新型Fe掺杂钙钛矿型KMgF3光催化剂制备及性能

doi:10.7517/j.issn.1674-0475.2017.01.061

摘要/Abstract

摘要：

通过微乳液法制备了Fe掺杂钙钛矿型KMgF₃光催化剂，运用扫描电子显微观察（SEM）、X射线衍射光谱（XRD）、紫外可见漫反射光谱（UV-Vis DRS）、光致发光光谱（PL spectra）、X射线光电子能谱（XPS）等对催化剂形貌、结构及理化特性等进行表征。考察了制备材料对水体中罗丹明B和甲基橙的光降解性能和其稳定性。结果表明，Fe³⁺通过取代Mg²⁺掺杂进入KMgF₃晶格形成均质固溶体，抑制晶粒长大和团聚的同时形成新的掺杂能级和浅电子陷阱，显著改善催化剂的光谱响应和抑制催化剂表面光生电子和空穴的复合。最适Fe³⁺掺杂量为Mg²⁺的1/4（摩尔分数），掺杂催化剂对水体罗丹明B、甲基橙的降解率30 min内分别可达92%、91%，相比未掺杂的催化剂，降解率分别显著提升了约63%、68%。经5次光降解实验循环后，掺杂催化剂活性仍可保持新鲜催化剂的90%以上。

关键词: KMgF₃, Fe掺杂, 钙钛矿, 罗丹明B, 甲基橙, 光催化

Abstract:

The Fe doped perovskite-type Fe-KMgF₃ photocatalysts were synthesized by a microemulsion preparation. The as-prepared catalysts were characterized by scanning electron microscope (SEM), X-ray diffraction (XRD), UV-Vis diffuse reflectance spectra (UV-Vis DRS), photoluminescence spectra(PL spectra) and X-ray photoelectron spectroscopy (XPS). The photocatalytic activity of the materials was performed by the degradation of aqueous Rhodanmine B and Methyl Orange. Results demonstrate that Mg²⁺ in KMgF₃ may be substituted by a low amount of Fe³⁺ to form a homogenous solid solution while the perovskite-type structure of KMgF₃ remains unchanged. The doping by Fe can suppress the growth and aggregation of KMgF₃ crystallion, helps to improve the light response and inhibit the recombination of phtogenerated hole/electron pairs by forming the donor level of impurities and shallow traps in lattice matrix. The photocatalytic degradation rates of Rhodanmine B and Methyl Orange on doped catalyst under optimal content of Fe³⁺ (one quarter of Mg²⁺) reached 92% and 91% respectively in 30 min, and about 63% and 68% respectively of degradation rate enhancement which compared with non-doped KMgF₃ was observed. After 5th photocatalytic experiment, the photocatalytic degradation rate of Rhodanmine B remains more than 90% of the fresh.

Key words: KMgF₃, Fe doption, perovskite, rhodanmine B, methyl orange, photocatalysis

聂坤, 杨汉培, 孙慧华, 崔素珍, 吴俊明. 新型Fe掺杂钙钛矿型KMgF₃光催化剂制备及性能[J]. 影像科学与光化学, 2017, 35(1): 61-69.

NIE Kun, YANG Hanpei, SUN Huihua, CUI Suzhen, WU Junming. Synthesis and Properties of a Novel Fe Doped Perovskite-type KMgF₃ Photocatalyst[J]. Imaging Science and Photochemistry, 2017, 35(1): 61-69.

参考文献

[1] Nuengmmatcha P, Chanthai S, Mahachai R, Oh W C. Visible light-driven photocatalytic degradation of rho-damine B and industrial dyes (texbrite BAC-L and tex-brite NFW-L) by ZnO-graphene-TiO₂ composite[J]. Journal of Environmental Chemical Engineering, 2016,4(2):2170-2177.
[2] Dong W Y, Lee C W, Lu X C, Sun Y J, Hua W M, Zhuang G S, Zhang S C, Chen J M, Huo H Q, Zhao D Y. Synchronous role of coupled adsorption and photo-catalytic oxidation on ordered mesoporous anatase TiO₂-SiO₂ nanocomposites generating excellent de-gradation activity of RhB dye[J]. Applied Catalysis B:Environmental, 2010,95(3-4):197-207.
[3] Yagub M T, Sen T K, Afroze S, Ang H M. Dye and its removal from aqueous solution by adsorption:a review[J]. Advances in Colloid and Interface Science, 2014,209:172-184.
[4] Wang H L, Zhang L S, Chen Z G, Hu J Q, Li S J, Wang Z H, Liu J S, Wang X C. Semiconductor heterojunction photocatalysts:design, construction, and photocatalytic performances[J]. Chemical Society Reviews, 2014,43(15):5234-5244.
[5] Grabowska E. Selected perovskite oxides:Characteri-zation, preparation and photocatalytic properties-a review[J]. Applied Catalysis B:Environmental, 2016,186:97-126.
[6] Tanaka H, Misono M. Advances in designing perovskite catalysts[J]. Current Opinion in Solid State and Materials Science, 2001,5(5):381-387.
[7] Su P, Mei Y, Zheng W C, Liu H G. A research on the g factors and defect model for the tetragonal Sm³⁺ center in KMgF₃ crystal[J]. Physica B:Condensed Matter, 2013,420:1-5.
[8] Cheng F, Liu T Y, Zhang Q R, Qian H L, Zhou X W. First principle studies on the electronic structures and absorption spectra in KMgF₃ crystal with fluorine vacancy[J]. Nuclear Instruments and Methods in Physics Research Section B:Beam Interactions with Materials and Atoms, 2010,268(15):2403-2407.
[9] Hu R S, Li C, Wang X, Zhou T T, Yang X Z, Gao G J, Zhang Y L. Synthesis of perovskite KMgF₃ with microemulsion for photocatalytic removal of various pollutants under visible light[J]. Catalysis Communications, 2013,40:71-75.
[10] Ma A J, Wang S Z, Liu C, Xian H, Ding Q, Guo L, Meng M, Tan Y S, Tsubaki N, Zhang J, Zheng L R, Li X G. Effects of Fe dopants and residual carbonates on the catalytic activities of the perovskite-type La_0.7Sr_0.3Co_1-xFe_xO₃NO_x storage catalyst[J]. Applied Catalysis B:Environmental, 2014,146:24-34.
[11] Sood S, Umar A, Mehta S K, Kansal S K. Highly effective Fe-doped TiO₂ nanoparticles photocatalysts for visible-light driven photocatalytic degradation of toxic organic compounds[J]. Journal of Colloid and Interface Science, 2015,450:213-223.
[12] Song H, Li Y G, Lou Z R, Xiao M, Hu L, Ye Z Z, Zhu L P. Synthesis of Fe-doped WO₃ nanostructures with high visible-light-driven photocatalytic activities[J]. Applied Catalysis B:Environmental, 2015,166-167:112-120.
[13] 李菊芬.过渡离子Fe³⁺在KMgF₃中局域晶体结构理论的研究[J].西南民族大学学报(自然科学版), 2009,35(5):1049-1052.Li J F. Theoretical study of electron paramagnetic resonance spectrum for Fe³⁺ ion in KMgF₃:Fe³⁺ system[J]. Journal of Southwest University for Nationalities Natural Science Edition, 2009,35(5):1049-1052.
[14] Yang Z Y. Zero-field splitting of the ground state and local lattice distortions for Fe³⁺ ions at the tetragonal FeF₅O cluster center in Fe³⁺:KMgF₃ crystals[J]. Journal of Fluorine Chemistry, 2012,135:250-253.
[15] 李家科,刘欣,黄丽群,王艳香.溶液燃烧合成LaFe_1-xMg_xO₃超细粉体及其光催化性能[J].无机材料学报,2015,30(11):1223-1227.Li J K, Liu X, Huang L Q, Wang Y X. LaFe_1-xMg_xO₃ ultrafine powders synthesized by solution combustion and its photocatalytic performances[J]. Journal of Inorganic Materials, 2015,30(11):1223-1227.
[16] Sudha D, Sivakummar P. Review on the photocatalytic activity of various composite catalysts[J]. Chemical Engineering and Processing:Process Intensification, 2015,97:112-133.
[17] Zhu G X, Li Y D, Lian H Z, Yan J H, Wang X Q. Synthesis and fluorescence properties of cerium-KMgF₃ through a solvothermal process[J]. Chinese Chemical Letters, 2009,20(1):106-110.
[18] Tong H, Ouyang S X, Bi Y P, Umezawa N, Oshikiri M, Ye J H. Nano-photocatalytic materials:possibilities and challenges[J].Advanced Materials, 2012,24(2):229-251.
[19] Niu Y X, Xing M Y, Zhang J L, Tian B Z. Visible light activated sulfur and iron co-doped TiO₂ photocatalyst for the photocatalytic degradation of phenol[J]. Catalysis Today, 2013,201:159-166.
[20] Dong S Y, Feng J L, Fan M H, Pi Y Q, Hu L M, Han X, Liu M L, Sun J Y, Sun J H. Recent developments in heterogeneous photocatalytic water treatment using visible light-responsive photocatalysts:a review[J]. RSC Advances, 2015,5(19):14610-14630.
[21] Wu P, Luo X G, Zhang S Z, Li K, Qi F W. Novel near room-temperature andor light driven Fe-doped Sr₂Bi₂O₅ photo/thermocatalyst for methylene blue degradation[J]. Applied Catalysis A:General, 2015,497:216-224.

新型Fe掺杂钙钛矿型KMgF₃光催化剂制备及性能

Synthesis and Properties of a Novel Fe Doped Perovskite-type KMgF₃ Photocatalyst

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]	王佳, 王亚丽, 侯丽新, 刘贤豪. 高效钙钛矿太阳能电池吸光层的设计与优化[J]. 影像科学与光化学, 2020, 38(3): 416-423.
[2]	李玥, 李红英, 常玉雪, 周宏艳, 于翔. MoS₂/TiO₂纳米管阵列的一步沉积法制备及光电性能研究[J]. 影像科学与光化学, 2018, 36(4): 331-339.
[3]	李玥, 宋育泽, 陶雁忠, 高风仙, 汤宁. CdS/TiO₂复合纳米网的制备及光催化性能研究[J]. 影像科学与光化学, 2018, 36(3): 275-282.
[4]	李玲, 杜云舒, 王璇, 韩建, 王传义. 甲醛气体在ZnO表面光降解的机理研究[J]. 影像科学与光化学, 2018, 36(2): 171-177.
[5]	吴世康. 光催化中表面等离子体与半导体间的电子转移与能量转移[J]. 影像科学与光化学, 2018, 36(1): 1-13.
[6]	Samuel Lascio, 籍海峰. 磷纳米材料的光学、光电子和光催化应用[J]. 影像科学与光化学, 2017, 35(5): 587-602.
[7]	张庆宝, 刘强. 可见光催化需氧氧化在有机合成中的应用[J]. 影像科学与光化学, 2017, 35(5): 614-625.
[8]	桂梦茜, 俞洋, 朱诚逸, 刘宏芳, 王锋. 基于金属钴配合物的均相光催化还原二氧化碳研究进展[J]. 影像科学与光化学, 2017, 35(5): 649-657.
[9]	彭成云, 陈勇. 苝衍生物光催化氧化硫醚的研究[J]. 影像科学与光化学, 2017, 35(5): 675-685.
[10]	孔祥彬, 陈永振, 李志毅, 刘彦伟, 魏晓芳, 刘建君, 王瑞芳, 王鹰. 压强对钙钛矿薄膜形貌和结晶性影响的研究[J]. 影像科学与光化学, 2017, 35(5): 749-757.
[11]	朱哲欣, 叶美英. 光催化微反应器中水样光催化降解及Cd²⁺在线检测[J]. 影像科学与光化学, 2016, 34(5): 444-451.
[12]	张亚婷, 李可可, 任绍昭, 王黛玉, 周安宁, 邱介山. 金属改性煤基石墨烯复合材料的制备及其光催化性能[J]. 影像科学与光化学, 2016, 34(5): 475-481.
[13]	王勐, 夏静, 朱丹丹, 王磊, 孟祥敏. Fe掺杂ZnO空心微球的制备与光催化性能[J]. 影像科学与光化学, 2016, 34(3): 245-251.
[14]	蒋伟, 武祥. ZnS微米花的水热合成及光催化性质研究[J]. 影像科学与光化学, 2016, 34(3): 252-256.
[15]	黄奔, 李玄泽, 王磊, 夏静, 朱丹丹, 孟祥敏. 钼网衬底上大面积硅纳米线的制备及其光催化性能研究[J]. 影像科学与光化学, 2016, 34(3): 257-264.