石墨相氮化碳的共轭交联修饰及其对可见光催化产氢性能的影响

doi:10.6023/A22040183

摘要/Abstract

石墨相氮化碳(GCN)具有廉价易制和高度稳定性, 在光催化分解水制氢领域备受关注, 但其较窄的光谱响应范围和较低的光生电荷分离和转移效率制约了其光催化性能. 采用4,4'-(苯并[c][1,2,5]噻二唑-4,7-二基)二苯甲醛(BTD)与热聚法合成的GCN在260 ℃进行酸催化席夫碱反应, 使GCN片层发生共轭交联反应和表面修饰, 制备了四个BTD改性的氮化碳材料GCN-BTD_x (x为20、40、80和160, 代表每100 mg GCN原料对应BTD的毫克用量). 其中, GCN-BTD₁₆₀表现出最高的光催化还原水制氢性能, 制氢速率为863 μmol•g^–1•h^–1, 是未修饰GCN的2倍, 且展示出优秀的循环利用性能. 研究发现, BTD修饰拓宽了材料的光吸收范围, 调节了材料的能带结构, 提高了电荷分离效率并降低了界面的电荷转移阻力, 从而提高了材料的可见光催化制氢性能.

关键词: 石墨相氮化碳, 光催化, 分解水制氢, 可见光, 共轭修饰, 苯并噻二唑

Owing to their features of easy preparation, low cost and good stability, graphitic carbon nitrides (GCNs) have attracted increasing attention in the field of photocatalytic water-splitting hydrogen production for green and renewable energy as an alternative to fossil. However, their narrow light absorption spectra and low efficiencies in photogenerated charge separation and transfer processes restrict their photocatalytic performance. In this work, 4,4'-(benzo[c][1,2,5]thiadiazole- 4,7-diyl)dibenzaldehyde (BTD) was used to conjugated crosslink and surface modify GCN via acid-catalyzed Shiff-base condensation reaction at 260 ℃, affording four BTD-modified graphitic carbon nitride materials denoted as GCN-BTD_x (x represents the amount of BTD in mg used in the reaction with 100 mg GCN and equals to 20, 40, 80, and 160). Elemental analysis, Fourier transform infrared spectroscopy, powder X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, UV-vis diffuse reflectance spectroscopy, Mott-Schottky analysis, electrochemical impedance spectroscopy and photocurrent responsive measurements were used to characterize and investigate the synthesized materials. Using these materials as photocatalysts, triethanolamine as electron sacrificial agent, Pt nanoparticle as cocatalyst, visible light-driven photocatalytic hydrogen production from water have been studied. It was found the BTD modification can extend light absorption spectrum, tune energy band structure, and reduce interfacial charge transfer resistance, and thus finally improve the material photocatalytic hydrogen production performance. Among the family, GCN-BTD₁₆₀ behaved the best with the highest hydrogen evolution rate (863 μmol•g^–1•h^–1) and excellent stability and recyclability. Its hydrogen evolution rate is more than 2 folds as that of unmodified GCN. Moreover, GCN-BTD₁₆₀ exhibited good visible light responsibility, with apparent quantum yields of 2.4% at 420 nm, 1.8% at 450 nm, and 1.6% at 500 nm. Therefore, this work paves a new method in graphitic carbon nitride modification for photocatalytic performance improvement.

Key words: graphitic carbon nitrides, photocatalysis, water splitting hydrogen production, visible light, conjugated modification, benzothiadiazole

引用此文

解众舒, 薛中鑫, 许子文, 李倩, 王洪宇, 李维实. 石墨相氮化碳的共轭交联修饰及其对可见光催化产氢性能的影响[J]. 化学学报, 2022, 80(9): 1231-1237.

Zhongshu Xie, Zhongxin Xue, Ziwen Xu, Qian Li, Hongyu Wang, Wei-Shi Li. Conjugated Crosslinking Modification of Graphitic Carbon Nitrides and Its Effect on Visible Light-Driven Photocatalytic Hydrogen Production[J]. Acta Chimica Sinica, 2022, 80(9): 1231-1237.

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图/表 7

图式1. GCN-BTDx的合成

Scheme 1. Synthesis of GCN-BTDx

样品	C (%)	N (%)	H (%)	S (%)
GCN	37.0	59.0	2.0	0
GCN-BTD₂₀	39.1	52.7	2.2	1.2
GCN-BTD₄₀	45.3	46.8	2.4	2.3
GCN-BTD₈₀	47.4	43.2	2.5	2.9
GCN-BTD₁₆₀	53.0	34.0	2.7	4.7
GCN-BTD₅₀₀	54.7	32.9	2.8	5.0

表1. GCN-BTDx元素分析数据

Table 1. Elemental analysis of GCN-BTDx

图1. GCN、BTD和GCN-BTDx的(a) FT-IR和(b)粉末XRD谱图. (c) GCN、(d) GCN-BTD40、(e) GCN-BTD80和(f) GCN-BTD160的扫描电子显微图像

Figure 1. (a) FT-IR and (b) powder XRD of GCN, BTD and GCN- BTDx. SEM images of (c) GCN, (d) GCN-BTD40, (e) GCN-BTD80 and (f) GCN-BTD160

图2. GCN和GCN-BTDx的XPS (a)全谱、(b) C 1s、(c) N 1s和(d) S 2p精细谱

Figure 2. (a) Survey scanning, and high resolution (b) C 1s, (c) N 1s, and (d) S 2p XPS spectra of GCN and GCN-BTDx

图3. GCN和GCN-BTDx的(a)紫外可见漫反射光谱、(b) Tauc plot曲线、(c) Mott-Schottky曲线和(d)能带结构

Figure 3. (a) UV-vis diffuse reflectance spectra, (b) Tauc plots, (c) Mott-Schottky curves and (d) energy band structures of GCN and GCN-BTDx

图4. GCN和GCN-BTDx为催化剂在(a)不使用助催化剂和(b)使用 w=3% Pt助催化剂下的可见光催化产氢过程, 以及(c)相应的产氢速率. (d) GCN-BTD160光催化制氢的重复使用实验和(e)测定的表观量子效率. 其他条件: 15 mg考察的氮化碳催化剂, 15 mL H2O, 1.5 mL TEOA, 装配有λ>420 nm的可见光滤片或λ=420, 450或500 nm的单色光滤片的300 W氙灯

Figure 4. (a, b) The time course and (c) hydrogen evolution rate of visible light photocatalytic hydrogen production from water with GCN and GCN-BTDx as photocatalysts (a) in the absence of cocatalyst and (b) in the presence of w=3% Pt cocatalyst. (d) Repetitive use and (e) apparent quantum yield of GCN-BTD160 in photocatalysis. Other conditions: 15 mg tested catalyst, 15 mL H2O, 1.5 mL TEOA, irradiated with a 300 W Xe lamp equipped with a UV cut filter (λ>420 nm), or λ=420, 450, or 500 nm monochromatic band-pass filters

图5. GCN和GCN-BTDx的(a)稳态荧光光谱, (b)交流阻抗谱和(c)周期光电流响应曲线

Figure 5. (a) Steady-state photoluminescence spectra, (b) EIS profiles and (c) photocurrent responsive curves of GCN and GCN-BTDx

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