开放式氮缺陷氮化碳中空微球用于增强光解水制氢和<strong>CO<sub>2</sub></strong> 还原

doi:10.11901/1005.3093.2020.495

材料研究学报

2022, Vol. 36

Issue (2): 152-160 DOI: 10.11901/1005.3093.2020.495

研究论文

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开放式氮缺陷氮化碳中空微球用于增强光解水制氢和CO₂ 还原

欧阳杰, 李雪, 祝玉鑫, 曹福, 崔言娟(

)

江苏科技大学环境化学工程学院镇江 212100

Enhanced Photocatalytic Hydrogen Production and Carbon Dioxide Reduction

OUYANG Jie, LI Xue, ZHU Yuxin, CAO Fu, CUI Yanjuan(

)

School of Environmental and Chemical Engineering, Jiangsu University of Science and Technology, Zhenjiang 212100, China

引用本文:

欧阳杰, 李雪, 祝玉鑫, 曹福, 崔言娟. 开放式氮缺陷氮化碳中空微球用于增强光解水制氢和CO₂ 还原[J]. 材料研究学报, 2022, 36(2): 152-160.
Jie OUYANG, Xue LI, Yuxin ZHU, Fu CAO, Yanjuan CUI. Enhanced Photocatalytic Hydrogen Production and Carbon Dioxide Reduction[J]. Chinese Journal of Materials Research, 2022, 36(2): 152-160.

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摘要:

使用介孔SiO₂球为模板、二氰二氨为原料，用直接热聚合-刻蚀法制备开放式氮缺陷氮化碳中空微球OHCNs产物。这种OHCNS产物具有开放式半球结构、较大的比表面积和孔隙率，尺寸大小复制SiO₂模板。局部“热刻蚀”生成开放式中空微球，并使产物产生大量氮缺陷和丰富的表面氨基。测试结果表明，适量的合成原料有利于优化产物的物理化学性能，表现出增强的瞬时光电响应和加速的光生载流子传输性能。同时，N缺陷拓宽了产物的可见光吸收范围。二氰二胺与SO₂模板质量比为1∶1的产物OHCNS-1，具有显著增强的光催化活性。在可见光下照射下OHCNS-1的光解水制氢和光催化还原CO₂生产的CO分别达到了45.9和47.3 μmol·h^-1，分别是非SO₂模板法合成产物的4.4倍和4.0倍。同时，在模拟废水环境OHCNs-1能保持稳定的光解水制氢活性，且能降解部分环境污染物。

关键词 ：无机非金属材料, 氮化碳, 硬模板法, 光解水, 开放式中空微球

Abstract：

Open hollow microsphere carbon nitride with nitrogen defects (OHCNs) were synthesized by means of direct thermal polymerization-etching method with mesoporous SiO₂ spheres as templates and dicyandiamide as raw materials. The resulted OHCNs present a hemispherical structure with large specific surface area and open porosity. The size of OHCNs can be replicated from the SiO₂ templates. The presence of the local 'thermal etching' during the process favors the formation of open hollow microspheres, at the same time, makes the generation of lots of nitrogen defects and abundant surface amino groups. The appropriate proportion of raw materials is beneficial to optimizing the physical-chemical properties of the products, such as the enhanced transient photoelectric response and accelerated photo-generated carrier transport. Furthermore, the existence of nitrogen defects broadens the visible light absorption range of the products. OHCNs-1 (the mass ratio of dicyandiamide to SiO₂ template is 1∶1) demonstrates significantly enhanced photocatalytic activity. Under visible light irradiation the photocatalytic water splitting for hydrogen production and photocatalytic reduction of CO₂ to produce CO on OHCNs-1 reach 45.9 and 47.3 μmol·h^-1, which is 4.4 times and 4.0 times of the products prepared without SiO₂ template, respectively. Furthermore, OHCNs-1 can maintain stable hydrogen production activity in simulated sewage environment, whilst degrade part of the environmental pollutants simultaneously.

Key words： inorganic nonmetallic materials carbon nitride hard template method photolysis water open hollow microsphere

收稿日期: 2020-11-20

ZTFLH:

O649

基金资助:江苏省研究生科研与实践创新计划(KYCX20-3152)

作者简介: 欧阳杰，男，1996年生，硕士生

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https://www.cjmr.org/CN/10.11901/1005.3093.2020.495 或 https://www.cjmr.org/CN/Y2022/V36/I2/152

图1 合成催化剂OHCNS的示意图

图2 催化剂的XRD谱

图3 CN和OHCNs-1的SEM照片、mSiO2模板以及OHCNs-1和OHCNs-3的TEM照片

图4 催化剂的N2吸附-脱附等温线和孔径分布

图5 CN和PFCN-1的XPS谱

表1 CN和OHCNs-1中C和N元素的含量

图6 催化剂的紫外-可见吸收光谱和禁带宽度值

图7 催化剂的稳态PL图谱、电化学阻抗图谱和光电流图谱

图8 催化剂的光解水制氢性能、循环制氢稳定性以及光催化还原CO2性能

表2 用硬模板法合成的多孔氮化碳及其光解水制氢性能

图9 催化剂在模拟海水、抗生素溶液和染料溶液中的光催化产氢率

表3 OHCNs-1在模拟废水环境下的产氢量及对污染物的降解率

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