In situ construction of Cs₃Bi₂I₉/WO₃ 0D/1D Z-scheme heterojunction photocatalyst for photochemical CO₂ reduction under visible light

Abstract

The photocatalytic efficiency of lead-free Bi-based halide perovskites, such as Cs₃Bi₂X₉ (X = Br, I) for CO₂ reduction is often hindered by self-aggregation and insufficient oxidation ability. In this work, a visible-light-driven (λ > 420 nm) Z-scheme heterojunction photocatalyst composed of 0D Cs₃Bi₂I₉ nanoparticles on 1D WO₃ nanorods for photocatalytic CO₂ reduction and water oxidation is synthesized using an in situ growing approach. The resulting 0D/1D Cs₃Bi₂I₉/WO₃ Z-scheme heterojunction photocatalyst exhibits a visible-light-driven photocatalytic CO₂ reduction performance for selective CO production, achieving a selectivity of 98.7% and a high rate of 16.5 μmol/(g·h), approximately three times that of pristine Cs₃Bi₂I₉. Furthermore, it demonstrates decent stability in the gas-solid photocatalytic CO₂ reduction system. The improved performance of Cs₃Bi₂I₉/WO₃ is attributed to the formation of the 0D/1D Z-scheme heterojunction, which facilitates charge transfer, reduces charge recombination, and maintains the active sites of both 0D Cs₃Bi₂I₉ for CO₂ reduction and 1D WO₃ for water oxidation. This work provides valuable insights into the potential of morphological engineering and the design of simultaneous Z-scheme heterojunction for lead-free halide perovskites.

Graphical abstract

Keywords

lead-free halide perovskites / 0D/1D structure / Z-scheme heterojunction / photocatalytic CO₂ reduction / morphological engineering

References

[1] Ee A W L, Lee J T E, Tian H. . Current status on utilizing a life cycle system perspective to evaluate renewable energy production systems for achieving UN SDGs. Resources, Conservation and Recycling, 2024, 203: 107381

[2] Wang H, Wang H, Wang Z. . Covalent organic framework photocatalysts: Structures and applications. Chemical Society Reviews, 2020, 49(12): 4135–4165

[3] Chen G, Zhou Z, Li B. . S-scheme heterojunction of crystalline carbon nitride nanosheets and ultrafine WO₃ nanoparticles for photocatalytic CO₂ reduction. Journal of Environmental Sciences, 2024, 140: 103–112

[4] ZouG, WangQ, YeG, et al. Copolymerization of poly (triazine imide) single crystal nanoplates with enhanced charge transfer for efficient photocatalytic overall water splitting. Advanced Functional Materials, 2024, 2420899

[5] Ortiz-Quiñonez J L, Pal U. Interface engineered metal oxide heterojunction nanostructures in photocatalytic CO₂ reduction: Progress and prospects. Coordination Chemistry Reviews, 2024, 516: 215967

[6] Wang H K, Zhang M R, Su K. . The Sb-N charge transfer bridge over Cs₃Sb₂Br₉/Sb-C₃N₄ Z-scheme heterojunction for boosting photocatalytic CO₂ reduction. Science China Materials, 2024, 67: 3176–3184

[7] Tang W, Meng J, Ding T. . Efficient interfacial charge transfer enables nearly 100% selectivity for solar-light-driven CO₂ conversion. ACS Catalysis, 2024, 14(10): 7506–7513

[8] Yu J, Muhetaer A, Li Q. . Solar energy-driven reverse water gas shift reaction: Photothermal effect, photoelectric activation and selectivity regulation. Small, 2024, 20(42): 2402952

[9] Li S, Li Y L, Bai H M. . Penta-coordinated aluminum species: Anchoring Au single atoms for photocatalytic CO₂ reduction. Applied Catalysis B: Environmental, 2024, 345: 123703

[10] Ding L, Ding Y, Bai F. . In situ growth of Cs₃Bi₂Br₉ quantum dots on Bi-MOF nanosheets via cosharing bismuth atoms for CO₂ capture and photocatalytic reduction. Inorganic Chemistry, 2023, 62(5): 2289–2303

[11] Zhang G, Li G, Heil T. . Tailoring the grain boundary chemistry of polymeric carbon nitride for enhanced solar hydrogen production and CO₂ reduction. Angewandte Chemie International Edition, 2019, 58: 3433–3437

[12] Feng Y, Chen D, Zhong Y. . A lead-free 0D/2D Cs₃Bi₂Br₉/Bi₂WO₆ S-scheme heterojunction for efficient photoreduction of CO₂. ACS Applied Materials & Interfaces, 2023, 15(7): 9221–9230

[13] Zhang C, Ding M, Ren Y. . The smallest superatom Au₄(PPh₃)₄I₂ with two free electrons: Synthesis, structure analysis, and electrocatalytic conversion of CO₂ to CO. Nanoscale Advances, 2023, 5(12): 3287–3292

[14] Hu M, Li L, Li J. . Two-dimensional Cu-based materials for electrocatalytic carbon dioxide reduction. iScience, 2024, 27(3): 109313

[15] Wang Y, Zhou Q, Zhu Y. . High efficiency reduction of CO₂ to CO and CH₄ via photothermal synergistic catalysis of lead-free perovskite Cs₃Sb₂I₉. Applied Catalysis B: Environmental, 2021, 294: 120236

[16] Wu C, Zhang Q, Liu G. . From Pb to Bi: A promising family of Pb-free optoelectronic materials and devices. Advanced Energy Materials, 2019, 10(13): 1902496

[17] JanP E, Liang H C, ChengR W, et al. Molecular design strategy for meta-substituted aromatic organic halides in zero-lead-release halide perovskites with efficient waterproof light emission. Advanced Functional Materials, 2024, 2408323

[18] He J, Hu X, Liu Z. . Prospect for bismuth/antimony chalcohalides-based solar cells. Advanced Functional Materials, 2023, 33(48): 2306075

[19] Lim E L, Hagfeldt A, Bi D. Toward highly efficient and stable Sn²⁺ and mixed Pb²⁺/Sn²⁺ based halide perovskite solar cells through device engineering. Energy & Environmental Science, 2021, 14(6): 3256–3300

[20] Priyadarshini P, Senapati S, Naik R. Lead-free organic inorganic hybrid halide perovskites: An emerging candidate for bifunctional applications. Renewable & Sustainable Energy Reviews, 2023, 186: 113649

[21] Shai X, Zuo L, Sun P. . Efficient planar perovskite solar cells using halide Sr-substituted Pb perovskite. Nano Energy, 2017, 36: 213–222

[22] Tang Y, Mak C H, Zhang J. . Unravelling the interfacial dynamics of bandgap funneling in bismuth-based halide perovskites. Advanced Materials, 2022, 35(2): 2207835

[23] Li M, Xu S, Wu L. . Perovskite Cs₃Bi₂I₉ hexagonal prisms with ordered geometry for enhanced photocatalytic hydrogen evolution. ACS Energy Letters, 2022, 7(10): 3370–3377

[24] Duan X, Jia H, Cao T. . Nitrate promoted ATZ degradation in Z-scheme Cs₃Bi₂I₉/BiVO₄ photocatalytic system: Coupling ·OH and RNS mediated reduction and oxidation. Applied Catalysis B. Environment and Energy, 2024, 352: 124016

[25] Paternò G M, Mishra N, Barker A J. . Broadband defects emission and enhanced ligand Raman scattering in 0D Cs₃Bi₂I₉ colloidal nanocrystals. Advanced Functional Materials, 2018, 29(21): 1805299

[26] Zhu Y, Wang F, Wang J. . Insight into interfacial dynamics of photogenerated carriers in Cs₃Bi₂I₉/Au heterostructure nanocomposites for high-sensitivity broadband photodetection with negative photoconductivity. Journal of Colloid and Interface Science, 2025, 680: 459–468

[27] Belousov A S, Parkhacheva A A, Markov A N. . Environmental application of versatile Bi-based perovskite photocatalysts and their Z-scheme and S-scheme heterojunctions. Journal of Environmental Chemical Engineering, 2024, 12(5): 113309

[28] Tang M, Ao Y, Wang C. . Facile synthesis of dual Z-scheme g-C₃N₄/Ag₃PO₄/AgI composite photocatalysts with enhanced performance for the degradation of a typical neonicotinoid pesticide. Applied Catalysis B: Environmental, 2020, 268: 118395

[29] Cheng Y, Chen J, Wang P. . Interfacial engineering boosting the piezocatalytic performance of Z-scheme heterojunction for carbamazepine degradation: Mechanism, degradation pathway and DFT calculation. Applied Catalysis B: Environmental, 2022, 317: 121793

[30] Jiang L, Du H, Li L. . Sequential growth of Cs₃Bi₂I₉/BiVO₄ direct Z-scheme heterojunction for visible-light-driven photocatalytic CO₂ reduction. Transactions of Tianjin University, 2023, 29(6): 462–472

[31] Zhang L J, Li S, Liu B K. . Highly efficient CdS/WO₃ photocatalysts: Z-scheme photocatalytic mechanism for their enhanced photocatalytic H₂ evolution under visible light. ACS Catalysis, 2014, 4(10): 3724–3729

[32] Jiang X, Ding Y, Zheng S. . In-situ generated CsPbBr₃ nanocrystals on O-defective WO₃ for photocatalytic CO₂ reduction. ChemSusChem, 2022, 15(4): e202102295

[33] Li X, Xu A, Fan H. . 0D–2D S-scheme CdS/WO₃ catalyst for efficiently boosting CO₂ photoreduction. Journal of Power Sources, 2022, 545: 231923

[34] Shi A, Sun D, Zhang X. . Direct Z-scheme photocatalytic system: Insights into the formative factors of photogenerated carriers transfer channel from ultrafast dynamics. ACS Catalysis, 2022, 12(15): 9570–9578

[35] Sarkar A, Acharyya P, Sasmal R. . Synthesis of ultrathin few-layer 2D nanoplates of halide perovskite Cs₃Bi₂I₉ and single-nanoplate super-resolved fluorescence microscopy. Inorganic Chemistry, 2018, 57(24): 15558–15565

[36] Feng Y X, Dong G X, Su K. . Self-template-oriented synthesis of lead-free perovskite Cs₃Bi₂I₉ nanosheets for boosting photocatalysis of CO₂ reduction over Z-scheme heterojunction Cs₃Bi₂I₉/CeO₂. Journal of Energy Chemistry, 2022, 69: 348–355

[37] Wang J, Li Y, Ma L. . Air-stabilized lead-free hexagonal Cs₃Bi₂I₉ nanocrystals for ultrahigh-performance optical detection. Advanced Functional Materials, 2022, 32(30): 2203072

[38] Aldrees A, Khan H, Alzahrani A. . Synthesis and characterization of tungsten trioxide (WO₃) as photocatalyst against wastewater pollutants. Applied Water Science, 2023, 13(7): 156

[39] ZhuB, HongX, TangL, et al. Enhanced photocatalytic CO₂ reduction over 2D/1D BiOBr_0.5Cl_0.5/WO₃ S-scheme heterostructure. Acta Physico-Chimica Sinica, 2021, 38(7): 2111008 (in Chinese)

[40] Ghosh B, Chakraborty S, Wei H. . Poor photovoltaic performance of Cs₃Bi₂I₉: An insight through first-principles calculations. Journal of Physical Chemistry C, 2017, 121(32): 17062–17067

[41] Wu F, Shi Z, Zhan K. . Exploring the photo-induced charge transfer behavior of Cs₃Bi₂I₉ and BiI₃ using in-situ surface photovoltage spectroscopy. Materials Letters, 2023, 347: 134596

[42] Ikake H, Hara S, Shimizu S. Skillful control of dispersion and 3D network structures: Advances in functional organic-inorganic nano-hybrid materials prepared using the sol-gel method. Polymers, 2022, 14(16): 3247

[43] Li L, Ye G, Luo T. . Centimeter-sized stable zero-dimensional Cs₃Bi₂I₉ single crystal for mid-infrared lead-free perovskite photodetector. Journal of Physical Chemistry C, 2022, 126(7): 3646–3652

[44] Wei Z, Wang W, Li W. . Steering electron-hole migration pathways using oxygen vacancies in tungsten oxides to enhance their photocatalytic oxygen evolution performance. Angewandte Chemie International Edition, 2021, 60(15): 8236–8242

[45] Xu J, Chong M, Li W. . Guiding electron transfer for selective C₂H₆ photoproduction from CO₂. Chem, 2024, 11: 1–9

[46] CaoS, ZhongB, BieC, et al. Insights into photocatalytic mechanism of H₂ production integrated with organic transformation over WO₃/Zn_0.5Cd_0.5S S-scheme heterojunction. Acta Physico-Chimica Sinica, 2024, 40(5): 2307016 (in Chinese)

[47] Zhao D, Wang Y, Dong C L. . Boron-doped nitrogen-deficient carbon nitride-based Z-scheme heterostructures for photocatalytic overall water splitting. Nature Energy, 2021, 6(4): 388–397

[48] Su J, Feng X, Sloppy J D. . Vertically aligned WO₃ nanowire arrays grown directly on transparent conducting oxide coated glass: synthesis and photoelectrochemical properties. Nano Letters, 2010, 11(1): 203–208

[49] Zhang J, Zhang P, Wang T. . Monoclinic WO₃ nanomultilayers with preferentially exposed (002) facets for photoelectrochemical water splitting. Nano Energy, 2015, 11: 189–195

[50] McCall K M, Stoumpos C C, Kontsevoi O Y. . From 0D Cs₃Bi₂I₉ to 2D Cs₃Bi₂I₆Cl₃: Dimensional expansion induces a direct band gap but enhances electron-phonon coupling. Chemistry of Materials, 2019, 31(7): 2644–2650

[51] Zhang L, Liu C, Wang L. . Pressure-induced emission enhancement, band-gap narrowing, and metallization of halide perovskite Cs₃Bi₂I₉. Angewandte Chemie International Edition, 2018, 57(35): 11213–11217

[52] Li Y Y, Wu Q N, Bu Q J. . An effective CdS/Ti-Fe₂O₃ heterojunction photoanode: Analyzing Z-scheme charge-transfer mechanism for enhanced photoelectrochemical water-oxidation activity. Chinese Journal of Catalysis, 2021, 42: 762–771

[53] Ding Y, Cao Y Y, Chen D. . Relay photo/thermal catalysis enables efficient cascade upgrading of sugars to lactic acid: Mechanism study and life cycle assessment. Chemical Engineering Journal, 2023, 452: 139687

[54] Chou J C, Lin S H, Lai T Y. . A facile fabrication of a potentiometric arrayed glucose biosensor based on nafion-GO_x/GO/AZO. Sensors, 2020, 20(4): 964

[55] Balducci L, Darjazi H, Gonzalo E. . Evaluation of electronic-ionic transport properties of a Mg/Zr-modified LiNi_0.5Mn_1.5O₄ cathode for Li-ion batteries. ACS Applied Materials & Interfaces, 2023, 15(48): 55620–55632

Acknowledgements

This work was supported by the National Key R&D Program of China (Grant No. 2022YFA1505000), the Key R&D Program of Shaanxi Province, China (Grant No. 2024CY-GJHX-28), the National Natural Science Foundation of China (Grant No. 52302308), the Outstanding Youth Science Foundation Project of the National Natural Science Foundation of China (Overseas), and the Qinchuangyuan Cited High-Level Innovative and Entrepreneurial Talents Project, China (Grant No. QCYRCXM-2022-143).

Competing Interests

The authors declare that they have no competing interests.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11708-025-0989-1 and is accessible for authorized users.

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