CN108543544A - 蜂窝状同型异质结氮化碳复合材料及其制备方法与在废气催化处理中的应用 - Google Patents

蜂窝状同型异质结氮化碳复合材料及其制备方法与在废气催化处理中的应用 Download PDF

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CN108543544A
CN108543544A CN201810403004.2A CN201810403004A CN108543544A CN 108543544 A CN108543544 A CN 108543544A CN 201810403004 A CN201810403004 A CN 201810403004A CN 108543544 A CN108543544 A CN 108543544A
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路建美
陈冬赟
蒋军
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Suzhou University
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Abstract

本发明公开了一种蜂窝状同型异质结氮化碳复合材料及其制备方法与在废气催化处理中的应用，以尿素、硫脲两种不同的氮化碳前聚体为原料，称取一定量于坩埚中，加入一定量的超纯水，放入马弗炉中煅烧成型。本发明通过一步法制备的蜂窝状的同型异质结的氮化碳，对NO的催化降解有着很好的光催化效果；并且生产原料丰富易得，稳定性好，可重复使用等优点，在处理空气中NO方面具有应用前景。

Description

蜂窝状同型异质结氮化碳复合材料及其制备方法与在废气催 化处理中的应用
技术领域
本发明涉及复合材料技术领域，具体涉及一种蜂窝状的同型异质结的氮化碳复合材料及其制备方法与在催化NO中的应用。
背景技术
随着近年来汽车业的迅速发展，汽车尾气的排放严重超标，已经损坏了生态环境、危害了人类的身体健康。
半导体光催化是一种非常有应用前景的技术，其在环境修复，太阳能转化和光合作用方面都具有广泛的应用。自从王课题组首次报道以来，类石墨氮化碳（g-C3N4）作为一种引人注目的可见光光催化剂已经引起了广泛的研究热潮。但是现有技术使得g-C3N4的产率较低。因此，需要寻找合成高产率、高性能的g-C3N4的新方法。
发明内容
本发明的目的是提供一种蜂窝状的同型异质结的氮化碳复合材料及其制备方法，创造性的在水存在下，采用一步煅烧的方法，将尿素、硫脲制备成蜂窝状的同型异质结的氮化碳，以实现处理废气中的NO。
为了达到上述目的，本发明采用如下具体技术方案：
一种蜂窝状同型异质结氮化碳复合材料的制备方法，包括以下步骤，以尿素、硫脲为前聚体，在水的存在下，煅烧制备蜂窝状同型异质结氮化碳复合材料。
本发明还公开了一种废气处理方法，包括以下步骤，以尿素、硫脲为前聚体，在水的存在下，煅烧制备蜂窝状同型异质结氮化碳复合材料；然后将待处理废气通过蜂窝状同型异质结氮化碳复合材料，完成废气处理。
优选的，将尿素、硫脲和水混合反应后，再煅烧制备蜂窝状同型异质结氮化碳复合材料；进一步优选的，所述反应为室温反应20～45分钟，混合溶解时是室温反应，操作条件简单，减少实验成本，对尿素、硫脲的损失少。
本发明中，尿素、硫脲、水的质量比为尿素、硫脲的质量和与水的质量比为5∶6～7；所述硫脲的质量为尿素、硫脲质量和的1%～10%。本发明是尿素加水，无模板，从而形成的蜂窝状结构的氮化碳，相比于现有技术（尿素加铵盐），更加绿色环保无污染，其次，本发明还掺杂的硫脲，从而形成蜂窝状的氮化碳同型异质结，进一步增加催化效果。
本发明中，所述煅烧在空气中进行，煅烧包括首次煅烧与再次煅烧；所述首次煅烧时，升温速率为10℃/min，煅烧的时间为1h，煅烧的温度为400℃；再次煅烧时，升温速率为10℃/min，煅烧的时间为1h，煅烧的温度为450℃。本发明实现了蜂窝状同型异质结氮化碳复合材料纳米结构以及优异的催化性能，同时解决了现有技术长时间的高温处理使得g-C3N4的产率较低的问题。
本发明创造性的采用简单的一步煅烧法的方法制备蜂窝状的同型异质结的氮化碳复合材料，具有蜂窝状的结构，带隙变小，产量大、成本低的优点，蜂窝状的结构可以促进催化性能，是一种良好的半导体催化剂。
本发明中，废气处理在光照下进行。
本发明还公开了所述制备方法制备的蜂窝状同型异质结氮化碳复合材料。
本发明进一步公开了上述蜂窝状同型异质结氮化碳复合材料在催化处理废气中的应用，优选废气为NO，进一步优选的，所述催化处理在光照下进行；以及上述蜂窝状同型异质结氮化碳复合材料在制备废气处理复合材料中的应用。
本发明的优点：
1、本发明公开的蜂窝状的同型异质结的氮化碳复合材料具有蜂窝状的结构，带隙变小，产量大、成本低的优点，蜂窝状的结构可以促进催化性能，是一种良好的半导体催化剂。
2、本发明公开的蜂窝状的同型异质结的氮化碳的复合材料中，类石墨烯氮化碳（g-C3N4）是一种无金属的共轭聚合物半导体，其具有高的物理化学稳定性，易于合成，而且来源丰富；然而，现有块状C3N4由于电荷的再结合率高，电导率低、比表面积小（7.7m2g-1），在实际应用中存在局限性，本发明的技术方案调节电子结构，光学性质，改变形貌、提高电荷的分离效率，解决了现有技术问题，从而提高了光催化效率。
3、本发明公开的蜂窝状的同型异质结的氮化碳的复合材料的制备方法中，蜂窝状的氮化碳制备简单，原料廉价易得，成本低，产量大；形成的蜂窝状的形貌可重现性高，同时对光的吸收利用率高，得到的产物可以高效地处理废气中的NO。
附图说明
图1为实施例一中450℃煅烧后蜂窝状同型异质结氮化碳的扫描电镜图；
图2为实施例一中450℃煅烧后蜂窝状同型异质结氮化碳的透射电镜图；
图3为实施例二中所述蜂窝状同型异质结氮化碳催化NO的效果图；
图4为实施例三中所述蜂窝状同型异质结氮化碳催化NO的循环效果图。
具体实施方式
实施例一
蜂窝状同型异质结的氮化碳制备，具体步骤如下：
将20mL超纯水、3g硫脲、12g尿素加入坩埚中，在室温下超声反应30分钟，接着加盖放入马弗炉中煅烧，以升温速率10 ℃/min加热至400℃并保持1h，继续以10 ℃/min升温加热至450℃并保持1h，得到蜂窝状同型异质结氮化碳复合材料，为粉体，产率20%，高于现有5%左右的产率。
取不同质量超纯水、硫脲、尿素为原料，根据上述制备方法制备得到不同硫脲比例的蜂窝状同型异质结氮化碳复合材料，为粉体，产率18%～20%；尿素、硫脲、水的质量比为（99∶1∶133）（1%）、（19∶1∶26）（5%）、（9∶1∶13）（10%）对应硫脲质量占（硫脲和尿素的总质量）的百分比为1%、5%、10%，对应于图3的曲线。
附图1为蜂窝状同型异质结氮化碳复合材料的扫描电镜图，从图中可以看出，一些小孔不规则的分散在氮化碳的表面；附图2为蜂窝状同型异质结氮化碳复合材料的透射电镜图，从图中可以更清楚直观的看出，有大量的蜂窝状的空洞分布在氮化碳各层，孔径大小不一致，形状不规则。
实施例二
蜂窝状同型异质结氮化碳复合材料对NO光催化降解试验，具体步骤如下：
50 mg催化剂蜂窝状同型异质结氮化碳复合材料摊平放置通着NO（600 ppb）的石英玻璃反应器（1.6 L（Φ 10 × 20 cm））的中间，光源为300W的氙灯，放置于反应器的外部，垂直照射催化剂。NO气体的原始浓度为10 ppm，通过和N2混合，平衡后稳定在600ppb的浓度，气流量控制在2.4 L min-1。气体与催化剂之间吸附脱附达到稳定后，打开氙灯并开始计时，记录30 min的数据。附图3为NO的残留率与时间的关系曲线图。从图中可以看出，蜂窝状同型异质结氮化碳复合材料光催化剂在施加光照的条件下，10分钟内约有65%的NO被催化去除；光照30 min后，NO的浓度保持不变。该实验中，由于尿素和硫脲形成同型异质结的协同作用，以及蜂窝状的形貌，使得光催化剂对NO催化效率大幅提高；与单纯额硫脲、尿素相比较，掺杂后的异质结表现出更好的光催化效果，提高的效率高达2倍左右。
实施例三
蜂窝状同型异质结氮化碳复合材料对光催化NO 的循环试验，具体步骤如下：
实施例二（2%硫脲）反应结束后，关掉氙灯，等待气体NO的浓度再次回到600 ppb，并保持稳定，达到吸附平衡后，打开氙灯，开始计时，记录30 min的数据，此后，重复上述操作，记录4次，得到催化剂的循环数据。附图4是重复使用实施例二中使用过的蜂窝状同型异质结氮化碳复合材料的光催化剂对起始浓度为600 ppb的NO循环四次光催化实验的NO去除效果统计图。实验中可以看到，在上述三次重复使用过程中，复合材料的稳定性高，始终保持优良的光催化性能，在600 ppb的NO浓度下，最终去除NO的效率均大于65%。所以，该催化剂可以重复使用，并且具有良好的稳定性。
本发明制备的蜂窝状同型异质结氮化碳复合材料是一种无金属、来源丰富的半导体材料，具有独特的电子特性和合适的带隙，制备简单，可以通过氮含量丰富的前聚体热缩合来制备；尤其尿素是一种非常便宜且含量丰富的工业试剂，是优质的前聚体。

Claims (10)

1.一种蜂窝状同型异质结氮化碳复合材料的制备方法，其特征在于，包括以下步骤，以尿素、硫脲为前聚体，在水的存在下，煅烧制备蜂窝状同型异质结氮化碳复合材料。
2.根据权利要求1所述蜂窝状同型异质结氮化碳复合材料的制备方法，其特征在于，将尿素、硫脲和水混合反应后，再煅烧制备蜂窝状同型异质结氮化碳复合材料；所述煅烧在空气中进行；所述煅烧包括首次煅烧与再次煅烧。
3.根据权利要求2所述蜂窝状同型异质结氮化碳复合材料的制备方法，其特征在于，所述反应为室温反应20～45分钟；所述首次煅烧时，升温速率为10℃/min，煅烧的时间为1h，煅烧的温度为400℃；所述再次煅烧时，升温速率为10℃/min，煅烧的时间为1h，煅烧的温度为450℃。
4.根据权利要求1所述蜂窝状同型异质结氮化碳复合材料的制备方法，其特征在于，尿素、硫脲的质量和与水的质量比为5∶6～7；所述硫脲的质量为尿素、硫脲质量和的1%～10%。
5.一种废气处理方法，其特征在于，包括以下步骤，以尿素、硫脲为前聚体，在水的存在下，煅烧制备蜂窝状同型异质结氮化碳复合材料；然后将待处理废气通过蜂窝状同型异质结氮化碳复合材料，完成废气处理。
6.根据权利要求5所述废气处理方法，其特征在于，将尿素、硫脲和水混合反应后，再煅烧制备蜂窝状同型异质结氮化碳复合材料；所述煅烧在空气中进行；所述煅烧包括首次煅烧与再次煅烧；废气处理在光照下进行。
7.根据权利要求6所述废气处理方法，其特征在于，所述反应为室温反应20～45分钟；所述首次煅烧时，升温速率为10℃/min，煅烧的时间为1h，煅烧的温度为400℃；所述再次煅烧时，升温速率为10℃/min，煅烧的时间为1h，煅烧的温度为450℃；所述光照为300W氙灯光照。
8.根据权利要求5所述废气处理方法，其特征在于，尿素、硫脲的质量和与水的质量比为5∶6～7；所述硫脲的质量为尿素、硫脲质量和的1%～10%。
9.根据权利要求1所述蜂窝状同型异质结氮化碳复合材料的制备方法制备的蜂窝状同型异质结氮化碳复合材料。
10.权利要求9所述蜂窝状同型异质结氮化碳复合材料在催化处理废气中的应用；权利要求9所述蜂窝状同型异质结氮化碳复合材料在制备废气处理复合材料中的应用。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111999358A (zh) * 2020-08-17 2020-11-27 合肥工业大学 类石墨相氮化碳纳米材料作为电化学修饰电极材料在检测甲基汞中的应用
CN114345394A (zh) * 2022-01-27 2022-04-15 中原工学院 一种可见光响应氮化硼/氮化碳复合光催化剂及其制备方法和应用

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108745404B (zh) * 2018-06-14 2020-12-04 苏州大学 基于黑磷/金属有机框架修饰的氮化碳膜复合材料及其制备方法与在废气处理中的应用
CN110813357B (zh) * 2019-11-15 2023-02-28 南宁师范大学 高效双孔g-C3N4光催化剂的制备方法
CN111298825A (zh) * 2020-04-21 2020-06-19 郑州大学 一种氮化碳-二硫化钼复合材料及制备方法
CN111545235A (zh) * 2020-04-23 2020-08-18 宁德师范学院 一种2D/2Dg-C3N4CoAl-LDH产氢异质结材料及其制备方法与应用
CN111732084B (zh) * 2020-06-23 2021-11-09 济南大学 利用二维氮化碳模板生长制备多孔氮化铝超级电容器材料的方法
CN111729683B (zh) * 2020-07-14 2023-01-31 广东石油化工学院 氧掺杂类石墨相氮化碳光催化剂及其制备方法和应用
CN112264063A (zh) * 2020-09-27 2021-01-26 广州环投设计研究院有限公司 一种垃圾电厂烟气脱汞光催化剂的制备方法
CN112570000B (zh) * 2021-01-27 2022-09-23 河南工程学院 一种MoS2/ND/g-C3N4复合材料及制备方法
CN113735074B (zh) * 2021-08-31 2024-05-10 大韩道恩高分子材料(上海)有限公司 一种可生物降解材料用无机成核剂的制备方法
CN113856767B (zh) * 2021-09-26 2023-11-17 武汉理工大学 S型异质结的Bismuthene/CsPbBr3量子点复合材料及其制备方法和应用
CN114100658B (zh) * 2021-11-23 2023-09-12 湖南农业大学 氮化碳/三氧化钨/硫掺杂氯氧化锑双z型复合光催化剂及其制备方法和应用
CN114678504A (zh) * 2022-03-30 2022-06-28 湘潭大学 一种锂硫电池正极材料及其制备方法、锂硫电池
CN114797910B (zh) * 2022-05-26 2023-05-12 青岛大学 一种二维超薄结构的异质结纳米片的制备方法及应用
CN115180679B (zh) * 2022-07-10 2024-04-19 湖南大学 利用硫掺杂氮化碳改性氧化钼复合光催化材料灭活水体中细菌的方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105498821A (zh) * 2015-12-17 2016-04-20 苏州大学 一种用于催化降解氮氧化物的复合材料及其制备方法和用途
CN106391085A (zh) * 2016-09-22 2017-02-15 江苏大学 一种二硫化镍空心微球/氮化碳复合光催化剂的制备方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106944119B (zh) * 2017-03-22 2020-01-14 北京师范大学 一种氮化碳负载单原子金属催化材料的制备方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105498821A (zh) * 2015-12-17 2016-04-20 苏州大学 一种用于催化降解氮氧化物的复合材料及其制备方法和用途
CN106391085A (zh) * 2016-09-22 2017-02-15 江苏大学 一种二硫化镍空心微球/氮化碳复合光催化剂的制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
FAN DONG 等: "In Situ Construction of g-C3N4/g-C3N4 Metal-Free Heterojunction for Enhanced Visible-Light Photocatalysis", 《ACS APPLIED MATERIALS & INTERFACES》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111999358A (zh) * 2020-08-17 2020-11-27 合肥工业大学 类石墨相氮化碳纳米材料作为电化学修饰电极材料在检测甲基汞中的应用
CN114345394A (zh) * 2022-01-27 2022-04-15 中原工学院 一种可见光响应氮化硼/氮化碳复合光催化剂及其制备方法和应用
CN114345394B (zh) * 2022-01-27 2023-07-14 中原工学院 一种可见光响应氮化硼/氮化碳复合光催化剂及其制备方法和应用

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