CN113398880A - 一种对染料分子具有吸附和催化降解功能的碳基复合微球的制备方法 - Google Patents
一种对染料分子具有吸附和催化降解功能的碳基复合微球的制备方法 Download PDFInfo
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Abstract
本发明涉及一种对染料分子具有吸附和催化降解功能的碳基复合微球的制备方法。以壳聚糖为碳源，首次通过喷雾干燥法与高温热解和碱活化技术相结合的方法，制备了对染料分子具有吸附和催化降解功能的掺杂银纳米粒子活性微孔碳球。本发明方法制备的掺杂银纳米粒子活性微孔碳球对刚果红染料表现出良好的吸附性能，并可以有效地催化硼氢化钠还原刚果红的反应。本发明得到的双功能复合碳球吸附性好，催化效率高且重复利用性好；此外，本发明所述掺杂银纳米粒子活性微孔碳球的制备方法所涉及的原料来源广泛、价格低廉，制备过程绿色环保，适合大规模生产，具有良好的应用前景。
Description
技术领域
本发明属于多功能复合材料开发技术领域，具体涉及一种对染料分子具有吸附和催化功能的碳基复合微球的制备方法，该碳基复合微球对刚果红具有良好的吸附性能，同时具有催化硼氢化钠降解刚果红的能力。
背景技术
随着纺织、印刷、皮革等行业的发展，含有有机染料的废水对环境安全和人类健康造成了严重的影响。研究人员研究和开发了多种去除染料分子的方法，例如吸附、催化降解、光催化、膜过滤等，其中，吸附法和催化降解法被认为是最具有应用前景的方法。多孔材料具有丰富的孔结构与超高的比表面积，可以吸附废水溶液中的染料分子。此外，多孔材料还可以作为催化降解染料分子的纳米催化剂的良好载体，有效地提高催化剂纳米粒子催化降解染料分子的能力。因此，将金属纳米粒子负载在多孔材料上可望制备出对染料分子同时具有吸附与催化功能的新型材料。但是，目前研究制备负载金属纳米粒子多孔材料的方法(如模板法、浸渍法等)大多存在制备过程复杂，产量较低的问题，在一定程度上限制了负载金属纳米粒子多孔材料的开发与应用。因此，开发一种步骤简单，产量较高的负载金属纳米粒子多孔材料的制备方法对去除水中染料分子具有重大意义。
发明内容
本发明旨在提供一种对染料分子具有吸附和催化降解功能的碳基复合微球的制备方法。
本发明的另一目的是提供上述碳基复合微球吸附刚果红染料与催化硼氢化钠降解刚果红的应用，获得该碳基复合微球的使用方法。
为解决以上技术问题，本发明采取的技术方案是：
一种对染料分子具有吸附和催化降解功能的碳基复合微球的制备方法，包括如下步骤：
(1)在磁力搅拌下将壳聚糖溶解在的醋酸溶液后，将硝酸银溶液缓慢滴加至壳聚糖溶液中。反应一定时间后，将硼氢化钠溶液滴加至上述溶液，得到银纳米粒子/壳聚糖混合溶液。
(2)通过喷雾干燥技术，对步骤(1)中的溶液进行喷雾干燥，得到掺杂银纳米粒子壳聚糖微球。
(3)取一定量步骤(2)得到的掺杂银纳米粒子壳聚糖微球在氮气保护下高温碳化，得到掺杂银纳米粒子碳球。
(4)将步骤(3)得到的掺杂银纳米粒子碳球与氢氧化钾混匀，在氮气保护下高温活化，得到掺杂银纳米粒子活性微孔碳球。
步骤(1)中，将2mL醋酸溶液稀释至100mL，各物质添加量为：1g的壳聚糖，1mL 0.1gmL-1的硝酸银溶液，1mL 0.05g mL-1的硼氢化钠溶液。
步骤(2)中，使用B-290小型喷雾干燥机。空气流量，泵流量和工作功率分别设定为600L h-1、30％和100％，入口温度为180℃。
步骤(3)中，碳化程序为：以6℃ min-1的速率升温到400℃，再以3℃ min-1的速率升温到700℃，并在700℃保温2h。
步骤(4)中，掺杂银纳米粒子碳球与氢氧化钾的质量比为1∶4，活化程序为：以5℃min-1的速率升温到750℃，并在750℃保温1.5h。
通过上述方法制备的对染料分子具有吸附和催化降解功能的碳基复合微球也在本发明的保护范围之内。通过扫描电子显微镜和透射电子显微镜表征掺杂银纳米粒子活性微孔碳球和掺杂其中的银纳米粒子的形貌，并通过吸附、催化模型实验，验证碳基复合微球的吸附与催化性能。
由于以上技术方案的实施，本发明与现有技术相比具有如下优点：
(1)以壳聚糖为碳源，原料为天然多糖衍生物，环境友好且价格低廉。
(2)采用喷雾干燥法制备掺杂银纳米粒子壳聚糖微球，该方法操作简单、产量较高，适宜批量生产。
(3)掺杂银纳米粒子活性微孔碳球的制备过程操作简单，重复性高，对设备要求低，适用范围广。
附图说明
图1(a)为研磨后的掺杂银纳米粒子活性微孔碳球的TEM图；图1(b)为掺杂银纳米粒子活性微孔碳球的SEM图。
图2(a)为掺杂银纳米粒子活性微孔碳球吸附刚果红的吸附等温线图；图2(b)为掺杂银纳米粒子活性微孔碳球催化硼氢化钠降解刚果红的紫外-可见吸收光谱图。
具体实施方式
根据下述实施例，可以更好地理解本发明。然而，本领域的技术人员容易理解，实施例所描述的内容仅用于说明本发明，而不应当也不会限制权利要求书中所详细描述的本发明。
以下实施例试剂及来源：硝酸银，国药集团化学试剂有限公司；醋酸，南京化学试剂股份有限公司；氢氧化钾，南京化学试剂有限公司；壳聚糖，国药集团化学试剂有限公司；硼氢化钠，Shanghai Aladdin Biochemical Technology Co.，Ltd.；刚果红，天津市化学试剂研究所。扫描电子显微镜(SEM，Regulus 8100，Hitachi)；透射电子显微镜(TEM，JEM-1400，日本电子株式会社)；紫外-可见分光光度计(UV-2450，岛津)。
实施例1：
取2mL的醋酸溶液稀释至100mL。在磁力搅拌下，将1g的壳聚糖加入醋酸溶液，待壳聚糖完全溶解后，取1mL 0.1g mL-1的硝酸银溶液添加到混合溶液中，一段时间后滴加1mL0.05g mL-1的硼氢化钠溶液，继续搅拌3小时。通过B-290小型喷雾干燥机将溶液喷雾干燥。得到的产物在氮气保护下以6℃ min-1的速率升温到400℃，再以3℃ min-1的速率升温到700℃，并在700℃保温碳化2h。将碳化后产物与氢氧化钾以1∶4的质量比均匀混合后在氮气保护下以5℃ min-1的速率升温到750℃，并在750℃保温活化1.5h，活化过程结束后，将复合材料多次清洗至溶液呈中性后进行冷冻干燥，干燥后的最终产物即为掺杂银纳米粒子活性微孔碳球。
实施例2：
将5mg的掺杂银纳米粒子活性微孔碳球分散在25mL不同浓度的刚果红溶液中，12h后测试溶液的吸光度值，根据标准曲线计算得到剩余浓度，并通过Freundlich和Langmuir模型进行拟合。
实施例3：
取6mL 0.086mM的刚果红溶液放入离心管，向其中加入2mL 0.5M的硼氢化钠溶液，混合均匀后加入1mg的掺杂银纳米粒子活性微孔碳球，间隔一段时间测试溶液的吸光度值，观察溶液吸收峰的位置变化。
测试结果分析：
图1(a)为研磨后的掺杂银纳米粒子活性微孔碳球的TEM图，从图中可以看到银纳米粒子表现出良好的球形形貌且均匀掺杂在活性微孔碳球中。从图1(b)的SEM图可以看到，活性微孔碳球表面有大量的银纳米粒子，且表面凹凸不平，有利于活性微孔碳球吸附性能的提高。
图2(a)为掺杂银纳米粒子活性微孔碳球吸附刚果红的吸附等温线，实验的吸附数据与Langmuir模型比较吻合并且根据非线性拟合方程计算出的最大吸附量为442mg g-1。图2(b)是掺杂银纳米粒子活性微孔碳球催化硼氢化钠还原刚果红的紫外-可见吸收光谱图。可以看到，经过9min的催化反应，刚果红已被完全降解。吸附与催化实验表明掺杂银纳米粒子活性微孔碳球具有优秀的吸附与催化性能。
Claims (10)
1.一种对染料分子具有吸附和催化降解功能的碳基复合微球的制备方法，其特征在于：它包括如下步骤：
(1)磁力搅拌下，将壳聚糖溶解在醋酸溶液，一段时间后，将硝酸银溶液滴加至壳聚糖溶液中，待混合均匀后，缓慢滴加硼氢化钠溶液，继续反应一段时间。
(2)使用喷雾干燥机对步骤(1)的溶液进行喷雾干燥，在喷雾干燥机的产品收集器中收集掺杂银纳米粒子壳聚糖微球。
(3)将步骤(2)收集的掺杂银纳米粒子壳聚糖微球转移到管式炉中，在氮气保护下进行高温碳化，得到掺杂银纳米粒子碳球。
(4)将步骤(3)得到的掺杂银纳米粒子碳球与氢氧化钾均匀混合后转移到管式炉中，在氮气保护下进行高温活化。活化过程结束后用去离子水多次清洗活化所得复合材料直至溶液呈中性，样品干燥后获得掺杂银纳米粒子活性微孔碳球。
2.根据权利要求1所述的一种对染料分子具有吸附和催化降解功能的碳基复合微球的制备方法，其特征在于：步骤(1)中，每2mL醋酸溶液稀释至100mL。
3.根据权利要求1所述的一种对染料分子具有吸附和催化降解功能的碳基复合微球的制备方法，其特征在于：步骤(1)中，在每100mL的醋酸溶液中溶解1g的壳聚糖。
4.根据权利要求1所述的一种对染料分子具有吸附和催化降解功能的碳基复合微球的制备方法，其特征在于：步骤(1)中，在每100mL的壳聚糖溶液中，加入1mL 0.1g mL-1的硝酸银溶液。
5.根据权利要求1所述的一种对染料分子具有吸附和催化降解功能的碳基复合微球的制备方法，其特征在于：步骤(1)中，银离子与壳聚糖分子的螯合时间为1-2h。
6.根据权利要求1所述的一种对染料分子具有吸附和催化降解功能的碳基复合微球的制备方法，其特征在于：步骤(1)中，硼氢化钠的添加量为1mL，浓度为0.05g mL-1。
7.根据权利要求1所述的一种对染料分子具有吸附和催化降解功能的碳基复合微球的制备方法，其特征在于：步骤(1)中，添加硼氢化钠后的反应时间为2-4h。
8.根据权利要求1所述的一种对染料分子具有吸附和催化降解功能的碳基复合微球的制备方法，其特征在于：步骤(2)中，使用B-290小型喷雾干燥机对溶液进行喷雾干燥，且空气流量，泵流量和工作功率分别设定为600L h-1、30％和100％，入口温度为180℃。
9.根据权利要求1所述的一种对染料分子具有吸附和催化降解功能的碳基复合微球的制备方法，其特征在于：步骤(3)中，先将步骤(2)中得到的掺杂银纳米粒子壳聚糖微球放在陶瓷舟中，再将陶瓷舟转移到管式炉里；碳化程序为：以6℃ min-1的速率升温到400℃，再以3℃ min-1的速率升温到700℃，并在700℃下保温2h。
10.根据权利要求1所述的一种对染料分子具有吸附和催化降解功能的碳基复合微球的制备方法，其特征在于：步骤(4)中，先将步骤(3)中得到的掺杂银纳米粒子碳球与氢氧化钾以1∶4的质量比均匀混合后放在陶瓷舟中，再将陶瓷舟转移到管式炉里；活化程序为：以5℃min-1的速率升温到750℃，并在750℃下保温1.5h。
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