CN112941064A - 一种改性增强碳基材料固定化的方法及应用 - Google Patents
一种改性增强碳基材料固定化的方法及应用 Download PDFInfo
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Abstract
本发明属于碳基材料改性领域，公开了一种改性增强碳基材料固定化的方法及应用。所述制备方法为：取一定体积的去离子水，加入糖或生物质原料，再加入强酸或中强酸为催化剂，混合均匀，然后加入适量的碳基材料，将其置于反应釜中，在一定温度下反应一定时间后，在碳基材料表面形成一层粗糙的碳层。本发明制备的改性碳基材料载体具有表面粗糙、亲水性强、活性官能团含量丰富等优点。实验测得经改性后的碳基材料的含氧官能团含量增加；比表面积增加了63‑103%；接触角减小了15‑30%；在固定化酶或固定化多酶***中，重复使用5‑7次后，酶的活力仍可保留65‑80%。
Description
技术领域
本发明涉及碳基材料改性领域，具体涉及一种改性碳基材料的方法及其在固定化中的应用。
背景技术
常见的碳基材料种类丰富多样，例如活性炭、碳纤维、石墨烯、碳纳米管等因其具有高强度，高密度，高硬度，化学稳定性，大的比表面积，丰富的孔径和生物相容性等优良性质，而在农业、环境保护、储能、催化、医疗等领域应用广泛。
近年来，碳基材料因碳具有良好的生物相容性而在固定化酶和固定化细胞领域具有广阔的发展前景。为了更好地实现碳基材料优良性能的发挥，人们采取了多种方法对其进行改性处理：氧化、接枝、等离子体处理、复合等。这些方法具有良好的改性效果，但可能消耗大量的酸碱或有机试剂对环境造成较大污染，除此之外，有些改性方法对设备要求较高，限制了改性方法的应用。
目前利用酸催化糖或生物质对碳基材料进行表面改性的相关研究及报道较少。在高温高压条件下，糖或生物质原料在水溶液中发生化学反应，可以生成微米级碳球负载于碳基材料表面形成一层粗糙的碳层，有利于增加碳基材料表面的比表面积，为酶提供更多的吸附位点。酸的催化促进来了糖或生物质原料的碳化效率，使碳球收率增加较快。同时，碳层的形成使碳基材料的表面活性官能团含量提高，亲水性增加，从而可以实现固定化性能的高效发挥。此外，当酸催化玉米芯等生物质改性碳基材料时，不仅可以解决农林废弃物堆积造成的环境污染，还可以实现生物质资源的有效利用，具有一定的社会效益和经济价值。
表1总结了部分相关的文件和专利，但与本申请存在显著区别：
表1部分公开文件或专利与申请文件的区别
发明内容
有鉴于此，本发明所要解决的问题是提供一种改性碳基材料的方法，以增加其表面粗糙度、比表面积、亲水性及活性官能团含量，进而充分发挥其固定化性能。
一种改性增强碳基材料固定化的方法及应用，具体步骤如下：
取一定体积的去离子水，加入糖或生物质原料10-100(g/L去离子水)，再加入适量浓度为30-98％的强酸或中强酸为催化剂，混合均匀，然后加入碳基材料0.1-40(g/L去离子水)，将其置于反应釜中，在100-300℃下反应1-10h后，取出过滤，然后对废液进行回收处理，并用适量去离子水将改性碳基材料清洗干净后烘干用于固定化酶。
改性碳基材料的固定化应用：
进一步，所述碳基材料包括活性炭、碳纤维、石墨烯、碳纳米管等材料，其中，活性炭包括木质活性炭、果壳活性炭、矿物原料活性炭、合成树脂活性炭等；碳纤维包括聚丙烯腈基碳纤维、黏胶基碳纤维或沥青基碳纤维等；石墨烯包括氧化石墨烯等；碳纳米管包括单壁碳纳米管或多壁碳纳米管等。
进一步，所述碳基材料为过20-150目的颗粒、粉状或长度为0.3-100cm的纤维状材料。
进一步，所述糖为葡萄糖、果糖、蔗糖、乳糖、淀粉、纤维素、玉米芯、稻草等单糖、双糖、多糖或生物质原料。
进一步，所述生物质原料应经过粉碎处理，过20-100目，且加入后能够将碳基材料包裹完全。
进一步，所述酸为硫酸、硝酸、盐酸、高氯酸、氢碘酸、氢溴酸、氢氟酸、磷酸等强酸或中强酸，酸与去离子水的比例为0.5-10％。
进一步，所述固定化酶步骤为：将改性碳基材料按照5-15g/L的加入量加至由一定pH的缓冲液配制的酶溶液中，在一定转速和温度下，搅拌一定时间后，用上述缓冲液洗去游离酶，得固定化酶备用。
有益效果
与现有技术相比，本发明的有益效果是在强酸或中强酸催化下，利用高温高压在碳基材料表面形成一层粗糙的碳层，增加了碳基材料的表面活性官能团含量、比表面积及亲水性。经改性后的碳基材料提供了更多的吸附位点，应用于固定化酶时，酶负载量增多，固定化酶的重复使用率有所提高。
本实验制备改性碳基材料的方法具有操作方便、步骤少、对环境污染小等优点。此外，对玉米芯等农林废弃物的利用实现了生物质资源的二次利用，避免了资源浪费和环境污染。
附图说明
图1为未处理碳基材料与改性碳基材料的红外图。
图2为未处理碳基材料与改性碳基材料的接触角。
具体实施方式
下面结合实施例，对本发明的具体的实施方式进一步详细描述，以便本领域的技术人员更了解本发明，但并不因此限制本发明。
实施例1
改性碳基材料载体的制备：
取1L去离子水，加入40-70g葡萄糖或蔗糖或乳糖，加入10-30ml的浓硫酸(98％)或磷酸(85％)或高氯酸(70％)或氢碘酸(47％)或氢溴酸(33％)，混合均匀，加入10-30g的聚丙烯腈基碳纤维或氧化石墨烯，将其置于反应釜中，在180℃反应3h后，取出过滤，然后将废液进行回收处理，并用适量去离子水将改性碳纤维或石墨烯清洗干净后烘干，取出测定性质并备用。
实验结果表明，经改性处理后的碳基材料载体表面的含氧官能团含量增加；比表面积增加了63-103％，接触角减小了15–30％。
实施例2
改性碳基材料用于固定化酶
取上述干燥后的改性碳基材料以5g/L的加入量加至由pH＝5.0的0.02M的磷酸缓冲液配制的1％木聚糖酶溶液中，在160r/min和30℃条件下搅拌24h后，用pH＝5.0的0.02M的磷酸缓冲液洗去游离酶，得固定化木聚糖酶备用。
木聚糖酶酶活定义：在55℃、pH＝5的条件下，每分钟催化分解木聚糖产生1μmol木糖所需要的酶量为一个酶活力单位(IU/g)。
将固定化木聚糖酶按照1g/L的加入量加至55℃的0.25-2％的木聚糖溶液中，并水浴反应30min，反应结束后测定酶活。同时，固定化木聚糖酶经过滤分离后，用pH＝5.0的0.02M的磷酸缓冲液洗涤，然后加至新的木聚糖溶液中按照上述步骤重复进行多批次实验。
实验结果表明，该法制备的固定化木聚糖酶重复使用5-7次后，木聚糖酶的活力仍可保留70-80％。
实施例3
改性碳基材料用于固定化多酶
固定化多酶不仅可以克服操作稳定性低和酶回收困难的问题，而且可以有效发挥多酶体系的协同催化作用。
取上述干燥后的改性碳基材料以10g/L的加入量加至由pH＝6.0的0.02M的磷酸缓冲液配制的0.1％的葡萄糖氧化酶和过氧化氢酶的混合溶液(按照活力比1:1加入)中，在160r/min和25℃条件下搅拌24h后，再向上述溶液中加入0.2％的戊二醛溶液继续反应30min，过滤，用pH＝6.0的0.02M的磷酸缓冲液洗去游离酶，得固定化多酶备用。
葡萄糖氧化酶酶活定义：在30℃、pH＝6.0的条件下，每分钟分解1μmol的β-D-葡萄糖氧化成D-葡萄糖酸和过氧化氢所需的酶量为一个酶活力单位(IU/g)。
将固定化多酶按照1g/L的加入量加至30℃的0.25-2％的葡萄糖溶液中，并水浴反应30min，反应结束后测定酶活。同时，固定化多酶经过滤分离后，用pH＝6.0的0.02M的磷酸缓冲液洗涤，然后加至新的葡萄糖溶液中按照上述步骤重复进行多批次实验。
实验结果表明，该法制备的固定化多酶重复使用5-7次后，葡萄糖氧化酶的活力仍可保留65-75％。
Claims (4)
1.一种改性增强碳基材料固定化的方法及应用，其特征在于，具体步骤如下：
取一定体积的去离子水，加入糖或生物质原料10-100（g/L去离子水），再加入适量浓度为30-98%的强酸或中强酸为催化剂，混合均匀，然后加入碳基材料0.1-40（g/L去离子水），将其置于反应釜中，在100-300℃下反应1-10 h后，取出过滤，然后对废液进行回收处理，并用适量去离子水将改性碳基材料清洗干净后烘干用于固定化酶。
2.根据权利要求1所述的碳基材料改性方法，其特征在于，所述碳基材料包括活性炭、碳纤维、石墨烯、碳纳米管等颗粒、粉状或纤维状材料。
3.根据权利要求1-2所述的碳基材料改性方法，其特征在于，所述糖为葡萄糖、果糖、蔗糖、乳糖、淀粉、纤维素、玉米芯、稻草等单糖、双糖、多糖或生物质原料。
4.根据权利要求1-3所述的碳基材料改性方法，其特征在于，所述酸为硫酸、硝酸、盐酸、高氯酸、氢碘酸、氢溴酸、氢氟酸、磷酸等强酸或中强酸。
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