Photocatalysis/
Articles/
2610005434
  • Open Access
  • Article

Enhanced Photocatalytic Activity of Cs3Bi2Br9 Nanocrystals: Colloidal vs. Supported Architecture

  • Joel Monfort 1,   
  • Alessandro Ciccone 1,   
  • Raman Singh Lamba 2,   
  • Dung Nguyen 3,4,   
  • Andrey Ryzhikov 3,4,   
  • Julia Pérez-Prieto 1,*,   
  • Dmitry Aldakov 2,* and 
  • Raquel E. Galian 1,*

Received: 11 July 2026 | Revised: 15 October 2026 | Accepted: 19 October 2026 | Published: 27 October 2026

Abstract

Lead-free halide nanocrystals have emerged as a sustainable alternative to lead halide perovskites materials; owing to their strong light absorption, low-toxicity and optimal bandgap for visible light driven applications. Herein, we aim to broaden the application of benzoyl bromide as Br-source in a modified hot-injection protocol for the synthesis of colloidal Cs3Bi2Br9 nanocrystals (cCBB NCs). Moreover, for comparative purposes CBB NCs incorporated into the mesoporous silica SBA-15 were prepared. The photocatalytic performance of both systems was evaluated using the degradation of cationic organic dyes, such as methylene blue (MB) and rhodamine B (RhB), as model reactions. Notably, complete dye degradation was achieved at very short irradiation times, ca. 300 s for RhB in both colloidal and supported systems, the fastest rate reported up to now, mediated predominantly by anion superoxide as selective oxidizing agent. However, in the case of MB, its strong binding to CBB surface and incorporation into the SBA-15 pores limit the photodegradation process, which is proposed to occur via direct charge transfer and anion superoxide formation. This work highlights the importance of the CBB synthetic procedure and the dye adsorption behavior on the NCs surface or into the silica pores in determining the photocatalytic activity of bismuth halide NCs.

Graphical Abstract

Image Viewer
Open in new tab
Download Image

References 

  • 1.

    Dey, A.; Ye, J.; De, A.; et al. State of the Art and Prospects for Halide Perovskite Nanocrystals. ACS Nano 2021, 15, 10775–10981. https://doi.org/10.1021/acsnano.0c08903.

  • 2.

    Protesescu, L.; Yakunin, S.; Bodnarchuk, M.I.; et al. Nanocrystals of Cesium Lead Halide Perovskites (CsPbX3, X = Cl, Br, and I): Novel Optoelectronic Materials Showing Bright Emission with Wide Color Gamut. Nano Lett. 2015, 15, 3692–3696. https://doi.org/10.1021/nl5048779.

  • 3.

    Akinbami, O.; Majola, T.; Ngubeni, G.N.; et al. CsSnBr3 and Cs3Bi2Br9: Structural, Optical Characteristics, and Application in a Schottky Barrier Diode. Adv. Photonics Res. 2024, 5, 2300337. https://doi.org/10.1002/adpr.202300337.

  • 4.

    Giustino, F.; Snaith, H.J. Toward Lead-Free Perovskite Solar Cells. ACS Energy Lett. 2016, 1, 1233–1240. https://doi.org/10.1021/acsenergylett.6b00499.

  • 5.

    Akinbami, O.; Moepya, R.; Ngubeni, G.N.; et al. Lead-Free Rudorffite-Type Cs3Bi2Br9 Nanoparticles for Photocatalytic Degradation of Rhodamine B and Methylene Blue. J. Photochem. Photobiol. A Chem. 2021, 419, 113460. https://doi.org/10.1016/j.jphotochem.2021.113460.

  • 6.

    Akkerman, Q.A.; Manna, L. What Defines a Halide Perovskite? ACS Energy Lett. 2020, 5, 604–610. https://doi.org/10.1021/acsenergylett.0c00039.

  • 7.

    Zhang, Y.; Yin, J.; Parida, M.R.; et al. Direct-Indirect Nature of the Bandgap in Lead-Free Perovskite Nanocrystals. J. Phys. Chem. Lett. 2017, 8, 3173–3177. https://doi.org/10.1021/acs.jpclett.7b01381.

  • 8.

    Creutz, S.E.; Liu, H.; Kaiser, M.E.; et al. Structural Diversity in Cesium Bismuth Halide Nanocrystals. Chem. Mater. 2019, 31, 4685–4697. https://doi.org/10.1021/acs.chemmater.9b00640.

  • 9.

    Lee, D.; Kim, M.; Woo, H.Y.; et al. Heating-up Synthesis of Cesium Bismuth Bromide Perovskite Nanocrystals with Tailored Composition, Morphology, and Optical Properties. RSC Adv. 2020, 10, 7126–7133. https://doi.org/10.1039/c9ra10106c.

  • 10.

    Imran, M.; Caligiuri, V.; Wang, M.; et al. Benzoyl Halides as Alternative Precursors for the Colloidal Synthesis of Lead-Based Halide Perovskite Nanocrystals. J. Am. Chem. Soc. 2018, 140, 2656–2664. https://doi.org/10.1021/jacs.7b13477.

  • 11.

    Rosa-Pardo, I.; Zhu, D.; Cortés-Villena, A.; et al. The Dark Side of Lead-Free Metal Halide Nanocrystals: Substituent-Modulated Photocatalytic Activity in Benzyl Bromide Reduction. ACS Energy Lett. 2023, 8, 2789–2798. https://doi.org/10.1021/acsenergylett.3c00771.

  • 12.

    Jang, W.J.; Park, P.J.; Ong, W.J.; et al. Stable and Eco-Friendly Inorganic Lead-Free Perovskite Solar Cells: Structural, Electronic, and Defect Engineering. Commun. Mater. 2026, 7, 110. https://doi.org/10.1038/s43246-026-01158-1.

  • 13.

    Bass, K.K.; Estergreen, L.; Savory, C.N.; et al. Vibronic Structure in Room Temperature Photoluminescence of the Halide Perovskite Cs3Bi2Br9. Inorg. Chem. 2017, 56, 42–45. https://doi.org/10.1021/acs.inorgchem.6b01571.

  • 14.

    Li, Y.J.; Mu, B.H.; Li, H.B.; et al. Bi-Based Metal Halide Perovskites and Their Photocatalytic Properties: A Review. Energy Fuels 2025, 39, 2986–3007. https://doi.org/10.1021/acs.energyfuels.4c06208.

  • 15.

    Yue, T.; Zhang, S.Z.; Li, M.M.; et al. Lead-Free Cs3Bi2Br9 Perovskite as Heterogeneous Photocatalyst for Oxidative Dehydrogenative Coupling of Thiols and P(O)H Compounds. ChemSusChem 2025, 18, e202501607. https://doi.org/10.1002/cssc.202501607.

  • 16.

    Wang, C.; Ding, Y.; Liu, B.; et al. Crystal Structure Engineering of Metal Halide Perovskites for Photocatalytic Organic Synthesis. Chem. Commun. 2023, 59, 3122–3125. https://doi.org/10.1039/d3cc00468f.

  • 17.

    Cui, X.; Zhang, Z.; Zhou, G.; et al. Cs3Bi2Br9 and BiOBr Self-Assemble to Form S-Scheme Heterojunction for Photocatalytic CO2 Photoreduction. J. Alloys Compd. 2026, 1079, 189779. https://doi.org/10.2139/ssrn.6674165.

  • 18.

    Fan, Q.; Guo, L.; Wu, G.; et al. Ce3+-Doped Cs3Bi2Br9 for Photocatalytic Selective Oxidation of Alcohols to Aldehydes/Ketones. Inorg. Chem. 2026, 65, 1852–1862. https://doi.org/10.1021/acs.inorgchem.5c04499.

  • 19.

    Ahmadi, B.; Fallah, A.; Ghamarpoor, R.; et al. Methylene Blue beyond the Dye: A Critical Review on Its Role as a Benchmark Pollutant in Photocatalyst Design. Results Chem. 2025, 18, 102910. https://doi.org/10.1016/j.rechem.2025.102910.

  • 20.

    Pandey, M.; Tsunoji, N.; Bhattacharyya, K.; et al. Photocatalytic Degradation of Organic Dyes under Sunlight Using a Mononuclear Zn Complex-Embedded-Functionalized Porous Material. Environ. Sci. Pollut. Res. 2024, 31, 63686–63703. https://doi.org/10.1007/s11356-024-35466-1.

  • 21.

    Masri, M.; Girisha, K.B.; Hezam, A.; et al. Enhanced Photocatalytic Activity and Stability of 2D Cs3Bi2Br9 Perovskite Nanosheets Synthesized via Modified Antisolvent Method. Colloids Surf. C Environ. Asp. 2024, 2, 100024. https://doi.org/10.1016/j.colsuc.2023.100024.

  • 22.

    Aragon, A.G.; Wiggins, T.E.; Ma, X.; et al. Lead-Free Cs3Bi2Br9 and Cs3Bi2-xSbxBr9 Nanocrystals as Photocatalysts with Enhanced Activity for the Degradation of Rhodamine in Aqueous Environments. J. Photochem. Photobiol. A Chem. 2023, 436, 114391. https://doi.org/10.1016/j.jphotochem.2022.114391.

  • 23.

    Motokura, K.; Ding, S.; Usui, K.; et al. Enhanced Catalysis Based on the Surface Environment of the Silica-Supported Metal Complex. ACS Catal. 2021, 11, 11985–12018. https://doi.org/10.1021/acscatal.1c03426.

  • 24.

    Malgras, V.; Tominaka, S.; Ryan, J.W.; et al. Observation of Quantum Confinement in Monodisperse Methylammonium Lead Halide Perovskite Nanocrystals Embedded in Mesoporous Silica. J. Am. Chem. Soc. 2016, 138, 13874–13881. https://doi.org/10.1021/jacs.6b05608.

  • 25.

    Athira, M.P.; Haridas, S. Functionalized SBA-15 as a Protective Template for CsPbBr3 Perovskite Quantum Dots. Nanoscale Adv. 2026, 8, 829–834. https://doi.org/10.1039/d5na00868a.

  • 26.

    Dupé, S.; Liu, D.; Ghosh, A.; et al. Quantum-Confined Bismuth Iodide Perovskite Nanocrystals in Mesoporous Matrices. Nanoscale 2024, 16, 11223–11231. https://doi.org/10.1039/d4nr00430b.

  • 27.

    Geng, H.; Huang, Z.; Geng, H.; et al. Controlled Synthesis of Highly Stable Lead-Free Bismuth Halide Perovskite Nanocrystals: Structures and Photophysics. Sci. China Mater. 2023, 66, 2079–2089. https://doi.org/10.1007/s40843-022-2299-6.

  • 28.

    Yao, M.M.; Jiang, C.H.; Yao, J.S.; et al. General Synthesis of Lead-Free Metal Halide Perovskite Colloidal Nanocrystals in 1-Dodecanol. Inorg. Chem. 2019, 58, 11807–11818. https://doi.org/10.1021/acs.inorgchem.9b01893.

  • 29.

    Tran, M.N.; Cleveland, I.J.; Aydil, E.S. Resolving the Discrepancies in the Reported Optical Absorption of Low-Dimensional Non-Toxic Perovskites, Cs3Bi2Br9 and Cs3BiBr6. J. Mater. Chem. C 2020, 8, 10456–10463. https://doi.org/10.1039/d0tc02783a.

  • 30.

    Mala, M.; Appadurai, T.; Chandiran, A.K. Structural Distortion Induced Broad Emission in Vacancy-Ordered Halide Triple Perovskites. Dalton Trans. 2022, 51, 2789–2797. https://doi.org/10.1039/d1dt03474j.

  • 31.

    Azmat, S.; Gregori, L.; Ventruti, G.; et al. A Closer Look at the Interface of Cs3Bi2Br9 Lead Free Perovskite in Photocatalytic Process. J. Phys. Chem. Solids 2025, 199, 112534. https://doi.org/10.1016/j.jpcs.2024.112534.

  • 32.

    Bonomi, S.; Galinetto, P.; Patrini, M.; et al. Optical and Structural Property Tuning in Physical Vapor Deposited Bismuth Halides Cs3Bi2(I1–XBrX)9 (0 ≤ X ≤ 1). Inorg. Chem. 2021, 60, 14142–14150. https://doi.org/10.1021/acs.inorgchem.1c01545.

  • 33.

    Zhang, J.; Yang, Y.; Deng, H.; et al. High Quantum Yield Blue Emission from Lead-Free Inorganic Antimony Halide Perovskite Colloidal Quantum Dots. ACS Nano 2017, 11, 9294–9302. https://doi.org/10.1021/acsnano.7b04683.

  • 34.

    Nguyen, Q.N.K.; Yên, N.T.; Hau, N.D.; et al. Synthesis and Characterization of Mesoporous Silica SBA-15 and ZnO/SBA-15 Photocatalytic Materials from the Ash of Brickyards. J. Chem. 2020, 2020, 1–8. https://doi.org/10.1155/2020/8456194.

  • 35.

    Joshi, S.; Singh, N.; Singh, B.; et al. Lysine-Capped Bi-Based Halide Perovskite (Cs3Bi2Br9−XIX, X = 0, 3, 9) Nanoparticles: Unraveling Structure–Property–Function Relationship upon Halide Substitution. ACS Appl. Nano Mater. 2026, 9, 5381–5391. https://doi.org/10.1021/acsanm.5c05717.

  • 36.

    Sunny, F.; John, S.; Parambil, P.C.; et al. Monovalent Cation Doping in Cesium Bismuth Bromide Perovskites: Insights into Structure–Property Correlation. J. Phys. Chem. C 2026, 130, 3135–3144. https://doi.org/10.1021/acs.jpcc.5c08110.

  • 37.

    Yang, H.; Song, X.; Cheng, Z.; et al. Synergistic Catalysis for Advanced Water Treatment Enabled by Precisely Constructed Ag–O–Bi Asymmetric Active Sites. Adv. Sustain. Syst. 2026, 10, e70503. https://doi.org/10.1002/adsu.70503.

  • 38.

    Li, S.; Li, J.; Ren, W.; et al. Schottky-Mediated Porphyrin-Metal-Organic Framework/Ti3C2-MXene Heterojunction for Water Decontamination via Photonic-Thermal-Enzyme Synergistic Catalysis. J. Colloid Interface Sci. 2025, 691, 137462. https://doi.org/10.1016/j.jcis.2025.137462.

  • 39.

    Romani, L.; Speltini, A.; Dibenedetto, C.N.; et al. Experimental Strategy and Mechanistic View to Boost the Photocatalytic Activity of Cs3Bi2Br9 Lead-Free Perovskite Derivative by g-C3N4 Composite Engineering. Adv. Funct. Mater. 2021, 31, 2104428. https://doi.org/10.1002/adfm.202104428.

  • 40.

    Alarcos, N.; Cohen, B.; Ziółek, M.; et al. Photochemistry and Photophysics in Silica-Based Materials: Ultrafast and Single Molecule Spectroscopy Observation. Chem. Rev. 2017, 117, 13639–13720. https://doi.org/10.1021/acs.chemrev.7b00422.

  • 41.

    Saita, S.; Anzai, M.; Mori, N.; et al. Controlled Aggregation of Methylene Blue in Silica–Methylene Blue Nanocomposite for Enhanced 1O2 Generation. Colloids Surf. A Physicochem. Eng. Asp. 2021, 617, 126360. https://doi.org/10.1016/j.colsurfa.2021.126360.

  • 42.

    Gupta, R.; Rastogi, P.K.; Srivastava, U.; et al. Methylene Blue Incorporated Mesoporous Silica Microsphere Based Sensing Scaffold for the Selective Voltammetric Determination of Riboflavin. RSC Adv. 2016, 6, 65779–65788. https://doi.org/10.1039/c6ra12336h.

  • 43.

    Franchi, D.; Amara, Z. Applications of Sensitized Semiconductors as Heterogeneous Visible-Light Photocatalysts in Organic Synthesis. ACS Sustain. Chem. Eng. 2020, 8, 15405–15429. https://doi.org/10.1021/acssuschemeng.0c05179.

  • 44.

    Hagberg, D.P.; Marinado, T.; Karlsson, K.M.; et al. Tuning the HOMO and LUMO Energy Levels of Organic Chromophores for Dye Sensitized Solar Cells. J. Org. Chem. 2007, 72, 9550–9556. https://doi.org/10.1021/jo701592x.

  • 45.

    Ding, L.; Hou, Y.; Liu, H.; et al. Alcohols as Scavengers for Hydroxyl Radicals in Photocatalytic Systems: Reliable or Not? ACS ES T Water 2023, 3, 3534–3543. https://doi.org/10.1021/acsestwater.3c00271.

  • 46.

    Nguyen, H.T.; Doan, V.D.; Huong Nguyen, T.L.; et al. Mechanistic Pathway and Optimization of Rhodamine B Degradation Using Mn3O4/ZnO Nanocomposite on Microalgae-Based Carbon. RSC Adv. 2025, 15, 6241–6259. https://doi.org/10.1039/d5ra00625b.

  • 47.

    Basuki, T.; Nakashima, S.; Philo, D.; et al. Temperature-Directed Synthesis of Hematite-Goethite Nanocomposites Having Mild Self-Leaching Properties with Enhanced Photocatalytic Activity Involving Photo-Fenton Mechanism. ChemistrySelect 2026, 11, e06971. https://doi.org/10.1002/slct.202506971.

  • 48.

    Tan, S.N.; Yuen, M.L.; Ramli, R.A. Photocatalysis of Dyes: Operational Parameters, Mechanisms, and Degradation Pathway. Green Anal. Chem. 2025, 12, 100230. https://doi.org/10.1016/j.greeac.2025.100230.

  • 49.

    Phuruangrat, A.; Thungprasert, S.; Sakhon, T.; et al. Degradation of Rhodamine B Photocatalyzed by Eu-Doped CdS Nanowires Illuminated by Visible Radiation. J. Indian Chem. Soc. 2022, 99, 100349. https://doi.org/10.1016/j.jics.2022.100349.

  • 50.

    Gao, Y.; Yang, G.; Zhang, J.; et al. A Metal-Free Microwave-Induced Carbon Cloth Discharge Technology for Efficient Degradation of Rhodamine B. J. Environ. Manag. 2026, 411, 130215. https://doi.org/10.1016/j.jenvman.2026.130215.

  • 51.

    Yang, J.; Zhu, H.; Peng, Y.; et al. Photocatalytic Performance and Degradation Pathway of Rhodamine B with TS-1/C3N4 Composite under Visible Light. Nanomaterials 2020, 10, 756. https://doi.org/10.3390/nano10040756.

  • 52.

    Rajalakshmi, S.; Pitchaimuthu, S.; Kannan, N.; et al. Enhanced Photocatalytic Activity of Metal Oxides/β-Cyclodextrin Nanocomposites for Decoloration of Rhodamine B Dye under Solar Light Irradiation. Appl. Water Sci. 2017, 7, 115–127. https://doi.org/10.1007/s13201-014-0223-5.

  • 53.

    Majeed, A.; Ibrahim, A.H.; Al-Rawi, S.S.; et al. Green Organo-Photooxidative Method for the Degradation of Methylene Blue Dye. ACS Omega 2024, 9, 12069–12083. https://doi.org/10.1021/acsomega.3c09989.

Share this article:
Download PDF
Supplementary Materials
DOI
10.53941/photocatalysis.2026.100010
Issue
Volume 2, Issue 4
How to Cite
Monfort, J.; Ciccone, A.; Singh Lamba, R.; Nguyen, D.; Ryzhikov, A.; Pérez-Prieto, J.; Aldakov, D.; Galian, R. E. Enhanced Photocatalytic Activity of Cs3Bi2Br9 Nanocrystals: Colloidal vs. Supported Architecture. Photocatalysis 2026, 2 (4), 10. https://doi.org/10.53941/photocatalysis.2026.100010.
RIS
BibTex
Copyright & License
article copyright Image
Copyright (c) 2026 by the authors.
Article Metrics
104
Article Views
0
Citations