室温构筑水稳定钙钛矿量子点用于六价铬检测与发光二极管

doi:10.6023/A26040131

摘要/Abstract

为解决钙钛矿量子点水稳定性差、合成条件苛刻的难题, 并实现六价铬(Cr(VI))的高效检测, 本研究通过双配体协同钝化设计, 采用3-溴-2-(溴甲基)丙酸(BPA)和油胺构筑配体界面, 在温和的室温环境中成功合成了高性能、水相发光稳定的CsPbBr₃@BPA量子点. 所合成量子点的发射半峰宽仅为22 nm, 量子产率可达62.7%. 基于其良好的水相荧光性能和Cr(VI)诱导的动态荧光猝灭机制, 建立了高灵敏度和高特异性的检测方法, 检测限低至4 nmol/L, 线性范围0.02~2.4 μmol/L. 该方法成功用于实际水样中Cr(VI)检测, 回收率在93.3%~106.0%之间, 证实了方法的可靠性和实用性. 合成的量子点还被用于制备高色纯度发光二极管, 展示了其在环境监测与固态照明领域的双功能应用价值.

关键词: CsPbBr₃@BPA量子点, 室温合成, 水稳定, Cr(VI)检测, 发光二极管

Hexavalent chromium (Cr(VI)), as a highly toxic heavy metal ion pollutant, poses severe threats to both aquatic ecosystems and human health. The development of rapid, sensitive, and selective methods for Cr(VI) detection is of great significance for environmental monitoring and public health protection. Perovskite quantum dots (QDs) have shown great potential in fluorescence sensing due to their excellent optical properties, but their practical applications are severely limited by poor water stability and harsh synthesis conditions (typically requiring high temperature). Herein, we report a room-temperature ligand engineering strategy that utilizes the synergistic effect of 3-bromo-2-(bromomethyl)propionic acid (BPA) and oleylamine (OLA) to one-step synthesize highly stable CsPbBr₃@BPA QDs in aqueous phase. The synergistic coordination of the dual bromine and carboxyl groups in the BPA molecule significantly lowers the nucleation energy barrier, effectively fills surface bromine vacancies, and suppresses non-radiative recombination. The as-prepared CsPbBr₃@BPA QDs exhibit excellent water dispersibility and luminescence performance, emitting bright green fluorescence with a photoluminescence quantum yield as high as 62.7% and a full width at half maximum of only 22 nm. Their fluorescence intensity remains stable in aqueous solution for over 144 h. Furthermore, based on the effective fluorescence quenching of the QDs by Cr(VI), a highly sensitive and specific analytical method for Cr(VI) was successfully constructed, with a detection limit as low as 4 nmol/L and a linear range of 0.02~2.4 μmol/L. The method was successfully applied to the spiked recovery analysis of Cr(VI) in real water samples, including tap water, spring water, and lake water, with the recoveries ranging from 93.3% to 106.0%. In addition, the developed CsPbBr₃@BPA QDs were used to fabricate high-color-purity green and white light-emitting diodes, expanding their application scenarios. This work provides a new strategy for the room-temperature preparation of highly stable perovskite QDs and demonstrates their dual-functional application potential in environmental monitoring and solid-state lighting.

Key words: CsPbBr₃@BPA quantum dots, room-temperature synthesis, water-stable, Cr(VI) detection, light-emitting diodes

引用此文

张颖敏, 仝欣欣, 陈玉凤, 李建彤, 王鑫, 吴兆申, 刘俊豪, 刘健, 杨升宏. 室温构筑水稳定钙钛矿量子点用于六价铬检测与发光二极管[J]. 化学学报, 2026, 84(7): 1049-1056.

Yingmin Zhang, Xinxin Tong, Yufeng Chen, Jiantong Li, Xin Wang, Zhaoshen Wu, Junhao Liu, Jian Liu, Shenghong Yang. Room-temperature Construction of Water-stable Perovskite Quantum Dots for Cr(VI) Detection and Light-emitting Diodes[J]. Acta Chimica Sinica, 2026, 84(7): 1049-1056.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 5

图1. CsPbBr3@BPA量子点室温合成示意图及Cr(VI)检测和LEDs应用示意图

Figure 1. Illustration of the room-temperature synthesis of CsPbBr3@BPA quantum dots and their applications in Cr(VI) detection and LEDs

图2. 利用不同配体合成CsPbBr3量子点的发射光谱(A), 不同OLA添加量合成CsPbBr3量子点的发射光谱(B)和归一化荧光强度(D), 不同BPA添加量合成CsPbBr3量子点的发射光谱(C)和归一化荧光强度(E)

Figure 2. Emission spectra of CsPbBr3 QDs synthesized with different ligands (A), emission spectra (B) and normalized photoluminescence intensity (D) of CsPbBr3 QDs synthesized with different OLA addition amounts, and emission spectra (C) and normalized photoluminescence intensity (E) of CsPbBr3 QDs synthesized with different BPA addition amounts

图3. CsPbBr3@BPA量子点的紫外可见吸收光谱和发射光谱(A, 内插图为对应的溶液光学照片), CsPbBr3@BPA量子点的透射电镜图片(B, 内插图为高分辨透射图片), CsPbBr3@BPA量子点的粒径分布(C), X-射线粉末衍射(D)及傅里叶变换红外光谱(E), Cs (F)、Pb (G)和Br (H)的高分辨X射线电子能谱图

Figure 3. The UV-Visible absorption and emission spectra of CsPbBr3@BPA QDs (A, the inset shows the corresponding optical photograph of the solution), the TEM and high-resolution image (inset) of CsPbBr3@BPA QDs (B), the size distribution (C), XRD pattern (D), FTIR spectrum (E) of CsPbBr3@BPA QDs, the high-resolution XPS spectra of (F) Cs, (G) Pb, and (H) Br elements of CsPbBr3@BPA QDs

图4. 添加Cr(VI)前后CsPbBr3@BPA量子点水溶液的发射光谱图(A), 20和30 ℃条件下荧光猝灭的Stern-Volmer图(B), 添加Cr(VI)前后CsPbBr3@BPA量子点溶液的荧光衰减曲线图(C), 添加不同浓度Cr(VI)后CsPbBr3@BPA量子点溶液的发射光谱图(D), Cr(VI)浓度与猝灭率的线性关系图(E), 不同金属离子存在时CsPbBr3@BPA量子点水溶液在365 nm紫外光照射下的照片(F), 含有不同金属离子的CsPbBr3@BPA量子点水溶液在添加Cr(VI)前后的相对荧光强度(G)

Figure 4. Emission spectra of CsPbBr3@BPA QDs aqueous solution before and after the addition of Cr(VI) (A). Stern-Volmer plots of fluorescence quenching at 20 and 30 ℃ (B). Fluorescence decay curves of CsPbBr3@BPA QDs solution before and after the addition of Cr(VI) (C). Emission spectra of CsPbBr3@BPA QDs solution after the addition of different concentrations of Cr(VI) (D). Linear relationship between Cr(VI) concentration and quenching efficiency (E). Photographs of CsPbBr3@BPA QDs aqueous solution under 365 nm UV irradiation in the presence of different metal ions (F). Relative fluorescence intensity of CsPbBr3@BPA QDs aqueous solution containing different metal ions before and after the addition of Cr(VI) (G)

图5. 绿光(A)和白光(B) LEDs的CIE色度坐标, 绿光(C)和白光(D) LEDs对应的发射光谱(内插图: 绿光和白光LEDs发光的光学照片)

Figure 5. CIE chromaticity coordinates of green (A) and white (B) LEDs, and the corresponding emission spectra of green (C) and white (D) LEDs (inset: optical photographs of the green and white LEDs in operation)

参考文献 50

[1]	Stern, C. M.; Jegede, T. O.; Hulse, V. A.; Elgrishi, N. Chem. Soc. Rev. 2021, 50, 1642. doi: 10.1039/D0CS01165G
[2]	Tang, J.; Hua, W.; Lu, R. X.; Lin, Y.; Chen, X. S.; Xu, K. K.; Yu, H. M.; Zhang, J. Y.; Zheng, C. B. Environ. Sci. Technol. 2025, 59, 20276. doi: 10.1021/acs.est.5c07765
[3]	Min, P.; Zhou, F. Q.; Yu, F. R.; Chen, J. Q.; Guo, R. X.; Liu, Y. H.; Fu, L. Environ. Chem. 2025, 44, 265 (in Chinese).
	(闵鹏, 周凡琪, 于凡芮, 陈建秋, 郭瑞昕, 刘艳华, 付岚, 环境化学, 2025, 44, 265.)
[4]	Yin, H. Y.; Huang, L.; Dai, Y. B.; Zheng, Z. L.; Li, Y. Q.; Tang, B.; Wang, X.; Shi, L. Chem. Eng. J. 2025, 503, 157946. doi: 10.1016/j.cej.2024.157946
[5]	Sun, J. B.; Zhao, Y.; Zhang, C. Y.; Xiong, J.; Bai, L. P.; Guo, X. X.; Zhou, Y. Y.; Ma, J. Environ. Chem. 2025, 44, 3683 (in Chinese).
	(孙金博, 赵莹, 张超艳, 熊杰, 白利平, 郭晓欣, 周友亚, 马杰, 环境化学, 2025, 44, 3683.)
[6]	Chen, L. H.; Zheng, K. Y.; Ma, Y. B.; Zhu, D.; Wu, Y.; Liu, T. X.; Zhong, S. X.; Li, Y. J. Hazard. Mater. 2026, 504, 141347. doi: 10.1016/j.jhazmat.2026.141347
[7]	Wang, Q.; Zhao, Y. X.; Liu, Y. N.; Zhang, C. G.; Bamanu, B.; Wu, Y. C.; Chao, C. F.; Liu, Y. W.; Tong, Y. D.; Nuramkhaan, M. Water Res. 2024, 252, 121230. doi: 10.1016/j.watres.2024.121230
[8]	Liu, Y. X.; Lin, Q. T.; Pan, J. Y.; Deng, Y. R.; Zheng, J. L.; Lyu, M. C.; Luo, H.; Luo, Y. J. Hazard. Mater. 2024, 480, 136399. doi: 10.1016/j.jhazmat.2024.136399
[9]	Aryal, P.; Boes, J.; Brack, E.; Alexander, T.; Henry, C. S. ACS Sens. 2024, 9, 5479. doi: 10.1021/acssensors.4c01708
[10]	Shirkhanloo, H.; Zarandi, A. F.; Faraji, M. Food Chem. 2026, 508, 148369. doi: 10.1016/j.foodchem.2026.148369
[11]	Wang, X.; Hu, J. S.; Yao, B. X.; Wei, H.; Zhang, C. Y.; Zhou, J. R.; Liu, J.; Yang, S. H. Chem. Eng. J. 2023, 451, 138524. doi: 10.1016/j.cej.2022.138524
[12]	Liu, L. L.; Li, Z. Z.; Liu, Y. F.; Zhang, X. A. Sci. Sin. Chim. 2020, 50, 39 (in Chinese). doi: 10.1360/SSC-2019-0077
	(刘璐璐, 李志泽, 刘毅飞, 张晓安, 中国科学: 化学, 2020, 50, 39.)
[13]	Zhu, P. P.; Zhang, Z. H.; Zhang, T.; Chen, W. Sci. Sin. Chim. 2022, 52, 1087 (in Chinese). doi: 10.1360/SSC-2022-0096
	(朱盼盼, 张展华, 张彤, 陈威, 中国科学: 化学, 2022, 52, 1087.)
[14]	Wang, X. R.; Luo, S. P.; Luo, J.; Liu, L. Y.; Hu, Y. X.; Jiang, L.; Qin, H. F. Carbohyd. Polym. 2025, 347, 122748. doi: 10.1016/j.carbpol.2024.122748
[15]	Guo, J. N.; Feng, W. Q.; Du, P. Y.; Zhang, R. Z.; Liu, J.; Liu, Y.; Wang, Z. M.; Lu, X. Q. Anal. Chem. 2020, 92, 14838. doi: 10.1021/acs.analchem.0c03709
[16]	Cui, W. B.; Zhao, X.; Song, J. L.; Zhao, J. W.; Zhang, C. F.; Ma, C. H.; Xu, M. C.; Wang, R. H.; Luo, S.; Liu, S. X.; Li, W. Chem. Eng. J. 2025, 526, 170513. doi: 10.1016/j.cej.2025.170513
[17]	Liang, B.; Li, L. N.; Zhao, Y. H.; Xia, R. Z.; Wang, Y.; Dai, P. D.; Yang, M.; Lin, J. Y.; Li, P. H.; Huang, X. J. J. Hazard. Mater. 2026, 504, 141366. doi: 10.1016/j.jhazmat.2026.141366
[18]	Wang, N. N.; Si, J. J.; Jin, Y. Z.; Wang, J. P.; Huang, W. Acta Chim. Sinica 2015, 73, 171 (in Chinese). doi: 10.6023/A14100711
	(王娜娜, 司俊杰, 金一政, 王建浦, 黄维, 化学学报, 2015, 73, 171.) doi: 10.6023/A14100711
[19]	Huang, G. G.; Sun, K. W.; Xiong, X. Y.; Song, L.; Liu, G. K.; Zheng, C. F.; Yu, F. L.; Du, Z. L. Laser Photonics Rev. 2025, 19, 2401121. doi: 10.1002/lpor.v19.1
[20]	Kunwar, N.; Naithani, S.; Goswami, T.; Dubey, R.; Layek, S.; Kumar, S.; Mangalam, J. Coordin. Chem. Rev. 2026, 552, 217517. doi: 10.1016/j.ccr.2025.217517
[21]	Lin, J. D.; Zhou, Z. H.; Lai, J. M.; Ye, W. C.; Pang, T.; Li, X. Y.; Zeng, L. W.; Lei, L.; Yu, D. C.; Chen, D. Q. Laser Photonics Rev. 2025, 19, 2401649. doi: 10.1002/lpor.v19.4
[22]	Peng, Y. J.; Zhao, Y. X.; Yang, J. H.; Zhang, X. X.; Cheng, J. L. Acta Chim. Sinica 2024, 82, 879 (in Chinese). doi: 10.6023/A24030066
	(彭亚晶, 赵雨新, 杨金辉, 仉昕昕, 程佳玲, 化学学报, 2024, 82, 879.) doi: 10.6023/A24030066
[23]	Zhu, Y.; Tong, F.; Si, H.; Dai, W. G.; Nie, S.; Chen, Z.; Huang, S.; Gu, X. Q. Chem. Eng. J. 2026, 529, 173123. doi: 10.1016/j.cej.2026.173123
[24]	Yan, S. S.; Zhang, S. P.; Gao, L. H.; Kong, Y. C.; Ma, X. Y.; Zhou, X. J.; Dai, H. Chem. Eng. J. 2026, 529, 172788. doi: 10.1016/j.cej.2026.172788
[25]	Wang, S.; Xu, Q.; Gan, Z. W.; Liu, Y. Z.; Hou, J. X.; Yu, L.; Xiao, Y. X. ACS Nano 2025, 19, 35468. doi: 10.1021/acsnano.5c08578
[26]	Cao, Y. X.; Wang, X. C.; Zheng, W. L.; Chun, F. J.; Xing, Z. F.; Guo, Y.; Wei, X. H.; Chen, J. K.; Li, S. H.; Fang, Y. Z.; Wang, F. J. Am. Chem. Soc. 2026, 148, 5754. doi: 10.1021/jacs.5c22209
[27]	Shan, L.; Lv, J. J.; Liang, J. X.; Xu, J. H.; Wu, C. J.; Wang, A. Z.; Zhang, L. N.; Ge, S. G.; Yu, J. H. Adv. Funct. Mater. 2025, 35, 2418023. doi: 10.1002/adfm.v35.36
[28]	Xu, B.; Chen, M. L.; Zhang, K. N.; Mu, J. B.; Cao, J.; Lv, H. Y.; Zhang, H. Y.; Zhou, X. T.; Shi, F.; Hao, Q. Adv. Sci. 2025, 12, 2504307. doi: 10.1002/advs.v12.26
[29]	Jin, X. Y.; Ma, K. L.; Gao, H. F. J. Am. Chem. Soc. 2022, 144, 20411. doi: 10.1021/jacs.2c08622
[30]	Yang, X. Y.; Yue, Z. H.; Deng, R. X.; Zhang, Z. L.; Zhang, T.; Song, L. X. J. Mater. Sci. Technol. 2025, 209, 185. doi: 10.1016/j.jmst.2024.05.017
[31]	Shi, W. B.; Zhang, X.; Xie, C.; Chen, H. S.; Yang, P. Chem. Eng. J. 2024, 493, 152638. doi: 10.1016/j.cej.2024.152638
[32]	Chi, J. M.; Zhang, Z. X.; Ning, B. B.; Cheng, L. J.; Xie, D. X.; Meng, Q. Y.; Ren, W. J.; Song, Y. L.; Su, M. Adv. Funct. Mater. 2026, 36, e15773. doi: 10.1002/adfm.v36.12
[33]	Lai, Y. L.; Gong, K. L.; Liu, H. N.; He, L.; Yu, B. Y.; Xu, L.; Zhao, X. L.; Wang, R. L.; Vomiero, A.; Zhou, Y. F. Chem. Eng. J. 2025, 514, 163360. doi: 10.1016/j.cej.2025.163360
[34]	Wu, X. Y.; Wang, L. J.; Zhang, G. S.; Ma, L.; Wang, D. W.; Zhang, Y. F.; Bao, Y. X.; Wu, X. J.; Li, X.; Hu, Y. F.; Peng, H. S. ACS Nano 2025, 19, 29470. doi: 10.1021/acsnano.5c07518
[35]	Kim, Y.; Um, M.; Shin, S.; Song, H.; Park, Y. P.; Yang, J. ACS Nano 2026, 20, 10651. doi: 10.1021/acsnano.6c00180
[36]	Shi, W. B.; Zhang, X.; Yang, P. Mater. Today Chem. 2025, 46, 102752.
[37]	Liu, Y. F.; Xie, Q. Y.; Ying, Y. P.; Gao, Z. J.; Shao, X. W.; Xia, W. Z.; Zhou, M.; Pei, W.; Tang, X. S.; Tu, Y. S. Chem. Eng. J. 2024, 498, 155515. doi: 10.1016/j.cej.2024.155515
[38]	Sarkar, D.; Stelmakh, A.; Karmakar, A.; Aebli, M.; Krieg, F.; Bhattacharya, A.; Pawsey, S.; Kovalenko, M. V.; Michaelis, V. K. ACS Nano 2024, 18, 21894. doi: 10.1021/acsnano.4c02057
[39]	Zhu, H.; Pan, Y. X.; Peng, C. D.; Lian, H. Z.; Lin, J. Angew. Chem. Int. Ed. 2022, 61, e202116702. doi: 10.1002/anie.v61.22
[40]	Sum, J.; Li, Q. F.; Li, X.; Yan, C. L.; Wang, G. K. Microchem. J. 2024, 199, 110043. doi: 10.1016/j.microc.2024.110043
[41]	Pradhan, N. ACS Energy Lett. 2025, 10, 1057. doi: 10.1021/acsenergylett.5c00128
[42]	He, S.; Zhu, M. F.; Dong, S. X.; Wang, J. J.; Du, L. Q.; Zhong, W. K.; Xie, W. J.; Ouyang, Z. Y.; Cheng, B. C.; Zhao, J. J. Energy Chem. 2026, 114, 194. doi: 10.1016/j.jechem.2025.09.084
[43]	Lee, M. H.; Choi, Y. J.; Kim, J.; Han, J.; Yang, J. K.; Kim, D.; Chae, H. G.; Jun, Y. C.; Song, M. H. Nano Energy 2026, 151, 111859. doi: 10.1016/j.nanoen.2026.111859
[44]	Meng, X.; Chen, J.; Liu, Y. X.; Wang, L. J.; Zhou, Q.; Ma, X. R.; Kong, C. P.; Shi, Y. G.; Zheng, L. Y.; Cao, Q. Y. Adv. Funct. Mater. 2024, 34, 2407790. doi: 10.1002/adfm.v34.46
[45]	He, S. M.; Li, R. K.; Xu, M.; Wang, Y.; Guo, R. B.; Liu, N. J.; Mo, Z. L. Chem. Eng. J. 2025, 512, 162689. doi: 10.1016/j.cej.2025.162689
[46]	Tang, K.; Chen, Y. T.; Zhao, Y. X. Chem. Commun. 2024, 60, 4511. doi: 10.1039/D4CC00619D
[47]	Tong, X. X.; Chen, Y. F.; Zhang, Y. M.; Zhao, L. Z.; Zhang, W. J.; Lei, Y. Q.; Guo, P. R.; Liu, J.; Yang, S. H. J. Colloid Inter. Sci. 2026, 718, 140486. doi: 10.1016/j.jcis.2026.140486
[48]	Tong, X. X.; Li, Z. H.; Li, X. Q.; Tan, Z. Y.; Liu, X. Y.; Zhao, X. J.; Zhou, M. Y.; Lei, Y. Q.; Guo, P. R.; Liu, J.; Yang, S. H. J. Hazard. Mater. 2025, 498, 139959. doi: 10.1016/j.jhazmat.2025.139959
[49]	Shu, Y.; Ye, Q. Y.; Dai, T.; Guan, J.; Ji, Z. P.; Xu, Q.; Hu, X. Y. J. Hazard. Mater. 2022, 430, 128360. doi: 10.1016/j.jhazmat.2022.128360
[50]	Li, Y.; Li, J. H.; Xu, L. M.; Chen, J. W.; Song, J. Z. Acta Chim. Sinica 2021, 79, 126 (in Chinese). doi: 10.6023/A20080386
	(李严, 李金航, 许蕾梦, 陈嘉伟, 宋继中, 化学学报, 2021, 79, 126.) doi: 10.6023/A20080386