Sequential Growth of Cs₃Bi₂I₉/BiVO₄ Direct Z-Scheme Heterojunction for Visible-Light-Driven Photocatalytic CO₂ Reduction

Abstract

The high exciton binding energy and lack of a positive oxidation band potential restrict the photocatalytic CO₂ reduction efficiency of lead-free Bi-based halide perovskites Cs₃Bi₂X₉ (X = Br, I). In this study, a sequential growth method is presented to prepare a visible-light-driven (λ > 420 nm) Z-scheme heterojunction photocatalyst composed of BiVO₄ nanocrystals decorated on a Cs₃Bi₂I₉ nanosheet for photocatalytic CO₂ reduction coupled with water oxidation. The Cs₃Bi₂I₉/BiVO₄ Z-scheme heterojunction photocatalyst is stable in the gas–solid photocatalytic CO₂ reduction system, demonstrating a high visible-light-driven photocatalytic CO₂-to-CO production rate of 17.5 μmol/(g·h), which is approximately three times that of pristine Cs₃Bi₂I₉. The high efficiency of the Cs₃Bi₂I₉/BiVO₄ heterojunction was attributed to the improved charge separation in Cs₃Bi₂I₉. Moreover, the Z-scheme charge-transfer pathway preserves the negative reduction potential of Cs₃Bi₂I₉ and the positive oxidation potential of BiVO₄. This study offers solid evidence of constructing Z-scheme heterojunctions to improve the photocatalytic performance of lead-free halide perovskites and would inspire more ideas for developing lead-free halide perovskite photocatalysts.

Keywords

Lead-free halide perovskite / Z-scheme heterojunction / CO₂ reduction / Visible-light photocatalysis / Charge transfer

References

[1] Fang S, Rahaman M, Bharti J, et al. Photocatalytic CO₂ reduction. Nat Rev Meth Primers, 2023, 3: 61.

[2] White JL, Baruch MF, Pander Iii JE, et al. Light-driven heterogeneous reduction of carbon dioxide: photocatalysts and photoelectrodes. Chem Rev, 2015, 115(23): 12888-12935.

[3] Yao S, He J, Gao F, et al. Highly selective semiconductor photocatalysis for CO₂ reduction. J Mater Chem A, 2023, 11(24): 12539-12558.

[4] Chen S, Yin H, Liu P, et al. Stabilization and performance enhancement strategies for halide perovskite photocatalysts. Adv Mater, 2023, 35(6

[5] Chen J, Dong C, Idriss H et al (2020) Halide perovskites: metal halide perovskites for solar-to-chemical fuel conversion (adv. energy mater. 13/2020). Adv Energy Mater 10(13):1902433

[6] Huo H, Wu F, Kan E, et al. Overall photocatalytic CO₂ reduction over heterogeneous semiconductor photocatalysts. Chemistry, 2023, 29(40

[7] Kojima A, Teshima K, Shirai Y, et al. Organometal halide perovskites as visible-light sensitizers for photovoltaic cells. J Am Chem Soc, 2009, 131(17): 6050-6051.

[8] Shi D, Adinolfi V, Comin R et al (2015) Solar cells. Low trap-state density and long carrier diffusion in organolead trihalide perovskite single crystals. Science 347(6221):519–522

[9] Yang Y, Yan Y, Yang M, et al. Low surface recombination velocity in solution-grown CH₃NH₃PbBr₃ perovskite single crystal. Nat Commun, 2015, 6: 7961.

[10] Liu J, Song K, Shin Y, et al. Light-induced self-assembly of cubic CsPbBr₃ perovskite nanocrystals into nanowires. Chem Mater, 2019, 31(17): 6642-6649.

[11] De Wolf S, Holovsky J, Moon SJ, et al. Organometallic halide perovskites: sharp optical absorption edge and its relation to photovoltaic performance. J Phys Chem Lett, 2014, 5(6): 1035-1039.

[12] Fu Y, Zhu H, Chen J, et al. Metal halide perovskite nanostructures for optoelectronic applications and the study of physical properties. Nat Rev Mater, 2019, 4(3): 169-188.

[13] Kovalenko MV, Protesescu L, Bodnarchuk MI Properties and potential optoelectronic applications of lead halide perovskite nanocrystals. Science, 2017, 358(6364): 745-750.

[14] Chen J, Luo Z, Fu Y, et al. Tin(IV)-tolerant vapor-phase growth and photophysical properties of aligned cesium tin halide perovskite (CsSnX₃; X = Br, I) nanowires. ACS Energy Lett, 2019, 4(5): 1045-1052.

[15] Jin Z, Zhang Z, Xiu J, et al. A critical review on bismuth and antimony halide based perovskites and their derivatives for photovoltaic applications: recent advances and challenges. J Mater Chem A, 2020, 8(32): 16166-16188.

[16] Kumar D, Kaur J, Mohanty PP, et al. Recent advancements in nontoxic halide perovskites: beyond divalent composition space. ACS Omega, 2021, 6(49): 33240-33252.

[17] Shi M, Yang H, Zhao Z, et al. Bismuth-based semiconductors applied in photocatalytic reduction processes: fundamentals, advances and future perspectives. Chem Commun, 2023, 59(29): 4274-4287.

[18] Zhou B, Xu S, Wu L, et al. Strain-engineering of mesoporous Cs₃Bi₂ Br₉/BiV_O4 S-scheme heterojunction for efficient C_O2 photoreduction. Small, 2023, 19(29

[19] Liu ZL, Liu RR, Mu YF, et al. in situ construction of lead-free perovskite direct Z-scheme heterojunction Cs₃Bi₂I₉/Bi₂WO₆ for efficient photocatalysis of CO₂ reduction. Sol RRL, 2021, 5(3): 2000691.

[20] Chen G, Wang P, Wu Y et al (2020) Lead-free halide perovskite Cs₃Bi_2xSb_2–2xI₉ (x ≈ 0.3) possessing the photocatalytic activity for hydrogen evolution comparable to that of (CH₃NH₃)PbI₃. Adv Mater 32(39):e2001344

[21] Dai Y, Tüysüz H Lead-free Cs₃Bi₂Br₉ perovskite as photocatalyst for ring-opening reactions of epoxides. Chemsuschem, 2019, 12(12): 2587-2592.

[22] Zhang W, Mohamed AR, Ong WJ Z-scheme photocatalytic systems for carbon dioxide reduction: where are we now?. Angew Chem Int Ed Engl, 2020, 59(51): 22894-22915.

[23] Zhang Z, Li L, Jiang Y, et al. Step-scheme photocatalyst of CsPbBr₃ quantum dots/BiOBr nanosheets for efficient C_O2 photoreduction. Inorg Chem, 2022, 61(7): 3351-3360.

[24] Cooper JK, Gul S, Toma FM, et al. Electronic structure of monoclinic BiVO₄. Chem Mater, 2014, 26(18): 5365-5373.

[25] Guan X, Tian L, Zhang Y, et al. Photocatalytic water splitting on BiVO₄: balanced charge-carrier consumption and selective redox reaction. Nano Res, 2023, 16(4): 4568-4573.

[26] Bresolin BM, Balayeva NO, Granone LI, et al. Anchoring lead-free halide Cs₃Bi₂I₉ perovskite on UV100-TiO₂ for enhanced photocatalytic performance. Sol Energy Mater Sol Cells, 2020, 204.

[27] Feng YX, Dong GX, Su K, et al. Self-template-oriented synthesis of lead-free perovskite Cs₃Bi₂I₉ nanosheets for boosting photocatalysis of CO₂ reduction over Z-scheme heterojunction Cs₃Bi₂I₉/CeO₂. J Energy Chem, 2022, 69: 348-355.

[28] Wang X, Li G, Ding J, et al. Facile synthesis and photocatalytic activity of monoclinic BiVO₄ micro/nanostructures with controllable morphologies. Mater Res Bull, 2012, 47(11): 3814-3818.

[29] Zhao D, Wang Y, Dong CL, et al. Boron-doped nitrogen-deficient carbon nitride-based Z-scheme heterostructures for photocatalytic overall water splitting. Nat Energy, 2021, 6(4): 388-397.

[30] Wang Y, Chen D, Zhang J, et al. Charge relays via dual carbon-actions on nanostructured BiVO₄ for high performance photoelectrochemical water splitting. Adv Funct Materials, 2022, 32(13): 2112738.

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

[32] Zhang L, Liu C, Wang L, et al. Pressure-induced emission enhancement, band-gap narrowing, and metallization of halide perovskite Cs₃Bi₂I₉. Angew Chem Int Ed Engl, 2018, 57(35): 11213-11217.

[33] Wu JM, Chen Y, Pan L, et al. Multi-layer monoclinic BiVO₄ with oxygen vacancies and V⁴⁺ species for highly efficient visible-light photoelectrochemical applications. Appl Catal B Environ, 2018, 221: 187-195.

[34] Cao F, Hu Z, Yan T, et al. A dual-functional perovskite-based photodetector and memristor for visual memory. Adv Mater, 2023, 35(44

[35] Dey KK, Gahlawat S, Ingole PP BiVO₄ optimized to nano-worm morphology for enhanced activity towards photoelectrochemical water splitting. J Mater Chem A, 2019, 7(37): 21207-21221.

[36] Yue X, Cheng L, Fan J, et al. 2D/2D BiVO₄/CsPbBr₃ S-scheme heterojunction for photocatalytic C_O2 reduction: insights into structure regulation and Fermi level modulation. Appl Catal B Environ, 2022, 304.

[37] Li L, Ye G, Luo T, et al. Centimeter-sized stable zero-dimensional Cs₃Bi₂I₉ single crystal for mid-infrared lead-free perovskite photodetector. J Phys Chem C, 2022, 126(7): 3646-3652.

[38] Wei T, Zhu YN, An X, et al. Defect modulation of Z-scheme TiO₂/Cu₂O photocatalysts for durable water splitting. ACS Catal, 2019, 9(9): 8346-8354.

[39] Hu Y, Hao X, Cui Z, et al. Enhanced photocarrier separation in conjugated polymer engineered CdS for direct Z-scheme photocatalytic hydrogen evolution. Appl Catal B Environ, 2020, 260.

[40] Kumar Y, Kumar R, Raizada P, et al. Novel Z-Scheme ZnIn₂S₄-based photocatalysts for solar-driven environmental and energy applications: progress and perspectives. J Mater Sci Technol, 2021, 87: 234-257.

[41] Hao X, Cui Z, Zhou J, et al. Architecture of high efficient zinc vacancy mediated Z-scheme photocatalyst from metal-organic frameworks. Nano Energy, 2018, 52: 105-116.