高结晶氮化碳空心球的制备及其增强光催化产氢活性

doi:10.1016/S1872-2067(20)63684-1

催化学报 ›› 2021, Vol. 42 ›› Issue (4): 627-636.DOI: 10.1016/S1872-2067(20)63684-1

高结晶氮化碳空心球的制备及其增强光催化产氢活性

李阳^a^,^b, 张岱南^a, 范佳杰^c, 向全军^a^,^*()

^a电子科技大学电子科学与工程学院, 电子薄膜与集成器件国家重点实验室, 四川成都610054
^b华中农业大学资源与环境学院, 湖北武汉430070
^c郑州大学材料科学与工程学院, 河南郑州450002

收稿日期:2020-05-26 接受日期:2020-07-11 出版日期:2021-04-18 发布日期:2021-01-22
通讯作者: 向全军
基金资助:
国家自然科学基金(51672099);国家自然科学基金(21403079);四川省科技计划(2019JDRC0027);中央高校基金(2017-QR-25)

Highly crystalline carbon nitride hollow spheres with enhanced photocatalytic performance

Yang Li^a^,^b, Dainan Zhang^a, Jiajie Fan^c, Quanjun Xiang^a^,^*()

^aState Key Laboratory of Electronic Thin Film and Integrated Devices, School of Electronic Science and Engineering, University of Electronic Science and Technology of China, Chengdu 610054, Sichuan, China
^bCollege of Resources and Environment, Huazhong Agricultural University, Wuhan 430070, Hubei, China
^cSchool of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450002, Henan, China

Received:2020-05-26 Accepted:2020-07-11 Online:2021-04-18 Published:2021-01-22
Contact: Quanjun Xiang
About author:^*Tel/Fax: +86-28-83207063; E-mail: xiangqj@uestc.edu.cn
Supported by:
Natural Science Foundation of China(51672099);Natural Science Foundation of China(21403079);Sichuan Science and Technology Program(2019JDRC0027);Fundamental Research Funds for the Central Universities(2017-QR-25)

摘要/Abstract

摘要：

石墨烯型氮化碳(g-C₃N₄)已经成为解决环境污染和能源危机问题的较为理想的光催化剂, 但由于其较低的比表面积和较高的光生载流子重组效率而表现出较弱的光催化活性. 因此, 研究者们已经提出了许多策略, 例如纳米结构设计, 杂原子掺杂和增加结晶度, 用来克服氮化碳的这些缺点, 从而提高其光催化性能. 其中, 引起了较多关注的是增加g-C₃N₄的结晶度, 因为晶化g-C₃N₄(CCN)的内层堆积密度高, 外层结构缺陷少, 可以提供更快的光生载流子迁移效率, 从而增加参与光催化反应的光生电子和空穴. 即便如此, 通过常规方法制备的晶化g-C₃N₄依然显示出不规则的形貌和较低的比表面积. 基于此, 本文以氰尿酸-三聚氰胺(CM)超分子自组装混合物作为前驱体, 通过熔盐法成功地制备了高结晶度的g-C₃N₄空心球(CCNHS). 采用XRD、FTIR、¹³C固相CP-MAS NMR、XPS和时间分辨PL谱对CCNHS样品的基本性质进行了表征, 并通过SEM、HRTEM、氮吸附-脱附和紫外-可见DRS光谱对CCNHS样品的形貌结构进行了表征. 结果表明, CCNHS样品呈现出由纳米棒组成的非常规则的空心球结构, 因而表现出比传统CCN样品更大的比表面积以及更强的光利用效率. CCNHS样品XRD谱出现晶化氮化碳的特征峰; 其HRTEM照片出现了对应晶化氮化碳的0.33 nm晶格条纹; FFT衍射斑点的出现以及光吸收能力的增强进一步证明了CCNHS样品结晶度的提高. XPS谱元素分析以及EPR谱结果表明, CCNHS样品中还存在有利于提高光生电子转移的氮空位. 光电流、阻抗谱以及与三嗪晶化氮化碳的对比结果证明, CCNHS样品中存在内在电场. 同时, 采用具有一定毒性的双酚A增塑剂替代了从粮食中提取出来的传统醇类牺牲剂, 既保证了对有毒污染物的降解, 也减少了粮食的浪费. 即使以难降解的双酚A作为牺牲剂, CCNHS样品在降解双酚A(降解率为21%)的同时, 依然表现出较好的光催化产氢活性(151.2 μmol∙h^-1∙g^-1). 本文为超分子自组装的结构优化以及晶化氮化碳的改善提供了新视角.

关键词: 晶化, 空心球, 石墨化氮化碳, 光催化析氢, 光催化降解, 增塑剂

Abstract:

Graphitic carbon nitride (g-C₃N₄) has emerged as a remarkably promising photocatalyst for addressing environmental and energy issues; however, it exhibits only moderate photocatalytic activity because of its low specific surface area and high recombination of carriers. Preparation of crystalline g-C₃N₄ by the molten salt method has proven to be an effective method to improve the photocatalytic activity. However, crystalline g-C₃N₄ prepared by the conventional molten salt method exhibits a less regular morphology. Herein, highly crystalline g-C₃N₄ hollow spheres (CCNHS) were successfully prepared by the molten salt method using cyanuric acid-melamine as a precursor. The higher crystallization of the CCNHS samples not only repaired the structural defects at the surface of the CCNHS samples but also established a built-in electric field between heptazine-based g-C₃N₄ and triazine-based g-C₃N₄. The hollow structure improved the level of light energy utilization and increased the number of active sites for photocatalytic reactions. Because of the above characteristics, the as-prepared CCNHS samples simultaneously realized photocatalytic hydrogen evolution with the degradation of the plasticizer bisphenol A. This research offers a new perspective on the structural optimization of supramolecular self-assembly.

Key words: Crystalline, Hollow spheres, Graphitic carbon nitride, Photocatalytic hydrogen evolution, Photocatalytic degradation, Plasticizer

李阳, 张岱南, 范佳杰, 向全军. 高结晶氮化碳空心球的制备及其增强光催化产氢活性[J]. 催化学报, 2021, 42(4): 627-636.

Yang Li, Dainan Zhang, Jiajie Fan, Quanjun Xiang. Highly crystalline carbon nitride hollow spheres with enhanced photocatalytic performance[J]. Chinese Journal of Catalysis, 2021, 42(4): 627-636.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(20)63684-1

https://www.cjcatal.com/CN/Y2021/V42/I4/627

图/表 9

Fig. 1. Schematic diagram of synthesis process over CCNHS samples by using the CM as a precursor by molten salts method and the corresponding morphological structure and chemical molecular structure of as-prepared samples.

Fig. 2. (a, b) SEM images of CM-CN; (c, d) SEM images of CCNHS, the scale bar of the inset in (d) is 100 nm; (e, g) HRTEM images of CM-CN, the scale bar of the inset in (e) is 100 nm; (f, h) HRTEM images of CCNHS, the scale bar of the inset in (f) is 50 nm.

Table 1 Textural properties and chemic composition of the as-prepared samples.

Samples	FWHM₍₀₀₂₎^a	Surface area ^b (m² g^-1)	Pore volume ^b (cm³ g^-1)	C^c (Atom%)	N ^c (Atom%)	N/C ^d
CCNHS	1.043	185.6	0.689	32.77	46.78	1.43
CM-CN	2.455	60.46	0.209	35.82	56.51	1.58
BCN	1.470	13.12	0.081	38.67	57.45	1.48

Fig. 3. (a) XRD patterns of the as-prepared samples; (b) solid-state 13C CP-MAS NMR analysis of CM-CN and CCNHS samples; (c) N 1s spectra of CM-CN and CCNHS; (d) EPR spectra of the as-prepared BCN, CM-CN and CCNHS samples.

Fig. 4. (a) UV-vis DRS spectrum of as-prepared samples, the inset at the top right shows the corresponding color of as-prepared samples, the inset at the lower left shows schematic diagram of multiple reflections of light in a hollow spherical structure; (b) time-resolved PL spectra of as-prepared samples; (c) hydrogen evolution reaction (HER) rate with degradation of plasticizer BPA over the as-prepared samples under irradiation for 1 h; (d) wavelength-dependent HER with BPA degradation over CCNHS under monochromatic light irradiation for 1h, the concentration of BPA solution is 10 mg?L-1.

Table 2 Fluorescence decay lifetimes and their percentages of photo-induced carriers in the BCN, CM-CN, and CCNHS samples.

Samples	Components	Lifetime (ns)	Intensity (%)	Δτ (ns)
CM-CN	τ₁	4.272	47.078	12.45
CM-CN	τ₂	19.731	52.922	12.45
CCNHS	τ₁	3.581	47.506	9.68
CCNHS	τ₂	15.207	52.494	9.68
BCN	τ₁	4.554	43.029	13.89
BCN	τ₂	20.944	56.971	13.89

Fig. 5. (a) XRD patterns of TCN and CCNHS samples. The TCN sample shows the typical XRD pattern of triazine-based g-C3N4; (b) FT-IR spectrum of TCN and CCNHS samples; (c) UV-vis DRS spectrum of TCN and CCNHS samples; (d) The estimated band gaps of TCN and CCNHS samples by Kubellka-Munk function.

Fig. 6. The transient photocurrent responses (a) and electrochemical impedance spectroscopy (b) of as-prepared samples.

Fig. 7. Schematic of the tentative photocatalytic mechanisms of CM-CN and CCNHS samples under visible-light irradiation.

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高结晶氮化碳空心球的制备及其增强光催化产氢活性

Highly crystalline carbon nitride hollow spheres with enhanced photocatalytic performance

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