Key Takeaways & Executive Findings
- •• This paper reviews the fundamentals and research progress of metal halide perovskites (MHPs)-based heterojunctions for solar-driven redox reactions. • A comprehensive summary is presented for the construction of various MHPs-based heterojunctions (e.g., Schottky-junction, type-I/II, Z-scheme, and S-scheme). • The versatile use of MHPs-based heterojunctions in key photocatalytic redox reactions are summarized, including H2 evolution, CO2 reduction, pollutant degradation, and organic synthesis. • The review identifies challenges and prospects for future development in solar-light-driven redox reactions with MHPs-based heterojunctions.
Abstract
Metal halide perovskites (MHPs) with striking electrical and optical properties have appeared at the forefront of semiconductor materials for photocatalytic redox reactions but still suffer from some intrinsic drawbacks such as inferior stability, severe charge-carrier recombination, and limited active sites. Heterojunctions have recently been widely constructed to improve light absorption, passivate surface for enhanced stability, and promote charge-carrier dynamics of MHPs. However, little attention has been paid to the review of MHPs-based heterojunctions for photocatalytic redox reactions. Here, recent advances of MHPs-based heterojunctions for photocatalytic redox reactions are highlighted. The structure, synthesis, and photophysical properties of MHPs-based heterojunctions are first introduced, including basic principles, categories (such as Schottky junction, type-I, type-II, Z-scheme, and S-scheme junction), and synthesis strategies. MHPs-based heterojunctions for photocatalytic redox reactions are then reviewed in four categories: H2 evolution, CO2 reduction, pollutant degradation, and organic synthesis. The challenges and prospects in solar-light-driven redox reactions with MHPs-based heterojunctions in the future are finally discussed.
1. Introduction
Owing to the advantages of mild reaction conditions and clean solar energy input, semiconductor photocatalysis technology exhibits great potential in resolving environmental concerns and energy crisis [1–5]. Semiconductor materials as the heart of photocatalytic technology have emerged in an endless stream. Metal halide perovskites (MHPs) with unique and outstanding optoelectronic properties have appeared at the forefront of semiconductor materials for photocatalysis [6]. The chemical formula of MHPs is ABX3, where A is a monovalent metal cation (e.g., Cs+) or an organic cation (e.g., CH3NH3+ (MA+), CH(NH2)2+ (FA+)), B is usually a divalent metal cation (e.g., Pb2+, Sn2+), and X is a halogen anion (e.g., Cl−, Br−, I−). The divalent metal B is surrounded by six halogen ions leading to a BX6 octahedral structure, while the A cation is in the cubo-octahedral cavity within the corner-shared BX6 octahedral framework forming a three-dimensional (3D) structure (Fig. 1) [7–9]. Compared to traditional II-VI, III-V, and IV-VI semiconductors, MHPs possess the unique advantages as following: i) the high molar extinction coefficient of MHPs (e.g., 105–107 L mol−1 cm−1 for CsPbX3 nanocrystals, ~10 times higher than that of CdSe with similar band gap) [10], is beneficial to the capture of solar light; ii) the optical band gaps could be facilely regulated for target reactions by quantum confinement effect or tuning compositions of anions. In combination with other striking electrical and optical properties, such as high carrier mobilities, long carrier-diffusion lengths, MHPs are considered as a promising class of candidate for photocatalytic redox reactions.
Inspired by the first photocatalytic work reported by Nam in 2016 [11], various MHP-based photocatalysts, such as CsPbX3 [12–14], Cs3Bi2X9 [15], CsSnX3 [16], and Cs2AgBiBr6 [17], have been explored for solar-light-driven reactions. However, the inferior stability, severe charge-carrier recombination, and limited active sites of bare MHPs greatly restrict the photocatalytic activity and durability. Many strategies have been developed to overcome these drawbacks, such as structural and compositional modifications [18–21]. For instance, dimensionality engineering of CsPbBr₃ significantly boosted H₂ evolution activity [22], while alkali metal doping—despite its non-active nature—unveiled the critical role of dopant sites in charge-carrier dynamics [23]. Furthermore, facet engineering enabled precise regulation of product yield and selectivity in photocatalytic organic synthesis [24], demonstrating the versatility of MHP photocatalysts design. Particularly, construction of heterojunction has shown great potential to optimize light absorption properties and photoinduced charge-carrier dynamics. The concept of heteroju
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Qing Guo, Jin-Dan Zhang, Jian Li, Xiyuan Feng (2026). Solar-Driven Redox Reactions with Metal Halide Perovskites Heterogeneous Structures. Nano-Micro Letters. https://doi.org/10.1007/s40820-025-01886-y
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Frequently Asked Questions
What are metal halide perovskites (MHPs) and why are they important for photocatalysis?
Metal halide perovskites (MHPs) are a class of semiconductor materials with the general formula ABX3, where A is a monovalent cation (e.g., Cs+ or organic cations like MA+ or FA+), B is a divalent metal cation (e.g., Pb2+ or Sn2+), and X is a halogen anion (e.g., Cl−, Br−, I−). They exhibit exceptional optoelectronic properties, including high molar extinction coefficients, tunable band gaps, high carrier mobilities, and long carrier-diffusion lengths, making them highly promising for photocatalytic redox reactions such as H2 evolution, CO2 reduction, pollutant degradation, and organic synthesis.
What are the main challenges of using bare MHPs in photocatalytic applications?
Bare MHPs suffer from several intrinsic drawbacks that limit their photocatalytic performance and durability, including inferior stability (especially under moisture, heat, and light), severe charge-carrier recombination, and limited active sites. These issues hinder their practical application in solar-driven redox reactions.
How do heterojunctions improve the photocatalytic performance of MHPs?
Heterojunctions are constructed by interfacing MHPs with other semiconductors or conductive materials. They enhance photocatalytic performance by improving light absorption, passivating surface defects to increase stability, and promoting charge-carrier separation and transfer, thereby reducing recombination and increasing the availability of active sites for redox reactions.
What types of heterojunctions are discussed in this review?
The review discusses various types of MHPs-based heterojunctions, including Schottky junctions, type-I and type-II heterojunctions, Z-scheme, and S-scheme junctions. Each type has distinct charge-transfer mechanisms that can be tailored for specific photocatalytic applications.
What are the future prospects for MHPs-based heterojunctions in solar-driven redox reactions?
The review highlights that while significant progress has been made, challenges remain in terms of long-term stability, scalability, and understanding of fundamental mechanisms. Future research should focus on developing more robust heterojunction designs, exploring new material combinations, and optimizing synthesis methods to achieve efficient and sustainable solar-to-chemical conversion.
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