CN110157015B - A kind of preparation method of nanometer zero-valent iron/cellulose composite hydrogel in ionic liquid - Google Patents
A kind of preparation method of nanometer zero-valent iron/cellulose composite hydrogel in ionic liquid Download PDFInfo
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Abstract
本发明涉及一种纳米零价铁/纤维素复合凝胶以及其在离子液体中的制备方法，属于材料科学领域；提供一种纳米零价铁/纤维素复合水凝胶在离子液体中的制备方法，包括如下步骤：(1)将离子液体加热到规定温度T1后，在恒温下加入纳米零价铁，搅拌并超声分散，得到一定浓度的纳米零价铁的离子液体溶液；(2)将离子液体加热到规定温度T2后，在恒温下加入质量分数为1％～10wt％的纤维素制备纤维素离子液体溶液；(3)将所述纳米零价铁离子液体溶液与所述纤维素离子液体溶液搅拌混合，并在规定温度和功率下超声分散；(4)将所得到的最终混合液进行脱泡，用凝固浴再生，洗涤，得到纳米零价铁/纤维素复合水凝胶。
The invention relates to a nano-zero-valent iron/cellulose composite gel and a preparation method thereof in an ionic liquid, belonging to the field of material science; and provides a preparation of a nano-zero-valent iron/cellulose composite hydrogel in an ionic liquid The method includes the following steps: ( 1 ) after heating the ionic liquid to a specified temperature T1, adding nano-zero valent iron at a constant temperature, stirring and ultrasonically dispersing, to obtain an ionic liquid solution of a certain concentration of nano-zero valent iron; (2) After heating the ionic liquid to a specified temperature T 2 , adding cellulose with a mass fraction of 1% to 10 wt % at a constant temperature to prepare a cellulose ionic liquid solution; (3) combining the nano-zero-valent iron ionic liquid solution with the fiber The ionic liquid solution is stirred and mixed, and dispersed by ultrasonic at a specified temperature and power; (4) the obtained final mixed solution is deaerated, regenerated with a coagulation bath, and washed to obtain a nano-zero valent iron/cellulose composite hydrogel .
Description
技术领域technical field
本发明涉及一种纳米零价铁/纤维素复合凝胶以及其在离子液体中的制备方法，属于材料科学领域。The invention relates to a nano zero-valent iron/cellulose composite gel and a preparation method thereof in an ionic liquid, belonging to the field of material science.
背景技术Background technique
纳米零价铁是指纳米尺度的单质铁，具有巨大的活性比表面积，并且兼具还原性和氧化性，适用范围广，已被用于去除地下水中染料、重金属、酚类化合物等污染的去除。但是，目前关于纳米零价铁在环境修复方面仍存在长效性、移动性和潜在的生物毒性等问题，而且在实际应用中，团聚和钝化都会导致纳米零价铁的活性降低，因为纳米零价铁颗粒之间容易团聚，粒径变大，导致其在水中的移动性和有效比表面积降低，而纳米零价铁易与水中的硝酸根和溶解性有机质等反应，使其钝化，从而阻隔了其与污染物的接触。同时，纳米零价铁的分离和恢复仍然是一个需要解决的问题。所以，纳米零价铁在环境修复方面的研究亟需进一步的改善。Nano zero-valent iron refers to nano-scale elemental iron, which has a huge active specific surface area, and has both reducing and oxidizing properties. It has a wide range of applications and has been used to remove dyes, heavy metals, phenolic compounds and other pollution in groundwater. . However, there are still problems such as long-term efficacy, mobility and potential biotoxicity of nano-zero valent iron in environmental remediation, and in practical applications, both agglomeration and passivation will lead to the reduction of the activity of nano-zero valent iron, because nano It is easy to agglomerate between zero-valent iron particles, and the particle size becomes larger, which reduces its mobility in water and effective specific surface area, while nano-zero-valent iron easily reacts with nitrate and dissolved organic matter in water, making it passivated. Thus blocking its contact with contaminants. Meanwhile, the separation and recovery of nano-zero valent iron is still a problem to be solved. Therefore, the research of nano-zero valent iron in environmental remediation urgently needs further improvement.
通过与高分子材料复合的方法，不仅可以实现纳米零价铁在宏观条件下均匀分散，而且可以通过纳米零价铁与基底材料的相互作用实现整体材料性能的大幅提高，从而获得具有优异机械性能、反应活性和热学性能的新材料。因此，关于纳米零价铁聚合物复合材料的研究已引起人们的广泛关注。Through the method of compounding with polymer materials, not only can the nano-zero valent iron be uniformly dispersed under macroscopic conditions, but also the overall material properties can be greatly improved through the interaction between the nano-zero valent iron and the substrate material, so as to obtain excellent mechanical properties. , reactivity and thermal properties of new materials. Therefore, research on nano-zero-valent iron-polymer composites has attracted extensive attention.
纤维素，作为世界上最丰富的天然高分子，具有可再生性，生物可降解性，相容性，特殊的机械性能等优点。如果将纤维素和纳米零价铁复合，纳米零价铁能够镶嵌在纤维素网络中，有利于阻止纳米零价铁的团聚，同时得到的一定形状的复合凝胶本身具有一定的比表面积和强的机械性能，更加易于回收和重复利用。Cellulose, as the most abundant natural polymer in the world, has the advantages of renewability, biodegradability, compatibility, special mechanical properties and so on. If cellulose and nano-zero-valent iron are composited, the nano-zero-valent iron can be embedded in the cellulose network, which is beneficial to prevent the agglomeration of nano-zero-valent iron. At the same time, the obtained composite gel itself has a certain specific surface area and strength. better mechanical properties, easier to recycle and reuse.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于提供一种性能优异的纳米零价铁/纤维素复合水凝胶和气凝胶及其制备新方法。The purpose of the present invention is to provide a nano zero-valent iron/cellulose composite hydrogel and aerogel with excellent performance and a new preparation method thereof.
本发明的目的在于提供一种纳米零价铁/纤维素复合凝胶在离子液体中的制备方法，包括如下步骤：The object of the present invention is to provide a kind of preparation method of nano zero-valent iron/cellulose composite gel in ionic liquid, comprising the following steps:
(1)将离子液体加热到规定温度T1后，在恒温下加入纳米零价铁，搅拌并超声分散，得到一定浓度的纳米零价铁的离子液体溶液；(1) after heating the ionic liquid to a specified temperature T 1 , adding nano-zero valent iron at a constant temperature, stirring and ultrasonically dispersing to obtain an ionic liquid solution of a certain concentration of nano-zero valent iron;
(2)将离子液体加热到规定温度T2后，在恒温下加入质量分数为1％～10wt％的纤维素制备纤维素离子液体溶液；(2) after heating the ionic liquid to a specified temperature T 2 , adding cellulose with a mass fraction of 1% to 10% by weight at a constant temperature to prepare a cellulose ionic liquid solution;
(3)将所述纳米零价铁离子液体溶液与所述纤维素离子液体溶液搅拌混合，并在规定温度和功率下超声分散；(3) stirring and mixing the nano zero-valent iron ionic liquid solution and the cellulose ionic liquid solution, and ultrasonically dispersing at a specified temperature and power;
(4)将所得到的最终混合液进行脱泡，用凝固浴再生，洗涤，得到纳米零价铁/纤维素复合水凝胶。(4) defoaming the obtained final mixed solution, regenerating it with a coagulation bath, and washing to obtain a nano-zero-valent iron/cellulose composite hydrogel.
本发明所述的制备方法，其中，所述离子液体选自咪唑盐类离子液体、吡啶盐类离子液体、新型胆碱类和非咪唑盐类离子液体。In the preparation method of the present invention, the ionic liquid is selected from imidazolium salt ionic liquids, pyridinium salt ionic liquids, novel cholines and non-imidazolium salt ionic liquids.
本发明所述的方法，步骤(1)中，所述温度T1为80℃，所述纳米零价铁在所述离子液体中的分散温度为70℃～100℃，处理时间为0.5～3小时。In the method of the present invention, in step (1), the temperature T 1 is 80° C., the dispersion temperature of the nano-zero valent iron in the ionic liquid is 70° C. to 100° C., and the treatment time is 0.5 to 3° C. Hour.
本发明所述的方法，步骤(2)中，所述温度T2为100℃，所述纤维素在所述离子液体中的分散温度为70℃～100℃，处理时间为0.5～3小时。In the method of the present invention, in step (2), the temperature T 2 is 100°C, the dispersion temperature of the cellulose in the ionic liquid is 70°C to 100°C, and the treatment time is 0.5 to 3 hours.
本发明所述的方法，步骤(3)中，所述纳米零价铁和纤维素的质量比为0.1％～50％。In the method of the present invention, in step (3), the mass ratio of the nano-zero valent iron to cellulose is 0.1% to 50%.
本发明所述的方法，在步骤(2)中，所述的纳米零价铁的浓度为1～6mg/ml。In the method of the present invention, in step (2), the concentration of the nano-zero valent iron is 1-6 mg/ml.
本发明所述的方法，步骤(3)所述纳米零价铁和纤维素离子液体溶液的混合温度为70～100℃，时间为0.3～5h。In the method of the present invention, the mixing temperature of the nano-zero-valent iron and the cellulose ionic liquid solution in step (3) is 70-100° C., and the time is 0.3-5 h.
本发明所述的方法，步骤(3)所述超声分散用超声波清洗器，超声波清洗器的参数条件为：80～325W超声0.3～3h，超声温度为30～60℃。In the method of the present invention, in step (3), an ultrasonic cleaner is used for ultrasonic dispersion, and the parameters of the ultrasonic cleaner are: 80-325W ultrasonic for 0.3-3h, and ultrasonic temperature is 30-60°C.
本发明所述的方法，步骤(2)所述的纤维素原料是棉短绒、针叶木纸浆、阔叶木纸浆和微晶纤维素中的一种或两种以上。In the method of the present invention, the cellulose raw material in step (2) is one or more of cotton linter, softwood pulp, hardwood pulp and microcrystalline cellulose.
本发明的第二方面，提供一种纳米零价铁/纤维素复合水凝胶，按照本发明所述的方法制备得到。The second aspect of the present invention provides a nano zero-valent iron/cellulose composite hydrogel, which is prepared according to the method of the present invention.
本发明的第三方面，提供一种纳米零价铁/纤维素复合气凝胶的制备方法，其特征在于，包括如下步骤：(1)将离子液体加热到规定温度T1后，在恒温下加入纳米零价铁，搅拌并超声分散，得到一定浓度的纳米零价铁的离子液体溶液；(2)将离子液体加热到规定温度T2后，在恒温下加入质量分数为1％～10wt％的纤维素制备纤维素离子液体溶液；(3)将所述纳米零价铁离子液体溶液与所述纤维素离子液体溶液搅拌混合，并在规定温度和功率下超声分散；(4)将所得到的最终混合液进行脱泡，用凝固浴再生，洗涤，得到纳米零价铁/纤维素复合水凝胶；(5)干燥步骤：冷冻干燥，或者，溶剂交换后利用超临界二氧化碳干燥。The third aspect of the present invention provides a preparation method of nano-zero-valent iron/cellulose composite aerogel, which is characterized by comprising the following steps: (1) after heating the ionic liquid to a predetermined temperature T 1 , at a constant temperature Add nano-zero valent iron, stir and disperse ultrasonically to obtain an ionic liquid solution of nano-zero valent iron with a certain concentration; (2) after heating the ionic liquid to a specified temperature T 2 , add a mass fraction of 1% to 10wt% at a constant temperature (3) stirring and mixing the nano-zero-valent iron ionic liquid solution with the cellulose ionic liquid solution, and ultrasonically dispersing it at a specified temperature and power; (4) mixing the obtained The final mixed solution is defoamed, regenerated with a coagulation bath, and washed to obtain a nano-zero-valent iron/cellulose composite hydrogel; (5) Drying step: freeze drying, or drying with supercritical carbon dioxide after solvent exchange.
本发明的第四方面，提供一种纳米零价铁/纤维素复合气凝胶，按照上述方法制备的复合气凝胶。The fourth aspect of the present invention provides a nano-zero-valent iron/cellulose composite aerogel, the composite aerogel prepared according to the above method.
所述的纳米零价铁/纤维素复合水凝胶和气凝胶用于一种或者多种污染物的去除，包括吸附或催化。The nano-zero-valent iron/cellulose composite hydrogels and aerogels are used for the removal of one or more pollutants, including adsorption or catalysis.
可以通过改变凝固再生过程中容器的形状，来改变复合水凝胶和气凝胶的形状，可获得薄膜、柱形、方形等多种形状的水/气凝胶；通过再生过程方式的改变，可获得球状复合水凝胶和气凝胶。The shape of the composite hydrogel and aerogel can be changed by changing the shape of the container during the solidification regeneration process, and various shapes of water/aerogel such as film, column, square, etc. can be obtained; Spherical composite hydrogels and aerogels were obtained.
研究发现，纳米零价铁能够很好的分散在纤维素网络中。通过该方法制备的复合凝胶具有很好的导电性、机械性能和氧化还原活性，作为污染物的去除材料具有优异的重复利用性能。The study found that the nano-zero valent iron can be well dispersed in the cellulose network. The composite gel prepared by this method has good electrical conductivity, mechanical properties and redox activity, and has excellent recycling performance as a pollutant removal material.
本发明相对于现有的技术，有以下优点：Compared with the prior art, the present invention has the following advantages:
(1)本发明以天然的纤维素为基底，价格便宜，量大，整个过程没有水的参与，有利于纳米零价铁的分散和反应活性的提高。(1) The present invention is based on natural cellulose, which is cheap in price and large in quantity, without the participation of water in the whole process, which is beneficial to the dispersion of nano-zero valent iron and the improvement of reactivity.
(2)本发明采用离子液体为溶剂和分散剂，乙醇作为凝固浴，有利于纳米零价铁的分散，减少其团聚，提高纳米零价铁/纤维素复合凝胶的性能。(2) The present invention adopts ionic liquid as solvent and dispersant, and ethanol as coagulation bath, which is beneficial to the dispersion of nano-zero-valent iron, reduces its agglomeration, and improves the performance of nano-zero-valent iron/cellulose composite gel.
(3)本发明所制备的复合凝胶兼具有纳米零价铁和纤维素的性质，性能优异，如比表面积高、导电性好、机械性能强等。该复合凝胶能够在催化，吸附，能源储存等多个领域有广泛的应用。(3) The composite gel prepared by the present invention has both the properties of nano-zero-valent iron and cellulose, and has excellent properties, such as high specific surface area, good electrical conductivity, and strong mechanical properties. The composite gel can be widely used in catalysis, adsorption, energy storage and other fields.
(4)本发明制备方法巧妙，过程绿色，得到的材料性能优越，原料来源广泛，价格低廉，在环境功能材料、结构材料、能源等领域获得广泛应用。(4) The preparation method of the present invention is ingenious, the process is green, the obtained material has superior performance, wide raw material sources and low price, and is widely used in the fields of environmental functional materials, structural materials, energy and the like.
附图说明Description of drawings
图1为实施例1制备的柱状纳米零价铁/纤维素复合水凝胶。Figure 1 shows the columnar nano-zero-valent iron/cellulose composite hydrogel prepared in Example 1.
图2为实施例1制备的柱状纳米零价铁/纤维素复合气凝胶。Figure 2 shows the columnar nano-zero-valent iron/cellulose composite aerogel prepared in Example 1.
具体实施方式Detailed ways
下面结合具体实施例对本发明作进一步具体详细描述，但本发明的实施方式不限于此，对于未特别注明的工艺参数，可参照常规技术进行。The present invention will be further described in detail below with reference to specific examples, but the embodiments of the present invention are not limited thereto. For process parameters that are not particularly noted, reference may be made to conventional techniques.
在本发明中，一种纳米零价铁/纤维素复合水凝胶在离子液体中的制备方法，包括如下步骤：(1)将离子液体加热到规定温度T1后，在恒温下加入纳米零价铁，搅拌并超声分散，得到一定浓度的纳米零价铁的离子液体溶液；(2)将离子液体加热到规定温度T2后，在恒温下加入质量分数为1％～10wt％的纤维素制备纤维素离子液体溶液；(3)将所述纳米零价铁离子液体溶液与所述纤维素离子液体溶液搅拌混合，并在规定温度和功率下超声分散；(4)将所得到的最终混合液进行脱泡，用凝固浴再生，洗涤，得到纳米零价铁/纤维素复合水凝胶。In the present invention, a method for preparing a nano-zero-valent iron/cellulose composite hydrogel in an ionic liquid includes the following steps: (1) after heating the ionic liquid to a predetermined temperature T 1 , adding nano-zero zero-valent iron at a constant temperature ( 2 ) After heating the ionic liquid to a specified temperature T2, adding cellulose with a mass fraction of 1% to 10wt% at a constant temperature preparing a cellulose ionic liquid solution; (3) stirring and mixing the nano-zero-valent iron ionic liquid solution with the cellulose ionic liquid solution, and ultrasonically dispersing at a specified temperature and power; (4) mixing the obtained final The liquid is defoamed, regenerated with a coagulation bath, and washed to obtain a nano-zero-valent iron/cellulose composite hydrogel.
本发明中，所述离子液体选自咪唑盐类离子液体、吡啶盐类离子液体、新型胆碱类和非咪唑盐类离子液体。所述咪唑盐类离子液体可以举出1-丁基-3-甲基咪唑氯化物BmimCl、1-烯丙基-3-甲基咪唑氯盐离子液体(AmimCl)、1-乙基-3-甲基咪唑氯化物[C2MIM]Cl、1-羧甲基-3-甲基咪唑氯盐[CMIM]Cl等。In the present invention, the ionic liquid is selected from imidazolium salt ionic liquids, pyridinium salt ionic liquids, novel choline ionic liquids and non-imidazolium salt ionic liquids. The imidazolium salt ionic liquids include 1-butyl-3-methylimidazolium chloride BmimCl, 1-allyl-3-methylimidazolium chloride ionic liquid (AmimCl), 1-ethyl-3- Methylimidazolium chloride [C 2 MIM]Cl, 1-carboxymethyl-3-methylimidazolium chloride [CMIM]Cl, etc.
本发明所述的方法，步骤(1)中，所述温度T1为80℃，所述纳米零价铁在所述离子液体中的分散温度为70℃～100℃，处理时间为0.5～3小时。In the method of the present invention, in step (1), the temperature T 1 is 80° C., the dispersion temperature of the nano-zero valent iron in the ionic liquid is 70° C. to 100° C., and the treatment time is 0.5 to 3° C. Hour.
本发明所述的方法，步骤(2)中，所述温度T2为100℃，所述纤维素在所述离子液体中的分散温度为70℃～100℃，处理时间为0.5～3小时。In the method of the present invention, in step (2), the temperature T 2 is 100°C, the dispersion temperature of the cellulose in the ionic liquid is 70°C to 100°C, and the treatment time is 0.5 to 3 hours.
本发明所述的方法，步骤(3)中，所述纳米零价铁和纤维素的质量比为0.1％～50％。In the method of the present invention, in step (3), the mass ratio of the nano-zero valent iron to cellulose is 0.1% to 50%.
本发明所述的方法，在步骤(2)中，所述的纳米零价铁的浓度为1～6mg/ml。In the method of the present invention, in step (2), the concentration of the nano-zero valent iron is 1-6 mg/ml.
本发明所述的方法，步骤(3)所述纳米零价铁和纤维素离子液体溶液的混合温度为70～100℃，时间为0.3～5h。In the method of the present invention, the mixing temperature of the nano-zero-valent iron and the cellulose ionic liquid solution in step (3) is 70-100° C., and the time is 0.3-5 h.
本发明所述的方法，步骤(3)所述超声分散用超声波清洗器，超声波清洗器的参数条件为：80～325W超声0.3～3h，超声温度为30～60℃。In the method of the present invention, in step (3), an ultrasonic cleaner is used for ultrasonic dispersion, and the parameters of the ultrasonic cleaner are: 80-325W ultrasonic for 0.3-3h, and ultrasonic temperature is 30-60°C.
本发明所述的方法，步骤(2)所述的纤维素原料是棉短绒、针叶木纸浆、阔叶木纸浆和微晶纤维素中的一种或两种以上。In the method of the present invention, the cellulose raw material in step (2) is one or more of cotton linter, softwood pulp, hardwood pulp and microcrystalline cellulose.
在本发明中，步骤(1)所述离子液体为咪唑盐类离子液体、吡啶盐类离子液体或新型胆碱类和非咪唑盐类离子液体，例如，1-丁基-3-甲基咪唑氯化物BmimCl、1-烯丙基-3-甲基咪唑氯盐离子液体(AmimCl)、1-乙基-3-甲基咪唑氯化物[C2MIM]Cl、1-羧甲基-3-甲基咪唑氯盐[CMIM]Cl等。步骤(4)所述脱泡的方法包括用超声波清洗器超声(50～60℃，80～100W，3～6h)、真空脱泡(50～60℃，放置一夜)、离心脱泡，也可直接在50～60℃的烘箱或者加热器里直接静置脱泡等。In the present invention, the ionic liquid in step (1) is imidazolium salt ionic liquid, pyridinium salt ionic liquid or novel choline and non-imidazolium salt ionic liquid, for example, 1-butyl-3-methylimidazole Chloride BmimCl, 1-allyl-3-methylimidazolium chloride ionic liquid (AmimCl), 1-ethyl-3-methylimidazolium chloride [C 2 MIM]Cl, 1-carboxymethyl-3- Methylimidazolium chloride [CMIM]Cl, etc. The defoaming method in step (4) includes ultrasonication with an ultrasonic cleaner (50-60°C, 80-100W, 3-6h), vacuum defoaming (50-60°C, placed overnight), centrifugal defoaming, or Directly stand for defoaming in an oven or heater at 50-60°C.
在本发明中，所述再生用凝固浴为无水乙醇或丙酮。In the present invention, the coagulation bath for regeneration is absolute ethanol or acetone.
通过本发明制备得到的纳米零价铁/纤维素复合水凝胶和气凝胶，用于一种或者多种污染物的去除，包括吸附或催化。The nano-zero-valent iron/cellulose composite hydrogel and aerogel prepared by the present invention are used for the removal of one or more pollutants, including adsorption or catalysis.
在本发明中，还可以通过改变凝固再生过程中容器的形状，来改变复合水凝胶和气凝胶的形状，可制备得到薄膜状、柱形状、方形状等多种形状的水/气凝胶；通过再生过程方式的改变，可获得球状复合水凝胶和气凝胶。In the present invention, the shape of the composite hydrogel and aerogel can also be changed by changing the shape of the container during the coagulation and regeneration process, and various shapes of water/aerogel such as film, column, and square can be prepared. ; By changing the regeneration process, spherical composite hydrogels and aerogels can be obtained.
研究发现，在本发明中，所述纳米零价铁能够均匀分散在纤维素网络中。通过该方法制备的复合凝胶具有优异的导电性、机械性能和氧化还原活性，作为污染物的去除材料具有优异的重复利用性能。It is found that, in the present invention, the nano-zero valent iron can be uniformly dispersed in the cellulose network. The composite gel prepared by this method has excellent electrical conductivity, mechanical properties and redox activity, and has excellent recycling performance as a pollutant removal material.
实施例1纳米零价铁/纤维素复合水凝胶的制备Example 1 Preparation of nano zero-valent iron/cellulose composite hydrogel
(1)铁基纳米材料的离子液体溶液(1) Ionic liquid solution of iron-based nanomaterials
将50g离子液体[BMIM]Cl加到250ml三口瓶中，油浴加热升温至80℃。待离子液体完全溶解，呈淡黄色澄清透明液状后，加入3g的纳米零价铁，于氮气氛围下加热搅拌0.5h。将三口瓶转移至超声波清洁器超声分散纳米铁3h(50℃)。配成一定质量分数的铁基纳米材料的离子液体溶液待用。50g of ionic liquid [BMIM]Cl was added to a 250ml three-necked bottle, and the temperature was raised to 80°C by heating in an oil bath. After the ionic liquid was completely dissolved and turned into a light yellow, clear and transparent liquid, 3 g of nano-zero valent iron was added, and the mixture was heated and stirred for 0.5 h under a nitrogen atmosphere. Transfer the three-necked bottle to an ultrasonic cleaner to ultrasonically disperse the nano-iron for 3h (50°C). An ionic liquid solution of iron-based nanomaterials with a certain mass fraction is prepared for use.
(2)纤维素离子液体的制备(2) Preparation of cellulose ionic liquid
另外称取50g的[BMIM]Cl于250ml三口瓶中，油浴加热升温至100℃。待离子液体完全溶解，呈淡黄色澄清透明液状后，加入2.5g的溶解浆，在氮气保护下，于100℃油浴磁力搅拌，直到纸浆完全溶解，得到5wt％的纤维素离子液体。In addition, 50 g of [BMIM]Cl was weighed into a 250 ml three-necked bottle, and the temperature was raised to 100° C. by heating in an oil bath. After the ionic liquid was completely dissolved and turned into a light yellow, clear and transparent liquid, 2.5 g of dissolving pulp was added, and under nitrogen protection, magnetic stirring was carried out in an oil bath at 100 °C until the pulp was completely dissolved to obtain 5 wt% cellulose ionic liquid.
(3)最后，将一定量的纳米零价铁的离子液体溶液加入到溶解浆的纤维素离子液体溶液中，在100℃下将混合物磁力搅拌30min，超声分散。将得到的混合液转移到烧杯中，脱泡。(3) Finally, a certain amount of nano-zero-valent iron ionic liquid solution was added to the cellulose ionic liquid solution of the dissolving pulp, and the mixture was magnetically stirred at 100° C. for 30 min, and ultrasonically dispersed. The resulting mixture was transferred to a beaker and defoamed.
此后，将混合物浸入到乙醇中再生。得到柱状纳米零价铁/纤维素复合水凝胶(图1)，并将其用乙醇浸泡洗涤多次，直至用0.1mol mL-1的AgNO3溶液对浸泡液检测无沉淀为止。从而制备纳米零价铁/纤维素复合水凝胶。After that, the mixture was immersed in ethanol for regeneration. The columnar nano-zero-valent iron/cellulose composite hydrogel (Figure 1) was obtained, and it was soaked and washed with ethanol for several times until no precipitation was detected in the soaking liquid with 0.1 mol mL -1 AgNO 3 solution. Thereby, nano-zero-valent iron/cellulose composite hydrogels were prepared.
实施例2纳米零价铁/纤维素复合气凝胶的制备Example 2 Preparation of nano-zero valent iron/cellulose composite aerogel
(1)铁基纳米材料的离子液体溶液(1) Ionic liquid solution of iron-based nanomaterials
将50g离子液体[BMIM]Cl加到250ml三口瓶中，油浴加热升温至80℃。待离子液体完全溶解，呈淡黄色澄清透明液状后，加入3g的纳米零价铁，于氮气氛围下加热搅拌0.5h。将三口瓶转移至超声波清洁器超声分散纳米铁3h(50℃)。配成一定质量分数的铁基纳米材料的离子液体溶液待用。50g of ionic liquid [BMIM]Cl was added to a 250ml three-necked bottle, and the temperature was raised to 80°C by heating in an oil bath. After the ionic liquid was completely dissolved and turned into a light yellow, clear and transparent liquid, 3 g of nano-zero valent iron was added, and the mixture was heated and stirred for 0.5 h under a nitrogen atmosphere. Transfer the three-necked bottle to an ultrasonic cleaner to ultrasonically disperse the nano-iron for 3h (50°C). An ionic liquid solution of iron-based nanomaterials with a certain mass fraction is prepared for use.
(2)纤维素离子液体的制备(2) Preparation of cellulose ionic liquid
另外称取50g的[BMIM]Cl于250ml三口瓶中，油浴加热升温至100℃。待离子液体完全溶解，呈淡黄色澄清透明液状后，加入2.5g的溶解浆，在氮气保护下，于100℃油浴磁力搅拌，直到纸浆完全溶解，得到5wt％的纤维素离子液体。In addition, 50 g of [BMIM]Cl was weighed into a 250 ml three-necked bottle, and the temperature was raised to 100° C. by heating in an oil bath. After the ionic liquid was completely dissolved and turned into a light yellow, clear and transparent liquid, 2.5 g of dissolving pulp was added, and under nitrogen protection, magnetic stirring was carried out in an oil bath at 100 °C until the pulp was completely dissolved to obtain 5 wt% cellulose ionic liquid.
(3)然后，将一定量的纳米零价铁的离子液体溶液加入到溶解浆的纤维素离子液体溶液中，在100℃下将混合物磁力搅拌30min，超声分散。将得到的混合液转移到烧杯中，进行脱泡。此后，将混合物浸入到乙醇中再生。得到柱状纳米零价铁/纤维素复合水凝胶，并将其用乙醇浸泡洗涤多次，直至用0.1mol mL-1的AgNO3溶液对浸泡液检测无沉淀为止。从而制备纳米零价铁/纤维素复合水凝胶。(3) Then, a certain amount of nano-zero valent iron ionic liquid solution was added to the cellulose ionic liquid solution of the dissolving pulp, the mixture was magnetically stirred at 100° C. for 30 min, and ultrasonically dispersed. The obtained mixed solution was transferred to a beaker and defoamed. After that, the mixture was immersed in ethanol for regeneration. The columnar nano-zero-valent iron/cellulose composite hydrogel was obtained, and it was soaked and washed with ethanol for several times until no precipitation was detected in the soaking liquid with 0.1 mol mL -1 AgNO 3 solution. Thereby, nano-zero-valent iron/cellulose composite hydrogels were prepared.
最后，冷冻干燥得到柱状纳米零价铁/纤维素复合气凝胶(图2)。Finally, the columnar nano-zero-valent iron/cellulose composite aerogel was obtained by freeze-drying (Fig. 2).
研究发现，纳米零价铁能够均匀分散在纤维素网络中。通过该方法制备的复合凝胶具有优异的导电性、机械性能和氧化还原活性，作为污染物的去除材料具有优异的重复利用性能。The study found that the nano-zero valent iron can be uniformly dispersed in the cellulose network. The composite gel prepared by this method has excellent electrical conductivity, mechanical properties and redox activity, and has excellent recycling performance as a pollutant removal material.
本发明相对于现有的技术，有以下优点：Compared with the prior art, the present invention has the following advantages:
(1)本发明以天然的纤维素为基底，价格便宜，量大，整个过程没有水的参与，有利于纳米零价铁的分散和反应活性的提高。(1) The present invention is based on natural cellulose, which is cheap in price and large in quantity, without the participation of water in the whole process, which is beneficial to the dispersion of nano-zero valent iron and the improvement of reactivity.
(2)本发明采用离子液体为溶剂和分散剂，乙醇作为凝固浴，有利于纳米零价铁的分散，减少其团聚，提高纳米零价铁/纤维素复合凝胶的性能。(2) The present invention adopts ionic liquid as solvent and dispersant, and ethanol as coagulation bath, which is beneficial to the dispersion of nano-zero-valent iron, reduces its agglomeration, and improves the performance of nano-zero-valent iron/cellulose composite gel.
(3)本发明所制备的复合凝胶兼具有纳米零价铁和纤维素的性质，性能优异，如比表面积高、导电性好、机械性能强等。该复合凝胶有望在催化，吸附，能源储存等多个领域有广泛的应用。(3) The composite gel prepared by the present invention has both the properties of nano-zero-valent iron and cellulose, and has excellent properties, such as high specific surface area, good electrical conductivity, and strong mechanical properties. The composite gel is expected to have a wide range of applications in catalysis, adsorption, energy storage and other fields.
(4)本发明制备方法巧妙，过程绿色，得到的材料性能优越，原料来源广泛，价格低廉，有望在环境功能材料、结构材料、能源等领域获得应用。(4) The preparation method of the invention is ingenious, the process is green, the obtained material has superior performance, wide raw material sources and low price, and is expected to be applied in the fields of environmental functional materials, structural materials, energy and the like.
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。The above-mentioned embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above-mentioned embodiments, and any other changes, modifications, substitutions, combinations, The simplification should be equivalent replacement manners, which are all included in the protection scope of the present invention.
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| CN107670646A (en) * | 2017-09-22 | 2018-02-09 | 中国科学院合肥物质科学研究院 | A kind of bead structure nano zero valence iron/cellulose composite material and its application |
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2019
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007001309A2 (en) * | 2004-06-30 | 2007-01-04 | Auburn University | Preparation and applications of stabilized metal nanoparticles for dechlorination of chlorinated hydrocarbons in soils, sediments and groundwater |
| CN103962116A (en) * | 2014-04-25 | 2014-08-06 | 南开大学 | Preparation method of solid catalyst loaded with cellulose aiding body |
| CN103937010A (en) * | 2014-04-28 | 2014-07-23 | 华南理工大学 | High-performance graphene/cellulose composite hydrogel and aerogel and preparation methods thereof |
| CN104086783A (en) * | 2014-07-08 | 2014-10-08 | 黑龙江大学 | Method for preparing graphene oxide/carbon nano tube/cellulose composite gel from ionic liquid |
| CN107670646A (en) * | 2017-09-22 | 2018-02-09 | 中国科学院合肥物质科学研究院 | A kind of bead structure nano zero valence iron/cellulose composite material and its application |
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