宽光谱响应范围的氮化碳纳米片的制备及其光催化产氢性能研究

郭桂珍; 姚陈忠; 孙友谊; 辛德华; 吕宝华

doi:10.19906/j.cnki.JFCT.2023065

宽光谱响应范围的氮化碳纳米片的制备及其光催化产氢性能研究

doi: 10.19906/j.cnki.JFCT.2023065

1.
运城学院应用化学系, 山西运城 044000
2.
中北大学材料科学与工程学院, 山西太原 030051

基金项目: 山西省教育厅项目 (2020L0566) 和运城学院博士科研启动项目 (YQ2022008) 资助

详细信息

通讯作者:
E-mail address: guoguizhen1986@163.com

中图分类号: TB34
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出版历程
- 收稿日期: 2023-06-20
- 修回日期: 2023-08-01
- 录用日期: 2023-08-14
- 网络出版日期: 2023-09-18

Preparation of carbon nitride nanosheets with wide spectral response range and photocatalytic hydrogen production properties

GUO Guizhen^{1
, ,},
YAO Chenzhong^1
,,
SUN Youyi^2
,,
XIN Dehua^1
,,
LÜ Baohua^1
,

1.
Department of Applied Chemistry, Yuncheng University, Yuncheng 044000 Shanxi, China
2.
School of Materials Science and Engineering, North University of China, Taiyuan 030051 Shanxi, China

Funds: The project was supported by the General Program of Education Department of Shanxi Province (2020L0566) and the Doctoral research start project (YQ2022008).

摘要

摘要: 以块体氮化碳 (CN) 为前驱物，采用氧化剥离制备氧化型氮化碳纳米片 (o-CN NSs)，然后将o-CN NSs还原制得了还原型氮化碳纳米片 (r-CN NSs)。o-CN NSs和r-CN NSs厚度均约2 nm，且都保留了纯CN的庚嗪环骨架结构；相比于o-CN NSs，r-CN NSs具有更小的禁带宽度 (2.62 eV)、更宽的光响应范围 (485 nm) 和更高的产氢速率（(1700 μmol/(g·h)）；r-CN NSs的光催化产氢速率是CN的8.5倍、o-CN NSs的2.1倍。经过20 h的循环测试，r-CN NSs的光催化产氢速率没有衰减，具备良好的光催化稳定性。实验和理论分析表明，r-CN NSs是边缘基团为氨基的纳米片结构，氨基的引入改善了纳米片的结晶性，提高了电子和空穴的分离效率、拓宽了纳米片的光响应范围，从而导致光催化性能增强。
- 氮化碳 /
- 纳米片 /
- 光催化 /
- 光响应范围 /
- 产氢
Abstract: Oxidized carbon nitride nanosheets (o-CN NSs) was prepared by oxidative stripping with bulk carbon nitride (CN) as the precursor, and then reduced carbon nitride nanosheet (r-CN NSs) was prepared via reduced o-CN NSs. The thickness of o-CN NSs and r-CN NSs are both about 2 nm and retain the heptazine ring skeleton structure of pure CN. Compared with o-CN NSs, r-CN NSs has a smaller band gap (2.62 eV), wider photoresponse range (485 nm) and higher H₂ evolution rates (1700 μmol/g/h). The H₂ evolution rates of r-CN NSs is 8.5 times of CN and 2.1 times of o-CN NSs. After a 20 h cycle test, the photocatalytic hydrogen production efficiency of r-CN NSs has no attenuation, has well photocatalytic stability. Experimental and theoretical analysis revealed that r-CN NSs is nanosheet structure with amino group at the edge. The introduction of amino group improves the crystallinity of nanosheets, improve the separation efficiency of electrons and holes, broaden the photoresponse range of nanosheets, thus resulting in the enhanced photocatalytic performance.
- carbon nitride /
- nanosheet structure /
- photocatalysis /
- photoresponse range /
- hydrogen evolution

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图 1 (a) CN的SEM照片；(b) 块状CN的局部放大SEM照片；(c) o-CN NSs和 (d) r-CN NSs的SEM照片；(e) o-CN NSs和 (f) r-CN NSs的EDS谱图

Figure 1 (a) SEM images of CN; (b) Amagnified SEM image of CN; SEM images of (c) o-CN NSs and (d) r-CN NSs; EDS spectras of (e) o-CN NSs and (f) r-CN NSs

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图 2 (a) o-CN NSs和 (b) r-CN NSs的TEM照片；(c) o-CN NSs 和 (d) r-CN NSs的AFM照片

Figure 2 TEM images of (a) o-CN NSs and (b) r-CN NSs. AFM images of (c) o-CN NSs and (d) r-CN NSs (Inset: height plot along the red line)

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图 3 CN、o-CN NSs及r-CN NSs的 (a) XRD谱图和 (b) FT-IR光谱谱图

Figure 3 (a) XRD patterns and (b) FT-IR spectra of CN, o-CN NSs and r-CN NSs

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图 4 CN、o-CN NSs和r-CN NSs的结构示意图

Figure 4 Schematic diagram of the structures of CN, o-CN NSs and r-CN NSs.

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图 5 (a) 光催化产氢时间曲线图；(b) 光催化产氢速率图；(c) r-CN NSs光催化产氢稳定性测试；(d) r-CN NSs的光催化产氢在有光和无光环境中测试

Figure 5 (a) Time course of photocatalytic H₂ evolution; (b) Photocatalytic H₂ evolution rates of obtained samples; (c) Photostability test of r-CN NSs for photocatalytic H₂ evolution; (d) Photocatalytic H₂ evolution of r-CN NSs was tested in light and without light

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图 6 CN、o-CN NSs和r-CN NSs的 (a) UV-Vis光谱、(b) 能带曲线、(c) 光电流曲线和 (d) 阻抗谱.

Figure 6 (a) UV-Vis absorption spectra, (b) Band gap curve, (c) Photocurrent measurements and (d) EIS spectra of CN, o-CN NSs and r-CN NSs.

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表 1 单一氮化碳纳米片制备方法和性能对比

Table 1 Comparison of preparation methods and properties of naked carbon nitride nanosheets

S.No.	Exfloiated strategies and preparation methods	Thickness (nm)	Light source (nm)	Band gap (eV)	H₂ evolution rates (μmol/g/h)	Ref.	Year published
1.	Strong acid oxidation etching, then reduction	2	485	2.62	1700	this work	----
2.	Physical grinding + Thermal oxidation etching	6	<460	2.90	1254.75	[15]	2022
3.	Thermal oxidation etching	−	430	2.70	495	[16]	2021
4.	Chemical exfoliation + Thermal oxidation etching	0.8 ~ 1.4	435	3.10	115.5	[18]	2019
5.	High-temperature calcination in ammonia atmosphere	−	430	2.51	<10	[21]	2022
6.	Ultrasound-assisted method	−	450	2.86	20	[31]	2023
7.	Thermal oxidation etching	<0.8	440	2.67	241.2	[32]	2021

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