一种简单前驱体预处理策略制备多孔氮化碳和负载型多孔氮化碳及其高效可见光光催化活性

引用本文: 曾振兴, 李可心, 魏凯, 戴玉华, 颜流水, 郭会琴, 罗旭彪. 一种简单前驱体预处理策略制备多孔氮化碳和负载型多孔氮化碳及其高效可见光光催化活性[J]. 催化学报, 2017, 38(3): 498-508. doi: 10.1016/S1872-2067(17)62763-3 shu

Citation: Zhenxing Zeng, Kexin Li, Kai Wei, Yuhua Dai, Liushui Yan, Huiqin Guo, Xubiao Luo. Fabrication of porous g-C₃N₄ and supported porous g-C₃N₄ by a simple precursor pretreatment strategy and their efficient visible-light photocatalytic activity[J]. Chinese Journal of Catalysis, 2017, 38(3): 498-508. doi: 10.1016/S1872-2067(17)62763-3 shu

一种简单前驱体预处理策略制备多孔氮化碳和负载型多孔氮化碳及其高效可见光光催化活性

南昌航空大学, 江西省持久性污染物控制与资源循环利用重点实验室, 江西南昌 330063
基金项目:
国家自然科学基金（51568049，51208248，51468043，21366024）；国家优秀青年科学基金（51422807）；江西省自然科学基金（20161BAB206118，20114BAB213015）；江西省教育厅科技项目（GJJ14515，GJJ12456）.

摘要: 作为一种非金属半导体光催化剂，石墨相氮化碳（g-C₃N₄）已广泛应用于水中有机污染物去除、劈裂水产氢、二氧化碳还原制碳氢化合物燃料以及选择性氧化有机合成等许多光催化领域.然而，聚集态层状结构和粉末物理状态严重限制了g-C₃N₄在非均相光催化反应中的实际应用.一方面，g-C₃N₄的聚集态层状结构限制了光生载流子的表面迁移并增加了光催化反应的传质阻力.另一方面，由于附加的固-液分离步骤，粉体g-C₃N₄不便于实际应用.因此，为解决g-C₃N₄的上述缺点，一些研究已经进行并集中于g-C₃N₄的形貌控制合成及负载.
构建多孔微观结构是合成具有优异光催化活性g-C₃N₄的有效途径之一.本文研究表明，盐酸或乙二醇预处理的三聚氰胺均可用作制备多孔g-C₃N₄的前驱体.有趣的是，由于在多孔g-C₃N₄制备体系中不同制孔单元的共存，与通过盐酸或乙二醇单独预处理的三聚氰胺制备的多孔g-C₃N₄相比，通过二者共同预处理的三聚氰胺制备的多孔g-C₃N₄具有更丰富的多孔微观结构.
与制备负载型二氧化钛不同，由于在制备g-C₃N₄过程中缺少溶胶-凝胶步骤，因此负载型g-C₃N₄较难制备.而且，对于氟-锡氧化物（FTO）基底负载的g-C₃N₄，在实际应用中存在一些不足.首先，FTO基底的片状物理结构不利于反应底物的扩散.其次，FTO基底的吸光效应会导致光能损失，因此g-C₃N₄只能在FTO基底的单面负载.最后，在g-C₃N₄和FTO基底之间无化学作用，因此在光催化反应过程中不可避免造成g-C₃N₄的损失.
因此，以盐酸/乙二醇共同预处理的三聚氰胺作原料，氢氟酸/3-氨基丙基三甲氧基硅烷共同预处理的石英棒作基底，首次制备了多孔g-C₃N₄和负载型多孔g-C₃N₄.丰富的多孔微观结构使得所制多孔g-C₃N₄具有优异的光催化活性；且由于多孔g-C₃N₄与石英棒基底间存在化学作用，因而具有相当高的稳定性.另外，由于在构建石英棒反应器之后不影响光生载流子的表面迁移和目标有机污染物的扩散，因此负载型多孔g-C₃N₄的光催化活性与粉体多孔g-C₃N₄相似.
所制备多孔g-C₃N₄和负载型多孔g-C₃N₄的光催化活性通过在可见光条件下单组份有机废水的处理进行初步评价.在有机污染物降解同时产氢系统中，由于水和有机污染物之间的氧化还原反应难于进行，因此与传统的光催化降解和产氢系统相比，所制多孔g-C₃N₄的氢气产率和降解效率均显著降低；然而，在有机污染物降解同时产氢系统中，随着该材料光催化活性的提高，氢气产率和降解效率同时提高.这是因为光催化剂电子传递能力的提高促进了有机污染物和水之间的氧化还原反应.

关键词:

English

Fabrication of porous g-C₃N₄ and supported porous g-C₃N₄ by a simple precursor pretreatment strategy and their efficient visible-light photocatalytic activity

Key Laboratory of Jiangxi Province for Persistent Pollutants Control and Resources Recycle, NanChang Hangkong University, NanChang 330063, JiangXi, China
Received Date: 28 October 2016
Revised Date: 31 December 2016
Fund Project:
This work was supported by the National Natural Science Foundation of China (51568049, 51208248, 51468043, 21366024), the National Science Fund for Excellent Young Scholars (51422807), the Natural Science Foundation of Jiangxi Province, China (20161BAB206118, 20114BAB213015), and the Natural Science Foundation of Jiangxi Provincial Department of Education, China (GJJ14515, GJJ12456).

Abstract: Porous g-C₃N₄ and supported porous g-C₃N₄ were fabricated for the first time by a simple strategy using pretreated melamine as a raw material and pretreated quartz rod as a substrate. The formation of a richly porous microstructure can be attributed to the co-existence of different pore-fabricating units in the preparation system for porous g-C₃N₄. The richly porous microstructure endowed the as-prepared porous g-C₃N₄ with an excellent photocatalytic activity. The as-prepared supported porous g-C₃N₄ exhibited considerable stability because of the existence of chemical interaction between porous g-C₃N₄ and the quartz rod substrate. The photocatalytic activity of the supported porous g-C₃N₄ was competitive with that of porous g-C₃N₄ in powder form because neither the surface migration of photogenerated electrons nor the diffusion of the target organic pollutant were affected by the construction of the quartz rod reactor. The photocatalytic activity of the as-prepared porous g-C₃N₄ and supported porous g-C₃N₄ was preliminarily evaluated by the treatment of single-component organic wastewater under visible-light irradiation. Subsequently, the as-prepared porous g-C₃N₄ was further applied in conventional hydrogen evolution and a new system for simultaneous hydrogen evolution with organic-pollutant degradation. The hydrogen yield and degradation efficiency both increased with increasing photocatalytic activity of the as-prepared materials in the system for simultaneous hydrogen evolution with organic-pollutant degradation.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

一种简单前驱体预处理策略制备多孔氮化碳和负载型多孔氮化碳及其高效可见光光催化活性

English

Fabrication of porous g-C₃N₄ and supported porous g-C₃N₄ by a simple precursor pretreatment strategy and their efficient visible-light photocatalytic activity

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

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中国化学会秘书处

一种简单前驱体预处理策略制备多孔氮化碳和负载型多孔氮化碳及其高效可见光光催化活性

English

Fabrication of porous g-C3N4 and supported porous g-C3N4 by a simple precursor pretreatment strategy and their efficient visible-light photocatalytic activity

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

Fabrication of porous g-C₃N₄ and supported porous g-C₃N₄ by a simple precursor pretreatment strategy and their efficient visible-light photocatalytic activity

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs