One-pot Synthesis of Phosphorus Doped G-C3N4 with Enhanced Visible-light Photocatalytic Activity

doi:10.15541/jim20160256

Abstract

Abstract:

A series of P-doped g-C₃N₄(P-CN) samples were prepared using urea (CO(NH₂)₂) and diammonium hydrogen phosphate ((NH₄)₂HPO₄) as raw materials by a simple thermal condensation method. The surface morphologies and structures of the as-prepared samples were characterized by X-ray diffraction (XRD), fourier transform infrared spectroscope (FT-IR), X-ray photoelectron spectroscope(XPS), scanning electron microscope (SEM), transmission electron microscope (TEM), UV-Vis diffuse reflection spectra (UV-Vis DRS) and N₂ adsorption-desorption isotherms, respectively. The visible-light photocatalytic property was demonstrated for photodegradation of Rhodamine (RhB) solution, and the photocatalytic mechanism for the P-CN samples under visible-light was tentatively proposed. The corresponding results indicate that C atoms in g-C₃N₄ are replaced by P atoms, which modifies the surface morphologies and electronic structures. The as-prepared P-CN samples show remarkably higher photocatalytic efficiency than pure g-C₃N₄ for RhB degradation under visible-light irradiation. 3%P-CN sample demonstrates the highest photocatalytic activity, which degrades 96.8% RhB after reaction for 30 min. The replacement of P to C atoms in g-C₃N₄ makes the surface of P-CN in an electron-rich state. Furthermore, the research indicates the conduction band of P-CN shifts to more negative values, which improves the reduction performance of photoelectron. The electrons in conduction band of P-CN reduce O₂ to ·O₂^- in the reaction system, so that the photocatalytic property are improved significantly.

Key words: phosphorus, g-C3N4, visible-light, photocatalysis

CLC Number:

TQ174

XU Zan, YU Xue-Gang, SHAN Yan, LIU Feng-Feng, ZHANG Xian-Ming, CHEN Ke-Zheng. One-pot Synthesis of Phosphorus Doped G-C₃N₄ with Enhanced Visible-light Photocatalytic Activity[J]. Journal of Inorganic Materials, 2017, 32(2): 155-162.

Figures/Tables 12

Fig. 1 XRD patterns of the as-prepared photocatalysts

Fig. 2 FT-IR spectra of the as-prepared photocatalysts

Fig. 3 XPS spectra of (a) C1s, (b) N1s and (c) P2p for 3%P-CN and XPS valence band (VB) spectra of g-C3N4 and 3%P-CN (d) with inset showing the magnification of the area marked with a box

Fig. 4 SEM images and EDS pattern of the as-prepared photocatalysts (a) g-C3N4; (b) 1% P-CN; (c) 3% P-CN; (d) 5% P-CN; (e) 7% P-CN; (f) 9% P-CN; (g) EDS pattern of 3%P-CN

Fig. 5 TEM images of the as-prepared photocatalysts(a) g-C3N4; (b) 1% P-CN; (c) 3% P-CN; (d) 5% P-CN; (e) 7% P-CN; (f) 9% P-CN

Table1 Element contents of 3%P-CN measured by EDS

Element	wt%	at%
C K	33.42	37.81
N K	54.31	52.70
P K	2.29	1.01
O K	9.98	8.48
Total	100	100

Fig. 6 Degradation curves of RhB under visible-light irradiation over g-C3N4 and P-CN

Fig. 7 Cycling runs for the photocatalytic degradation of RhB over 3%P-CN under visible-light irradiation

Fig. 8 N2 adsorption-desorption isotherms of the as-prepared photocatalysts

Fig. 9 UV-Vis diffuse reflectance spectra of the photocatalysts

Fig. 10 Effects of a series of scavengers on the degradation efficiency

Fig. 11 Schematic illustration for photocatalytic mechanism of P-CN samples under visible-light irradiation

References 32

[1]	陈秀芳. 石墨相氮化碳的制备、表征及其光催化性能研究. 福州: 福州大学化学化工学院博士学位论文, 2011: 1.
[2]	WANG YU-GUANG.Present research status of nano-sized TiO2 photocatalyst.Inorganic Chemicals Industry, 2012, 44(3): 50-53.
[3]	HUANG TAO, ZHANG GUO-LIANG, ZHANG HUI,et al. Progress in preparation of TiO2 nanoparticles with high performance.Chemical Industry And Engineering Progress, 2010, 29(3): 498-504.
[4]	ZHANG JING, ZHANG YA-PING, YU LIAN-QING,et al. Preparation of nanatitania by hydrothermal method and progress in research of photocatalytic properties thereof.Inorganic Chemicals Industry, 2010, 42(9): 6-9.
[5]	NI GUANG-HONG, FENG PING.Research status and application of nano-titanium dioxide for photocatalyst.Nanoscience & nanotechnolgy, 2010, 7(2): 81-86.
[6]	ZHANG YA-PING, ZHANG AN-YU, YU LIAN-QING,et al.Photoelectrochemical properties of AgX(Cl, Br)-TiO2 heterojunction nanocomposites.Journal of Inorganic Materials, 2016, 31(3): 269-273.
[7]	WU SI-ZHAN, LI KUI, ZHANG WEI-DE.On the heterostructured photocatalysts Ag3VO4/g-C3N4 with enhanced visible light photocatalytic activity.Applied Surface Science, 2015, 324: 324-331.
[8]	LI CHEN-LU, LUO JIE-RU, CHANG FEI,et al. Preparation and applications progress of exfoliated g-C3N4 nanosheets.Guangzhou Chemical Industry, 2014, 42(17): 10-12.
[9]	闫婷婷. 典型全氟化合物在介孔氮化碳和磁性介孔氮化碳上的吸附. 南京: 南京理工大学, 2014: 9.
[10]	RAN JING-RUN, MA TIAN-YI, GAO GUO-PING,et al. Porous P-doped graphitic carbon nitride nanosheets for synergistically enhanced visible-light photocatalytic H2 production.Energy Environ. Sci., 2015, 8: 3708-3717.
[11]	GUO SHI-EN, DENG ZHAO-PENG, LI MING-XIA.Phosphorus-doped carbon nitride tubes with a layered micro-nanostructure for enhanced visible-light photocatalytic hydrogen evolution.Angew. Chem. Int. Ed., 2016, 55: 1830-1834.
[12]	WANG XIN-CHEN, MAEDA K, THOMAS A,et al. A metal-free polymeric photocatalyst for hydrogen production from water under visible light.Nat. Mater. , 2009, 8: 76-80.
[13]	HUANG ZE-AI, SUN QIONG, LV KANG-LE,et al. Effect of contact interface between TiO2 and g-C3N4 on the photoreactivity of g-C3N4/TiO2 .photocatalyst:(001) vs, 2015, 164: 420-427.
[14]	XU DONG-DONG, LI XIAO-NI, LIU JUAN,et al. Synthesis and photocatalytic performance of europium-doped graphitic carbon nitride.Journal of Rare Earths, 2013, 31(11): 1085-1091.
[15]	LI YE-PING, WU SHI-LONG, HUANG LI-YING,et al. Synthesis of carbon-doped g-C3N4 composites with enhanced visible-light photocatalytic activity.Materials Letters, 2014, 137: 281-284.
[16]	ZHENG REN-YANG, LIN LI, XIE JING-LIN,et al. State of doped phosphorus and its influence on the physicochemical and photocatalytic properties of P-doped titania.J. Phys. Chem. C, 2008, 112: 15502-15509.
[17]	KATO H, TAKEUCHI D, OGURA M,et al. Heavily phosphorus-doped nano-crystalline diamond electrode for thermionic emission application.Diamond & Related Materials, 2016, 63: 165-168.
[18]	ZHANG YUAN-JIAN, MORI T, YE JIN-HUA,et al. Phosphorus-doped carbon nitride solid: enhanced electrical conductivity and photocurrent generation.J. Am. Chem. Soc., 2010, 132: 6294-6295.
[19]	ZHOU YA-JUN, ZHANG LING-XIA, LIU JIAN-JUN,et al. Brand new P-doped g-C3N4: enhanced photocatalytic activity for H2 evolution and Rhodamine B degradation under visible light.J. Mater. Chem. A, 2015, 3: 3862-3867.
[20]	DUAN JING-JING, CHEN SHENG, JARONIEC M,et al. Porous C3N4 nanolayers@N-graphene films as catalyst electrodes for highly efficient hydrogen evolution.ACS Nano, 2015, 9: 931-940.
[21]	RONG XIN-SHAN, QIU FENG-XIAN, RONG JIAN,et al. Synthesis of porous g-C3N4/La and enhanced photocatalytic activity for the degradation of phenol under visible light irradiation.Journal of Solid State Chemistry, 2015, 230: 126-134.
[22]	LI KE-XIN, ZENG ZHEN-XING, YAN LIU-SHUI,et al.Fabrication of platinum-deposited carbon nitride nanotubes by a one-step solvothermal treatment strategy and their efficient visible-light photocatalytic activity.Applied Catalysis B: Environmental, 2015, 165: 428-437.
[23]	WANG KE, LI QIN, LIU BAO-SHUN, et al.Sulfur-doped g-C3N4 with enhanced photocatalytic CO2-reduction performance.Applied Catalysis B: Environmental, 2015,176-177: 44-52.
[24]	CHEN WEI, LIU TIAN-YU, HUANG TING,et al. Novel mesoporous P-doped graphitic carbon nitride nanosheets coupled with ZnIn2S4 nanosheets as efficient visible light driven heterostructures with remarkably enhanced photo-reduction activity.Nanoscale, 2016, 8: 3711-3719.
[25]	ZHU YUN-PEI, REN TIE-ZHEN, YUAN ZHONG-YONG.Mesoporous phosphorus-doped g-C3N4 nanostructured flowers with superior photocatalytic hydrogen evolution performance.ACS Appl. Mater. Interfaces, 2015, 7: 16850-16856.
[26]	HOU YANG, LI JIAN-YANG, WEN ZHEN-HAI,et al. N-doped graphene/porous g-C3N4 nanosheets supported layered-MoS2 hybrid as robust anode materials for lithiumion batteries.Nano Energy, 2014, 8: 157-164.
[27]	赵东元, 万颖, 周午纵. 有序介孔分子筛材料. 北京: 高等教育出版社, 2013: 149-151.
[28]	LI WEI-BING, FENG CHANG, DAI SHI-YUAN, et al. Fabrication of sulfur-doped g-C3N4/Au/CdS Z-scheme photocatalyst to improve the photocatalytic performance under visible light.Applied Catalysis B: Environmental.2015,168-169: 465-471.
[29]	DONG FAN, ZHAO ZAI-WANG, XIONG TING,et al.In situ construction of g-C3N4/g-C3N4 metal-free heterojunction for enhanced visible-light photocatalysis.ACS Appl. Mater. Interfaces, 2013, 5: 11392-11401.
[30]	YE CHEN, LI JIA-XIN, LI ZHI-JUN,et al.Enhanced driving force and charge separation efficiency of protonated g-C3N4 for photocatalytic O2 evolution.ACS Catal. 2015, 5: 6973-6979.
[31]	ZHANG JIN-FENG, HU YING-FEI, JIANG XIAO-LIANG,et al. Design of a direct Z-scheme photocatalyst: Preparation and characterization of Bi2O3/g-C3N4 with high visible light activity.Journal of Hazardous Matrials, 2014, 280: 713-722.
[32]	RUAN LIN-WEI, QIU LING-GUANG, ZHU YU-JUN,et al. Analysis of electrical and optical properties of g-C3N4 with carbon-position doping.Acta Phys. -Chim. Sin., 2014, 30(1): 43-52.

One-pot Synthesis of Phosphorus Doped G-C₃N₄ with Enhanced Visible-light Photocatalytic Activity

RichHTML

PDF (PC)

Knowledge

Cited

Abstract

Cite this article

share this article

Figures/Tables 12

References 32

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	TUERHONG Munire, ZHAO Honggang, MA Yuhua, QI Xianhui, LI Yuchen, YAN Chenxiang, LI Jiawen, CHEN Ping. Construction and Photocatalytic Activity of Monoclinic Tungsten Oxide/Red Phosphorus Step-scheme Heterojunction [J]. Journal of Inorganic Materials, 2023, 38(6): 701-707.
[2]	WU Lin, HU Minglei, WANG Liping, HUANG Shaomeng, ZHOU Xiangyuan. Preparation of TiHAP@g-C₃N₄ Heterojunction and Photocatalytic Degradation of Methyl Orange [J]. Journal of Inorganic Materials, 2023, 38(5): 503-510.
[3]	MA Xinquan, LI Xibao, CHEN Zhi, FENG Zhijun, HUANG Juntong. BiOBr/ZnMoO₄ Step-scheme Heterojunction: Construction and Photocatalytic Degradation Properties [J]. Journal of Inorganic Materials, 2023, 38(1): 62-70.
[4]	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.
[5]	XUE Hongyun, WANG Congyu, MAHMOOD Asad, YU Jiajun, WANG Yan, XIE Xiaofeng, SUN Jing. Two-dimensional g-C₃N₄ Compositing with Ag-TiO₂ as Deactivation Resistant Photocatalyst for Degradation of Gaseous Acetaldehyde [J]. Journal of Inorganic Materials, 2022, 37(8): 865-872.
[6]	CHI Congcong, QU Panpan, REN Chaonan, XU Xin, BAI Feifei, ZHANG Danjie. Preparation of SiO₂@Ag@SiO₂@TiO₂ Core-shell Structure and Its Photocatalytic Degradation Property [J]. Journal of Inorganic Materials, 2022, 37(7): 750-756.
[7]	WANG Xiaojun, XU Wen, LIU Runlu, PAN Hui, ZHU Shenmin. Preparation and Properties of Ag@C₃N₄ Photocatalyst Supported by Hydrogel [J]. Journal of Inorganic Materials, 2022, 37(7): 731-740.
[8]	CAO Zhijun, LI Zaijun. Ruthenium-biocarbon Mimic Enzyme: Synthesis and Application in Colorimetric Detection of Pesticide Chlorpyrifos [J]. Journal of Inorganic Materials, 2022, 37(5): 554-560.
[9]	FU Mingfu, YANG Wen, LI Jiabao, DENG Shukang, ZHOU Qihang, FENG Xiaobo, YANG Peizhi. Synthesis of Orthorhombic Black Phosphorus by Chemical Vapor Transport Method [J]. Journal of Inorganic Materials, 2022, 37(10): 1102-1108.
[10]	LIU Xuechen, ZENG Di, ZHOU Yuanyi, WANG Haipeng, ZHANG Ling, WANG Wenzhong. Selective Oxidation of Biomass over Modified Carbon Nitride Photocatalysts [J]. Journal of Inorganic Materials, 2022, 37(1): 38-44.
[11]	ZHANG Xian, ZHANG Ce, JIANG Wenjun, FENG Deqiang, YAO Wei. Synthesis, Electronic Structure and Visible Light Photocatalytic Performance of Quaternary BiMnVO₅ [J]. Journal of Inorganic Materials, 2022, 37(1): 58-64.
[12]	LIU Peng, WU Shimiao, WU Yunfeng, ZHANG Ning. Synthesis of Zn_0.4(CuGa)_0.3Ga₂S₄/CdS Photocatalyst for CO₂ Reduction [J]. Journal of Inorganic Materials, 2022, 37(1): 15-21.
[13]	WANG Luping, LU Zhanhui, WEI Xin, FANG Ming, WANG Xiangke. Application of Improved Grey Model in Photocatalytic Data Prediction [J]. Journal of Inorganic Materials, 2021, 36(8): 871-876.
[14]	CAI Miao, CHEN Zihang, ZENG Shi, DU Jianghui, XIONG Juan. CuS Nanosheet Decorated Bi₅O₇I Composite for the Enhanced Photocatalytic Reduction Activity of Aqueous Cr(VI) [J]. Journal of Inorganic Materials, 2021, 36(6): 665-672.
[15]	AN Weijia, LI Jing, WANG Shuyao, HU Jinshan, LIN Zaiyuan, CUI Wenquan, LIU Li, XIE Jun, LIANG Yinghua. Fe(III)/rGO/Bi₂MoO₆ Composite Photocatalyst Preparation and Phenol Degradation by Photocatalytic Fenton Synergy [J]. Journal of Inorganic Materials, 2021, 36(6): 615-622.