制備類石墨相氮化碳多孔光催化劑的模板法發展

鞏正奇; 閆楚璇; 宣之易; 陳穎芝; 李靜媛; 王魯寧

doi:10.13374/j.issn2095-9389.2020.09.07.003

制備類石墨相氮化碳多孔光催化劑的模板法發展

doi: 10.13374/j.issn2095-9389.2020.09.07.003

北京科技大學材料科學與工程學院，北京 100083

基金項目: 國家自然科學基金資助項目（51503014）；中央高校基本科研業務費專項資金資助項目（230201818-002A3）

詳細信息

通訊作者:
E-mail：chenyingzhi@ustb.edu.cn

中圖分類號: TG142.71
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出版歷程
- 收稿日期: 2020-09-07
- 刊出日期: 2021-03-26

Development of template methods for the preparation of porous photocatalysts of graphite-like carbon nitride

School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, China

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Corresponding author: E-mail: chenyingzhi@ustb.edu.cn

摘要

摘要: 氮化碳作為一種具有高催化性能的光催化劑，具有無毒無害，自然環境下穩定的性質，在水解制氫氣氧氣以及降解有機污染物領域得到了廣泛的關注. 其中類石墨相氮化碳(g-C₃N₄)因其特殊的片層結構而具有較高比表面積，常配合孔結構的構造，提供光生載流子及反應物質的運輸通道以及大量活性位點用于氧化還原反應，是具有高光電性能的一種光催化劑.制備該種催化劑孔結構的方法有硬模板法，軟模板法與非模板法，其中硬模板法需要在實驗后除去模板，軟模板法的模板會隨著高溫除去，非模板法的制備過程沒有模板的參與。本文根據近年文獻的整理，著重闡述和比較各制備方法的優劣，結合常用的修飾手段總結各制備方法的變化趨勢和發展方向，并對后續研究中制備方法的使用前景做出判斷.
- 類石墨相氮化碳 /
- 光催化 /
- 多孔結構 /
- 模板法 /
- 非模板法
Abstract: As a metal-free photocatalyst with high catalytic performance, carbon nitride is non-toxic, harmless, and stable in the natural environment. Owing to its facile synthesis, stable physical and chemical properties, tunable structure, and suitable band gap, graphite-like carbon nitride (g-C₃N₄) plays an increasing role in the field of photocatalysis. It has attracted extensive attention in the fields of evolution of hydrogen and oxygen via water-splitting hydrolysis and in the degradation of organic pollutants. In particular, g-C₃N₄ is identified to have a high specific surface area (SSA) because of its special lamellar structure. Meanwhile, the abundant pores intrinsic in it are able to provide both transporting channels for photogenic carriers or reactive species and a large number of active sites for redox reactions. These merits endow it with high photoelectrical properties. The preparation methods of the pore structures of such catalyst include hard templates, soft templates, and non-template ones. The hard template method enables the preparation of regular pore structures but requires additional removal treatment. However, the soft templates can be decomposed during the high-temperature preparation of g-C₃N₄, which avoids the use of toxic reagents and consequently is harmless to the environment, and the template-free method does not involve any templates, which will simplify the experimental process from the aspect of sample preparation with reduced cost. In this paper, the advantages and disadvantages of various preparation methods were elaborated and compared based on the literature review in recent years. The developments and applications in the environmental and energy aspects were summarized by combining the commonly used modification methods, which provided the perceptions with respect to the development of metal-free g-C₃N₄-based photocatalysts in the future. Further, the photocatalytic mechanism was explained, and the four different precursors of g-C₃N₄ were compared. Finally, the ongoing outlook and perspectives will be covered in this review.
- graphite-like carbon nitride /
- photocatalyst /
- porous structure /
- template method /
- template-free method

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圖 1 C₃N₄基本單元和能帶結構^[2]

Figure 1. Basic unit and band structure of C₃N₄^[2]

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圖 2 投射電鏡圖像^[23]。（a）bulk-g-C₃N₄；（b）g-C₃N₄（SBA-15）；（c）g-C₃N₄（CLBM-SBA-15）

Figure 2. TEM images^[23]: (a) bulk-g-C₃N₄; (b) g-C₃N₄(SBA-15); (c) g-C₃N₄(CLBM-SBA-15)

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圖 3 投射電鏡圖像^[26]。（a）DCS；（b~d）DCS/gCN；（e）OCS；（f~h）OCS/gCN

Figure 3. TEM images^[26]: (a)DCS; (b?d)DCS/gCN; (e)OCS; (f?h)OCS/gCN

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圖 4 （a）圖解說明由不同前體合成的聚合C₃N₄形成的示意圖；（b）由不同前體合成的C₃N₄的X射線衍射圖譜；（c）由不同前體合成的C₃N₄的N₂吸附?解吸等溫線；（d）由不同前體合成的C₃N₄的UV-Vis吸收光譜；（e）使用由不同前體合成的C₃N₄降解TC的效率圖；（f）由不同前體合成的C₃N₄對TC的光降解速率^[36]

Figure 4. (a) Schematic illustrating the formation of polymeric C₃N₄ synthesized from different precursors; (b) XRD pattern of C₃N₄ synthesized from different precursors; (c) nitrogen adsorption?desorption isotherms of C₃N₄ synthesized from different precursors; (d) UV-Vis absorption spectra of C₃N₄ synthesized from different precursors; (e) degradation pattern of TC using C₃N₄ synthesized from different precursors; (f) photodegradation rate of TC using C₃N₄ synthesized from different precursors ^[36]

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圖 5 介孔氮化碳形成過程^[39]

Figure 5. Formation process of mesoporous carbon nitride^[39]

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圖 6 （a）g-C₃N₄；（b）CNF-0.005的掃描電鏡圖像; （c~f）CNF-0.005的透射電鏡和高分辨透射電鏡圖像^[39]

Figure 6. SEM images of g-C₃N₄ (a) and CNF-0.005 (b); (c?f) TEM and HRTEM images of CNF-0.005^[39]

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圖 7 掃描電鏡圖像^[43]。（a）B-C₃N₄；（b）M-C₃N₄；（c, d）P-C₃N₄

Figure 7. SEM images^[43]: (a) B-C₃N₄; (b) M-C₃N₄; and (c, d) P-C₃N₄

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表 1 不同模板法調控g-C₃N₄孔結構總括

Table 1. Summary of the different template methods in adjusting the pore structure of g-C₃N₄

Sample	Reaction precursor, temperature, time, heating rate, & atmosphere	Template type& requirement	Removal reagents& requirement	Specific surface area/(m²?g^?1)	Pore volume/ (cm³?g^?1)	Average pore size/nm	Refs.
Porous-C₃N₄	Dicyandiamide, 500 °C, 4.5 h	7?40 nm SiO₂ hard template	20% HF, 4 h	~109	—	~20	[20]
MCN1.0	Cyanamide, 550 °C, 4 h, 2 °C?min^?1, N2	12 nm SiO₂ nanosphere hard template	4.0 mol?L^?1 NH₄HF₂, 24 h	~190.7	~0.52	~10.9	[22]
CLBM?SBA-15	Cyanamide, stirring at room temperature, 1 h, 550 °C, 6 h, air	9.5 nm SBA-15 hard template	4.0 mol?L^?1 NH₄HF₂	~145	~0.43	~44	[23]
C₃N₄?MCF	Melamine, 300 °C, 1 h, 600 °C, 2 h, Ar	MCF hard template	15% HF, 12 h	~70	~0.3	—	[24]
Bulk-g-C₃N₄	Dicyandiamide, 560 °C, 2 h, N₂	12 nm PSB hard template	NH₄HF₂	~37	~0.28	~36	[25]
TiO₂ trapped g-C₃N₄	Dicyandiamide, 560 °C, 2 h, N₂	12 nm PSB hard template	NH₄HF₂	~63	~0.29	~20	[25]
OCS/gCN	Melamine, 550 °C, 2 h, 2 °C?min^?1, air	260?320 nm SiO₂ nanosphere hard template	HF	~105	~0.123	~260?320	[26]
Meso-g-C₃N₄/WP/Meso-g-C₃N₄	Cyanamide, 550 °C, 4 h, 3 °C?min^?1, N₂	8?15 nm SiO₂ hard template	0.5 mol?L^?1 HF	~82	—	~8?15	[27]
CN?MCF-0.4	Carbon tetrachloride, ethylenediamine, 90 °C, 6 h, 600 °C, 5 h, 3 °C?min^?1, Ar	35.7 nm MCF hard template	4.0 mol?L^?1 NH₄HF₂	~498	~1.36	~5.3	[29]
mpg?C₃N_4-δ	Dicyandiamide, 550 °C, 4 h, 2.3 °C?min^?1, N₂	12 nm SiO₂ hard template	4.0 mol?L^?1 NH₄HF₂, 24 h	~218.15	~0.69	~12.57	[30]
PCNCs?ANT^a	Melamine, 550 °C, 2 h, 2 °C?min^?1	6.7 nm ZnO hard template	4.0 mol?L^?1 NaOH	~32	~0.103	~16.8	[31]
g-C₃N₄	Melamine, 500 °C, 2 h, air	P123 soft template		~90	—	—	[34]
Bulk-g-C₃N₄	Melamine, 600 °C, 2 h, Ar	P123 soft template		~90	—	~15	[34]
g-C₃N₄/SnO₂	Thiourea, SnCl₄, 550 °C, 2 h, 10 °C?min^?1	HCl, H₂O soft template		~44.3	2.638	~100?430	[35]
C₃N₄@TiO₂	Melamine, 400 °C, 2 h, N₂, 2 h, air	Melamine soft template		~44.7	~0.11	~10.7	[37]
N-RGO	Graphene oxide, melamine, 900 °C, 30 min, 5 °C?min^?1	Ice soft template		~190	~0.99	~20?200	[38]
CNF-0.005	Melamine, 550 °C, 4 h, 3 °C?min^?1, N₂	Cyanuric acid-melamine supramolcular aggregates & ionic liquid soft template		~381	~0.85	~15	[39]
PCNM	Melamine, urea, 550 °C, 4 h, N₂	Melamine soft template		~78	~0.76	—	[40]
g-C₃N₄ ultrathin nanosheet	Melamine, glutaraldehyde, 800 °C, 2 h, Ar	Cyanuric acid soft template		~84	—	~3	[48]
g-C₃N₄ bundles	Melamine, 500 °C, 4 h, N₂	PEG-PPG-PEG soft template		~40.974	—	~100	[49]
g-C₃N₄ beads	Dicyandiamide, 530?600 °C, 2 h, N₂	PSB soft template		~58	~0.15	~30?90	[50]
P-C₃N₄	Melamine, 550 °C, 4 h	Free		~40.89	~0.2	—	[43]
2MCN/2UCN	Melamine, urea, 550 °C, 1.5 h, 5 °C?min^?1, N₂	Free		~41	~0.24	~23	[44]
5% La/g-CNT	Melamine, 550 °C, 2 h, air	Free		~4	~0.0623	~2.8	[45]
CN/Fe-1	Urea, 600 °C, 4 h, 5 °C?min^?1	Free		~48.19	—	—	[46]
g-C₃N₄ NS/TMC	Melamine, 550 °C, 3 h, 2.3 °C?min^?1, air	Free		~57.4	—	—	[47]
g-C₃N₄/Ag₃PO₄	Urea, 550 °C, 4 h, Ar	Free		~20.84	~0.083	~16	[51]
Brookite/anatase TiO₂/g-C₃N₄	Hexadecylamine, 550 °C, 4 h, 3 °C?min^?1, N₂	Free		~37	~0.2	~18	[52]
g-C₃N₄ nanosheet	Melamine, 550 °C, 4 h, 500 °C, 2 h, Ar	Free		~190.1	~0.61	~5?25	[53]
Fe₂O₃(6.6)/CNS^b	Thiourea, 535 °C, 3 h, 3 °C?min^?1, air	Free		~33.5	~0.195	~25	[54]
g-C₃N₄/MoS₂	Thiourea, 500 °C, 2 h, 2 °C?min^?1	Free		~45	—	—	[55]

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