CN116408128B - 采用苦樱桃树胶制备Cu-N掺杂树胶炭催化剂的方法及应用 - Google Patents
采用苦樱桃树胶制备Cu-N掺杂树胶炭催化剂的方法及应用 Download PDFInfo
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Abstract
本发明公开了一种采用苦樱桃树胶制备Cu‑N掺杂树胶炭催化剂的方法，该方法是将纯净苦樱桃树胶、铜盐置于去离子水中，在室温下搅拌使树胶充分溶胀并且络合Cu2+，制得树胶/Cu2+水凝胶；将树胶/Cu2+水凝胶浸泡在含乙二胺的水溶液中，在55～65℃下配位反应至水凝胶变为蓝色，制得树胶/乙二胺/Cu2+络合物水凝胶；将树胶/乙二胺/Cu2+络合物水凝胶干燥粉碎后，置于管式炉中，在惰性气氛、500～700℃下煅烧制得Cu‑N掺杂树胶炭催化剂；本发明方法制得的催化剂用于光催化降解污水中磺胺类抗生素，实验结果显示磺胺类抗生素在Cu‑N掺杂树胶炭催化剂作用下能完全降解。
Description
技术领域
本发明属于光-芬顿催化剂制备技术领域，具体涉及一种以苦樱桃树胶为原料制备Cu-N掺杂树胶炭催化剂的方法及其在光照下催化降解磺胺类抗生素的用途。
背景技术
天然树胶是蔷薇科核果类树木伤口分泌的一类粘稠的胶状物质，桃树胶是最常见的一种树胶。我国各类树胶的年采集量高达数百吨，由于树胶粘度高，且化学性质稳定，常被用于食品、医药等领域，中医认为桃树胶有保健作用。长期以来，人们对树胶的化学性质研究甚少，在树胶的改性利用方面的研究也相对滞后。近年来，国外一些学者首先对树胶的化学成分展开研究，他们的研究表明树胶是一类天然高分子杂多糖，其结构是由多种单糖通过糖苷键聚合而成的高度支链化的大分子多糖。树胶分子中有大量羟基（-OH），因而具有良好的亲水性，其吸水后形成水凝胶，溶解在水中则形成水溶胶。云南苦樱桃（Prunus emarginata）又叫云南樱花，是蔷薇科观赏乔木，雨水多的季节枝干会分泌大量树胶。
生物质炭材料是以生物质为原料在惰性气氛下经高温煅烧，形成内部孔隙结构发达、比表面积大、吸附能力强的微晶质活性炭。活性炭是第一代生物质炭材料，由于只含有碳一种元素，使其应用范围受到限制，目前常被用作吸附剂。随着现代工业对碳基功能材料的新需求，功能化的新型碳基催化剂是生物质炭材料发展的重要方向。以生物质炭作为载体，在炭的表面及内部构筑大量催化活性中心，可以得到化学性质稳定、催化活性优异的碳基催化材料。目前，制备生物质炭的原料主要是木材、竹材以及各种农林废弃物。现有研究表明，以木材、竹材以及各种农林废弃物制备的功能化生物质炭催化剂存在明显的结构缺陷，即催化活性中心无法均匀分布在生物质炭基体中。催化活性中心的不均匀分布直接导致生物质炭催化剂的催化活性降低，催化效果不稳定。因此，设计、合成催化活性中心分布均匀的生物质炭材料是目前生物质炭应用领域亟待解决的一项重要技术难题。
发明内容
针对现有技术存在的问题，本发明提供了一种采用苦樱桃树胶制备Cu-N掺杂树胶炭催化剂的方法，本发明方法以过渡金属配位化学理论为基础，首先将云南苦樱桃树胶杂多糖、Cu2+、乙二胺置于水相中，通过分子自组装制备树胶/乙二胺/Cu2+络合物水凝胶，然后在惰性气体保护下将树胶/乙二胺/Cu2+络合物干凝胶在管式炉中高温煅烧，制得Cu-N掺杂树胶炭催化剂，具体制备过程如下：
（1）苦樱桃树胶/乙二胺/Cu2+络合物水凝胶的制备
将苦樱桃树胶浸泡在去离子水中，搅拌使其充分溶解，然后用纱布过滤除去不溶性杂质，鼓风干燥得到纯净苦樱桃树胶；在去离子水中加入纯净苦樱桃树胶和铜盐，室温下搅拌使树胶充分溶胀并且络合Cu2+，得到绿色的树胶/ Cu2+水凝胶；
所述铜盐为Cu(NO3)2；纯净苦樱桃树胶与铜盐的质量比为1 : 0.1～0.4；
将上述树胶/Cu2+水凝胶浸泡在含乙二胺的水溶液中，搅拌下升温至55～65℃反应2～6小时，乙二胺分子的-NH2与树胶分子中的-OH形成稳定的氢键，因而乙二胺分子被均匀地吸附在树胶中，随着反应的进行，可以观察到水凝胶颜色由绿色逐渐变为蓝色，表明树胶中的乙二胺已经与Cu2+发生配位反应，生成树胶/乙二胺/Cu2+络合物水凝胶；
所述纯净树胶与乙二胺的质量比为1:0.2～0.5；
（2）树胶/乙二胺/Cu2+络合物干凝胶的制备
将树胶/乙二胺/Cu2+络合物水凝胶放入烘箱内，鼓风干燥20～24 h得到失水后的树胶/乙二胺/Cu2+络合物干凝胶，粉碎；
（3）Cu-N掺杂树胶炭催化剂的制备
将树胶/乙二胺/Cu2+络合物干凝胶粉末放入管式炉中，通入氩气25min除去氧气，在氩气气氛下以5℃/min的速度从室温升温至500～700℃并在此温度下煅烧2～4h，使树胶/乙二胺/Cu2+络合物完全热解，自然冷却至室温后，得到黑色的Cu-N掺杂树胶炭催化剂。
本发明另一目的是将上述方法制得的Cu-N掺杂的树胶炭催化剂应用在光催化降解磺胺类抗生素中。
本发明的优点和技术效果：
（1）本发明采用天然高分子杂多糖--树胶作为原料，利用树胶独特的高枝化结构和优良的水溶性，使过渡金属铜离子均匀的络合到树胶大分子中，然后利用铜离子与含氮有机分子乙二胺的配位作用，在树胶中构筑分布均匀的铜-氮催化中心；
（2）在Cu-N掺杂树胶炭的结构中，氮原子掺杂在石墨相碳的六元环结构中，从而得到具有结构稳定、掺杂均匀、高光催化活性的Cu-N掺杂型炭催化剂；
（3）将Cu-N掺杂树胶炭用于光催化降解磺胺类抗生素，实验结果显示磺胺类抗生素在催化剂作用下能完全降解，本发明为解决抗生素污染提供了一种新的途径。
附图说明
图1为苦樱桃树胶在不同制备阶段下的颜色和形态图，其中a图为苦樱桃树胶，b图为树胶/Cu2+水凝胶，c图为树胶/乙二胺/Cu2+干凝胶粉末，d图为Cu-N掺杂树胶炭催化剂；
图2为Cu-N掺杂树胶炭催化剂的扫描电子显微镜图，其中A图为放大2000倍，B图为放大5000倍；
图3为Cu-N掺杂树胶炭催化剂的X-射线光电子能谱图，其中左图survey谱，右图为C1s谱；
图4为Cu-N掺杂树胶炭催化剂的X-射线光电子能谱图，其中左图N1s谱，右图为O1s谱；
图5为Cu-N掺杂树胶炭催化剂的X-射线光电子能谱图，其中左图Cu2p谱，右图为CuLM2谱；
图6为Cu-N掺杂树胶炭催化剂的X-射线粉末衍射图；
图7为600℃制备的Cu-N掺杂树胶炭光催化降解磺胺抗生素的实验结果，其中a图是在Cu-N掺杂树胶炭催化下磺胺嘧啶的吸收光谱随光照时间的变化图，b图为磺胺嘧啶降解率随光照时间的变化图。
具体实施方式
下面结合附图和实施例对本发明作进一步详细说明，但所述内容不应看作对本发明的限制，本实施例中方法如无特殊说明的均按常规方法操作，所用试剂如无特殊说明的采用常规试剂或按常规方法配置的试剂。
实施例1
1、将苦樱桃树胶（图1的a图）浸泡在去离子水中12小时，搅拌使其充分溶解，然后用纱布过滤除去不溶性杂质，滤液置于鼓风干燥箱中50℃下干燥5h后得到纯净的树胶；在50mL去离子水中加入2.0g纯净的树胶和0.2g Cu(NO3)2，在室温下搅拌12小时使树胶充分溶胀并且络合Cu2+达到饱和，得到绿色的树胶/ Cu2+水凝胶（图1的b图）；将树胶/Cu2+水凝胶浸泡在50mL含0.5g乙二胺的水溶液中，搅拌下升温至60℃反应，反应过程中，可以观察到水凝胶颜色由绿色逐渐变为蓝色，表明树胶中的乙二胺已经与Cu2+发生配位反应，生成树胶/乙二胺/Cu2+络合物水凝胶。
2、将上述树胶/乙二胺/Cu2+络合物水凝胶放入70℃的烘箱内，鼓风干燥20h得到失水后的树胶/乙二胺/Cu2+络合物干凝胶，为了在高温煅烧时受热均匀，把干凝胶粉碎成粉末，见图1的c图。
3、将5g树胶/乙二胺/Cu2+络合物干凝胶粉末放入管式炉中，通入氩气30min除去氧气，保持氩气气氛，以5℃/min升温至600℃，保持600℃煅烧3h后，自然降温至室温，得到黑色的Cu-N掺杂树胶炭催化剂，见图1的d图。
为了观察Cu-N掺杂树胶炭催化剂的微观结构，使用扫描电子显微镜对树胶炭催化剂的形貌进行了表征，结果见图2，由扫描电镜图可以看到，树胶炭的内部有很多泡孔，泡孔直径约为2～5μm，而且部分泡孔彼此连通，树胶炭内部泡孔的形成是由于在管式炉中高温煅烧时树胶有机质分解生成H2O分子和CO2分子膨胀外溢形成的。
Cu-N掺杂树胶炭催化剂的X-射线光电子能谱（XPS）见图3-5，XPS全谱显示制备的树胶炭中含有C、N、O、Cu四种元素，通过四种元素的精细谱进一步分析元素的价态和成键形式：C1s谱显示树胶炭中的碳元素以C-C和C=C键相连接，说明树胶炭主要以石墨相碳形式存在；C1s谱和N1s谱都显示有N-C=N键的存在，说明N元素直接以成键的方式掺杂在树胶炭中，即N原子掺杂在石墨相碳的六元环结构中；由Cu2p和CuLM2谱可以发现Cu元素以Cu+和Cu2+两种价态存在于树胶炭中，结合O1s谱可以得知Cu元素以CuO和Cu2O两种物质形式掺杂在树胶炭中；利用X-射线粉末衍射（XRD）进一步对Cu-N掺杂树胶炭进行表征，结果见图6，XRD谱表明Cu元素以CuO和Cu2O两种物质形式掺杂在树胶炭中，XRD谱位于23.7°的宽峰和位于42°的弱峰都是石墨相碳的特征衍射峰，XRD谱与XPS谱的结果一致；
上述结果表明铜元素和氮元素已经成功均匀的掺杂进树胶炭中，CuO和Cu2O的存在是树胶炭具有良好光-芬顿催化活性的主要原因。
4、Cu-N掺杂树胶炭催化剂光催化降解磺胺抗生素
实验中使用北京中教金源CEL-HXF300-T3型氙灯作为光源，调节功率至150 W，通过添加滤光片过滤掉紫外光，使设备输出波长为400～800nm的可见光辐射，实验过程中固定光源至液面的距离为5cm，降解溶液盛放于通有冷凝水的夹层石英烧杯中，以便在光照时保持恒温。
在通有冷凝水的夹层石英烧杯中依次加入50mL磺胺嘧啶抗生素溶液（20mg/L）、20mg Cu-N掺杂树胶炭催化剂，避光搅拌均匀后静置1h，使体系达到吸附平衡。取上清液在紫外-可见分光光度计上扫描磺胺嘧啶溶液的吸收光谱，记为t=0时的光谱曲线。在烧杯中加入0.1mL过氧化氢（质量浓度30%）作为氧化剂，将反应液置于光源下，打开光源，在持续搅拌下催化反应。每隔一段时间取适量反应液扫描光谱曲线，记为t时的光谱曲线。根据磺胺嘧啶在特征吸收峰（264nm）处的吸光度值跟踪监测浓度变化。磺胺嘧啶抗生素的降解率计算公式为：D= (A0－At) / A0 ×100%，式中A0为磺胺嘧啶在t=0时的初始吸光度值，At为光照t时间后的吸光度值。
实验结果显示，以树胶/乙二胺/Cu2+络合物干凝胶为前驱体，在600℃煅烧制备的Cu-N掺杂树胶炭在可见光照射下能快速催化降解磺胺嘧啶抗生素。由图7的a图磺胺嘧啶的紫外-可见吸收光谱可以看到，在20mg Cu-N掺杂树胶炭的催化下，磺胺嘧啶水溶液吸收峰的强度随着光照时间的延长逐渐减弱，表明溶液中的磺胺嘧啶逐渐被降解。由降解率图7的b图可以看到，光照30min后磺胺嘧啶的降解率为56%，光照60min后磺胺嘧啶的降解率高达87%，当光照90min后磺胺嘧啶的特征吸收峰完全消失，表明已经完全降解。
实施例2：本实施例制备方法同实施例1，不同之处在于树胶/乙二胺/Cu2+络合物干凝胶在500℃下煅烧3h后制得Cu-N掺杂树胶炭催化剂；以该Cu-N掺杂树胶炭为催化剂光催化降解磺胺嘧啶，其他光催化实验条件同实施例1，结果显示，光照30min后磺胺嘧啶的降解率为48%，光照60min后磺胺嘧啶的降解率为74%，光照90min后磺胺嘧啶的降解率为83%。
实施例3：本实施例制备方法同实施例1，不同之处在于树胶/乙二胺/Cu2+络合物干凝胶在700℃下煅烧3h后制得Cu-N掺杂树胶炭催化剂，以该Cu-N掺杂树胶炭为催化剂光催化降解磺胺嘧啶，其他光催化实验条件同实施例1，结果显示，光照30min后磺胺嘧啶的降解率为52%，光照60min后磺胺嘧啶的降解率为78%，光照90min后磺胺嘧啶的降解率为91%。
Claims (5)
1.一种采用苦樱桃树胶制备Cu-N掺杂树胶炭催化剂的方法，其特征在于：将纯净苦樱桃树胶、铜盐置于去离子水中，在室温下搅拌使树胶充分溶胀并且络合Cu2+，制得树胶/ Cu2 +水凝胶；将树胶/ Cu2+水凝胶浸泡在含乙二胺的水溶液中，在55～65℃下配位反应至水凝胶变为蓝色，制得树胶/乙二胺/Cu2+络合物水凝胶；将树胶/乙二胺/Cu2+络合物水凝胶干燥粉碎后，置于管式炉中，在惰性气氛、500～700℃下煅烧，制得Cu-N掺杂树胶炭催化剂。
2.根据权利要求1所述的采用苦樱桃树胶制备Cu-N掺杂树胶炭催化剂的方法，其特征在于：铜盐为Cu(NO3)2。
3.根据权利要求2所述的采用苦樱桃树胶制备Cu-N掺杂树胶炭催化剂的方法，其特征在于：纯净苦樱桃树胶是将苦樱桃树胶浸泡在去离子水中搅拌使其充分溶解，过滤除去不溶性杂质，干燥后制得，纯净苦樱桃树胶与铜盐的质量比为1 : 0.1～0.4。
4.根据权利要求1所述的采用苦樱桃树胶制备Cu-N掺杂树胶炭催化剂的方法，其特征在于：纯净苦樱桃树胶与乙二胺的质量比为1 : 0.2～0.5。
5.权利要求1-4任一项所述的采用苦樱桃树胶制备Cu-N掺杂树胶炭催化剂的方法制得的Cu-N掺杂树胶炭催化剂在光照条件下催化降解磺胺类抗生素中的应用。
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