CN104941540B - A kind of nano-ZnO/cellulose gel particle and preparation method thereof - Google Patents
A kind of nano-ZnO/cellulose gel particle and preparation method thereof Download PDFInfo
- Publication number
- CN104941540B CN104941540B CN201510280270.7A CN201510280270A CN104941540B CN 104941540 B CN104941540 B CN 104941540B CN 201510280270 A CN201510280270 A CN 201510280270A CN 104941540 B CN104941540 B CN 104941540B
- Authority
- CN
- China
- Prior art keywords
- zno
- cellulose
- nano
- cellulose gel
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
本发明公开了一种纳米ZnO/纤维素凝胶颗粒及其制备方法，该纳米ZnO/纤维素凝胶颗粒以纤维素凝胶为核，外层负载纳米ZnO。制备方法中以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、共析出、水热合成和冷冻干燥，制备获得纳米ZnO/纤维素凝胶颗粒。由于本发明巧妙地以ZnCl2水溶液作为纤维素的溶剂和纳米ZnO的锌源，因此，无需外加其他纤维素溶剂，制备工艺清洁环保。另外，纤维素溶解后，其分子上的羟基与锌离子结合，有力地促进了纳米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。
The invention discloses a nanometer ZnO/cellulose gel particle and a preparation method thereof. The nanometer ZnO/cellulose gel particle uses cellulose gel as a core, and the outer layer is loaded with nanometer ZnO. In the preparation method, ZnCl2 aqueous solution is used as the solvent of cellulose and the zinc source of nano-ZnO, and the cellulose fiber of dissolving pulp is used as the cellulose raw material. Glue particles. Since the present invention skillfully uses ZnCl2 aqueous solution as the solvent of cellulose and the zinc source of nanometer ZnO, there is no need to add other cellulose solvents, and the preparation process is clean and environment-friendly. In addition, after the cellulose is dissolved, the hydroxyl groups on its molecules combine with zinc ions, which effectively 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.
Description
技术领域technical field
本发明涉及纳米ZnO/纤维素凝胶颗粒技术领域，具体涉及一种纳米ZnO/纤维素凝胶颗粒及其制备方法。The invention relates to the technical field of nano ZnO/cellulose gel particles, in particular to a nano ZnO/cellulose gel particle and a preparation method thereof.
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 due to 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, it is one of the effective ways to realize the industrial application of photocatalysis by assembling nano-ZnO and specific carriers into composite materials and improving the activity, efficiency and stability of nano-materials.
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，制备纳米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 preparation 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；该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。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；该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。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 material; this method uses fiber or membrane as the carrier, and the zinc source is not easy to penetrate into the carrier; and the final product The shape of catalyst is fiber or film, while the shape of industrial catalyst is generally granular or strip. The second is to prepare nano-ZnO first, then disperse nano-ZnO in a solution of cellulose or cellulose derivatives (such as cellulose acetate, etc.), and finally precipitate cellulose or cellulose derivatives to obtain nano-ZnO/cellulose Composite materials; this method requires the selection of solvents for cellulose or cellulose derivatives, causing environmental pollution; nano-ZnO particles are not easy to disperse 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：针对以上方法存在的不足，本发明的目的是提供一种纳米ZnO/纤维素凝胶颗粒，为以纤维素凝胶为核，外层负载纳米ZnO的纳米ZnO/纤维素凝胶颗粒新材料。本发明的另一目的是提供一种上述纳米ZnO/纤维素凝胶颗粒的制备方法。Goal of the invention: for the deficiencies in the above method, the purpose of the invention is to provide a kind of nanometer ZnO/cellulose gel particle, be to take cellulose gel as core, the nanometer ZnO/cellulose gel particle of outer layer load nanometer ZnO new material. Another object of the present invention is to provide a method for preparing the aforementioned nano ZnO/cellulose gel particles.
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 solution: In order to realize the above-mentioned purpose of the invention, the technical solution adopted in the present invention is as follows:
一种纳米ZnO/纤维素凝胶颗粒的制备方法，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，采用原位溶胶-凝胶、低温水热合成技术和冷冻干燥得到的纳米ZnO/纤维素凝胶颗粒新材料。A kind of preparation method of nanometer ZnO/cellulose gel particle, use ZnCl2 aqueous solution as the solvent of cellulose and the zinc source of nanometer ZnO, make cellulose and ZnCl2 two kinds of raw materials become homogeneous phase, adopt in - situ sol-gel Nano-ZnO/cellulose gel particle new material obtained by glue, low-temperature hydrothermal synthesis technology and freeze-drying.
一种纳米ZnO/纤维素凝胶颗粒的制备方法，包括以下步骤：A preparation method of nano ZnO/cellulose gel particles, comprising the following steps:
1）将纤维素纤维加入到65-70wt%的ZnCl2水溶液中，在-10~30℃的低温浴槽中预处理0.5-3h；1) Add cellulose fiber to 65-70wt% ZnCl 2 aqueous solution, and pretreat it in a low-temperature bath at -10~30°C for 0.5-3h;
2）将步骤1）获得的液-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 liquid-solid material obtained in step 1) in a water bath at 60-90°C to obtain a transparent and uniform cellulose solution;
3）向纤维素溶液中，缓慢滴加5-20%NaOH水溶液，当体系的pH值为7-10时，停止滴加，静置24-48h，得到ZnO前驱体/纤维素凝胶；3) Slowly add 5-20% NaOH aqueous solution dropwise to the cellulose solution. When the pH value of the system is 7-10, stop the dropwise addition and let stand for 24-48h to obtain ZnO precursor/cellulose gel;
4）将步骤3）中的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 ZnO precursor/cellulose gel in step 3) into a hydrothermal synthesis kettle, and perform a 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ZnO/纤维素凝胶颗粒。5) After washing the ZnO/cellulose gel in step 4) 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, the ZnO/cellulose gel is obtained. Glue particles.
所述的纤维素纤维为木浆、竹浆或棉浆纤维。The cellulose fibers are wood pulp, bamboo pulp or cotton pulp fibers.
所述的纳米ZnO/纤维素凝胶颗粒的制备方法所制备获得的纳米ZnO/纤维素凝胶颗粒。Nano ZnO/cellulose gel particles prepared by the method for preparing nano ZnO/cellulose gel particles.
所述的纳米ZnO/纤维素凝胶颗粒，ZnO在外层，纤维素凝胶在内层。In the nanometer ZnO/cellulose gel particle, ZnO is in the outer layer, and the cellulose gel is in the inner layer.
有益效果：与现有技术相比，本发明纳米ZnO/纤维素凝胶颗粒及其制备方法具备的优点包括：Beneficial effects: Compared with the prior art, the advantages of the nano-ZnO/cellulose gel particle and its preparation method of the present invention include:
1）该纳米ZnO/纤维素凝胶颗粒，是以纤维素凝胶为核，在外层负载纳米ZnO的纳米ZnO/纤维素凝胶颗粒新材料。1) The nano-ZnO/cellulose gel particle is a new nano-ZnO/cellulose gel particle material with cellulose gel as the core and nano-ZnO loaded on the outer layer.
2）本发明的方法无需外加其他纤维素溶剂，制备工艺清洁环保。2) The method of the present invention does not need to add other cellulose solvents, and the preparation process is clean and environmentally friendly.
3）本发明的方法，纤维素溶解后，其分子上的羟基与锌离子结合，有力地促进了纳米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。3) In the method of the present invention, after the cellulose is dissolved, the hydroxyl groups on its molecules combine with zinc ions, which effectively 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.
附图说明Description of drawings
图1是实施例1的ZnO/纤维素凝胶颗粒的SEM图；Fig. 1 is the SEM picture of the ZnO/cellulose gel particle of embodiment 1;
图2是实施例1的颗粒表面上的纳米ZnO的SEM图；Fig. 2 is the SEM figure of the nanometer ZnO on the particle surface of embodiment 1;
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是实施例1的水热温度为120℃时ZnO颗粒的XRD图；Fig. 4 is the XRD figure of ZnO particle when the hydrothermal temperature of embodiment 1 is 120 ℃;
图5是实施例1的ZnO/纤维素凝胶颗粒的XRD图；Fig. 5 is the XRD figure of the ZnO/cellulose gel particle of embodiment 1;
图6是实施例1的水热温度为240℃时ZnO颗粒的XRD图；Fig. 6 is the XRD pattern of ZnO particle when the hydrothermal temperature of embodiment 1 is 240 ℃;
图7是实施例2的ZnO/纤维素凝胶颗粒的SEM图；Fig. 7 is the SEM picture of the ZnO/cellulose gel particle of embodiment 2;
图8是实施例2的ZnO/纤维素凝胶颗粒XRD图；Fig. 8 is the ZnO/cellulose gel particle XRD figure of embodiment 2;
图9是实施例3的ZnO/纤维素凝胶颗粒的SEM图；Fig. 9 is the SEM picture of the ZnO/cellulose gel particle of embodiment 3;
图10是实施例3的ZnO/纤维素凝胶颗粒XRD图。FIG. 10 is the XRD pattern of the ZnO/cellulose gel particles of Example 3.
具体实施方式detailed description
下面结合具体实施例对本发明作进一步的说明。The present invention will be further described below in conjunction with specific examples.
实施例1Example 1
将1g木浆纤维素加入到68%（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。向溶解纤维素的ZnCl2水溶液中，缓慢滴加10%NaOH水溶液，当体系的pH值为9时，停止滴加，静置24小时，得到ZnO前驱体/纤维素凝胶。）将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ZnO/纤维素凝胶颗粒新材料。Add 1 g of wood pulp cellulose into 68% (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. Slowly add 10% NaOH aqueous solution dropwise to the ZnCl2 aqueous solution in which cellulose is dissolved. When the pH value of the system is 9, stop the dropwise addition and let stand for 24 hours to obtain ZnO precursor/cellulose gel. ) Put the ZnO precursor/cellulose gel into the hydrothermal synthesis kettle, and carry out the hydrothermal reaction under the conditions of pH=9 and temperature 120°C, and the reaction time is 6h. After the ZnO/cellulose gel was washed with water to be free of Cl- , it was first placed in an ultra-low temperature refrigerator. After freezing, the sample was placed in a freeze dryer. After drying, a new material of ZnO/cellulose gel particles was obtained.
同时，采用相同方法（不加纤维素，其他条件同上）制备ZnO颗粒，作为对照。At the same time, ZnO particles were prepared by the same method (without adding cellulose, other conditions were the same as above) as a control.
由图1可知，所制备的ZnO/纤维素凝胶颗粒，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 ZnO/cellulose gel particles, ZnO is in the outer layer and cellulose gel is in 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，说明纤维素有助于纳米ZnO的生成。由图3和图5可知，制备的ZnO/纤维素凝胶颗粒含有纤维素和ZnO晶体，无碱式氯化锌。It can be seen from Figure 3 and Figure 4 that the ZnO particle crystals prepared without cellulose are impure and contain more basic zinc chloride impurities, indicating that cellulose is helpful to the formation of nano-ZnO. It can be seen from Figure 3 and Figure 5 that the prepared ZnO/cellulose gel particles contain cellulose and ZnO crystals, without basic zinc chloride.
采用相同方法（不加纤维素，改变温度，其他条件同上）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。Using the same method (without adding cellulose, changing the temperature, and other conditions as above) to prepare ZnO particles, the experimental results show that when the hydrothermal temperature reaches 240°C, relatively pure ZnO crystals can be obtained. The results are 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竹浆纤维素加入到65%（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。向溶解纤维素的ZnCl2水溶液中，缓慢滴加5%NaOH水溶液，当体系的pH值为7时，停止滴加，静置36小时，得到ZnO前驱体/纤维素凝胶。）将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ZnO/纤维素凝胶颗粒新材料。1 g of bamboo pulp cellulose was added to 65% (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. Slowly add 5% NaOH aqueous solution dropwise to the ZnCl2 aqueous solution in which cellulose is dissolved. When the pH value of the system is 7, stop the dropwise addition and let stand for 36 hours to obtain ZnO precursor/cellulose gel. ) Put the ZnO precursor/cellulose gel into the hydrothermal synthesis kettle, and carry out the hydrothermal reaction under the conditions of pH=7 and temperature of 170°C, and the reaction time is 4h. After the ZnO/cellulose gel was washed with water to be free of Cl- , it was first placed in an ultra-low temperature refrigerator. After freezing, the sample was placed in a freeze dryer. After drying, a new material of ZnO/cellulose gel particles was obtained.
由图7可知，所制备的ZnO/纤维素凝胶颗粒，纳米ZnO在外层，纤维素凝胶在内层。由图3和图8可知，制备的ZnO/纤维素凝胶颗粒含有ZnO晶体，无碱式氯化锌。It can be seen from Fig. 7 that for the prepared ZnO/cellulose gel particles, the nano-ZnO is in the outer layer, and the cellulose gel is in the inner layer. It can be seen from Figure 3 and Figure 8 that the prepared ZnO/cellulose gel particles contain ZnO crystals and no basic zinc chloride.
实施例3Example 3
将1g棉浆纤维素加入到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。向溶解纤维素的ZnCl2水溶液中，缓慢滴加20%NaOH水溶液，当体系的pH值为10时，停止滴加，静置48小时，得到ZnO前驱体/纤维素凝胶。）将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ZnO/纤维素凝胶颗粒新材料。Add 1 g of cotton pulp cellulose into 70% (wt%) ZnCl 2 aqueous solution, and pretreat it in a low-temperature bath at 30 °C for 0.5 h. The above-mentioned liquid-solid material is placed in a water bath at 90° C. and heated and stirred to obtain a transparent and uniform cellulose solution. Slowly add 20% NaOH aqueous solution dropwise to the ZnCl2 aqueous solution in which cellulose is dissolved. When the pH value of the system is 10, stop the dropwise addition and let stand for 48 hours to obtain ZnO precursor/cellulose gel. ) Put the ZnO precursor/cellulose gel into the hydrothermal synthesis kettle, and carry out the hydrothermal reaction under the conditions of pH=10 and temperature 100°C, and the reaction time is 10h. After the ZnO/cellulose gel was washed with water to be free of Cl- , it was first placed in an ultra-low temperature refrigerator. After freezing, the sample was placed in a freeze dryer. After drying, a new material of ZnO/cellulose gel particles was obtained.
由图9可知，制备的ZnO/纤维素凝胶颗粒，纳米ZnO在外层，纤维素凝胶在内层。由图3和图10可知，制备的ZnO/纤维素凝胶颗粒含有ZnO晶体，无碱式氯化锌。It can be seen from Figure 9 that for the prepared ZnO/cellulose gel particles, the nano-ZnO is in the outer layer and the cellulose gel is in the inner layer. It can be seen from Figure 3 and Figure 10 that the prepared ZnO/cellulose gel particles contain ZnO crystals and no basic zinc chloride.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510280270.7A CN104941540B (en) | 2015-05-28 | 2015-05-28 | A kind of nano-ZnO/cellulose gel particle and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510280270.7A CN104941540B (en) | 2015-05-28 | 2015-05-28 | A kind of nano-ZnO/cellulose gel particle and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104941540A CN104941540A (en) | 2015-09-30 |
| CN104941540B true CN104941540B (en) | 2017-10-20 |
Family
ID=54156911
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510280270.7A Expired - Fee Related CN104941540B (en) | 2015-05-28 | 2015-05-28 | A kind of nano-ZnO/cellulose gel particle and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104941540B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106046423B (en) * | 2016-05-25 | 2018-08-17 | 南京林业大学 | A kind of preparation method of nano-ZnO/cellulose composite material |
| CN106279763B (en) * | 2016-08-10 | 2018-09-25 | 南京林业大学 | A kind of hydrothermal preparing process of the nano-ZnO cellulose composite material based on NaOH/ urea liquids and application |
| CN108889338B (en) * | 2018-08-22 | 2020-09-01 | 南京林业大学 | A kind of ZnO nanosheet regenerated cellulose film composite material and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102008902B (en) * | 2010-10-13 | 2013-03-13 | 天津大学 | Bacterial cellulose-inorganic nanoparticle hybrid membrane and preparation method thereof |
| CN103318945B (en) * | 2013-07-11 | 2014-12-31 | 苏州大学 | Preparation method of colloidal solution of nano-ZnO |
| CN103964502B (en) * | 2014-05-26 | 2016-04-13 | 国家纳米科学中心 | A kind of nano-TiO 2monocrystal material and its preparation method and application |
-
2015
- 2015-05-28 CN CN201510280270.7A patent/CN104941540B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN104941540A (en) | 2015-09-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107282030B (en) | A three-dimensional lignin porous carbon/zinc oxide composite material and its preparation and application in the field of photocatalysis | |
| CN103193273B (en) | Preparation method of extra-long manganese dioxide nanowires | |
| CN102443180A (en) | Method for preparing cellulose composite aerogel | |
| CN103908979A (en) | A kind of supported nanometer TiO2 catalyst and preparation method thereof | |
| CN106732708A (en) | Graphite phase carbon nitride nanometer sheet load individual layer Bismuth tungstate nano-sheet heterojunction material and its preparation method and application | |
| CN104014355B (en) | A kind of nanometer sheet and particle composite structures visible light catalyst and preparation method thereof | |
| CN104801246A (en) | Preparation method for mycelium nano composite pellet of core-shell structure | |
| CN102190909A (en) | Novel method of preparing biomass based nano carbon black | |
| CN104941540B (en) | A kind of nano-ZnO/cellulose gel particle and preparation method thereof | |
| CN105056927B (en) | A kind of TiO2Nanotube composite S iO2Aeroge base optic catalytic material and preparation method thereof | |
| CN113372612B (en) | A kind of preparation method of cellulose-based radiation temperature regulating material | |
| CN104944405A (en) | Preparation method of carbon spheres | |
| CN104941537B (en) | A kind of preparation method of strip nano ZnO/cellulose gel material | |
| CN108452767A (en) | A kind of preparation method of nano zine oxide-sisal fiber Carbon composites | |
| CN106732498A (en) | The preparation method of halloysite nanotubes/nanometer titanium dioxide composite material | |
| CN103934036A (en) | Novel preparation method of titanium dioxide-cellulose composite material | |
| CN102266764A (en) | Expanded graphite/zinc oxide composite photocatalyst and preparation method thereof | |
| CN105129770A (en) | Morphological control method for functional hydrothermal carbon | |
| CN110143581B (en) | Preparation method of carbon aerogel material with ultrahigh specific surface area | |
| CN107557410A (en) | Enzymolysis pretreatment collaboration acid system prepares the nanocrystalline method of low amylose | |
| CN104941683B (en) | One kind receives micro- ZnO/ compound cellulose strip material and preparation method thereof | |
| CN106219606A (en) | A kind of preparation method of nano flower spherical Ag3VO4 | |
| CN1948222A (en) | Method of metal oxide cladding carbon nano-tube material | |
| CN103721695A (en) | Preparation method of titanium oxide active carbon | |
| CN104892961B (en) | A kind of preparation method of fibre strip element gel mesoporous material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20150930 Assignee: Jiangsu Acer Zixin Energy Technology Co.,Ltd. Assignor: Nanjing Forestry University Contract record no.: 2018320000227 Denomination of invention: Nano ZnO/ cellulose gel particle and preparation method thereof Granted publication date: 20171020 License type: Common License Record date: 20181024 Application publication date: 20150930 Assignee: NINGXIA BEST PHARMACEUTICAL CHEMICAL CO.,LTD. Assignor: Nanjing Forestry University Contract record no.: 2018320000226 Denomination of invention: Nano ZnO/ cellulose gel particle and preparation method thereof Granted publication date: 20171020 License type: Common License Record date: 20181024 |
|
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EC01 | Cancellation of recordation of patent licensing contract | ||
| EC01 | Cancellation of recordation of patent licensing contract |
Assignee: Jiangsu Acer Zixin Energy Technology Co.,Ltd. Assignor: Nanjing Forestry University Contract record no.: 2018320000227 Date of cancellation: 20191126 |
|
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20150930 Assignee: Jiangsu Acer Zixin Energy Technology Co.,Ltd. Assignor: Nanjing Forestry University Contract record no.: X2019320000313 Denomination of invention: Nano ZnO/ cellulose gel particle and preparation method thereof Granted publication date: 20171020 License type: Common License Record date: 20191127 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171020 |