CoN/g-C3N4 0D/2D复合结构及其光催化制氢性能研究

doi:10.15541/jim20210806

无机材料学报 ›› 2022, Vol. 37 ›› Issue (9): 1001-1008.DOI: 10.15541/jim20210806

CoN/g-C₃N₄ 0D/2D复合结构及其光催化制氢性能研究

陈瀚翔¹(), 周敏¹, 莫曌², 宜坚坚³, 李华明², 许晖²()

1.江苏大学环境与安全工程学院, 镇江 212013
2.江苏大学能源研究院, 镇江 212013
3.扬州大学环境科学与工程学院, 扬州 225127

收稿日期:2021-12-30 修回日期:2022-04-27 出版日期:2022-09-20 网络出版日期:2022-05-09
通讯作者: 许晖, 教授. E-mail: xh@ujs.edu.cn
作者简介:陈瀚翔(1993-), 男, 博士研究生. E-mail: 2350505633@qq.com
基金资助:
国家自然科学基金(22108110);江苏省杰出青年科学家基金(BK20190045);江苏省研究生科研创新计划(KYCX21_3391);中国博士后基金(2021M691305);江苏省博士后基金(2021K079A)

0D/2D CoN/g-C₃N₄ Composites: Structure and Photocatalytic Performance for Hydrogen Production

CHEN Hanxiang¹(), ZHOU Min¹, MO Zhao², YI Jianjian³, LI Huaming², XU Hui²()

1. School of the Environment and Safety Engineering, Jiangsu University, Zhenjiang 212013, China
2. School of the Institute for Energy Research, Jiangsu University, Zhenjiang 212013, China
3. College of Environmental Science and Engineering, Yangzhou University, Yangzhou 225127, China

Received:2021-12-30 Revised:2022-04-27 Published:2022-09-20 Online:2022-05-09
Contact: XU Hui, professor. E-mail: xh@ujs.edu.cn
About author:CHEN Hanxiang (1993-), male, PhD candidate. E-mail: 2350505633@qq.com
Supported by:
National Natural Science Foundation of China(22108110);Jiangsu Funds for Distinguished Young Scientists(BK20190045);Postgraduate Research & Practice Innovation Program of Jiangsu Province(KYCX21_3391);China Postdoctoral Science Foundation(2021M691305);Jiangsu Province Postdoctoral Science Foundation(2021K079A)

摘要/Abstract

摘要：

在光催化产氢反应中引入助催化剂可促进光生电子快速转移, 是提高光催化活性的有效方法。而目前, 高效助催化剂主要仍然是贵金属, 其高昂的价格极大限制了实际应用。本研究探讨了构筑非贵金属助催化剂CoN与g-C₃N₄ 0D/2D紧密界面对光催化制氢性能的影响。负载非贵金属助催化剂CoN可以有效提高2D g-C₃N₄的光催化制氢活性, 负载量对其活性也有影响。构筑的0D/2D紧密界面有利于光生电子快速传输。两者的共同作用使得10% CoN/2D g-C₃N₄复合物光催化制氢效率达到403.6 μmol·g^-1·h^-1, 是2D g-C₃N₄单体的20倍。在CoN/2D g-C₃N₄复合材料中, 负载CoN作为析氢助催化剂可以显著促进电荷转移过程, 从而大幅提高光催化析氢活性。

关键词: 非贵金属, CoN, 助催化剂, 光催化, 产氢

Abstract:

In the photocatalytic hydrogen production reaction, the introduction of cocatalyst to promote the rapid transfer of photogenerated electrons is an effective way to improve the photocatalytic activity. At present, the most efficient cocatalysts are mainly precious metals, greatly restricting the use of this method. In this study, influence of the close interface between non-noble metal cocatalyst CoN and g-C₃N₄ 0D/2D on the performance of photocatalytic hydrogen production was explored. The results showed that the support of non-noble metal cocatalyst CoN can effectively improve the photocatalytic hydrogen production of 2D g-C₃N₄, and the support amount also has an positive effect on its activity. The compact 0D/2D interface is favorable for the rapid transmission of photogenerated electrons. Photocatalytic efficiency of 10% CoN/2D g-C₃N₄ composite reached 403.6 μmol·g^-1·h^-1, 20 times of that of 2D g-C₃N₄ monomer, which was comparable to that of noble metal cocatalyst. As a hydrogen evolution cocatalyst, loaded CoN can significantly promote the charge transfer process, thus greatly improving the activity of photocatalytic hydrogen evolution.

Key words: non-noble metal, CoN, cocatalyst, photocatalysis, hydrogen production

中图分类号:

TQ174

陈瀚翔, 周敏, 莫曌, 宜坚坚, 李华明, 许晖. CoN/g-C₃N₄ 0D/2D复合结构及其光催化制氢性能研究[J]. 无机材料学报, 2022, 37(9): 1001-1008.

CHEN Hanxiang, ZHOU Min, MO Zhao, YI Jianjian, LI Huaming, XU Hui. 0D/2D CoN/g-C₃N₄ Composites: Structure and Photocatalytic Performance for Hydrogen Production[J]. Journal of Inorganic Materials, 2022, 37(9): 1001-1008.

图/表 8

图1 (a)2D g-C3N4, CoN/2D g-C3N4复合催化剂和CoN的XRD图谱, (b)2D g-C3N4和CoN/2D g-C3N4复合催化剂的FT-IR谱图, (c)2D g-C3N4, CoN/2D g-C3N4复合催化剂和CoN的紫外-可见光漫反射吸收光谱图, (d)2D g-C3N4和10% CoN/2D g-C3N4的氮气吸附-脱附等温线

Fig. 1 (a) XRD patterns of 2D g-C3N4, and 10% CoN/2D g-C3N4 samples, and CoN, (b) FT-IR spectra of 2D g-C3N4, and CoN/2D g-C3N4 samples, (c) UV-Vis diffuse reflectance spectra of 2D g-C3N4, and CoN/2D g-C3N4 samples, and CoN, (d) N2 adsorption-desorption isomers of 2D g-C3N4 and 10% CoN/2D g-C3N4 Colorful figures are available on website

图2 (a)2D g-C3N4, (b)CoN和(c)10% CoN/2D g-C3N4的SEM照片, 10% CoN/2D g-C3N4的(d, e)TEM照片和(f)高倍TEM照片

Fig. 2 SEM images of (a) 2D g-C3N4, (b) CoN and (c) 10% CoN/2D g-C3N4, and (d, e) TEM images and (f) HR-TEM image of 10% CoN/2D g-C3N4

图3 (a)2D g-C3N4和CoN/2D g-C3N4复合催化剂的光催化制氢速率测试, (b)10% CoN/2D g-C3N4复合催化剂的制氢稳定性测试(10% TEOA作为牺牲剂, 10 mg催化剂, 氙灯作为光源, λ>400 nm)

Fig. 3 (a) Photocatalytic hydrogen evolution with photocatalysts under visible light irradiation, and (b) hydrogen evolution stability test of 10% CoN/2D g-C3N4 under visible light irradiation (10% TEOA as sacrificial agent, 10 mg catalyst usage, xenon lamp as light source, λ>400 nm) Colorful figures are available on website

图4 2D g-C3N4和10% CoN/2D g-C3N4的(a)稳态荧光光谱图(激发波长为384 nm), (b)光电流响应图, (c)电化学阻抗谱图和(d)2D g-C3N4和10% CoN/2D g-C3N4的莫特肖特基曲线

Fig. 4 (a) Steady-state PL spectra excited at 384 nm, (b) photocurrent-time dependence, (c) electrochemical impedance spectra (EIS) of 2D g-C3N4 and 10% CoN/2D g-C3N4, and (d) Motschottky (MS) curves of 2D g-C3N4 and 10% CoN/2D g-C3N4 Colorful figures are available on website

图5 2D g-C3N4和10% CoN/2D g-C3N4在(a, b)可见光照射和(c, d)暗处的(a, c)超氧自由基和(b, d)羟基自由基ESR谱图

Fig. 5 ESR spectra of (a, c) DMPO-·O2- and (b, d) ·OH O2- and (b, d) ·OH (a, b) under visible-light irradiation and (c, d) without light irradiation of the 2D g-C3N4 and 10% CoN/2D g-C3N4 Colorful figures are available on website

表S1 不同类型g-C3N4的策略及其析氢性能

Table S1 Different types of strategies for g-C3N4 and their hydrogen evolution performance

Photocatalyst	Type of strategy	HER performance /(μmol·g^-1·h^-1)	Ref.
CoN/2D g-C₃N₄	Nanosheets Nanostructure	403.6	This work
Melem Oligomer	Functional group	90	[6]
MoS₂/g-C₃N₄	Cocatalyst	7.5	[7]
BP/g-C₃N₄	Cocatalyst	43	[8]
MoSe₂/g-C₃N₄	Cocatalyst	7.5	[9]
p-n junction of g-C₃N₄	Type II	140	[10]
g-C₃N₄-NaI-WO₃	Z-scheme	36	[11]
W₁₈O₄₉/g-C₃N₄	Plasmonic effect	4.8	[12]

图S1 (a)10% CoN/2D g-C3N4的SEM照片, (b~d)C、N、Co的EDS元素分布图

Fig. S1 (a) SEM image of 10% CoN/2D g-C3N4, (b-d) EDS elemental mappings from C, N and Co corresponding to 10% CoN/2D g-C3N4

图S2 (a)10% CoN/2D g-C3N4和2D g-C3N4的XPS全谱图, (b)CoN和10% CoN/2D g-C3N4的Co2p高分辨XPS图谱, 2D g-C3N4和10% CoN/2D g-C3N4的(c)C1s和(d)N1s高分辨XPS图谱

Fig. S2 (a) XPS survey spectra of 10% CoN/2D g-C3N4 and 2D g-C3N4, (b) Co2p XPS spectra of CoN and 10% CoN/2D g-C3N4, (c) C1s and (d) N1s XPS spectra of 2D g-C3N4 and 10% CoN/2D g-C3N4

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CoN/g-C₃N₄ 0D/2D复合结构及其光催化制氢性能研究

0D/2D CoN/g-C₃N₄ Composites: Structure and Photocatalytic Performance for Hydrogen Production

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