CN104941537B - A kind of preparation method of strip nano ZnO/cellulose gel material - Google Patents
A kind of preparation method of strip nano ZnO/cellulose gel material Download PDFInfo
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- PTHCMJGKKRQCBF-UHFFFAOYSA-N Cellulose, microcrystalline Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC)C(CO)O1 PTHCMJGKKRQCBF-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000000463 material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920002678 cellulose Polymers 0.000 claims abstract description 39
- 239000001913 cellulose Substances 0.000 claims abstract description 39
- 239000007864 aqueous solution Substances 0.000 claims abstract description 23
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- 229920003043 Cellulose fiber Polymers 0.000 claims abstract description 13
- 239000011592 zinc chloride Substances 0.000 claims abstract description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000011701 zinc Substances 0.000 claims abstract description 9
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 9
- 239000003292 glue Substances 0.000 claims abstract description 6
- 238000004108 freeze drying Methods 0.000 claims abstract description 4
- 238000002347 injection Methods 0.000 claims abstract description 4
- 239000007924 injection Substances 0.000 claims abstract description 4
- 229920000875 Dissolving pulp Polymers 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 10
- 239000000835 fiber Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000007710 freezing Methods 0.000 claims description 5
- 230000008014 freezing Effects 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000011343 solid material Substances 0.000 claims description 5
- 229920000742 Cotton Polymers 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 3
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 3
- 241001330002 Bambuseae Species 0.000 claims description 3
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 3
- 229920001131 Pulp (paper) Polymers 0.000 claims description 3
- 239000011425 bamboo Substances 0.000 claims description 3
- -1 by dissolving Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 239000000499 gel Substances 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004090 dissolution Methods 0.000 abstract 1
- 238000004134 energy conservation Methods 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 107
- 239000011787 zinc oxide Substances 0.000 description 66
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- 239000013078 crystal Substances 0.000 description 8
- 235000005074 zinc chloride Nutrition 0.000 description 8
- 239000000969 carrier Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
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- 238000011065 in-situ storage Methods 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
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- 239000002070 nanowire Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
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- 239000004246 zinc acetate Substances 0.000 description 1
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Abstract
Description
技术领域technical field
本发明属于纤维新材料技术领域，具体涉及到一种条状纳米ZnO/纤维素凝胶材料的制备方法。The invention belongs to the technical field of new fiber materials, and in particular relates to a preparation method of a strip nano ZnO/cellulose gel material.
背景技术Background technique
自从Iijima 发现碳纳米管以来，纳米材料因具有许多特殊的化学性质而引起了人们的极大兴趣。ZnO是典型的且性能优良的宽禁带半导体材料，由于量子尺寸及小尺寸效应，纳米ZnO表现出特殊性质，广泛地应用于光催化、光电转换以及气体传感器等领域。ZnO纳米材料的制备方法主要有气相沉积法、模板法、微乳液法、溶胶-凝胶法、水热合成法等，所制得的产品形状有纳米颗粒、纳米棒、纳米线、纳米阵列及纳米膜等。由于纳米ZnO粒径小、表面能高，故极易团聚、难分离、不易回收且不如TiO2稳定，极大地限制了在光催化工业中的应用。因此，将纳米ZnO与特定载体组装成复合材料，提高纳米材料的活性、效率及稳定性是实现其光催化工业应用的有效途径之一。Since Iijima's discovery of carbon nanotubes, nanomaterials have attracted great interest because of their many special chemical properties. ZnO is a typical wide-bandgap semiconductor material with excellent performance. Due to the quantum size and small size effect, nano-ZnO exhibits special properties and is widely used in photocatalysis, photoelectric conversion, and gas sensors. The preparation methods of ZnO nanomaterials mainly include vapor phase deposition method, template method, microemulsion method, sol-gel method, hydrothermal synthesis method, etc. The shapes of the prepared products include nanoparticles, nanorods, nanowires, nanoarrays and Nanofilm, etc. Due to the small particle size and high surface energy of nano-ZnO, it is extremely easy to agglomerate, difficult to separate, difficult to recycle, and not as stable as TiO2 , which greatly limits its application in the photocatalytic industry. Therefore, assembling nano-ZnO and specific carriers into composite materials and improving the activity, efficiency and stability of nano-materials is one of the effective ways to realize its photocatalytic industrial application.
目前，常用的无机载体有二氧化硅、硅藻土、氧化铝、炭材料等，无机载体具有密度大（一般仅适用固定床反应器）的特点，限制了其在光催化工程中的应用；有机聚合物载体有聚乙烯等，其密度小，不仅适用于固定床反应器，也可适用于悬浮床反应器，但石油基聚合物不易降解和再生，环境友好性差。At present, commonly used inorganic carriers include silica, diatomaceous earth, alumina, carbon materials, etc. Inorganic carriers have the characteristics of high density (generally only suitable for fixed bed reactors), which limits their application in photocatalytic engineering; Organic polymer carriers include polyethylene, etc., which have low density and are not only suitable for fixed-bed reactors, but also for suspended-bed reactors. However, petroleum-based polymers are not easy to degrade and regenerate, and have poor environmental friendliness.
纤维素是葡萄糖结构单元通过β-1, 4糖苷键连接而成的线性高分子，它是地球上储量最高、环境友好且可再生的有机聚合物，由于具有多个可反应羟基且可生物降解，备受材料科学家的关注。因此，组装纳米ZnO/纤维素复合材料也是实现纤维素高值化利用的一条重要途径。Cellulose is a linear polymer composed of glucose structural units connected by β -1, 4 glycosidic bonds. It is the most abundant, environmentally friendly and renewable organic polymer on earth. It has multiple reactive hydroxyl groups and is biodegradable. , has attracted the attention of material scientists. Therefore, the assembly of nano-ZnO/cellulose composites is also an important way to realize the high-value utilization of cellulose.
目前，纳米ZnO/纤维素复合材料的制备方法主要有两类：一是以原纤维素纤维、再生棉纤维素膜、醋酸纤维素纤维和纸纤维等为纳米ZnO的载体，将锌源（如硝酸锌、醋酸锌等）负载在载体上，最后将锌源转化成纳米氧化锌，得到纳米ZnO/纤维素复合材料；二是先制备得到纳米ZnO，然后将纳米ZnO分散在纤维素或纤维素衍生物（如醋酸纤维素等）的溶液中，最后将纤维素或纤维素衍生物析出，得到出纳米ZnO/纤维素复合材料。At present, there are mainly two types of preparation methods for nano-ZnO/cellulose composite materials: one is to use raw cellulose fiber, regenerated cotton cellulose film, cellulose acetate fiber and paper fiber as the carrier of nano-ZnO, and zinc source (such as Zinc nitrate, zinc acetate, etc.) are loaded on the carrier, and finally the zinc source is converted into nano-zinc oxide to obtain nano-ZnO/cellulose composite materials; the second is to prepare nano-ZnO first, and then disperse nano-ZnO in cellulose or cellulose In the solution of derivatives (such as cellulose acetate, etc.), the cellulose or cellulose derivatives are finally precipitated to obtain nano-ZnO/cellulose composite materials.
以上两类方法分别存在以下缺点：第一类方法，以纤维或膜为载体，锌源不易渗透进入载体；且最终产品的形状为纤维或膜，而工业催化剂的形状一般为颗粒状、条状。第二类方法，需要选用纤维素或纤维素衍生物的溶剂，造成环境污染；纳米ZnO颗粒不易分散在纤维素或纤维素衍生物溶液中，且对纺丝成纤维或成膜过程造成不利的影响；单独制备纳米ZnO一般需要较高的温度。The above two types of methods have the following disadvantages respectively: the first type of method uses fibers or membranes as carriers, and the zinc source is not easy to penetrate into the carriers; and the shape of the final product is fibers or membranes, while the shape of industrial catalysts is generally granular or strip . The second type of method requires the selection of solvents for cellulose or cellulose derivatives, which causes environmental pollution; nano-ZnO particles are not easily dispersed in cellulose or cellulose derivative solutions, and cause adverse effects on spinning into fibers or film-forming processes. Influence; the preparation of nano-ZnO alone generally requires a higher temperature.
发明内容Contents of the invention
发明目的：针对上述方法存在的不足，本发明的目的是提供一种条状纳米ZnO/纤维素凝胶材料的制备方法，以ZnCl2水溶液作为纤维素的溶剂和纳米ZnO的锌源，将纤维素和ZnCl2两种原料变成均相，采用注射方式、原位溶胶-凝胶、低温水热合成技术和冷冻干燥得到的条状纳米ZnO/纤维素凝胶新材料。Goal of the invention: for the deficiencies that the above-mentioned method exists, the purpose of this invention is to provide a kind of preparation method of strip nano - ZnO/cellulose gel material, with ZnCl aqueous solution as the zinc source of the solvent of cellulose and nano-ZnO, fiber The two raw materials of element and ZnCl2 become homogeneous, and the strip-shaped nano-ZnO/cellulose gel new material is obtained by injection method, in-situ sol-gel, low-temperature hydrothermal synthesis technology and freeze-drying.
技术方案：为了实现上述发明目的，本发明采用的技术方案如下：Technical scheme: in order to realize the above-mentioned purpose of the invention, the technical scheme adopted in the present invention is as follows:
一种条状纳米ZnO/纤维素凝胶材料的制备方法，以ZnCl2水溶液作为纤维素的溶剂和纳米ZnO的锌源，溶解浆纤维素纤维为纤维素原料，通过溶解、注射共析出、水热合成和冷冻干燥，制备出条状纳米ZnO/纤维素凝胶新材料。A kind of preparation method of strip nano - ZnO/cellulose gel material, with ZnCl2 aqueous solution as the solvent of cellulose and the zinc source of nano-ZnO, dissolving pulp cellulose fiber is cellulose raw material, through dissolving, injection co-precipitation, water Thermal synthesis and freeze-drying prepared a strip-shaped nano-ZnO/cellulose gel new material.
所述条状纳米ZnO/纤维素凝胶材料的制备方法，包括以下步骤：The preparation method of described strip nano ZnO/cellulose gel material, comprises the following steps:
1）取纤维素纤维加入到65-70wt%的ZnCl2水溶液中，在-10℃-30℃的低温浴槽中预处理0.5h-3h；1) Take cellulose fiber and add it to 65-70wt% ZnCl 2 aqueous solution, and pretreat it in a low-temperature bath at -10°C-30°C for 0.5h-3h;
2）将上述液-固物料置于60℃-90℃的水浴锅中加热搅拌，得到透明均一的纤维素溶液；2) Heat and stir the above liquid-solid material in a water bath at 60°C-90°C to obtain a transparent and uniform cellulose solution;
3）用注射器将溶解纤维素的ZnCl2水溶液缓慢注射到15%-30%NaOH水溶液，调节体系的pH值为7-10，静置24-48小时，得到条状ZnO前驱体/纤维素凝胶；3) Use a syringe to slowly inject the ZnCl 2 aqueous solution that dissolves cellulose into a 15%-30% NaOH aqueous solution, adjust the pH of the system to 7-10, and let it stand for 24-48 hours to obtain a strip-shaped ZnO precursor/cellulose gel. glue;
4）将步骤3）中的条状ZnO前驱体/纤维素凝胶放入水热合成釜中，在pH=7-10、温度为100-170℃的条件下进行水热反应，反应时间为4-10h；4) Put the strip-shaped ZnO precursor/cellulose gel in step 3) into a hydrothermal synthesis kettle, and perform hydrothermal reaction under the conditions of pH=7-10 and temperature 100-170°C, and the reaction time is 4-10h;
5）将步骤4）中的条状ZnO/纤维素凝胶水洗至无Cl-后，先放入超低温冰箱内，冷冻结束后将样品置于冷冻干燥机中，干燥结束后，得到条状纳米ZnO/纤维素凝胶材料。5) Wash the strip-shaped ZnO/cellulose gel in step 4) to be free of Cl- , put it in an ultra-low temperature refrigerator, and place the sample in a freeze dryer after freezing. After drying, strip-shaped nano ZnO/cellulose gel material.
所述的纤维素纤维包括木浆、竹浆或棉浆纤维。The cellulose fibers include wood pulp, bamboo pulp or cotton pulp fibers.
所述的纤维素纤维与ZnCl2水溶液的用量关系为1:30~60（质量之比）。The dosage relationship between the cellulose fiber and the ZnCl 2 aqueous solution is 1:30-60 (mass ratio).
有益效果：与现有产品和技术相比，本发明巧妙地以ZnCl2水溶液作为纤维素的溶剂和纳米ZnO的锌源，无需外加其他纤维素溶剂，制备工艺清洁环保。纤维素溶解后，其分子上的羟基与锌离子结合，促进了纳米ZnO的生成，水热合成温度也相应明显降低，因此，制备工艺具有节能的优点。所得到的材料为条状纳米ZnO/纤维素凝胶新材料。具备很好的实用性。Beneficial effects: Compared with existing products and technologies, the present invention cleverly uses ZnCl 2 aqueous solution as the solvent of cellulose and the zinc source of nano-ZnO, without adding other cellulose solvents, and the preparation process is clean and environmentally friendly. After the cellulose is dissolved, the hydroxyl groups on its molecules combine with zinc ions, which promotes the formation of nano-ZnO, and the hydrothermal synthesis temperature is correspondingly significantly reduced. Therefore, the preparation process has the advantage of energy saving. The obtained material is a new strip nano ZnO/cellulose gel material. It has very good practicality.
附图说明Description of drawings
图1是例1条状ZnO/纤维素凝胶的SEM图；Fig. 1 is the SEM figure of example 1 strip ZnO/cellulose gel;
图2是例1条状ZnO/纤维素凝胶表面上纳米ZnO的SEM图；Fig. 2 is the SEM figure of nanometer ZnO on the surface of example 1 strip ZnO/cellulose gel;
图3是ZnO和碱式氯化锌晶体XRD标准图；Fig. 3 is ZnO and basic zinc chloride crystal XRD standard figure;
图4是水热温度为120℃时ZnO颗粒的XRD图；Figure 4 is the XRD pattern of ZnO particles when the hydrothermal temperature is 120°C;
图5是例1 条状ZnO/纤维素凝胶的XRD图；Fig. 5 is the XRD figure of example 1 strip ZnO/cellulose gel;
图6是水热温度为240℃时ZnO颗粒的XRD图；Figure 6 is the XRD pattern of ZnO particles when the hydrothermal temperature is 240°C;
图7是例2条状ZnO/纤维素凝胶的XRD图；Fig. 7 is the XRD pattern of example 2 strip ZnO/cellulose gel;
图8例3条状ZnO/纤维素凝胶的XRD图。Figure 8 Example 3 XRD pattern of strip ZnO/cellulose gel.
具体实施方式detailed description
实施例1Example 1
将1g木浆纤维素纤维加入到65%（wt%）的ZnCl2水溶液中，在10℃的低温浴槽中预处理1h。将上述液-固物料置于70℃的水浴锅中加热搅拌，得到透明均一的纤维素溶液。采用注射器将溶解纤维素的ZnCl2水溶液中缓慢注射到20%NaOH水溶液，调节体系的pH值为9时，静置24小时，得到条状ZnO前驱体/纤维素凝胶。将条状ZnO前驱体/纤维素凝胶放入水热合成釜中，在pH=9、温度为120℃的条件下进行水热反应，反应时间为6h。将条状ZnO/纤维素凝胶水洗至无Cl-后，先放入超低温冰箱内，冷冻结束后将样品置于冷冻干燥机中，干燥结束后，得到条状纳米ZnO/纤维素凝胶新材料。Add 1 g of wood pulp cellulose fiber into 65% (wt%) ZnCl2 aqueous solution and pretreat it in a low-temperature bath at 10 °C for 1 h. The above liquid-solid material was placed in a water bath at 70° C. and heated and stirred to obtain a transparent and uniform cellulose solution. Use a syringe to slowly inject the cellulose-dissolving ZnCl 2 aqueous solution into a 20% NaOH aqueous solution, adjust the pH of the system to 9, and let it stand for 24 hours to obtain a strip-shaped ZnO precursor/cellulose gel. The strip ZnO precursor/cellulose gel was put into a hydrothermal synthesis kettle, and the hydrothermal reaction was carried out under the conditions of pH = 9 and temperature 120 ° C, and the reaction time was 6 h. After washing the strip-shaped ZnO/cellulose gel with water to be free of Cl- , put it in an ultra-low temperature refrigerator first, and place the sample in a freeze dryer after freezing. After drying, a strip-shaped nano-ZnO/cellulose gel is obtained. Material.
采用相同方法（不加纤维素，其他条件相同）制备了ZnO颗粒作为对比。ZnO particles were prepared by the same method (without adding cellulose, other conditions were the same) as a comparison.
由图1可知，制备的条状ZnO/纤维素凝胶，ZnO在外层，纤维素凝胶在内层。由图2可知，制备的纳米ZnO，尺寸为100-200nm。It can be seen from Figure 1 that for the prepared strip ZnO/cellulose gel, ZnO is on the outer layer and cellulose gel is on the inner layer. It can be seen from Fig. 2 that the prepared nano-ZnO has a size of 100-200nm.
由图3和图4可知，不加纤维素制备的ZnO颗粒晶体不纯，含有较多的碱式氯化锌杂质；由图3和图5可知，制备的条状ZnO/纤维素凝胶含有纤维素和ZnO晶体，无碱式氯化锌。As can be seen from Figure 3 and Figure 4, the ZnO granular crystals prepared without cellulose are impure and contain more basic zinc chloride impurities; as can be seen from Figure 3 and Figure 5, the prepared strip ZnO/cellulose gel contains Cellulose and ZnO crystals, zinc chloride free.
为了考察纳米ZnO的水热温度，采用相同方法（不加纤维素，改变温度，其他条件相同）制备ZnO颗粒，实验结果表明：当水热温度达到240℃时，才能得到比较纯的ZnO晶体，结果如图6所示。因此，纤维素的存在促进了ZnO晶体的生成，降低了ZnO晶体的水热合成温度。In order to investigate the hydrothermal temperature of nano-ZnO, ZnO particles were prepared by the same method (without adding cellulose, changing the temperature, and other conditions were the same). The experimental results showed that relatively pure ZnO crystals could be obtained when the hydrothermal temperature reached 240°C. The result is shown in Figure 6. Therefore, the presence of cellulose promotes the formation of ZnO crystals and reduces the hydrothermal synthesis temperature of ZnO crystals.
实施例2Example 2
将1g竹浆纤维素纤维加入到68%（wt%）的ZnCl2水溶液中，在-10℃的低温浴槽中预处理3h。将上述液-固物料置于60℃的水浴锅中加热搅拌，得到透明均一的纤维素溶液。采用注射器将溶解纤维素的ZnCl2水溶液中缓慢注射到15%NaOH水溶液，调节体系的pH值为7时，静置48小时，得到条状ZnO前驱体/纤维素凝胶。将条状ZnO前驱体/纤维素凝胶放入水热合成釜中，在pH=7、温度为170℃的条件下进行水热反应，反应时间为4h。将条状ZnO/纤维素凝胶水洗至无Cl-后，先放入超低温冰箱内，冷冻结束后将样品置于冷冻干燥机中，干燥结束后，得到条状纳米ZnO/纤维素凝胶新材料。1 g of bamboo pulp cellulose fiber was added to 68% (wt%) ZnCl 2 aqueous solution, and pretreated in a low-temperature bath at -10 °C for 3 h. The above liquid-solid material was placed in a water bath at 60° C. and heated and stirred to obtain a transparent and uniform cellulose solution. Use a syringe to slowly inject the cellulose-dissolving ZnCl 2 aqueous solution into a 15% NaOH aqueous solution, adjust the pH of the system to 7, and let it stand for 48 hours to obtain a strip-shaped ZnO precursor/cellulose gel. The strip-shaped ZnO precursor/cellulose gel was put into a hydrothermal synthesis kettle, and the hydrothermal reaction was carried out under the conditions of pH=7 and temperature of 170°C, and the reaction time was 4h. After washing the strip-shaped ZnO/cellulose gel with water to be free of Cl- , put it in an ultra-low temperature refrigerator first, and place the sample in a freeze dryer after freezing. After drying, a strip-shaped nano-ZnO/cellulose gel is obtained. Material.
由图7可知，制备的条状ZnO/纤维素凝胶含有纤维素和ZnO晶体，无碱式氯化锌。It can be seen from Figure 7 that the prepared strip ZnO/cellulose gel contains cellulose and ZnO crystals, without basic zinc chloride.
实施例3Example 3
将1g棉浆纤维素纤维加入到70%（wt%）的ZnCl2水溶液中，在30℃的低温浴槽中预处理0.5h。将上述液-固物料置于90℃的水浴锅中加热搅拌，得到透明均一的纤维素溶液。采用注射器将溶解纤维素的ZnCl2水溶液中缓慢注射到30%NaOH水溶液，调节体系的pH值为10时，静置36小时，得到条状ZnO前驱体/纤维素凝胶。将条状ZnO前驱体/纤维素凝胶放入水热合成釜中，在pH=10、温度为100℃的条件下进行水热反应，反应时间为10h。 将条状ZnO/纤维素凝胶水洗至无Cl-后，先放入超低温冰箱内，冷冻结束后将样品置于冷冻干燥机中，干燥结束后，得到条状纳米ZnO/纤维素凝胶新材料。Add 1 g of cotton pulp cellulose fiber into 70% (wt%) ZnCl 2 aqueous solution, and pretreat it in a low-temperature bath at 30 °C for 0.5 h. The above liquid-solid material was placed in a water bath at 90° C. and heated and stirred to obtain a transparent and uniform cellulose solution. Use a syringe to slowly inject the cellulose-dissolving ZnCl 2 aqueous solution into a 30% NaOH aqueous solution, adjust the pH of the system to 10, and let it stand for 36 hours to obtain a strip-shaped ZnO precursor/cellulose gel. The strip-shaped ZnO precursor/cellulose gel was put into a hydrothermal synthesis kettle, and the hydrothermal reaction was carried out under the conditions of pH=10 and temperature 100 °C, and the reaction time was 10 h. After washing the strip-shaped ZnO/cellulose gel with water to be free of Cl- , put it in an ultra-low temperature refrigerator first, and place the sample in a freeze dryer after freezing. After drying, a strip-shaped nano-ZnO/cellulose gel is obtained. Material.
由图8可知，制备的条状ZnO/纤维素凝胶含有纤维素和ZnO晶体，无碱式氯化锌。It can be seen from Figure 8 that the prepared strip ZnO/cellulose gel contains cellulose and ZnO crystals, without basic zinc chloride.
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