vapour is weighed under certain relative partial pressure after the absorption of Nd-MOFs material by microbalance, Nd-MOFs sample absorption front and back
The variation of weight measures sample to the adsorption desorption amount of specific gas with this.Adsorption experiment can at most be surveyed in parallel simultaneously
Four parts of samples are tried, Adsorbate Gas is same.
Absorption of the 2.2 Nd-MOFs gas adsorption materials to carbon tetrachloride
2.2.1 ligand AGE(hereinafter referred to as AGE) influence of the preparation time to carbon tetrachloride adsorbance
When table 2, table 3, table 4 are the preparation time differences of AGE, adsorbance of the Nd-MOFs to carbon tetrachloride.By table 2, table 3, table 4
It is found that in adsorption process relative partial pressure (P/P 0) it is 0.9, Nd3+With the synthesis material methyl-of the molar ratio 3:1, AGE of ligand AGE
The molar ratio of α-D- galactopyranoside and phthalic anhydride is respectively to all show under the conditions of 1:3,1:4,1:5, AGE preparation
When time is 9 h, Nd-MOFs gas adsorption material is peak to the adsorbance of carbon tetrachloride, continues growing AGE preparation time
When for 10 h, Nd-MOFs gas adsorption material does not continue growing carbon tetrachloride adsorbance, it is thus determined that AGE preparation time is 9
H is preferred；
The molar ratio of 2 methyl-α-D- galactopyranoside of table and phthalic anhydride is 1:3
The molar ratio of 3 methyl-α-D- galactopyranoside of table and phthalic anhydride is 1:4
The molar ratio of 4 methyl-α-D- galactopyranoside of table and phthalic anhydride is 1:5
2.2.2 influence of the two kinds of raw material feed ratios of AGE to carbon tetrachloride adsorbance is prepared
Table 5 is the preparation time of AGE when being 9 h, the adsorbance of the feed ratios of two kinds of ligand stocks to carbon tetrachloride.It can by table 5
Know, is 0.9, Nd at adsorption process relative partial pressure (P/P0)3+When molar ratio 3:1, AGE preparation time with ligand AGE is 9 h,
Synthesis material methyl-α-D- the galactopyranoside of AGE and the molar ratio of phthalic anhydride are respectively 1:1,1:2,1:3,1:
4, under the conditions of five kinds of 1:5, when two kinds of material molar ratios of AGE are 1:3, obtained Nd-MOFs gas adsorption material is to carbon tetrachloride
Adsorbance peak be 206.9470 mg/g.It is thus determined that the throwing of methyl-α-D- galactopyranoside and phthalic anhydride
Material molar ratio is 1:3.
The adsorption effect of the different mol ratio of 5 methyl-α-D- galactopyranoside of table and phthalic anhydride
2.2.3 Nd3+Influence with the molar ratio of AGE to carbon tetrachloride adsorbance
Fig. 6 be AGE preparation time be 9 h when, Nd3+The influence to carbon tetrachloride adsorbance is not bent simultaneously with the molar ratio of AGE
Line.It will be appreciated from fig. 6 that adsorption process relative partial pressure (P/P 0) when to be 0.9, AGE preparation time be 9 h, the synthesis material first of AGE
When the molar ratio of base-α-D- galactopyranoside and phthalic anhydride is respectively 1:3, Nd3+Molar ratio with ligand AGE is 3:
Under the conditions of 1, Nd-MOFs gas adsorption material obtained is 206.9470 mg/g of maximum value to the adsorbance of carbon tetrachloride.
Absorption of the 2.3 Nd-MOFs gas adsorption materials to nopinene
2.3.1 influence of the preparation time of AGE to nopinene adsorbance
When table 6, table 7, table 8 are the preparation time differences of AGE, adsorbance of the Nd-MOFs to nopinene.It can by table 6, table 7, table 8
Know, is 0.9, Nd at adsorption process relative partial pressure (P/P0)3+With the synthesis material methyl-α-of the molar ratio 3:1, AGE of ligand AGE
The molar ratio of D- galactopyranoside and phthalic anhydride is respectively to all show under the conditions of 1:3,1:4,1:5, when prepared by AGE
Between when being 9 h, Nd-MOFs gas adsorption material is peak to the adsorbance of nopinene.Continue growing AGE preparation time gas
Adsorbent material totally begins to decline the adsorbance of nopinene.
The molar ratio of 6 methyl-α-D- galactopyranoside of table and phthalic anhydride is 1:3
The molar ratio of 7 methyl-α-D- galactopyranoside of table and phthalic anhydride is 1:4
The molar ratio of 8 methyl-α-D- galactopyranoside of table and phthalic anhydride is 1:5
2.3.2 influence of the two kinds of raw material feed ratios of AGE to nopinene adsorbance is prepared
Table 9 is the preparation time of AGE when being 9 h, the adsorbance of the feed ratios of two kinds of ligand stocks to nopinene.As shown in Table 9,
Adsorption process relative partial pressure (P/P 0) it is 0.9, Nd3+When molar ratio 3:1, AGE preparation time with ligand AGE is 9 h, AGE
Synthesis material methyl-α-D- galactopyranoside and the molar ratio of phthalic anhydride be respectively 1:1,1:2,1:3,1:4,1:
Under the conditions of 5 three kinds, when two kinds of material molar ratios of AGE are 1:3, absorption of the obtained Nd-MOFs gas adsorption material to nopinene
Amount peak is 183.4970 mg/g.
Table 9 prepares influence of the two kinds of raw material feed ratios of AGE to nopinene adsorbance
2.3.3 Nd3+Influence with the molar ratio of AGE to nopinene adsorbance
Fig. 7 be AGE preparation time be 9 h when, Nd3+The influence to nopinene adsorbance is not bent simultaneously with the molar ratio of AGE
Line.As shown in Figure 7, adsorption process relative partial pressure (P/P 0) when to be 0.9, AGE preparation time be 9 h, the synthesis material first of AGE
When the molar ratio of base-α-D- galactopyranoside and phthalic anhydride is respectively 1:3, Nd3+Molar ratio with ligand AGE is 3:
Under the conditions of 1, adsorbance maximum value 186.8840 mg/g of the Nd-MOFs gas adsorption material obtained to nopinene.
Absorption of the 2.4 Nd-MOFs gas adsorption materials to benzene
2.4.1 influence of the preparation time of AGE to benzene adsorbance
When table 10,11,12 is the preparation time difference of AGE, adsorbance of the Nd-MOFs to benzene.By table 10,11,12 it is found that inhaling
Attached process relative partial pressure (P/P 0) it is 0.9, Nd3+With the synthesis material methyl-α-D- pyrans of the molar ratio 3:1, AGE of ligand AGE
The molar ratio of galactoside and phthalic anhydride is respectively to all show under the conditions of 1:3,1:4,1:5, and AGE preparation time is 9
When h, Nd-MOFs gas adsorption material is peak to the adsorbance of benzene.
The molar ratio of 10 methyl-α-D- galactopyranoside of table and phthalic anhydride is 1:3
The molar ratio of 11 methyl-α-D- galactopyranoside of table and phthalic anhydride is 1:4
The molar ratio of 12 methyl-α-D- galactopyranoside of table and phthalic anhydride is 1:5
2.4.2 influence of the two kinds of raw material feed ratios of AGE to benzene adsorbance is prepared
Table 13 is the preparation time of AGE when being 9 h, the influence curve of the feed ratios of two kinds of ligand stocks to benzene adsorbance.By table
13 it is found that adsorption process relative partial pressure (P/P 0) it is 0.9, Nd3+Molar ratio 3:1, AGE preparation time with ligand AGE is 9 h
When, the synthesis material methyl-α-D- galactopyranoside of AGE and the molar ratio of phthalic anhydride be respectively 1:1,1:2,1:3,
Under the conditions of tri- kinds of 1:4,1:5, when two kinds of material molar ratios of AGE are 1:3, suction of the obtained Nd-MOFs gas adsorption material to benzene
Attached amount peak is 132.2270 mg/g.
Table 13 prepares influence of the two kinds of raw material feed ratios of AGE to benzene adsorbance
Absorption of the 2.5 Nd-MOFs gas adsorption materials to australene
2.5.1 influence of the preparation time of AGE to australene adsorbance
When table 14, table 15, the preparation time difference that table 16 is AGE, adsorbance of the Nd-MOFs to australene.By table 14, table 15,
Table 16 it is found that adsorption process relative partial pressure (P/P 0) it is 0.9, Nd3+With the synthesis material of the molar ratio 3:1, AGE of ligand AGE
The molar ratio of methyl-α-D- galactopyranoside and phthalic anhydride is respectively to all show under the conditions of 1:3,1:4,1:5,
When AGE preparation time is 9 h, Nd-MOFs gas adsorption material is optimal to the adsorption effect of australene.
The molar ratio of 14 methyl-α-D- galactopyranoside of table and phthalic anhydride is 1:3
The molar ratio of 15 methyl-α-D- galactopyranoside of table and phthalic anhydride is 1:4
The molar ratio of 16 methyl-α-D- galactopyranoside of table and phthalic anhydride is 1:5
2.5.2 influence of the two kinds of raw material feed ratios of AGE to australene adsorbance is prepared
Table 17 is the preparation time of AGE when being 9 h, and the influence of the feed ratios of two kinds of ligand stocks to the adsorbance of australene is bent
Line.As shown in Table 17, adsorption process relative partial pressure (P/P 0) it is 0.9, Nd3+With the molar ratio 3:1 of ligand AGE, when prepared by AGE
Between when being 9 h, the synthesis material methyl-α-D- galactopyranoside of AGE and the molar ratio of phthalic anhydride be respectively 1:1,
Under the conditions of five kinds of 1:2,1:3,1:3,1:4,1:5, when two kinds of material molar ratios of AGE are 1:3, obtained Nd-MOFs gas absorption
Material is 42.4350 mg/g to the adsorbance peak of australene.
Table 17 prepares influence of the two kinds of raw material feed ratios of AGE to australene adsorbance
By experiment 2.2-2.5 it is found that the Nd-MOFs gas adsorption material that the present invention synthesizes does low temperature drying to domestic pinus sylvestris var. mongolica material
The Study on adsorption properties of the specific VOCs gas of four kinds discharged in the process (carbon tetrachloride, nopinene, benzene and australene) shows:
Nd-MOFs gas adsorption material is to carbon tetrachloride, nopinene, benzene and australene absorption property by ligand preparation time, two kinds
Molar ratio, the center Nd of ligand stock3+With the shadow of the factors such as the relative partial pressure of the molar ratio of ligand and adsorption experiment
It rings, any change parameter will result directly in the decline of absorption property.The experimental results showed that with gas during adsorption experiment
The increase of relative partial pressure, Nd-MOFs gas adsorption material gradually increase the adsorbance of four kinds of gases；Nd-MOFs gas absorption
The optimal preparation technology parameter of material are as follows: the preparation time of ligand AGE is 9 h, two kinds of ligand stock (methyl-α-D- pyrans half
Lactoside and phthalic anhydride) molar ratio be 1:3, central rare earth Nd3+Molar ratio with ligand AGE is 3:1.
By the novel Nd-MOFs gas adsorption material that is prepared under above-mentioned optimum condition to carbon tetrachloride, nopinene, benzene and australene
The adsorbance that four kinds of domestic pinus sylvestris var. mongolica materials do the four kinds of specific VOCs gases discharged during low temperature drying reaches maximum value.
3 different materials are tested to four kinds of VOCs gas sorption ability correlation datas
As a result known by table 18:
To the adsorbance of carbon tetrachloride: Nd-MOFs is 1.34 times of La-MOFs, is 5.2 times of Ce-MOFs；It is the wooden fibre of nanometer
Tie up element/3.5 times of montmorillonite Composite adsorbent material；
To the adsorbance of nopinene: Nd-MOFs is 1.23 times of La-MOFs, is 1.79 times of Ce-MOFs；It is the wooden fibre of nanometer
Tie up element/3.78 times of montmorillonite Composite adsorbent material；
To the adsorbance of benzene: Nd-MOFs is 47 times of La-MOFs, is 2.2 times of Ce-MOFs；It is nano lignocellulose/illiteracy
De- 140 times of composite adsorbing material of soil；Ce-MOFs and nano lignocellulose/montmorillonite Composite adsorbent material to benzene almost without
Adsorption effect.
To the adsorbance of australene: Nd-MOFs is 0.66 times of La-MOFs, is 2.1 times of Ce-MOFs；It is that nanometer is wooden
Cellulose/2.6 times of montmorillonite Composite adsorbent material；
Almost do not have by Ce-MOFs known to above-mentioned comparative analysis and nano lignocellulose/montmorillonite Composite adsorbent material to benzene
There is adsorption effect.Ce-MOFs will be far smaller than Nd-MOFs for the adsorbance of above-mentioned four kinds of gas, therefore can be simultaneously to upper
State only Nd-MOFs of four kinds of gases with excellent adsorption effect.Nd-MOFs gas adsorption material pair provided in the present invention
The specific VOCs gas discharged in timber drying has excellent absorption property.
It analyzes and also knows from table 18: the absorption of Nd-MOFs prepared by embodiment 1, embodiment 2, embodiment 3 to carbon tetrachloride
Amount is stablized in 200mg/g or so, stablizes the adsorbance of nopinene in 180mg/g or so, stablizes to the adsorbance of benzene
130mg/g or so stablizes in 40mg/g or so the adsorbance of australene, and the present invention further proved is protected in claims
The Nd-MOFs prepared in range is protected, there is excellent absorption property for the specific VOCs gas discharged in timber drying.
The different adsorbents of table 18 are to carbon tetrachloride, β-pinane
Claims (6)
1. a kind of preparation method of Nd-MOFs gas adsorption material, including ligand AGE synthesis, materials synthesis, it is characterised in that:
Ligand AGE synthesis specifically includes the following steps:
It accurately weighs 10.5-12.5 g phthalic anhydride to pour into boiling flask, 40 mL-55mL acetone solns, magnetic force is added
Stirring, dissolves it sufficiently, adds 4.5-5.5 g methyl-α-D- galactopyranoside, be warming up to
After 60-80 DEG C, 2-8mL catalyst n, N- diisopropylethylamine is added, is uniformly mixed, heating stirring, back flow reaction 8-9 h, it will
Resulting liquid is cooled to room temperature, and the anhydrous magnesium sulfate that 1-3 g is added dries, filters, and gained filtrate is used at 58-62 DEG C
Rotary Evaporators boil off acetone solvent, obtain sticky colourless liquid i.e. ligand AGE；
The materials synthesis specifically includes the following steps:
Ligand solution preparation: the above-mentioned ligand AGE of 5.5-7.0 g that accurately weighs is placed in conical flask, and 25-35mL third is added
Ketone sufficiently dissolves it；
Neodymium chloride solution preparation: it weighs 2.6-2.9 g neodymium chloride and is dissolved in 10-12 mL distilled water；
Material preparation: measuring 10-12mL ligand solution respectively and neodymium chloride solution be added in conical flask, is uniformly mixed, magnetic force
Under stirring condition, the pH value of N, N- diisopropylethylamine adjusting solution is added dropwise to pH 7-8, stirring is anti-under room temperature
Answer 2.5-5.5 h, then filtered with vacuum pump, by obtained solid first with acetone washing 2-5 times, be washed with distilled water 2- again
It 4 times, is subsequently placed in drying to constant weight in 60 DEG C -70 DEG C of baking oven and obtains Nd-MOFs gas adsorption material.
2. a kind of preparation method of Nd-MOFs gas adsorption material according to claim 1, including ligand AGE synthesis, material
Material synthesis, it is characterised in that:
The ligand AGE synthesis is poured into boiling flask specifically includes the following steps: accurately weighing 11.5 g phthalic anhydrides,
50 mL acetone solns are added, magnetic agitation dissolves it sufficiently under the conditions of 40 DEG C, adds 5 g methyl-α-D- pyrans half
Lactoside after being warming up to 75 DEG C, is added 4 mL catalyst ns, N- diisopropylethylamine, is uniformly mixed, heating stirring, back flow reaction
Resulting liquid is cooled to room temperature by 9 h, and the anhydrous magnesium sulfate that appropriate 2g is added dries, filters, by gained filtrate at 60 DEG C
Acetone solvent is boiled off using Rotary Evaporators, obtains sticky colourless liquid i.e. ligand AGE；
The materials synthesis specifically includes the following steps:
Ligand solution preparation: the above-mentioned ligand AGE of 6.25 g that accurately weighs is placed in conical flask, be added 30 mL acetone by its
Sufficiently dissolution；
Neodymium chloride solution preparation: 2.77 g neodymium chlorides are weighed and are dissolved in 10 mL distilled water；
Material preparation；10 mL ligand solutions are measured respectively and neodymium chloride solution is added in conical flask, are uniformly mixed, magnetic force stirs
Under the conditions of mixing, the pH value of N, N- diisopropylethylamine adjusting solution is added dropwise to pH 7-8, is stirred to react 4 under room temperature
Then h is filtered with vacuum pump, obtained solid is first used acetone washing 3 times, then is washed with distilled water 3 times, is subsequently placed in 60
DEG C baking oven in dry to constant weight and obtain Nd-MOFs gas adsorption material.
3. a kind of Nd-MOFs gas adsorption material, it is characterised in that: -2 described in any item Nd-MOFs gas according to claim 1
Body adsorbent material preparation method is prepared.
4. Nd-MOFs gas adsorption material according to claim 3, it is characterised in that: be used for VOCs gas absorption.
5. Nd-MOFs gas adsorption material according to claim 4, it is characterised in that: the VOCs includes aldehydes, fragrance
Hydrocarbon, firpene, carbon tetrachloride and alkane.
6. Nd-MOFs gas adsorption material according to claim 4, it is characterised in that: the VOCs include carbon tetrachloride,
Nopinene, benzene and australene.
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Cited By (5)
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| CN111974354B (en) * | 2020-08-25 | 2023-04-25 | 内蒙古农业大学 | Mg-MOFs single crystal adsorption material and preparation method and application thereof |
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