铒掺杂g-C3N4催化剂的合成及其红光催化降解活性的研究

摘要/Abstract

摘要： 石墨相氮化碳(g-C₃N₄)的研究已成为光催化领域热点。本文以三聚氰氨为前驱体,采用甲醇回流法制备Er掺杂的g-C₃N₄催化剂。利用扫描电镜(SEM)、X射线光电子能谱(XPS)、X射线衍射仪(XRD)、紫外-可见-近红外分光光度计(UV-Vis-NIR DRS)、傅里叶红外光谱仪(IR)、荧光光谱(PL)、物理吸附(N₂-physisorption)及共聚焦显微镜(CLSM)等手段对Er/g-C₃N₄催化剂进行系统表征。结果表明,稀土金属Er高分散于g-C₃N₄上,促使氮化碳表面氮空穴的产生。Er掺杂优化了氮化碳的能带结构,增强了其对可见光的吸收,提升电子-空穴对的分离效率,此外还发现Er/g-C₃N₄具有较强的上转换能力。在660 nm红光LED照射下,对罗丹明B的水溶液进行光催化降解,发现Er/g-C₃N₄的降解速率是g-C₃N₄的2.0倍,且发现超氧自由基为该体系中的主要活性物种。

关键词: g-C₃N₄, 铒掺杂, 甲醇回流法, 光催化, 红光, 上转换, 降解活性

Abstract: Graphite carbon nitride (g-C₃N₄) has become the hot research material in the field of photocatalysis. In this study, Er-doped g-C₃N₄ was synthesized by methanol-refluxing method using melamine as precursor. The resulting composite photocatalysts were characterized by scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), ultraviolet-visible-near infrared reflection spectrophotometer (UV-Vis-NIR Spectrophotometer), infrared spectrum (IR), photoluminescence spectroscopy (PL), N₂-physisorption and confocal laser scanning microscopy (CLMS). Results indicate that the rare-earth metal Er is highly disperse on g-C₃N₄ and it is favor for the introduction of nitrogen vacancies. The addition of Er optimize the energy band structure of g-C₃N₄, enhance the absorption of visible light, improve the electron-hole separation rate, furthermore, it is also found that Er/g-C₃N₄ photocatalyst process strong upconversion ability. The photocatalytic degradation of rhodamine B solution is performed under 660 nm LED red-light irradiation, and the rate constant of the Er/g-C₃N₄ is 2.0 times as high as that of pure g-C₃N₄. It is also found that the superoxide radical is the main active species for catalytic reaction in this system.

Key words: g-C₃N₄, Er doped, methanol-refluxing method, photocatalysis, red light, upconversion, degradation activity

中图分类号:

徐启立, 沈朝峰, 何昌春, 史伟, 张慧, 尹宇洁, 田静, 张资越, 陈娜, 王鹏. 铒掺杂g-C₃N₄催化剂的合成及其红光催化降解活性的研究[J]. 人工晶体学报, 2020, 49(12): 2313-2321.

XU Qili, SHEN Chaofeng, HE Changchun, SHI Wei, ZHANG Hui, YIN Yujie, TIAN Jing, ZHANG Ziyue, CHEN Na, WANG Peng. Synthesis of Erbium Doped g-C₃N₄ Catalyst and Its Photocatalytic Degradation Activity under Red Light[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2020, 49(12): 2313-2321.

参考文献

[1] Tong H, Ouyang S, Bi Y, et al. Nano-photocatalytic materials: possibilities and challenges[J]. Advanced Materials, 2012, 24(2): 229-251.
[2] Zhang Q, Deng J, Xu Z, et al. High-efficiency broadband C₃N₄ photocatalysts: synergistic effects from upconversion and plasmons[J]. ACS Catalysis, 2017, 7(9): 6225-6234.
[3] Li X, Liang L, Sun Y, et al. Ultrathin conductor enabling efficient IR light CO₂ reduction[J]. Journal of the American Chemical Society, 2019, 141(1): 423-430.
[4] Lian Z, Sakamoto M, Vequizo J J M, et al. Plasmonic p n junction for infrared light to chemical energy conversion[J]. Journal of the American Chemical Society, 2019, 141(6): 2446-2450.
[5] Liu Y, Zhu G, Gao J, et al. A novel synergy of Er³⁺/Fe³⁺ co-doped porous Bi₅O₇I microspheres with enhanced photocatalytic activity under visible-light irradiation[J]. Applied Catalysis B: Environmental, 2017, 205: 421-432.
[6] Yang R, Cai J, Lv K, et al. Fabrication of TiO₂ hollow microspheres assembly from nanosheets (TiO₂-HMSs-NSs) with enhanced photoelectric conversion efficiency in DSSCs and photocatalytic activity[J]. Applied Catalysis B: Environmental, 2017, 210: 184-193.
[7] Xu T, Zhang L, Cheng H, et al. Significantly enhanced photocatalytic performance of ZnO via graphene hybridization and the mechanism study[J]. Applied Catalysis B:Environmental, 2011, 101(3): 382-387.
[8] 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.
[9] Xu F, Zhang L, Cheng B, et al. Direct z-scheme TiO₂/NiS core-shell hybrid nanofibers with enhanced photocatalytic H₂-production activity[J]. ACS Sustainable Chemistry & Engineering, 2018, 6(9): 12291-12298.
[10] Wang X C, Maeda K, Thomas A, et al. A metal-free polymeric photocatalyst for hydrogen production from water under visible light[J]. Nature Materials, 2009, 8(1): 76-80.
[11] Wang X C, Chen X, Thomas A, et al. Metal-containing carbon nitride compounds: a new functional organic metal hybrid material[J]. Advanced Materials, 2009, 21(16): 1609-1612.
[12] Zhu B, Cheng B, Zhang L, et al. Review on DFT calculation of s triazine based carbon nitride[J]. Carbon Energy, 2019(1): 32-56.
[13] Chen X, Zhang J, Fu X, et al. Fe-g-C₃N₄-catalyzed oxidation of benzene to phenol using hydrogen peroxide and visible light[J]. Journal of the American Chemical Society, 2009, 131(33): 11658-11659.
[14] Zhang J, Zhang G, Chen X, et al. Co-monomer control of carbon nitride semiconductors to optimize hydrogen evolution with visible light[J]. Angewandte Chemie International Edition, 2012, 51(13): 3183-3187.
[15] Zhang X, Yuan X, Jiang L, et al. Powerful combination of 2D g-C₃N₄ and 2D nanomaterials for photocatalysis: recent advances[J]. Chemical Engineering Journal, 2020, 390: 124475.
[16] Ren Y, Zeng D, Ong W J. Interfacial engineering of graphitic carbon nitride (g-C₃N₄)-based metal sulfide heterojunction photocatalysts for energy conversion: A review[J]. Chinese Journal of Catalysis, 2019, 40(3): 289-319.
[17] Huang D, Li Z, Zeng G, et al. Megamerger in photocatalytic field: 2D g-C₃N₄ nanosheets serve as support of 0D nanomaterials for improving photocatalytic performance[J]. Applied Catalysis B: Environmental, 2019, 240: 153-173.
[18] Cui Y, Ding Z, Fu X, et al. Construction of conjugated carbon nitride nanoarchitectures in solution at low temperatures for photoredox catalysis[J]. Angewandte Chemie International Edition, 2012, 51(47): 11814-11818.
[19] Zhang G, Li G, Lan Z A, et al. Optimizing optical absorption, exciton dissociation, and charge transfer of a polymeric carbon nitride with ultrahigh solar hydrogen production activity[J]. Angewandte Chemie International Edition, 2017, 56(43): 13445-13449.
[20] Yang P, Wang R, Zhou M, et al. Photochemical construction of carbonitride structures for red-Light redox catalysis[J]. Angewandte Chemie International Edition, 2018, 57(28): 8674-8677.
[21] Fu F, Shen H, Sun X, et al. Synergistic effect of surface oxygen vacancies and interfacial charge transfer on Fe(III)/Bi₂MoO₆ for efficient photocatalysis[J]. Applied Catalysis B:Environmental, 2019, 247: 150-162.
[22] Liu J, Fang W, Wei Z, et al. Efficient photocatalytic hydrogen evolution on N-deficient g-C₃N₄ achieved by a molten salt post-treatment approach [J]. Applied Catalysis B:Environmental, 2018, 238: 465-470.
[23] Yang P, Zhuzhang H, Wang R, et al. Carbon vacancies in a melon polymeric matrix promote photocatalytic carbon dioxide conversion[J]. Angewandte Chemie, 2019, 131: 1146-1149.
[24] Han S, Deng R, Xie X, et al. Enhancing luminescence in lanthanide doped upconversion nanoparticles[J]. Angewandte Chemie International Edition, 2014, 53(44): 11702-11715.
[25] Yang X, Qian F, Zou G, et al. Facile fabrication of acidified g-C₃N₄/g-C₃N₄ hybrids with enhanced photocatalysis performance under visible light irradiation[J]. Applied Catalysis B:Environmental, 2016, 193: 22-35.
[26] Shi L, Chang K, Zhang H, et al. Drastic enhancement of photocatalytic activities over phosphoric acid protonated porous g-C₃N₄ nanosheets under visible light[J]. Small, 2016, 12(32): 4431-4439.
[27] Gao J, Wang Y, Zhou S, et al. A facile one-step synthesis of Fe-doped g-C₃N₄ nanosheets and their improved visible-light photocatalytic performance[J]. Chem Cat Chem, 2017, 9(9): 1708-1715.
[28] Wang P, Chen S, Bai Y, et al. Effect of the promoter and support on cobalt-based catalysts for higher alcohols synthesis through CO hydrogenation[J]. Fuel, 2017, 195: 69-81.
[29] Liu L Y, Xu H, Xu Y G, et al. Graphene quantum dots modified mesoporous graphite carbon nitride with significant enhancement of photocatalytic activity[J]. Applied Catalysis B:Environmental, 2017, 207: 429-437.
[30] Tay Q, Kanhere P, Ng C F, et al. Defect engineered g-C₃N₄ for efficient visible light photocatalytic hydrogen production[J]. Chemistry of Materials, 2015, 27(14): 4930-4933.
[31] Lin Z, Wang X. Nanostructure engineering and doping of conjugated carbon nitride semiconductors for hydrogen photosynthesis[J]. Angewandte Chemie International Edition,2013, 52(6): 1735-1738.
[32] Yan W, Yan L, Jing C. Impact of doped metals on urea-derived g-C₃ N₄ for photocatalytic degradation of antibiotics: structure, photoactivity and degradation mechanisms[J]. Applied Catalysis B:Environmental, 2019, 244: 475-485.
[33] Zhang J, Zhang M, Sun R Q, et al. A facile band alignment of polymeric carbon nitride semiconductors to construct isotype heterojunctions[J]. Angewandte Chemie International Edition, 2012, 51(40): 10145-10149.
[34] Tiwari J N, Seo Y K, Yoon T, et al. Accelerated bone regeneration by two photon photoactivated carbon nitride nanosheets[J]. ACS Nano, 2017, 11(1): 742-751.
[35] Liu J, Yang Y, Liu N, et al. Total photocatalysis conversion from cyclohexane to cyclohexanone by C₃N₄/Au nanocomposites[J]. Green Chemistry, 2014, 16(10): 4559-4565.

铒掺杂g-C₃N₄催化剂的合成及其红光催化降解活性的研究

Synthesis of Erbium Doped g-C₃N₄ Catalyst and Its Photocatalytic Degradation Activity under Red Light

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]	王超, 陈杰, 尹玉, 刘蓉, 王珊珊, 刘治刚. Mn²⁺掺杂Gd₂O₃:Yb³⁺,Er³⁺花状微晶的制备及上转换发光性能[J]. 人工晶体学报, 2023, 52(4): 604-612.
[2]	余海燕, 梁海欧, 白杰, 李春萍. 铜基硫化物光催化改性研究进展[J]. 人工晶体学报, 2023, 52(3): 394-404.
[3]	李敬远. 双钙钛矿结构Rb₃GaF₆∶Er³⁺,Yb³⁺的合成及上转换发光特性研究[J]. 人工晶体学报, 2023, 52(2): 327-333.
[4]	熊智慧, 孔博, 李志西, 曾体贤, 帅春. La掺杂氧空位的α-Bi₂O₃电子结构和光学性质的第一性原理研究[J]. 人工晶体学报, 2023, 52(1): 98-104.
[5]	梁发文, 官海汕, 李江鸿, 李帅, 黄俊兰, 江学顶, 李富华, 陈忻, 许伟城. 非金属掺杂改性g-C₃N₄光催化降解水中有机污染物的研究进展[J]. 人工晶体学报, 2023, 52(1): 170-181.
[6]	孟汝浩, 班新星, 左宏森, 李跃, 栗正新, 邵俊永, 孙冠男, 郝素叶, 韩少星, 张霖, 张国威, 周少杰. TiO₂/g-C₃N₄复合粉体的制备及其在紫外/芬顿反应中光催化性能[J]. 人工晶体学报, 2022, 51(8): 1466-1472.
[7]	潘多桥, 庞国旺, 刘晨曦, 史蕾倩, 张丽丽, 雷博程, 赵旭才, 黄以能. 双轴应变对g-ZnO/WS₂异质结电子结构及光学性质影响的第一性原理计算[J]. 人工晶体学报, 2022, 51(7): 1202-1211.
[8]	王静怡, 张众, 王梓兰, 于鑫颖, 由君颐, 朱君怡, 杨琳. 吡啶鎓盐配体构筑的多钼酸基配合物的合成、结构及光催化性能[J]. 人工晶体学报, 2022, 51(7): 1227-1232.
[9]	张雷, 李瑞, 樊彩梅. Bi₄O₅Br₂/Ti₃C₂-Ru复合光催化剂的合成及其对磺胺甲噁唑药物废水降解性能研究[J]. 人工晶体学报, 2022, 51(7): 1248-1256.
[10]	秦英恋, 秦建芳. 基于构象灵活的N-杂环配体构筑的3D拟卤化亚铜配合物的合成、结构和性质研究[J]. 人工晶体学报, 2022, 51(6): 1059-1068.
[11]	杜康, 寇丽芳, 张小超. EDTA辅助水热法合成BiYO₃及其高效光还原CO₂性能研究[J]. 人工晶体学报, 2022, 51(6): 1085-1091.
[12]	杨思琪, 郑永杰, 张宏瑞, 赵云鹏, 田景芝. g-C₃N₄基异质结的光催化应用研究进展[J]. 人工晶体学报, 2022, 51(6): 1110-1121.
[13]	朱丽, 夏杨雯, 何莉莉, 朱晓东. 水热法制备银修饰混晶二氧化钛及其光催化性能研究[J]. 人工晶体学报, 2022, 51(4): 673-678.
[14]	刘晨曦, 潘多桥, 庞国旺, 史蕾倩, 张丽丽, 雷博程, 赵旭才, 黄以能. X/g-C₃N₄(X=g-C₃N₄、AlN及GaN)异质结光催化活性的理论研究[J]. 人工晶体学报, 2022, 51(3): 450-458.
[15]	石明凤, 顾江红, 卢森源, 徐中轩. 两个基于2,5-二甲氧基对苯二甲酸和咪唑衍生物的超分子钴配位聚合物的结构及光催化反应[J]. 人工晶体学报, 2022, 51(3): 485-492.