自掺杂SnO2微球的水热合成及其可见光催化性能

摘要/Abstract

摘要： 本研究采用水热法,以柠檬酸为螯合剂,通过控制n(Sn⁴⁺)/n(Sn²⁺)的数值,合成了由具有丰富氧空位的SnO₂纳米晶体组装成的微球。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、傅里叶红外光谱(FT-IR)、X射线光电子能谱(XPS)及UV-Vis漫反射光谱对SnO₂纳米微球进行表征分析,结果表明:在酸性水热条件和柠檬酸的螯合作用下,二氧化锡纳米晶体聚集形成微球;在Sn⁴⁺/Sn²⁺摩尔比例为3:7时,其微球尺寸最小,整体分散性较好;同时适量二价锡离子的掺杂使得该样品氧空位浓度达到最佳,氧空位的存在将使得样品光吸收范围拓展至可见光,因而该样品显示出较强的可见光催化效率,在8 min内完全降解甲基橙。

关键词: SnO₂, 氧空位, 光催化, 水热法, 自掺杂, 可见光

Abstract: In this study, the microspheres assembled from SnO₂ nanocrystals with abundant oxygen vacancies were synthesized by hydrothermal method using citric acid as a chelating agent and controlling the molar ratio of Sn⁴⁺/Sn²⁺. The SnO₂ nano-microspheres were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS) and UV-Vis diffuse reflectance spectroscopy. The results show that under the acidic hydrothermal conditions and the chelating effect of citric acid, the tin dioxide nanocrystals aggregate to form microspheres; at a Sn⁴⁺/Sn²⁺ molar ratio of 3:7, the size of the microspheres is the smallest and the overall dispersion is good. The presence of the oxygen vacancies will extend the light absorption range to visible light; thus, the sample shows a strong visible light catalytic efficiency and complete degradation of methyl orange within 8 min.

Key words: SnO₂, oxygen vacancy, photocatalysis, hydrothermal method, self doping, visible light

中图分类号:

刘权, 展红全, 袁梦磊, 李芾, 谢志鹏, 汪长安. 自掺杂SnO₂微球的水热合成及其可见光催化性能[J]. 人工晶体学报, 2022, 51(1): 139-147.

LIU Quan, ZHAN Hongquan, YUAN Menglei, LI Fu, XIE Zhipeng, WANG Chang'an. Hydrothermal Synthesis and Visible Light Photocatalytic Properties of Self-Doped SnO₂ Microspheres[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2022, 51(1): 139-147.

参考文献

[1] WANG H, LIU W, HE X, et al. An excitonic perspective on low-dimensional semiconductors for photocatalysis[J]. Journal of the American Chemical Society, 2020, 142(33): 14007-14022.
[2] KISCH H. Semiconductor photocatalysis-mechanistic and synthetic aspects[J]. Angewandte Chemie International Edition, 2013, 52(3): 812-847.
[3] WU H, YUAN C, CHEN R, et al. Mechanisms of interfacial charge transfer and photocatalytic NO oxidation on BiOBr/SnO₂ p-n heterojunctions[J]. ACS Applied Materials & Interfaces, 2020, 12(39): 43741-43749.
[4] ZHONG Y, LI W, ZHAO X, et al. High-response room-temperature NO₂ sensor and ultrafast humidity sensor based on SnO₂ with rich oxygen vacancy[J]. ACS Applied Materials & Interfaces, 2019, 11(14): 13441-13449.
[5] LI S, QIN F, PENG Q, et al. Van der waals mixed valence tin oxides for perovskite solar cells as UV-stable electron transport materials[J]. Nano Letters, 2020, 20(11): 8178-8184.
[6] HAN D, JIANG B, FENG J, et al. Photocatalytic self-doped SnO_2-x nanocrystals drive visible-light-responsive color switching[J]. Angewandte Chemie International Edition, 2017, 56(27): 7792-7796.
[7] PERIYASAMY M, KAR A. Modulating the properties of SnO₂ nanocrystals: morphological effects on structural, photoluminescence, photocatalytic, electrochemical and gas sensing properties[J]. Journal of Materials Chemistry C, 2020, 8(14): 4604-4635.
[8] ULLAH I, MUNIR A, MUHAMMAD S, et al. Influence of W-doping on the optical and electrical properties of SnO₂ towards photocatalytic detoxification and electrocatalytic water splitting[J]. Journal of Alloys and Compounds, 2020, 827: Article 154247.
[9] KING L A, YANG Q, GROSSETT M L, et al. Photosensitization of natural and synthetic SnO₂ single crystals with dyes and quantum dots[J]. The Journal of Physical Chemistry C, 2016, 120(29): 15735-15742.
[10] BUI D P, NGUYEN M T, TRAN H H, et al. Green synthesis of Ag@SnO₂ nanocomposites for enhancing photocatalysis of nitrogen monoxide removal under solar light irradiation[J]. Catalysis Communications, 2020, 136: Article 105902.
[11] SHAN H, WANG X, SHI F, et al. Hierarchical porous structured SiO₂/SnO₂ nanofibrous membrane with superb flexibility for molecular filtration[J]. ACS Applied Materials & Interfaces, 2017, 9(22): 18966-18976.
[12] YU C, HE H, LIU X, et al. Novel SiO₂ nanoparticle-decorated BiOCl nanosheets exhibiting high photocatalytic performances for the removal of organic pollutants[J]. Chinese Journal of Catalysis, 2019, 40(8): 1212-1221.
[13] ZENG D, YANG K, YU C, et al. Phase transformation and microwave hydrothermal guided a novel double Z-scheme ternary vanadate heterojunction with highly efficient photocatalytic performance[J]. Applied Catalysis B: Environmental, 2018, 237: 449-463.
[14] YU C, ZENG D, FAN Q, et al. The distinct role of boron doping in Sn₃O₄ microspheres for synergistic removal of phenols and Cr(Ⅵ) in simulated wastewater[J]. Environmental Science: Nano, 2020, 7(1): 286-303.
[15] ZHA R, SHI T, HE L, et al. Synergetic excitonic and defective effects in confined SnO₂/α-Fe₂O₃ nanoheterojunctions for efficient photocatalytic molecular oxygen activation[J]. Chemical Engineering Journal, 2021, 421: Article 129883.
[16] CHEN X, LIU L, YU P Y, et al. Increasing solar absorption for photocatalysis with black hydrogenated titanium dioxide nanocrystals[J]. Science, 2011, 331(6018): 746-750.
[17] FAN C M, PENG Y, ZHU Q, et al. Synproportionation reaction for the fabrication of Sn²⁺ self-doped SnO_2-x nanocrystals with tunable band structure and highly efficient visible light photocatalytic activity[J]. The Journal of Physical Chemistry C, 2013, 117(46): 24157-24166.
[18] SHAO M, LIU J, DING W, et al. Oxygen vacancy engineering of self-doped SnO_2-x nanocrystals for ultrasensitive NO₂ detection[J]. Journal of Materials Chemistry C, 2020, 8(2): 487-494.
[19] DENG H, LAMELAS F J, HOSSENLOPP J M. Synthesis of tin oxide nanocrystalline phases via use of tin(Ⅱ) halide precursors[J]. Chemistry of Materials, 2003, 15(12): 2429-2436.
[20] SONG M, WU Y, ZHAO Y, et al. Structural insight on defect-rich tin oxide for smart band alignment engineering and tunable visible-light-driven hydrogen evolution[J]. Inorganic Chemistry, 2020, 59(5): 3181-3192.
[21] GURLO A. Interplay between O₂ and SnO₂: oxygen ionosorption and spectroscopic evidence for adsorbed oxygen[J]. ChemPhysChem, 2006, 7(10): 2041-2052.
[22] UCHIYAMA H, SHIRAI Y, KOZUKA H. Formation of spherical SnO₂ particles consisting of nanocrystals from aqueous solution of SnCl₄ containing citric acid via hydrothermal process[J]. Journal of Crystal Growth, 2011, 319(1): 70-78.
[23] LI J, WU Y, YANG M, et al. Electrospun Fe₂O₃ nanotubes and Fe₃O₄ nanofibers by citric acid sol-gel method[J]. Journal of the American Ceramic Society, 2017, 100(12): 5460-5470.
[24] KARMAOUI M, JORGE A B, MCMILLAN P F, et al. One-step synthesis, structure, and band gap properties of SnO₂ nanoparticles made by a low temperature nonaqueous sol-gel technique[J]. ACS Omega, 2018, 3(10): 13227-13238.
[25] RIBEIRO C, LEE E J H, GIRALDI T R, et al. Study of synthesis variables in the nanocrystal growth behavior of tin oxide processed by controlled hydrolysis[J]. The Journal of Physical Chemistry B, 2004, 108(40): 15612-15617.
[26] SIKHWIVHILU L M, PILLAI S K, HILLIE T K. Influence of citric acid on SnO₂ nanoparticles synthesized by wet chemical processes[J]. Journal of Nanoscience and Nanotechnology, 2011, 11(6): 4988-4994.
[27] DONG W, SUN Y, HUA W, et al. Preparation of secondary mesopores in mesoporous anatase-silica nanocomposites with unprecedented-high photocatalytic degradation performances[J]. Advanced Functional Materials, 2016, 26(6): 964-976.
[28] ZHAN H, DENG C, SHI X L, et al. Correlation between the photocatalysis and growth mechanism of SnO₂ nanocrystals[J]. Journal of Physics D: Applied Physics, 2020, 53(15): Article 154005.
[29] ZHAN H, DENG C, LIU Q, et al. Growth process, photoluminescence property and photocatalytic activity of SnO₂ nanorods[J]. Chinese Journal of Inorganic Chemistry, 2020, 36(8): 1605-1612.
[30] GAUR L K, CHANDRA MATHPAL M, KUMAR P, et al. Observations of phonon anharmonicity and microstructure changes by the laser power dependent Raman spectra in Co doped SnO₂ nanoparticles[J]. Journal of Alloys and Compounds, 2020, 831: Article 154836.
[31] LIU Q, ZHAN H, HUANG X, et al. High visible light photocatalytic activity of SnO_2-x nanocrystals with rich oxygen vacancy[J]. European Journal of Inorganic Chemistry. 2021, doi: 10.1002/ejic.202100617.
[32] ZENG D, YU C, FAN Q, et al. Theoretical and experimental research of novel fluorine doped hierarchical Sn₃O₄ microspheres with excellent photocatalytic performance for removal of Cr (Ⅵ) and organic pollutants[J]. Chemical Engineering Journal, 2020, 391: Article 123607.
[33] XU Y, ZHENG L, YANG C, et al. Oxygen vacancies enabled porous SnO₂ thin films for highly sensitive detection of triethylamine at room temperature[J]. ACS Applied Materials & Interfaces, 2020, 12(18): 20704-20713.

自掺杂SnO₂微球的水热合成及其可见光催化性能

Hydrothermal Synthesis and Visible Light Photocatalytic Properties of Self-Doped SnO₂ Microspheres

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	孟晓燕, 吴斌, 刘清, 王意, 吴秀平. NaY(WO₄)₂:Sm³⁺粉末的制备及荧光性能[J]. 人工晶体学报, 2022, 51(1): 120-125.
[2]	赵蕴璞, 程宏飞, 曹洲, 贾悦发. 高岭石基复合材料在光催化领域应用的研究进展[J]. 人工晶体学报, 2022, 51(1): 170-184.
[3]	李佩欣, 辛浪, 宋佳, 杨爱云, 崔娟, 殷春浩. 稀土金属Ce³⁺掺杂ZnO材料的光催化机理[J]. 人工晶体学报, 2021, 50(9): 1723-1728.
[4]	李瑞, 张潇, 张璐璐, 谢芳霞, 张小超, 王雅文, 樊彩梅. 原位合成Bi₃O₄Br/Bi₁₂O₁₇Br₂光催化剂及其对磺胺甲噁唑降解性能[J]. 人工晶体学报, 2021, 50(9): 1735-1744.
[5]	范兴其, 姚梦琴, 刘飞, 王晓丹, 曹建新. 制备方法对Al₂O₃-CeO₂物化性质及CO₂加氢制甲醇催化性能的影响[J]. 人工晶体学报, 2021, 50(9): 1745-1755.
[6]	谭思慧, 刘婷, 钟国清. 2,2'-联吡啶-6,6'-二甲酸镍(Ⅱ)配合物的合成与表征[J]. 人工晶体学报, 2021, 50(8): 1452-1456.
[7]	张静, 师倩莹, 龚浩, 郭雨菲, 张卫珂. MCNOs/CdS双效光催化剂的制备及其性能研究[J]. 人工晶体学报, 2021, 50(8): 1485-1495.
[8]	栾照金, 闫共芹, 谈尚华. SnO₂/石墨分级纳米异质结构的合成及其电化学性能研究[J]. 人工晶体学报, 2021, 50(8): 1503-1510.
[9]	刘艺蕊, 段敏娜, 顾希煊, 高艳红, 何勇, 宋娟. 一例镉(Ⅱ)配合物的合成、结构及发光性质研究[J]. 人工晶体学报, 2021, 50(6): 1044-1048.
[10]	徐衡, 桂乃成, 严达, 熊志, 黄荣谊. 新型镉(Ⅱ)配合物荧光探针的合成及性能[J]. 人工晶体学报, 2021, 50(6): 1049-1055.
[11]	徐艳, 崔磊, 卜康. 一例混合配体构筑的钴(Ⅱ)一维配位聚合物的合成、晶体结构与磁性质[J]. 人工晶体学报, 2021, 50(5): 894-899.
[12]	谷莹蕾, 李勇, 卜景龙, 马超, 王志发. 纳米级SnO₂或Yb₂O₃对熔融石英陶瓷析晶性能的影响[J]. 人工晶体学报, 2021, 50(5): 927-932.
[13]	王泽岩, 王朋, 刘媛媛, 郑昭科, 程合锋, 黄柏标. 基于晶体学原理的高效光催化材料的设计与制备[J]. 人工晶体学报, 2021, 50(4): 685-707.
[14]	罗楠楠, 曹国炜, 郄元元, 张然, 王春晓, 公丕富, 李志华, 林哲帅. 碱式磷酸锌光学性质的理论计算及其实验验证[J]. 人工晶体学报, 2021, 50(3): 454-460.
[15]	王鑫伟, 车致远, 张兴, 李玲薇, 张伟, 苏适, 马晋文. 不同形貌TiO₂薄膜的可控制备及其光电化学性能研究[J]. 人工晶体学报, 2021, 50(3): 516-522.