MoS2/g-C3N4 S型异质结的构建及光催化性能研究

doi:10.15541/jim20230096

无机材料学报 ›› 2023, Vol. 38 ›› Issue (10): 1176-1182.DOI: 10.15541/jim20230096 CSTR: 32189.14.10.15541/jim20230096

所属专题：【能源环境】光催化(202312)；【能源环境】污染物去除(202312)

MoS₂/g-C₃N₄ S型异质结的构建及光催化性能研究

马润东¹^,²(), 郭雄¹^,², 施凯旋¹^,², 安胜利¹^,², 王瑞芬¹^,²(), 郭瑞华¹^,²

1.内蒙古科技大学材料与冶金学院, 包头 014010
2.稀土资源绿色提取与高效利用教育部重点实验室, 包头 014010

收稿日期:2023-02-25 修回日期:2023-03-13 出版日期:2023-10-20 网络出版日期:2023-04-11
通讯作者: 王瑞芬, 副教授. E-mail: wrf2008@imust.edu.cn
作者简介:马润东(1999-),男, 硕士. E-mail: 896164876@qq.com
基金资助:
内蒙古自治区科技计划(2021GG0042);内蒙古自治区高等学校青年科技英才(NJYT22064);内蒙古自治区自然科学基金(2022MS05018)

S-type Heterojunction of MOS₂/g-C₃N₄: Construction and Photocatalysis

MA Rundong¹^,²(), GUO Xiong¹^,², SHI Kaixuan¹^,², AN Shengli¹^,², WANG Ruifen¹^,²(), GUO Ruihua¹^,²

1. School of Materials and Metallurgy, Inner Mongolia University of Science and Technology, Baotou 014010, China
2. Laboratory of Green Extraction & Efficient Utilization of Light Rare-Earth Resources, Ministry of Education, Baotou 014010, China

Received:2023-02-25 Revised:2023-03-13 Published:2023-10-20 Online:2023-04-11
Contact: WANG Ruifen, associate professor. E-mail: wrf2008@imust.edu.cn
About author:MA Rundong (1999-), male, Master. E-mail: 896164876@qq.com
Supported by:
Inner Mongolia Autonomous Region Science and Technology Program(2021GG0042);Inner Mongolia Autonomous Region Youth Science and Technology Excellence in Higher Education(NJYT22064);Inner Mongolia Autonomous Region Natural Science Foundation Program(2022MS05018)

摘要/Abstract

摘要：

制备高效稳定的光催化剂对于光催化技术的发展至关重要。本研究采用超声辅助沉积加低温煅烧的方法制备了2H相MoS₂/g-C₃N₄S型异质结光催化剂(MGCD), 并综合考察了材料的相结构、微观形貌、光吸收性能、X射线光电子能谱、电化学交流阻抗和光电流等对光催化性能的影响。结果表明: 经过超声辅助沉积-煅烧处理, MoS₂微米球发生破碎分散结合在g-C₃N₄纳米片层表面上并形成异质结。可见光下5%MGCD(添加5% MoS₂)对罗丹明B(RhB)在20 min时的降解率达到了99%, 且样品重复使用5次后对RhB的降解率仍能达到95.2%, 表现出良好的光催化性能及稳定性。从内建电场形成的角度进一步分析表明, 异质结中MoS₂与g-C₃N₄间耦合形成的内建电场引起的能带弯曲可以有效引导载流子的定向迁移, 并促进光生载流子的分离, 从而提高了光催化反应效率。异质结光催化剂的自由基捕获实验表明: O₂^-和·OH在催化降解RhB中是主要的活性物种, h⁺的贡献次之。

关键词: 石墨相氮化碳, MoS₂, S型异质结, 稳定性, 光催化机理

Abstract:

Preparation of highly efficient and stable photocatalysts is crucial for the development of photocatalysis technology. In this study, the method of ultrasonic-assisted deposition and low-temperature calcination was used to prepare MoS₂/g-C₃N₄ S-type heterojunction photocatalyst (MGCD). Effects of the phase structure, micro-morphology, optical absorption performance, X-ray photoelectron spectroscopy, electrochemical AC impedance, and photocurrent of the materials on the photocatalytic activity were comprehensively investigated. The results show that, after ultrasonic-assisted deposition-calcination treatment, MoS₂microspheres were broken, dispersed and combined on the surface of g-C₃N₄ nanosheets, and formed a kind of heterojunction. Under visible light, the degradation rate of 5%MGCD (with 5% MoS₂ addition) for Rhodamine B (RhB) reached 99% in 20 min, and still reach 95.2% when the sample was reused for 5 times, showing good photocatalytic performance and stability. Further analysis from the point of view of the formation of built-in electric field shows that the band bending caused by built-in electric field, coupled with MoS₂ and g-C₃N₄ in heterojunction, can effectively guide the directional migration of carriers, which can efficiently promote the separation of photogenerated carriers, thus improving the efficiency of photocatalytic reaction. Free radical capture experiment of heterojunction photocatalyst reveals that O₂^- and ·OH are the main active species in the catalytic degradation of RhB, followed by H⁺.

Key words: g-C₃N₄, MoS₂, S-type heterojunction, stability, photocatalytic mechanism

中图分类号:

O649

马润东, 郭雄, 施凯旋, 安胜利, 王瑞芬, 郭瑞华. MoS₂/g-C₃N₄ S型异质结的构建及光催化性能研究[J]. 无机材料学报, 2023, 38(10): 1176-1182.

MA Rundong, GUO Xiong, SHI Kaixuan, AN Shengli, WANG Ruifen, GUO Ruihua. S-type Heterojunction of MOS₂/g-C₃N₄: Construction and Photocatalysis[J]. Journal of Inorganic Materials, 2023, 38(10): 1176-1182.

图/表 6

图1 不同样品的XRD谱图(a), 煅烧前后的MoS2的XRD谱图(b)和样品的红外光谱图(c)

Fig. 1 XRD patterns of different samples (a), XRD patterns of MoS2 samples before and after calcination (b), and FT-IR spectra of samples (c)

图2 g-C3N4 (a), MoS2 (b)和5%MGCD(c, d)的SEM照片、HR-TEM照片(e, f)、元素分布总图(g)及其元素C(h), N(i), S(j), Mo(k)分布图

Fig. 2 FE-SEM images of g-C3N4 (a), MoS2 (b) and FE-SEM images (c, d), HR-TEM images (e, f),element mapping (g) and C (h), N (i), S (j), Mo (k) mapping of 5%MGCD

图3 样品的紫外-可见吸收光谱图(a), Tauc曲线(b), 荧光光谱图(c)、瞬态光电流响应图谱(d)及EIS图谱(e)

Fig. 3 UV-Vis (a) spectra, Tauc curves (b), PL spectra (c), instantaneous meter photocurrents (d), and EIS (e) patterns of samples Colorful figures are available on website

图4 (a) 不同光催化剂样品对RhB随时间变化的降解率对比图, (b) 5%MGCD的循环降解率随时间变化图, (c) 5%MGCD循环降解实验前后的XRD谱图, 以及(d) 自由基捕获实验图

Fig. 4 Degradation rate of different photocatalyst samples (a), cyclic degradation rate of 5%MGCD with time (b), XRD patterns of 5%MGCD before and after circulation experiment (c), and histogram of free radical trapping experiment (d)

图5 (a) 异质结能带图, (b) 样品异质结的构建及能费米能级的弯曲, (c) 内建电场引起的能带弯曲图

Fig. 5 Energy bands diagram of heterojunction (a), construction of heterojunction of sample and bending of Fermi energy level (b), and diagram of energy band bending caused by built-in electric field (c)

图6 样品的光催化机理图

Fig. 6 Photocatalytic mechanism diagram of sample

参考文献 31

[1]	HUANG R, HUANG W, LI D F, et al. Self-assembled hierarchical carbon/g-C₃N₄ composite with high photocatalytic activity. Journal of Physics D: Applied Physics, 2018, 51(13): 135501. DOI URL
[2]	ZHEN W, XIAO N, SHEN, JI Y F, et al. Synthesis of novel MoS₂/g-C₃N₄nanocomposites for enhanced photocatalytic activity. Journal of Materials Science: Materials in Electronics, 2020, 31(18): 15885. DOI
[3]	JIANG Y B, SUN Z Z, CHEN Q W, et al. Sulfate modified g-C₃N₄ with enhanced photocatalytic activity towards hydrogen evolution: the role of sulfate in photocatalysis. Physical Chemistry Chemical Physics, 2020, 22(18): 10116. DOI URL
[4]	LI K Y, LIANG Y D, YANG H, et al. New insight into the mechanism of enhanced photo-Fenton reaction efficiency for Fe-doped semiconductors: a case study of Fe/g-C₃N₄. Catalysis Today, 2020, 371: 58.
[5]	WANG X, XIONG W, LI X Y, ZHAO Q D, et al. Fabrication of MoS₂@g-C₃N₄ core-shell nanospheresfor visible light photocatalytic degradation of toluene. Journal of Nanoparticle Research, 2018, 20(9): 243. DOI
[6]	YUN H J, LEE H, KIM N D, et al. A combination of two visible-light responsive photocatalysts for achieving the Z-Scheme in the solid state. ACS Nano, 2011, 5(5): 4084. DOI PMID
[7]	AKIHIDE I, YUN H, YOSHIMI I, et al. Reduced graphene oxide as a solid-state electron mediator in z-scheme photocatalytic water splitting under visible light. Journal of the American Chemical Society, 2011, 133(29): 11054. DOI PMID
[8]	CHU K, LIU Y P, LI Y B, GUO Y L, et al. Two-dimensional (2D)/2D interface engineering of a MoS₂/C₃N₄ heterostructure for promoted electrocatalytic nitrogen fixation. ACS Applied Materials & Interfaces, 2020, 12(6): 7081.
[9]	CHOUDARI B V R, ZHANG S P, WEN, Z Y, et al. Constructing highly oriented configuration by few-layer MoS₂: toward high-performance lithium-ion batteries and hydrogen evolution reactions. ACS Nano, 2015, 9(12): 12464. DOI PMID
[10]	DONG H C, LI J Z, CHEN M G, et al. High-throughput production of ZnO-MoS₂ graphene heterostructures for highly efficient photocatalytic hydrogen evolution. Materials, 2019, 12(14): 22. DOI URL
[11]	SARANYA J, SUPANAN A, ORAPHAN T, et al. Photocatalytic activity enhancement of g-C₃N₄/BiOBr in selective transformation of primary amines to imines and its reaction mechanism Chemical Engineering Journal, 2020, 394: 124934.
[12]	VITALY E S, DMITRY A P, Ekaterina YR, et al. Anilinonaphthalene sulfonate binds to central cavity of humanhemo globin. Biochemical and Biophysical Research Communications, 2004, 317(3): 761. DOI URL
[13]	YANG X L, QIAN F F, ZOU G J, et al. Facile fabrication of acidified g-C₃N₄/g-C₃N₄ hybrids with enhanced photocatalysis performance under visible light irradiation. Applied Catalysis B Environmental, 2016, 193: 22.
[14]	LIU J, ZHANG T, WANG Z, et al. Enhancement of visible light photocatalytic activities via porous structure of g-C₃N₄. Applied Catalysis B: Environmental, 2014, 405(3): 229.
[15]	HUANG W Z, XU Z D, LIU R, et al. Tungstenic acid induced assembly of hierarchical flower-like MoS₂ spheres. Materials Research Bulletin 2008, 43(10): 2799. DOI URL
[16]	LIU Y J, LIU H X, et al. A Z-scheme mechanism of N-ZnO/g-C₃N₄ for enhanced H₂ evolution and photocatalytic degradation. Applied Surface Science, 2019, 466:133.
[17]	YUAN Y J, YE Z J, LU H W, et al. Constructing anatase TiO₂ nanosheets with exposed (001) facets/layered MoS₂ two-dimensional nanojunctions for enhanced solar hydrogen generation. ACS Catalysis, 2016, 6(2): 532. DOI URL
[18]	SUN L L, LI Y F, JIAO X D, et al. Fundamentals and challenges of ultrathin 2D photocatalysts in boosting CO₂ photoreduction. Chemical Society Reviews, 2020, 49(18): 6592.
[19]	HOU Y D, LAURSEN A B, ZHANG J S, et al. Layered nanojunctions for hydrogen-evolution catalysis. Angewandte Chemie International Edition, 2013, 52(13): 3621. DOI URL
[20]	YANG J, SHI Q, ZHANG R, et al. BiVO₄ quantum tubes loaded on reduced graphene oxide aerogel as efficient photocatalyst for gaseous formaldehyde degradation. Carbon, 2018, 138: 118.
[21]	TIAN S C, ZHANG X H, ZHANG Z H, et al. Capacitive deionization with MoS₂/g-C₃N₄ electrodes. Desalination, 2020, 479: 114.
[22]	LIU S S, ZHANG X B, HAO S, et al. Preparation of MoS₂ nanofibers by electrospinning. Materials Letters, 2012,73: 223.
[23]	LI X L, LI Y D, et al. Formation of MoS₂ inorganic fullerenes (IFs) by the reaction of MoO₃ nanobelts and S. Chemistry-a European Journal, 2003(9): 22.
[24]	ZHOU X S, LUO Z H, TAO P F, et al. Facile preparation and enhanced photocatalytic H₂-production activity of Cu(OH)₂ nanospheres modified porous g-C₃N₄. Materials Chemistry and Physics, 2014, 143: 1462.
[25]	YU J G, WANG S H, CHENG B, et al. Noble metal-free Ni(OH)₂-g-C₃N₄ composite photocatalyst with enhanced visible- light photocatalytic H₂-production activity. Catalysis Science & Technology, 2013, (3): 1782.
[26]	GUO B R, LIU B, LI C, et al. S-scheme Ti_0.7Sn_0.3O₂/g-C₃N₄ heterojunction composite for enhanced photocatalytic pollutants degradation. Journal of Environmental Chemical Engineering, 2022, 10(2): 107.
[27]	崔晓莉. 半导体电极的平带电位. 化学通报, 2017(80): 1160.
[28]	HUANG Z F, SONG J, WANG X, et al. Switching charge transfer of C₃N₄/W₁₈O₄₉ from type-II to Z-scheme by interfacial band bending for highly efficient photocatalytic hydrogen evolution. Nano Energy, 2017, 40: 308.
[29]	YU W, CHEN J, SHANG T, et al. Direct Z-scheme g-C₃N₄/WO₃ photocatalyst with atomically defined junction for H₂ production. Applied Catalysis B: Environmental, 2017, 219: 693.
[30]	YANG B, ZHAO J J, YANG W D, et al. A step-by-step synergistic stripping approach toward ultra-thin porous g-C₃N₄ nanosheets with high conduction band position for photocatalystic CO₂ reduction. Journal of Colloid and Interface Science, 2021, 589(12): 179. DOI URL
[31]	DONG F, ZHAO Z W, XIONG T, et al. In situ construction of g-C₃N₄/g-C₃N₄ metal-free heterojunction for enhanced visible-light photocatalysis. Applied Materials & Interfaces, 2013, 5(21): 11392.

MoS₂/g-C₃N₄ S型异质结的构建及光催化性能研究

S-type Heterojunction of MOS₂/g-C₃N₄: Construction and Photocatalysis

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