CN114515588A - 一种基于蜀葵茎秆合成g-C3N4/C复合材料的方法 - Google Patents
一种基于蜀葵茎秆合成g-C3N4/C复合材料的方法 Download PDFInfo
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Abstract
本发明公开了一种基于蜀葵茎秆合成g‑C3N4/C复合材料的方法，包括以下步骤：（1）蜀葵茎秆的预处理；（2）制备g‑C3N4/C复合材料。该方法以蜀葵茎秆为碳骨架，g‑C3N4在模板表面铺展形成薄片层，构建具有特殊结构的复合体系，该复合材料相比纯相g‑C3N4大幅提升了比表面积，界面清晰，碳骨架不仅起到了刚性支撑的作用，而且提升了复合材料的电子转移效率，从而提高了光生载流子的分离效率，提高了可见光的利用率。本方法采用的原料低廉且对环境友好，可应用于工业生产，批量制备治理环境有机污染物的环保材料。
Description
技术领域
本发明属于材料合成领域，具体涉及一种基于蜀葵茎秆合成g-C3N4/C复合材料的方法。
背景技术
作为一种无机非金属半导体光催化材料，石墨相氮化碳（g-C3N4）由于具有独特的能带结构和晶体结构特征，在环境治理和清洁能源领域受到了广泛的关注。然而单一相g-C3N4存在对太阳光的响应范围偏小、比表面积小、反应活性位点少和光生电子-空穴对易复合等问题，限制了其在光催化领域的大规模利用。
蜀葵茎秆具有天然生物结构，能为g-C3N4提供刚性骨架支撑，使前驱体能沿茎秆表面结晶，宏观上形成特殊的管状形貌。同时茎秆表面凹凸不平，能避免前驱体热聚合过程中形成的g-C3N4片层结块。制备得到的复合材料结构疏松，呈多孔状，比表面积大大提高。
经对现有技术的文献检索，围绕g-C3N4/C复合材料的制备有一些专利报道，如中国专利申请号CN201610873847.X，名称为“一种基于纤维素的三维多孔g-C3N4/C气凝胶及其制备方法”，该专利将三聚氰胺负载至纤维素气凝胶上，采用高温煅烧法将三聚氰胺转化为石墨相氮化碳气相沉积至碳气凝胶上，形成具有三维多孔结构的g-C3N4/C气凝胶。此所得的三维多孔g-C3N4/C气凝胶易于回收利用，且具有均匀孔径和大比表面积，但制备方法较为繁琐，且后续负载第三相光催化剂较为困难，不利于进行多相复合。中国专利申请号CN202010046036.9，名称为“一种含氮空位的g-C3N4/C复合材料的制备方法”，该专利通过常用煅烧法制备了含氮空位g-C3N4/C复合材料，此发明制得的氮空位的g-C3N4/C复合材料对光催化固氮反应有着优异的催化性能，但制备方法较为常见，且制备得到的材料不具备较为特殊的微观形貌。
发明内容
为了解决以上现有技术存在的问题，本发明的目的在于提供一种基于蜀葵茎秆合成g-C3N4/C复合材料的方法。本发明通过借助生物天然模板的结构，构建具有特殊形貌的g-C3N4/C复合材料，得到的g-C3N4片层薄而均匀，比表面积相对于块状g-C3N4大大提高，增强复合材料对可见光的吸收，促进光生电子与空穴的分离，提升光能的利用效率，从而达到提升光催化活性的作用。
为实现上述目的，本发明提供以下技术方案：
一种基于蜀葵茎秆合成g-C3N4/C复合材料的方法，包括以下步骤：
（1）蜀葵茎秆的预处理
将新鲜采摘的蜀葵茎秆切段并用去离子水多次洗涤，浸泡于预处理液中以脱除其中的叶绿素和生物活性物质，浸泡结束后将茎秆用去离子水洗涤后自然晾干，避免阳光直射，收集备用；
（2）制备g-C3N4/C复合材料
以双氰胺为前驱体配制浸渍溶液，将步骤（1）预处理过的茎秆浸渍于其中进行处理，然后经脱水并热处理即可生成g-C3N4/C复合材料；其中蜀葵茎秆和双氰胺的质量比为1:1-1:4。
进一步的，所述步骤（1）中茎秆切段的长度为3-5cm。
进一步的，所述步骤（1）中预处理液的成分为：体积比为1:1-1:2的水和乙醇的混合液，pH为2-3，浸泡时间为三至四周，浸泡结束后将茎秆洗涤至洗涤液pH呈中性后方可晾干。
进一步的，所述步骤（2）中将预处理过的茎秆先于浸渍溶液中于50℃下水浴搅拌1-2h，待前驱体完全溶解后停止搅拌，继续水浴保温20-24h，后在60-80℃下隔夜烘干。
进一步的，所述步骤（2）中的热处理条件为于马弗炉内进行热处理，反应条件为：空气气氛下以3-5℃/min升温至500-550℃并保温4-6h。
有益效果：本发明提供了一种蜀葵茎秆合成g-C3N4/C复合材料的合成方法，本发明针对现有双氰胺为前驱体煅烧g-C3N4光催化材料进行微观结构的改进，纯相g-C3N4存在片层结构易重叠结块，比表面积偏小等问题，导致光生载流子复合率高和光能利用效率偏低。以蜀葵茎秆为模板，为复合材料提供刚性支撑结构，同时碳骨架能为复合材料提供电子转移通道，提高光生载流子的复合效率，从而提高材料光催化性能。其优势在于该催化材料具有特殊微观形貌，界面清晰可实现光生载流子的有效分离，提升了光能利用效率，在可见光激发下，具有很高降解有机污染物的能力，当光照时间持续120min，20mg/L罗丹明B的降解率接近53.91%，远超单相生物炭和石墨烯氮化碳的光催化性能，且大幅提升了石墨烯氮化碳的利用效率。该催化材料易于合成，原料低廉，可以批量生产，是一种适于工业化推广应用的清洁高效和能耗较低的有机污染物治理用材料。
附图说明
图1 为g-C3N4/C复合材料的XRD图谱；
图2 为g-C3N4/C复合材料的SEM图；
图3 为g-C3N4/C复合材料的TEM图；
图4 为不同样品的可见光降解罗丹明B曲线图；
图5 (a)为g-C3N4/C复合材料4次循环降解RhB染料曲线图；(b)为g-C3N4/C复合材料在循环光催化实验前后的XRD图谱；
图6 为g-C3N4/C复合材料的光催化原理图。
具体实施方式
以下结合实施例对本发明做进一步详细、完整地说明，但并不限制本发明的内容。
实施例1：
（1）将洗涤后的蜀葵茎秆切段（3cm），浸泡于预处理液（水和乙醇的体积比为1：1，并用0.1mol/L 稀盐酸将溶液pH调节至2，浸泡时间为三至四周）中以脱除其中的叶绿素和生物活性物质，浸泡结束后将茎秆用去离子水洗涤后自然晾干，避免阳光直射，收集备用；
（2）取1.5g预处理过的干燥蜀葵茎秆和3g双氰胺，溶于50mL 去离子水中，于50℃下水浴搅拌1h，待双氰胺完全溶解后停止搅拌，在50℃水浴保温24h，将混合物转移至氧化铝坩埚中，在60℃下隔夜烘干。
（3）将得到的固体置于马弗炉内，空气气氛下以3℃/min升温至550℃并保温4h，煅烧结束后研磨即得g-C3N4/C复合材料。
图1为g-C3N4/C复合材料的XRD图谱。从图中可以看出g-C3N4相（002）较为明显，峰形尖锐，C相（001）不明显，主要原因是C相主要呈非晶态，结晶峰不明显。图2的扫描电镜图中能清晰看到蜀葵茎秆模板的碳骨架结构和负载在模板表面的g-C3N4片层，图3的透射电镜图中能看到g-C3N4片层具有多孔结构，比表面积较大，可有效促进有机染料和光催化材料表面的化学反应活性位点相结合，提高其光催化降解效率。
将30mg产物加入到盛有100 mL，20 mg/L的罗丹明B溶液中，在氙灯模拟可见光照射下每隔20min取样，利用紫外-可见光分光光度计，结合标准曲线分析其浓度变化，绘制光催化降解效率曲线，如图4，显示光照120 min后其降解率达53.91%。图5的循环实验结果表明，在四次循环降解催化反应后，g-C3N4/C复合材料的光催化活性下降的不明显，且催化反应前后，催化剂的XRD图谱之间并无显著差异。
光催化机理图（图6）表明，在g-C3N4光催化材料中，蜀葵茎秆经过煅烧形成的碳骨架起到了电子转移介质的作用，为光生载流子提供电子转移通道，从而降低光生电子和光生空穴的复合效率，提高了体系光催化降解有机染料的效率。同时碳骨架也为材料提供了微观形貌的刚性支撑，使其能保持较高的比表面积，从而具有更多的化学反应活性位点，光催化降解效率得到进一步提高。
实施例2：
（1）将洗涤后的蜀葵茎秆切段（5cm），浸泡于预处理液（水和乙醇的体积比为1：2，并用0.1mol/L 稀盐酸将溶液pH调节至2，浸泡时间为三至四周）中以脱除其中的叶绿素和生物活性物质，浸泡结束后将茎秆用去离子水洗涤后自然晾干，避免阳光直射，收集备用；
（2）取1.5g预处理过的干燥蜀葵茎秆和1.5g双氰胺，溶于50mL 去离子水中，于50℃下水浴搅拌1h，待双氰胺完全溶解后停止搅拌，在50℃水浴保温24h，将混合物转移至氧化铝坩埚中，在80℃下隔夜烘干。
（3）将得到的固体置于马弗炉内，空气气氛下以4℃/min升温至520℃并保温6h，煅烧结束后研磨即得g-C3N4/C复合材料。
实施例3：
（1）将洗涤后的蜀葵茎秆切段（4cm），浸泡于预处理液（水和乙醇的体积比为1：2，并用0.1mol/L 稀盐酸将溶液pH调节至3，浸泡时间为三至四周）中以脱除其中的叶绿素和生物活性物质，浸泡结束后将茎秆用去离子水洗涤后自然晾干，避免阳光直射，收集备用；
（2）取1.5g预处理过的干燥蜀葵茎秆和6.0g双氰胺，溶于50mL 去离子水中，于50℃下水浴搅拌1h，待双氰胺完全溶解后停止搅拌，在50℃水浴保温24h，将混合物转移至氧化铝坩埚中，在60℃下隔夜烘干。
（3）将得到的固体置于马弗炉内，空气气氛下以5℃/min升温至500℃并保温6h，煅烧结束后研磨即得g-C3N4/C复合材料。
Claims (5)
1.一种基于蜀葵茎秆合成g-C3N4/C复合材料的方法，其特征在于，包括以下步骤：
（1）蜀葵茎秆的预处理
将新鲜采摘的蜀葵茎秆切段并用去离子水多次洗涤，浸泡于预处理液中以脱除其中的叶绿素和生物活性物质，浸泡结束后将茎秆用去离子水洗涤后自然晾干，避免阳光直射，收集备用；
（2）制备g-C3N4/C复合材料
以双氰胺为前驱体配制浸渍溶液，将步骤（1）预处理过的茎秆浸渍于其中进行处理，然后经脱水并热处理即可生成g-C3N4/C复合材料；其中蜀葵茎秆和双氰胺的质量比为1:1-1:4。
2.根据权利要求1所述的合成方法，其特征在于，所述步骤（1）中茎秆切段的长度为3-5cm。
3.根据权利要求1所述的合成方法，其特征在于，所述步骤（1）中预处理液的成分为：体积比为1:1-1:2的水和乙醇的混合液，pH为2-3，浸泡时间为三至四周，浸泡结束后将茎秆洗涤至洗涤液pH呈中性后方可晾干。
4.根据权利要求1所述的合成方法，其特征在于，所述步骤（2）中将预处理过的茎秆先于浸渍溶液中于50℃下水浴搅拌1-2h，待前驱体完全溶解后停止搅拌，继续水浴保温20-24h，后在60-80℃下隔夜烘干。
5.根据权利要求1所述的合成方法，其特征在于，所述步骤（2）中的热处理条件为于马弗炉内进行热处理，反应条件为：空气气氛下以3-5℃/min升温至500-550℃并保温4-6h。
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