CN110091397B - 一种木材细胞壁2d片层材料的制备方法 - Google Patents
一种木材细胞壁2d片层材料的制备方法 Download PDFInfo
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Abstract
本发明属于一种木材细胞壁2D片层材料的制备方法，方法是首先通过化学试剂处理去除木材中半纤维素，再经TEMPO氧化处理，然后将得到的处理后材料与高纯水混合，进行超声处理和冷冻干燥得到由木材细胞壁原位剥离出的2D片层材料。用本发明方法得到的木材细胞壁2D片层材料具有片状的独特微观结构，使木材细胞壁2D片层材料具备丰富优异特性，如良好的机械性能，包裹性。本发明能通过化学处理和机械处理相结合得到木材细胞壁2D片层材料，具有制备过程简单，工艺控制容易，原料来源广泛，制备成本低的优点。
Description
技术领域
本发明属于一种木材细胞壁2D片层材料的制备方法。
背景技术
细胞壁2D片层材料（或称二维纳米片层材料；纳米片层材料）通常具有层状、片状、带状等独特的微观结构，使二维纳米材料具有优异的光学、电学、力学等性能，未来可以在储能、吸附、催化、高性能生物质材料、传感等领域得到广泛应用。
超薄的原子结构和巨大的比表面积赋予二维纳米材料不同于体相的独特物理性质。石墨烯等作为最常见的二维纳米材料，拥有高度对称的晶体结构，表现出各向同性的物理性质，在材料学、能源、生物医学等方面有很大的应用优势。而另外一类二维纳米材料，如黑磷、IV族硫属化合物等，在不同取向上表现出差异显著的优良特性，为发展多功能低维电子及光电子器件等提供了可能。
生物质二维纳米材料，是以木材、工业废弃物以及植物纤维等生物质为原料，通过化学或机械处理方式制得。木材是一种绿色可再生材料，来源广泛，目前人们多关注于基于木块本身进行机械处理或化学处理或者利用木材为原料制备一维纳米纤维素材料在经过功能化改性后利用于各个领域，但关于木材细胞壁2D片层材料的制备及开发应用研究极少。
发明内容
本发明的目的是提供一种木材细胞壁2D片层材料的制备方法，通过化学处理和机械处理相结合得到木材细胞壁2D片层材料，具有制备过程简单，工艺控制容易，原料来源广泛，制备成本低的优点。
为此，本发明的方法包括如下步骤：
（1）木材的烘干处理：将木材制成0.5mm×0.5mm×2cm的小木棍，置于烘箱中，进行烘干处理，烘干温103±2℃，干燥1h后，每隔1小时称量一次木棍材质量，直至呈木棍材质量恒定的绝干状态。
（2）将绝干木棍材置在处理罐中，按每6g木棍材，加入150mL浓度为2wt%的碱性溶液，90℃油浴加热，250rmp/min机械搅拌2h脱半纤维素，反应结束后,用蒸馏水反复洗涤木棍材,至木棍材的pH呈中性，得脱半纤维素的木棍材。
（3）将脱半纤维素的木棍材置于10%的过氧化氢溶液中，煮沸，200rmp/min对脱半纤维素的木棍材进行漂白处理，使得脱半纤维素的木棍材颜色变浅；反应结束后,用蒸馏水反复洗涤木棍材,至木棍材的pH呈中性，得脱色木棍材。
（4）按每6g脱色木棍材，加入450mL pH=6.8～7.0的磷酸缓冲液，搅拌均匀后，再加入8.55mL（5%有效氯）次氯酸钠、0.576g TENPO氧化剂(2,2,6,6-四甲基哌啶-氮-氧化物)、10.2gNaClO2(亚氯酸钠)，80℃油浴加热，250rmp/min机械搅拌2h，反应结束后,按每6g脱色木棍材加入10mL乙醇，停止反应1～2h，排除反应液。用超纯水冲洗，去除木棍材表面的杂质，得洁净木棍材。
（5）将洁净木棍材与纯水混合后，进行超声处理。超声功率为1050W、额定功率1500W，选择70%额定功率，处理时间为30～60min，静止沉淀3～5h，取上清液。
（6）将上清液置于-70℃冷冻5h，再将其置于冷冻干燥机中，干燥72h,得到原位剥离的大片细胞壁2D片层材料。
所述的洁净木棍材与超纯水混合的体积比为1:20～1:200。
所述的步骤(1)中将木材制成0.5mm×0.5mm×2cm的小木棍，或粉碎为粉末。
所述的碱性溶液为氢氧化钠、氢氧化钾、LiOH(氢氧化锂)的水溶液中的任选一种。
所述的超纯水为蒸馏水，冲洗的水温为40～45℃。
所述的步骤（4）中脱色木棍材TEMPO(2,2,6,6-四甲基哌啶-氮-氧化物)氧化处理，能先将脱色木棍材置于pH=6.8～7.0的磷酸缓冲液、或醋酸缓冲液，搅拌均匀，然后在溶液中依次加入次氯酸钠、亚氯酸钠、TEMPO氧化剂，反应结束后，加入乙醇停止反应。
所述的步骤（6）中将上清液进行冷冻干燥，还可采用介质为二氧化碳的临界干燥、或超临界干燥。
所述的超声处理中，不同的超声时间得到细胞壁2D片层的大小及微观结构不同。
所述的将洁净木棍材与纯水混合后，进行超声处理中，纯水为蒸馏水。
所述的粉末为粒径小于0.5mm的木材粉末。
上述方法达到了本发明的目的。
本发明能通过化学处理和机械处理相结合得到木材细胞壁2D片层材料，具有制备过程简单，工艺控制容易，原料来源广泛，制备成本低的优点。
本发明方法有如下优点：
1、本发明首先通过化学试剂处理去除木材中半纤维素，再经TEMPO氧化处理，然后将得到的处理后材料与高纯水混合，进行超声处理和冷冻干燥得到由木材细胞壁原位剥离出的2D片层材料。用本发明方法得到的木材细胞壁2D片层材料具有片状的独特微观结构，使木材细胞壁2D片层材料具备丰富优异特性，如良好的机械性能，包裹性，各向异性等。因而木材细胞壁2D片层材料若经功能化改性后未来可以在储能、吸附、催化、传感等领域得到应用，同时能为高性能生物质材料的设计与制备提供新思路。
2、本发明方法还具有无毒、无环境污染等优点。本发明使用的原料是以木材、以及植物纤维等生物质为原料，来源广泛、廉价、可再生。
3、本发明的木材细胞壁2D片层材料可为电极材料、吸附材料等多个领域提供木材基体二维材料，极大提高了木材附加值。
具体实施方式
实施例1：一种木材细胞壁2D片层材料的制备方法，包括如下步骤：
（1）木材的烘干处理：将木材制成0.5mm×0.5mm×2cm的小木棍，置于烘箱中，进行烘干处理，烘干温103±2℃，干燥1h后，每隔1小时称量一次木棍材质量，直至呈木棍材质量恒定的绝干状态。
（2）将绝干木棍材置在处理罐中，按每6g木棍材，加入150mL浓度为2wt%的碱性溶液，90℃油浴加热，250rmp/min机械搅拌2h脱半纤维素，反应结束后,用蒸馏水反复洗涤木棍材,至木棍材的pH呈中性，得脱半纤维素的木棍材。
（3）将脱半纤维素的木棍材置于10%的过氧化氢溶液中，煮沸，200rmp/min对脱半纤维素的木棍材进行漂白处理，使得脱半纤维素的木棍材颜色变浅；反应结束后,用蒸馏水反复洗涤木棍材,至木棍材的pH呈中性，得脱色木棍材。
（4）按每6g脱色木棍材，加入450mL pH=6.8～7.0的磷酸缓冲液，搅拌均匀后，再加入8.55mL（5%有效氯）次氯酸钠、0.576g TENPO氧化剂、10.2gNaClO2，80℃油浴加热，250rmp/min机械搅拌2h，反应结束后,按每6g脱色木棍材加入10mL乙醇，停止反应1～2h，排除反应液。用超纯水冲洗，去除木棍材表面的杂质，得洁净木棍材。
（5）将洁净木棍材与纯水混合后，进行超声处理。超声功率为1050W、额定功率1500W，选择70%额定功率，处理时间为30～60min，静止沉淀3～5h，取上清液。
（6）将上清液置于-70℃冷冻5h，再将其置于冷冻干燥机中，干燥72h,得到原位剥离的大片细胞壁2D片层材料。
所述的洁净木棍材与超纯水混合的体积比为1:20～1:200。
所述的步骤(1)中将木材制成0.5mm×0.5mm×2cm的小木棍，或粉碎为粉末。
所述的碱性溶液为氢氧化钠、氢氧化钾、LiOH的水溶液中的任选一种。
所述的超纯水为蒸馏水，冲洗的水温为40～45℃。
所述的步骤（4）中脱色木棍材TEMPO氧化处理，能先将脱色木棍材置于pH=6.8～7.0的磷酸缓冲液、或醋酸缓冲液，搅拌均匀，然后在溶液中依次加入次氯酸钠、亚氯酸钠、TEMPO氧化剂，反应结束后，加入乙醇停止反应。
所述的步骤（6）中将上清液进行冷冻干燥，还可采用介质为二氧化碳的临界干燥、或超临界干燥。
所述的超声处理中，不同的超声时间得到细胞壁2D片层的大小及微观结构不同。
所述的将洁净木棍材与纯水混合后，进行超声处理中，纯水为蒸馏水。
所述的粉末为粒径小于0.5mm的木材粉末。
实施例2：
将杉木进行初步剪碎为火柴棍粗细，0.5mm长短小棍，置于烘箱中，烘干温103±2℃，干燥1h后，每隔1小时称量一次木棍材质量，直至呈木棍材质量恒定的绝干状态。
将绝干木棍材置在处理罐中，按每6g杉木木棍材，加入150mL，浓度为2wt%的KOH水溶液，90℃油浴加热，250rmp/min机械搅拌2h脱半纤维素，反应结束后用蒸馏水反复洗涤至中性。然后置于10%H2O2溶液中，煮沸，200rmp/min对木棍材进行漂白处理，使得脱半纤维素木棍材颜色变浅。反应结束后，用蒸馏水反复洗涤木棍材至中性。最后，按每6g杉木木棍材，加入450mL pH=6.8的磷酸缓冲液，搅拌均匀后，加入8.55mL（5%有效氯）NaClO、0.576gTENPO氧化剂、10.2gNaClO2，80℃油浴加热，250rmp/min机械搅拌2.5h，反应结束后，加入10mL乙醇停止反应，用超纯水冲洗去除木棍材表面杂质，洁净木棍材。
将洁净木棍材与纯水混合后，进行超声处理，超声功率为1050W（额定功率1500，选择70%额定功率），处理时间为30min，静止沉淀3～5h，取上清液。将得到的上清液置于-70℃冷冻5h，将其置于冷冻干燥机中干燥72h，得到原位剥离的细胞壁2D片层材。
实施例3：
将杉木进行粉碎为粒径小于0.5mm的木材粉末，置于烘箱中，烘干温103±2℃，干燥1h后，每隔1小时称量一次木材粉末，直至呈木材粉末质量恒定的绝干状态。
将绝干木材粉末置在处理罐中，按每6g木材粉末，加入150mL，浓度为2wt%的KOH水溶液，90℃油浴加热，250rmp/min机械搅拌2h脱半纤维素，反应结束后用蒸馏水反复洗涤木材粉末至中性。然后置于10%H2O2溶液中，煮沸，200rmp/min对木材粉末进行漂白处理，使得脱半纤维素木材粉末颜色变浅；反应结束后用蒸馏水反复洗涤木材粉末至中性。最后，按的比例，加入450mL pH=6.8的磷酸缓冲液，搅拌均匀后，加入8.55mL（5%有效氯）NaClO、0.576gTENPO氧化剂、10.2gNaClO2，80℃油浴加热，250rmp/min机械搅拌4h，反应结束后加入10mL乙醇停止反应，用超纯水冲洗木材粉末，去除表面杂质。将冲洗后的木材粉末与纯水混合后，进行超声处理，超声功率为1050W（额定功率1500，选择70%额定功率），处理时间为60min，静止沉淀3～5h，取上清液。
将得到的上清液置于-70℃冷冻5h，将其置于冷冻干燥机中干燥72h得到具有不同的微观结构的细胞壁2D片层材。
总之，本发明能通过化学处理和机械处理相结合得到木材细胞壁2D片层材料，具有制备过程简单，工艺控制容易，原料来源广泛，制备成本低的优点。
Claims (1)
1.一种木材细胞壁2D片层材料的制备方法，其特征在于：该制备方法包括如下步骤：
（1）木材的烘干处理：将木材制成0.5mm×0.5mm×2cm的小木棍，置于烘箱中，进行烘干处理，烘干温103±2℃，干燥1h后，每隔1小时称量一次木棍材质量，直至呈木棍材质量恒定的绝干状态；
（2）将绝干木棍材置在处理罐中，按每6g木棍材，加入150mL浓度为2wt%的碱性溶液，90℃油浴加热，250rmp/min机械搅拌2h脱半纤维素，反应结束后,用蒸馏水反复洗涤木棍材,至木棍材的pH呈中性，得脱半纤维素的木棍材；
（3）将脱半纤维素的木棍材置于10%的过氧化氢溶液中，煮沸，200rmp/min对脱半纤维素的木棍材进行漂白处理，使得脱半纤维素的木棍材颜色变浅；反应结束后,用蒸馏水反复洗涤木棍材,至木棍材的pH呈中性，得脱色木棍材；
（4）按每6g脱色木棍材，加入450mL pH=6.8～7.0的磷酸缓冲液，搅拌均匀后，再加入8.55mL5%有效氯的次氯酸钠、0.576g TEMPO氧化剂、10.2gNaClO2，80℃油浴加热，250rmp/min机械搅拌2h，反应结束后,按每6g脱色木棍材加入10mL乙醇，停止反应1～2h，排除反应液，用超纯水冲洗，去除木棍材表面的杂质，得洁净木棍材；
（5）将洁净木棍材与纯水混合后，进行超声处理，超声功率为1050W、额定功率1500 W，选择70%额定功率，处理时间为30～60min，静止沉淀3～5h，取上清液；
（6）将上清液置于-70℃冷冻5h，再将其置于冷冻干燥机中，干燥72h,得到原位剥离的大片细胞壁2D片层材料；所述的洁净木棍材与超纯水混合的体积比为1:20～1:200；所述的碱性溶液为氢氧化钠、氢氧化钾、LiOH的水溶液中的任选一种；所述的超纯水为蒸馏水，冲洗的水温为40～45℃；所述的步骤（4）中脱色木棍材TEMPO氧化处理，能先将脱色木棍材置于pH=6.8～7.0的磷酸缓冲液、或醋酸缓冲液，搅拌均匀，然后在溶液中依次加入次氯酸钠、亚氯酸钠、TEMPO氧化剂，反应结束后，加入乙醇停止反应；所述的步骤（6）中将上清液进行冷冻干燥，还可采用介质为二氧化碳的临界干燥、或超临界干燥；所述的超声处理中，不同的超声时间得到细胞壁2D片层的大小及微观结构不同；所述的将洁净木棍材与纯水混合后，进行超声处理中，纯水为蒸馏水。
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