All-inorganic lead halide perovskites for photocatalysis: a review

Abstract

Nowadays, environmental pollution and the energy crisis are two significant concerns in the world, and photocatalysis is seen as a key solution to these issues. All-inorganic lead halide perovskites have been extensively utilized in photocatalysis and have become one of the most promising materials in recent years. The superior performance of all-inorganic lead halide perovskites distinguish them from other photocatalysts. Since pure lead halide perovskites typically have shortcomings, such as low stability, poor active sites, and ineffective carrier extraction, that restrict their use in photocatalytic reactions, it is crucial to enhance their photocatalytic activity and stability. Huge progress has been made to deal with these critical issues to enhance the effects of all-inorganic lead halide perovskites as efficient photocatalysts in a wide range of applications. In this manuscript, the synthesis methods of all-inorganic lead halide perovskites are discussed, and promising strategies are proposed for superior photocatalytic performance. Moreover, the research progress of photocatalysis applications are summarized; finally, the issues of all-inorganic lead halide perovskite photocatalytic materials at the current state and future research directions are also analyzed and discussed. We hope that this manuscript will provide novel insights to researchers to further promote the research on photocatalysis based on all-inorganic lead halide perovskites.

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1 Background and development of perovskite materials

1.1 Non-perovskite photocatalysts and oxide perovskite photocatalysts

Globally, the challenges of the energy crisis and environmental pollution are becoming more severe.¹ An increasing number of studies have investigated the efficient use of solar energy to overcome these problems.^2–4 Among these methods, visible light catalysis technique has demonstrated considerable promise. A wide range of photocatalysts has been extensively studied in photocatalytic processes.

TiO₂ was originally used as a photocatalyst to break down water into H₂ and O₂.⁵ Different catalysts have been employed, including metal oxides (ZnO, WO₃, Co₂O, CeO₂),^6–8 metal sulfides (MoS₂, WS₂, Co₃S₄),^9–14 nitrides (C₃N₄, GaN),^15,16 phosphides (InP, Ni₂P, CoP, FeP),^17–26 and carbides (C₃N₄, rGO, MoC).^27–31 Photocatalysts with band gap (E_g) larger than 3 eV, such as TiO₂, ZnO, and MnS, have a fatal flaw: they can only be activated by UV light and cannot respond to a wide range of visible light regions. However, independent photocatalysts with E_g less than 3 eV, such MoS₂, WO₃, and C₃N₄, are impacted by the quick recombination of photogenerated carriers even though they exhibit photocatalytic activity under visible light irradiation. In short, these conventional photocatalysts still have several issues such as poor light absorption,³² low quantum efficiency,^33–36 high interfacial charge transfer resistance,³⁷ and rapid photogenerated carrier complexation,^38–41 thus significantly restricting the development and practical applications of photocatalysis. A range of efficient techniques, such as doping, implementing cocatalysts, building heterostructures, as well as controlling the morphology and crystallography, have been employed to conquer the aforementioned drawbacks and enhance the photocatalytic activity (Table 1).

Table 1 Comparison and summary of the photocatalytic performance of inorganic halide perovskites and non-perovskites^a

No.	Sample	Application	Synthesis method	Photocatalytic performance	Ref.
a MB: methylene blue, PMMA: polymethyl methacrylate, TC: tetracycline hydrochloride, RhB: rhodamine B.
1	Ag/TiO2	Degradation of MB wastewater	Sol–gel method	Degradation efficiency of MB is 98.86% (5 mg per L MB, 250 min)	49
	CsPbBr3/PMMA	Degradation of MB wastewater	Electrospinning technology	Degradation efficiency of MB is 99.18% (5 mg per L MB, 60 min)	50
2	TiO2/PCN-224	H2 production	Vacuum filtration	H2 production rate (1.88 mmol g^−1 h^−1)	51
	CsPbBr3	H2 production	Hot injection	H2 evolution rate is 133.3 μmol g^−1 h^−1 (saturated HBr aqueous solution)	52
3	ZnS/ZnIn2S4	CO2 reduction	Hydrothermal	Acetaldehyde yield 367.63 μmol g^−1 (selectivity 99.6%)	53
	Co/CsPbBr3/TiOx	CO2 reduction	Electrostatic self-assembling	The rate of CO2 reduction reaches 405.2 μmol g^−1 h^−1	54
4	TiO2/rGO/Cu2O	Degradation of antibiotic wastewater	Hummers method	Removal rate of TC is 99.38% (100 mg L^−1, 40 min)	55
	CsPbBr3–TiO2	Degradation of antibiotic wastewater	Solvothermal method	Removal rate of TC is 94% (20 mg L^−1, 60 min)	56
5	InP/InPS/ZnS	H2 evolution	Hot injection	The rate of H2 production reached 102 μmol mg^−1 h^−1	57
	CsPbX3@ZIF-8	H2 evolution	Mechanical milling	The rate of H2 production reached 7.852 μmol g^−1 h^−1	58
6	MoS2	Heavy metal degradation	Ball milling	Cr(VI) removal rate can reach 98.9% (180 min)	59
	CsPbI3/ZnO	Heavy metal degradation	Hot injection	Degradation efficiency of heavy metal is 52%	60
7	g-C3N4/CeO2	Degradation of RhB wastewater	Calcination and hydrothermal	The RhB degradation rate reached 99.07% (7 mg L^−1 60 min)	61
	CsPbBr3/PMMA	Degradation of RhB wastewater	Ball milling	The RhB degradation rate reached 92.2% (10 mg L^−1 60 min)	62

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Perovskite materials have drawn considerable attention as suitable photocatalysts. The general chemical formula of perovskites is ABX₃, where A, B, and X represent monovalent cations (La⁺, Bi⁺, CH(NH₂)₂⁺, CH₃NH₃⁺, Cs⁺, etc.), divalent cations (Pb²⁺, Mn²⁺, Co²⁺, Ti²⁺, etc.), and oxygen, halogen, etc. (O, Cl⁻, I⁻, Br⁻, etc.), respectively.⁴² When X is O, ABO₃ is called an oxide perovskite; organic–inorganic hybrid perovskites generally use CH₃NH₃⁺ (MA) or CH(NH₂)₂⁺ (FA) as the A-site cation. When Pb²⁺ is the B-site cation and Cl⁻, I⁻, Br⁻ or their mixtures are the halide ions (X), CsPbX₃ is called an all-inorganic lead halide perovskite.⁴³ The three-dimensional structure of a perovskite is formed by connecting the vertex corners of the (BX₆)ⁿ⁻ octahedron, which is made up of X⁻ and B²⁺, with B²⁺ occupying the middle position within the octahedron. The photocatalytic performance of perovskites will be influenced by its crystal structure. The hybridization of the O 2p orbital of the cation in the crystal structure and the 3d orbital of the transition metal in the (BO₆) octahedron will not only induce lattice distortion but also induce changes in the dipole and electronic structure, thereby affecting the separation of photogenerated carriers, finally leading to perovskites that have unique and variable photocatalytic properties. Furthermore, researchers can specifically build the electronic structure to enhance the stability, charge migration, and light absorption because of a variety of A and B site ions.^44,45 Perovskite materials can also enhance the photocatalytic activity by combining ferroelectric and piezoelectric phenomena.^46,47

Due to differences in the photoelectric characteristics, different perovskites exhibit varying photocatalytic efficiency. The following characteristics are mostly indicative of the attributes that influence photocatalytic efficiency: (i) light absorption coefficient. The light absorption ability of catalysts affects their photocatalytic performance. The intensity and range of light absorption are crucial markers. (ii) The length of carrier diffusion. Long carrier diffusion length improves photocatalytic efficacy, decreases charge recombination, and helps separate electrons and holes. (iii) Bandgap width. The narrower the band gap of the perovskite, the worse its stability. With an appropriate E_g (2.4–2.7 eV), the all-inorganic perovskite CsPbX₃ exhibits excellent stability.

ABO₃ perovskite has been the target of most studies, with impressive findings being obtained in the field of photocatalysis. Mulani et al. prepared Ni-doped LaFe_0.6Ni_0.4O₃ through a hydrothermal method to degrade crystal violet (CV), Congo red (CR), and their mixtures under visible light. The degradation efficiencies were 99.2% (210 min), 99.1% (100 min), and 98.4% (70 min), respectively, which were far higher than that of LaFeO₃. LaFe_0.6Ni_0.4O₃ degraded CV dye through dealkylation and benzene ring cleavage, while azo bond cleavage and oxidation lead to the production of low molecular weight intermediate products of CR dye.⁴⁸ In recent years, oxide perovskites have been rapidly developed in the field of photocatalysis (Fig. 1). Table 2 summarizes the synthesis methods, reaction conditions, and photocatalytic performances of oxide perovskites compared with traditional photocatalysts.

Fig. 1 Development process of perovskite in the photocatalysis field.

Table 2 Summary of typical work of oxide perovskite catalysts (ABO₃) in the field of photocatalysis^a

Catalysts	Synthesis method	Eg (eV)	Application	Photocatalytic performance	Ref.
a ARS: alizarin red S, BP: phenol, BPA: bisphenol A, PNP: p-nitrophenol, DCP: dichlorophenol, MO: methyl orange.
LaFeO3/g-C3N4/ZnO	Hydrothermal	2.43	Degradation of BP wastewater	Degraded 97.43% of BP (120 min, 20 mg L^−1), 90.14% (BPA), 93.68% (PNP), and 92.37% (DCP) (1 h, 20 mg L^−1)	63
BaTiO3@SrTiO3	Ultrasonic and hydrothermal method	3.23	Water spitting	H2 evolution rate is 18 μmol g^−1 min^−1	64
MgFe2O4/Bi2WO6	Wet ball milling	2.5	Degradation of TC wastewater	Degradation rate of TC is 95.82% (90 min, 20 mg L^−1)	65
Ag/CaZrO3	Solid-phase method	5.8	CO2 reduction	CO production rate (286 μmol g^−1 h^−1)	66
Fe–SrWO4	Hydrothermal	3.39	Nitrogen fixation	NH3 production rate is 385 μmol g^−1 h^−1	67
LaCoO3/MoS2	Sol–gel, hydrothermal, and ultrasonication method	2.10	Degradation of dye wastewater	Degraded 96% ARS and 90% RhB in 40 min and 80 min, respectively	68
BiFeO3/Bi2O3	Auto-combustion method	2.27	Degradation of nitrobenzene	Degraded 100% nitrobenzene	69
La0.9Sr0.1Fe0.8Co0.2O3	Pechini method	2.17	Degradation of dye wastewater	Degraded 98% reactive black 5 (20 ppm, 160 min)	70
NaTiO3/g-C3N4	Hydrothermal method	2.3	Degradation of mixed dye wastewater	Degraded 100% mixture of MB and CV in 25 min	71
Pt–LaMnO3	Green solid-state combustion method	2.82	H2 production	H2 production rate (40 μmol g^−1 h^−1) (20 vol% methanolic aqueous) solution	72
BaTiO3	Ceramic and complex polymerization methods	3.24	Diclofenac degradation	Presented the DIC removal (61%) (25 mg L^−1, 180 min)	73
Bi2O4/NaBiO3	Hydrothermal method	1.77	Degradation of MO and BP	Degraded 96.3% MO/BP (20 mg L^−1, 60 min)	74
BiVO4/BaSnO3	Facile precipitation method	2.38	Degradation of MB wastewater	With decolorization rate of 94.1% (20 mg L^−1, 2 h)	75
TiO2/CaTi4O9/CaTiO3	Solvothermal combination with calcination	3.21	H2 production and Cr(VI) reduction	Produced H2 at a rate of 25.28 mmol h^−1 g^−1 (methanol solution) Cr(VI) reduction rates reached 30.1% (10 mg L^−1, 150 min)	76

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1.2 Oxide perovskite to all-inorganic lead halide perovskites

ABO₃ perovskite exhibited structural flexibility and stability compared with metal oxides; however, it also has shortcomings including large band gap, rapid carrier recombination, small specific surface area, and poor selectivity. Due to the high tunability of band gap, excellent charge mobility, and suitable redox capabilities, organic–inorganic hybrid lead halide perovskites stand out from various materials. Studies have demonstrated that MAPbI₃ is consistently and effectively capable of producing H₂ from HI under visible light irradiation, and the solar HI separation efficiency by MAPbI₃ is 0.81% when Pt is utilized as a noble catalyst.⁷⁷

Due to their poor stability, organic–inorganic hybrid lead halide perovskites have limited application in photocatalysis. In contrast, all-inorganic lead halide perovskites exhibit highly efficient semiconductor properties. They are employed in various applications, including X-ray fluorescence imaging,^78–82 visible light communication,^83–85 solar cells,^86–89 light-emitting diodes (LEDs),^90–92 lasers,^93,94 photodetectors,^95–97 and photocatalysis. However, most of the previous studies have focused on the optoelectronic properties of all-inorganic lead halide perovskites; a thorough overview of the all-inorganic lead halide perovskites in photocatalysis is urgently required to provide a guide for future research. Herein, all-inorganic lead halide perovskites are summarized in detail with an emphasis on the approaches of synthesis, modification, and applications in photocatalysis. Moreover, the problems and the future development in the field of photocatalysis are summarized and prospected.

2 Synthesis methods of all-inorganic lead halide perovskites

The properties of all-inorganic lead halide perovskites largely depend on their structures, which are directly related to the synthesis methods. Numerous techniques have been investigated to synthesize all-inorganic lead halide perovskites, such as hot injection,^98–100 room-temperature ligand-assisted deposition,^101–103 microwave synthesis,^104–106 ultrasound synthesis,¹⁰⁷ template method,^108–110 laser irradiation-assisted method,¹¹¹ ball milling method,¹¹² and solvothermal method.¹¹³ These methods can be broadly classified as “bottom-up” or “top-down” depending on the growth process.¹¹⁴ The two techniques covered in this paper are the hot-injection and ligand-assisted deposition in room-temperature method (LARP), which are widely used for creating all-inorganic lead halide perovskites. The synthesis methods, advantages, and disadvantages of all-inorganic lead halide perovskites are summarized in Tables 3 and 4.

Table 3 Summary of all-inorganic lead halide perovskite synthesis methods

No.	All-inorganic lead halide perovskite	Method	Reaction conditions	Ref.
1	CsPbX3 nanocubes (410–530 nm) (X = Cl, Br, I, and mixed systems)	Hot injection method	140–200 °C inert gas protection	115
2	CsPbBr3 nanocrystals (6.8–13.6 nm)	LARP	Room temperature (25 °C) octylphosphonic acid	116
3	CsPbBr3 (film)	Anti-solvent method	Room temperature (varies with season) toluene as an antisolvent	117
4	CsPbBr3 (bulk)	Ball milling method	Ball mill (500 rpm)	112
5	CsPbI3 (8–12 nm)	Ultrasonic method	Room temperature tip ultrasound (power 30 W)	107
6	CsPbX3 (X = Cl/Br, Br and Br/I) nanowires (diameters as small as 2.6 nm)	Solvothermal method	160 °C (high temperature reactor)	113
7	CsPbBr3 quantum dots	Template method	Kaolin as template	118
8	CsPbBr3 nanocrystals (nanoplates, nanocubes)	Microwave synthesis	Microwave reactor 80 °C (nano-plate) 160 °C (nano-cube)	119

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Table 4 Advantages and disadvantages of various synthesis methods

Synthesis method	Advantages	Disadvantages	Ref.
Hot injection method	The reaction process is simple and less time-consuming, and the nanocrystals are relatively uniform in morphology and size	Inert gas protection is required during high temperature processes, which will increase the costs in practical applications	134
LARP method	Low cost and simple operation	Nanocrystals have different sizes, poor crystallinity, and low experimental repeatability, making them unsuitable for mass production	135
Anti-solvent method	Small particle size, uniform particle distribution, high dispersion, and controllable morphology	There are many factors that affect the preparation effect of this method (such as the selection and dosage of antisolvent)	136
Ultrasonic method	Low reaction temperature, high purity, small particle size	The purity of synthetic materials differs	129
Solvothemal method	The synthesis conditions are mild, the product purity is high, the crystal grains are fully developed, the particle size is small and evenly distributed, and the morphology is highly controllable	Factors affecting the nucleation process and crystal growth process are difficult to be controlled; highly dependent on equipment	137
Template method	Get good nanoarrays	Templates have the problem of low yield and difficulty in separation. The templates need to be removed, which will destroy the structure of the nanomaterials to a certain extent	138

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2.1 Hot injection method

The hot-injection method is a typical complex decomposition procedure that involves developing CsPbX₃ nanocrystals by completely mixing the PbX₂ precursor material with oleic acid, oleylamine, and octadecene and then rapidly cooling them at high temperatures (140–200 °C). In general, perovskite precursors crystallize into nanoplate-like morphologies at lower reaction temperatures, while they frequently generate cubic nanocrystals at higher reaction temperatures. When the temperature cools down, the size of the perovskite nanocubes also minimizes. The hot injection method can usually obtain dispersed CsPbX₃ nanocubes, and the halide composition of the nanocubes can be easily adjusted by changing the proportion of the PbX₂ precursor.

Nedelcu et al. firstly achieved the successful hot-injection synthesis of the all-inorganic lead halide perovskite CsPbX₃, which also indicated that CsPbBr₃ and CsPbI₃ had higher photoluminescence quantum yield (PLQY) compared to CsPbCl₃.¹²⁰ For instance, the PLQY of CsPbBr₃ nanocrystals reached 90% ¹¹⁵ (Fig. 2). The hot injection method not only synthesizes pure CsPbX₃ but also yields CsPbX₃-based composites. Wang et al. designed CsPbBr₃–CdZnS heterojunctions to photocatalytically reduce CO₂ by the hot-injection method; it was found that the CsPbBr₃–CdZnS heterojunction achieved a higher CO yield (55.8 μmol g⁻¹ h⁻¹) than that of the pristine CsPbBr₃ (13.9 μmol g⁻¹ h⁻¹).¹²¹

Fig. 2 Colloidal perovskite CsPbX₃ (X = Cl, Br, I) exhibit size- and composition-tunable bandgap energies covering the entire visible spectral region with narrow and bright emission: (a) colloidal solutions in toluene under UV lamp (λ = 365 nm); (b) representative PL spectra (λ_exc = 400 nm for all but 350 nm for CsPbCl₃ samples); (c) typical optical absorption and PL spectra; (d) time-resolved PL decays for all samples shown in (c) except CsPbCl₃.¹¹⁵

The hot-injection method for synthesizing all-inorganic lead halide perovskite nanocrystals has been continuously optimized using different precursors and ligands to achieve the controlment of shape and size as well as better stability over the years.¹²² Leng et al. successfully synthesized highly stable nanocrystals by designing a “modified hot-injection method” to maximize the number of ligand molecules and lowering the temperature (<40 °C) during precursor mixing to separate the nucleation and growth processes.¹²³ However, in large-scale production, the inability to adjust the high temperature when combining precursor solutions leads to poor material reproducibility.

2.2 Room-temperature ligand-assisted deposition

Even though the hot-injection method has been widely used to produce all-inorganic perovskite nanocrystals, it is a laborious process that needs extra steps in the synthesis of the Cs-oleate precursor and is typically carried out in an inert environment. LARP is an appropriate remedy for these limitations. Organic ligands and perovskite precursors are dissolved in solvent, and then spontaneous crystallization in a supersaturated state of the crystal can be achieved by lowering the temperature, evaporating the solvent, or adding a lean solvent with a lower solubility of the substance.¹²⁴ If crystallization is carried out in the presence of ligands, crystal nucleation and growth can be controlled, which is LARP.

Guvenc et al. produced CsPbX₃ (X = Br, Cl, I) by LARP; the PLQY of synthesized CsPbBr₃ was 85%.¹²⁵ By altering the experimental conditions, the LARP method can be used to manufacture all-inorganic lead halide perovskite with various morphologies. Deng et al. formed all-inorganic CsPbX₃ perovskite in a variety of shapes, including 0D spherical quantum dots, 1D nanorods, and 2D nanoplates¹²⁶ (Fig. 3). Zhang et al. discovered that stable CsPbBr₃ nanocrystals could be manufactured by adding small amounts of water to the reaction mixture, and the PLQY of the CsPbBr₃ nanocrystals was 90%.¹²⁷

Fig. 3 Schematic illustrating the formation process for different CsPbX₃ (X = Cl, Br, I) nanocrystals mediated by organic acid and amine ligands at room temperature. Spherical quantum dots represent hexanoic acid and octylamine; nanocubes represent oleic acid and dodecylamine; nanorods represent acetate acid and dodecylamine; few unit cell-thick nanoplatelets represent oleic acid and octylamine.¹²⁶

It is worth noting that perovskite nanocrystals are sensitive to polar solvents; therefore, the synthesized nanocrystals have different sizes, poor crystallinity, and low experimental repeatability, which are not suitable for large-scale production. To create high-performance all-inorganic lead halide perovskites, the researchers modified the original room-temperature ligand-assisted deposition method. Zeng et al. developed a comparable room-temperature supersaturation recrystallization technique to produce CsPbX₃ quantum dots.¹¹⁸ A highly supersaturated state is produced as soon as the halide salt precursor is transferred from a polar (N,N-dimethylformamide) to a nonpolar solvent (toluene), and the process can be finished without using a protective environment, heating, or injection in only a few seconds. Pan et al. investigated the ligand-mediated synthesis of all-inorganic CsPbBr₃ perovskite nanocrystals, and the results revealed that CsOAc was a more versatile precursor substance than the commonly used Cs₂CO₃, displaying a greater solubility and a wider temperature.¹²²

2.3 Other synthesis methods

2.3.1 Ultrasonic method. The direct sonication of the appropriate precursor solution to create high-quality all-inorganic lead halide perovskite in the presence of organic capping molecules is referred to as the “ultrasonic method”. Rao et al. used ultrasonic-assisted method to synthesize CsPbBr₃ nanocrystals with various shapes and sizes.^128,129

2.3.2 Ball milling method. Ball milling can be used to produce all-inorganic lead halide perovskites on a large scale,¹³⁰ for example, Jiang et al. synthesized CsPbBr₃/Cs₂PbBr₅ with chemical stability and good photostability by ball milling,¹³¹ showing exceptional stability when exposed to UV light, heat, and water. However, mechanical grinding will result in surface flaws and diminish the photocatalytic effectiveness. Kim et al. created a simple two-step ball milling approach to create stable CsPbBr₃ ¹³² and discovered that these materials were more stable after 30 days than those that were thermally synthesized under the same circumstances.

2.3.3 Solvothermal method. The solvothermal method produces scattered nanocubes by loading precursors and ligands into an autoclave lined with Teflon and heating it to a high temperature for a predetermined amount of time. Chen et al. reported that high-quality all-inorganic cesium lead halide nanocrystals could be acquired by a simple solvothermal method,¹¹³ and the high-quality CsPbBr₃ nanocrystals are ideal for lighting applications.

2.3.4 Microwave synthesis. Pan et al. proposed a microwave-assisted strategy to synthesize high-quality CsPbX₃ with controllable morphologies (nanocubes, nanoplates, and nanorods),¹¹⁹ and the prepared CsPbX₃ nanocubes showed high PLQY (75%). In addition to the above-mentioned synthetic methods, two or more methods can be combined to synthesize all-inorganic lead halide perovskites. Li et al. prepared CsPbBr₃/SiO₂ using a template-assisted method¹³³ and then used high-temperature synthesis by adding a specific quantity of mesoporous silica template to a mixture of CsBr and PbBr₂.

3 Modification of all-inorganic lead halide perovskite

Although all-inorganic lead halide perovskites have a great deal of potential for photocatalysis, however, pure halide perovskites typically have some issues, such as low stability, lack of active sites, and ineffective carrier extraction, which restrict the utilization of photocatalytic materials.^139–142 To improve the photocatalytic activity, several techniques have been developed, including ion doping,^143,144 metal loading,^145,146 creation of heterojunctions,^147,148 and anion exchange.^149–152

3.1 Ion-doping

Doping is a valuable modification strategy that adjusts the chemical structure of the lattice by incorporating some “impurities” to broaden the photoresponse range or enhance the separation of photogenerated carriers.^153–156 To this end, researchers have explored methods of incorporating metal ions at the A-site and B-site. Generally speaking, A-site and B-site doping can be achieved through cation exchange or in situ synthesis. Mn²⁺ is the most common dopant ion in the B-site of all-inorganic lead halide perovskites.^157–162 Liu et al. prepared Mn²⁺-doped CsPbBr₃ to improve the efficiency of CO₂ reduction¹⁶³ (Fig. 4). The results showed that the yields of CO and CH₄ reached 1917 μmol g⁻¹ and 82 μmol g⁻¹, which were 14.2 and 1.4 times that of CsPbBr₃. In addition, other metal atoms have also been successfully doped into all-inorganic lead-halide perovskites. Patil et al. doped CsPbI₂Br nanocrystals with Sr²⁺ to obtain more stable solar cells,¹⁶⁴ and the CsPb_0.98Sr_0.02I₂Br device maintained more than 85% of its initial efficiency for 100 hours under ambient conditions. Shyamal et al. partially substituted Pb²⁺ with Fe²⁺ to create Fe²⁺-doped CsPbBr₃,¹⁶⁵ which was utilized in ethyl acetate/aqueous solution for the photocatalytic reduction of CO₂. Dong et al. produced Co²⁺-doped CsPbBr₃/Cs₄PbBr₆ for CO₂ reduction with 1835 mol per g CO₂ yield.¹⁶⁶ All-inorganic lead-halide perovskites are also doped with new ions. In addition to equivalent doping, heterovalent ions can also be introduced. Zhou et al. stabilized CsPbBr₃ by co-doping Na⁺, and the results showed that co-doping metal ions significantly improved the thermal stability and optical properties of quantum dots.¹⁶⁷ Using calculations based on density functional theory, Wang et al. investigated how Bi³⁺ doping affected the structural,¹⁶⁸ electrical, and optical characteristics of CsPbBr₃, and the results revealed that Bi³⁺ doping can improve the stability.

Fig. 4 TEM images of Mn-doped CsPb(Br/Cl)₃ mixed-halide perovskites (a) sample 1: the ratio of PbBr₂/MnCl₂ is 4 : 1, (b) sample 2: the ratio of PbBr₂/MnCl₂ is 2 : 1, (c) sample 3: the ratio of PbBr₂/MnCl₂ is 2 : 3, (d) sample 4: the ratio of PbBr₂/MnCl₂ is 3 : 7.¹⁶³

Studies on A-site doping are becoming increasingly prevalent. Ru⁺ and K⁺ are a couple of alkali metal ions that have drawn increased interest as possible dopants. These dopants can be applied to boost the photoluminescence efficiency and stability of perovskite nanocrystals. For example, Huang et al. created K–CsPbBr₃ nanocrystals that maintained 97.9% of their initial intensity after 30 hours.¹⁶⁹ Ouaaka et al. assessed the electrical, optical, thermoelectric, and elastic characteristics of Rb-doped CsPbBr₃ by density functional theory. The findings demonstrated that Rb_xCs_1−xPbBr₃ had excellent ultraviolet absorption capabilities, a low range of E_g, and enhanced thermal–electrical conductivity.¹⁷⁰

In brief, ion doping has been thoroughly investigated to modify the electronic structure or create new energy and charge transfer routes to enhance the optical, electrical, and structural stability of all-inorganic lead halide perovskites. By the interaction of excitons and dopants, doping can bring additional optical, electronic, and magnetic features in addition to increasing the photocatalytic efficiency.^171,172

3.2 Heterojunction construction

The formation of a heterojunction at the interface between two distinct materials can efficiently improve the separation efficiency of photogenerated carriers, thus enhancing the photocatalytic performance. There are three types of heterojunctions suitable for photocatalysis: type II heterojunction, direct Z-type heterojunction, and S-type heterojunction. Different types of heterojunctions and their applications are summarized in Table 5.

Table 5 Heterojunction type photocatalyst summary

No.	Photocatalyst	Type	Application	Reference
1	WO3/CsPbBr3	S	CO2 reduction	173
2	C3N4@CsPbBr3	Z	CO2 reduction	174
3	CsPbBr3–rGO/Bi2WO6	S	Norfloxacin degradation	175
4	α-Fe2O3/rGO/CsPbBr3	Z	CO2 reduction	176
5	CsxWO3/CsPbBr3	Z	Hydrogen generation	177
6	CsPbBr3–CdS	II	Contaminant degradation	178
7	CsPbBr3/GO	II	Photoconductivity	179
8	CsPbBr3/Bi2WO6	Z	Pyrotechnic tar reduction	180
9	Bi2O2Se/CsPbBr3	S	Light detection	181
10	CsPb(Br/I)3/SiO2	II	LED	90
11	CsPbBr3/GeSn	II	Photodetector	182
12	CsPbBr3/TiO2	S	CO2 reduction	183–186
13	CsPbBr3/PbS	Z	Light detection	187
14	CsPbBr3/CsPb2Br5	Z	LED	188
15	CsPbBrCl2/g-C3N4	II	Photodegradable dyes	189 and 190
16	CsPbBr3/GO–Pt	Z	Hydrogen generation	191
17	CsPbBr3/Cs4PbBr6@COF	Z	Water spilt	192
18	CsPbBr3–CdZnS	S	CO2 reduction	121
19	CsPbBr3/UiO-66	Z	Methyl orange degradation	193
20	CsPbBr3@SnO2	S	CO2 reduction	194
21	Ag/CsPbBr3/Bi2WO6	Z	Rhodamine B degradation	195
22	PCN-222/CsPbBr3	Z	CO2 reduction	196

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3.2.1 Type-II heterogeneous junction. As exhibited in Fig. 5a, type II heterojunction consists of two semiconductors with two energy levels interlocked. When exposed to light, photogenerated holes will be transfer from the semiconductor with lower valence band to the other semiconductor with higher valence band; meanwhile, photogenerated electrons will be excited from the semiconductor with higher conduction band to other semiconductor with lower conduction band for reduction, promoting the spatial separation of charge carriers.¹⁹⁷ Interestingly, the system of type-II heterojunctions not only enhances the photocatalytic ability but also improves the stability of all-inorganic lead-halide perovskites. Wang et al. developed a layer-by-layer NiO_x/CsPbBr₃/TiO₂ planar II heterojunction photocatalyst; the system demonstrated a 7-fold increase in photoactivity compared to CsPbBr₃.¹⁹⁸ Kamat et al. reported a quasi-type II CsPbBr₃–CdS core–shell heterojunction with significantly improved stability and photocatalytic performance.¹⁷⁸ Yin et al. reported an efficient CsPbBr₃/CdSe heterojunction photocatalytically to reduce CO₂ employing water as an electron donor in organic solutions.¹⁹⁹ The type II heterojunction with strong electronic coupling of the Pb–Se and Br–Cd bonds between CdSe and CsPbBr₃ facilitated the transfer of electrons, and the CO yield of the main product reached 115.26 μmol g⁻¹, which was 4.6 times higher than that of CsPbBr₃.

Fig. 5 Mechanism diagram of type-II heterojunction (a); mechanism diagram of Z-scheme heterojunction (b); mechanism diagram of S-scheme heterojunction (c).

However, the type II heterojunction still has some issues: on the one hand, the oxidizing capacity of two semiconductor photocatalysts decreased by the separation of photogenerated electron–holes; on the other hand, the presence of holes prevents the transfer of electron–holes between surfaces in other catalysts.

3.2.2 Z-type heterogeneous junction. Z-type heterojunction also consists of two semiconductors with an alternating band arrangement (Fig. 5b). Under photoexcitation, the photogenerated holes of the semiconductor with the higher valence band will recombine with the photogenerated electrons from the semiconductor with the lower conduction band. The Z-type heterojunction structure can maintain the photocatalyst in the proper valence band position and can spatially separate electron–hole pairs to enhance redox capability.¹⁹⁵ Jiang et al. created an all-solid Z-type heterojunction by connecting CsPbBr₃ with -Fe₂O₃, and this Z-type photocatalyst²⁰⁰ demonstrated a six-fold improvement in photocatalytic activity to convert CO₂ into fuel (CO and CH₄). Xue et al. fabricated a water-stable Z-type Ag/CsPbBr3/Bi₂WO₆ photocatalyst for the degradation of rhodamine B, and the catalyst degraded rhodamine B at a rate of 93.9% in 120 minutes, which was 4.41 times faster than Bi₂WO₆.¹⁹⁵

It should be noted that unanticipated side effects will result from Z-type heterojunction. The Z-type heterojunction increases the electron and hole-driving force of photogenerated chemical reactions; however, half of the electrons and holes produced during the photosynthesis process are lost. Therefore, when designing and building all-inorganic lead-halide perovskite-based heterojunction photocatalysts, the reaction process and the necessary redox potential should be taken into account.

3.2.3 S-type heterogeneous junction. As exhibited in Fig. 5c, the S-type heterojunction is formed by the interlaced structure of the reduced semiconductor photocatalyst with a low work function and high Fermi level as well as the oxidized semiconductor photocatalyst with a high work function and low Fermi level.²⁰¹ The S-type heterojunction achieves the spatial separation of photogenerated electron–holes in the semiconductor with stable redox ability through the three methods of built-in electric field, energy band bending, and electrostatic contact.^202,203 Zhang et al. created CsPbBr₃ quantum dot/BiOBr nanosheets to reduce CO₂ with an electron consumption rate of 72.3 mol g⁻¹ h⁻¹, which was 4.1 and 5.7 times higher than that of single CsPbBr₃ and BiOBr, respectively.²⁰⁴ Xu et al. also created TiO₂/CsPbBr₃ S-type heterojunctions, which exhibited higher CO₂ reduction rates.²⁰⁵ Pu et al. prepared CsPbBr₃/α-Fe₂O₃ S-type heterojunction,²⁰⁶ and the electron consumption rate was 3.38 mmol g⁻¹ h⁻¹, which was 2.4 times of that of the original CsPbBr₃.

In conclusion, all-inorganic halide perovskites are highly advantageous for photocatalysis due to their high absorption coefficient, defect tolerance, and variable band position. An extensive density of active sites, strong stability, and recyclability are also necessary for photocatalysts in addition to effective charge separation and transfer. In general, it is difficult for single-component halide perovskite photocatalysts to meet all these requirements. Integrating heterostructures of different functional materials into a single system through precise design is a common strategy to improve semiconductor performance because interactions between different components create synergistic effects. Consequently, halide-based perovskite heterostructures exhibit higher photocatalytic performance.

3.3 Other modification methods

3.3.1 Anion exchange method. By altering the X element in CsPbX₃, the anion exchange method could enhance the photocatalytic performance. Nedelcu et al. carried out anion exchange on CsPbX₃ (Cl, Br, I);¹²⁰ the results showed that this exchange can easily tune the emission color over the entire visible range. Guo et al. reported the use of mixed halide chalcogenides CsPb(Br_x/Cl_1−x)₃ (x = 0.7, 0.5, 0.3) to reduce CO₂, which proceeded for 9 h under simulated sunlight with great stability and selectivity for the conversion of CO₂ to CO and CH₄.²⁰⁷ Zhao et al. successfully oxidized toluene using an anion-exchange synthesis of CsPbBr_xCl_3−x/TiO₂ composite catalyst.²⁰⁸ Faceting and morphological adjustment can also improve the photocatalytic activity of all-inorganic lead halide perovskites. Das et al. prepared CsPbBr₃ nanocrystals by adjusting the (110) and (200) facets and found that CsPbBr₃ exhibits shape-dependent optoelectronic properties.²⁰⁹

3.3.2 Ligand modification. The surface modification of all-inorganic lead halide compounds,^210,211 such as ligand modification,^212–214 can also increase their stability and photocatalytic performance. Surface ligands play a key role in forming perovskites, which not only affect the nucleation and growth processes but are also extremely important for charge transport and structural stability.^215–217

3.3.3 Encapsulation. The resistance of all-inorganic lead halide perovskites to moisture, oxygen, light, and high temperatures is still a significant challenge because of their intrinsic ionic characteristics, which restricts their further development and practical applications.^218,219 Efforts have been made to encapsulate it in various materials over the years. It has been demonstrated that encapsulation with inert materials is a practical and efficient technique to avoid decomposition and increase stability against treatment conditions involving light, heat, and water.²²⁰ Silica, organic polymers, metal oxides, and metal salts are some examples of the various protective materials that have been proposed.²²¹ It turns out that enhancing the thermal and photostability of mesoporous SiO₂ by incorporating perovskite nanocrystals is a wise decision. Liang et al. evaluated the difference in the optical stability before and after encapsulating CsPbBr₃ in nano-SiO₂.²²² These findings indicate that the SiO₂ shell can significantly increase the photothermal stability of the shell by successfully restraining anion exchange and photodegradation.

In addition to ion doping and heterostructure, other modification methods such as anion exchange, surface ligand modification, and encapsulation can improve the stability of all-inorganic lead halide perovskites while maintaining high photocatalytic activity. All-inorganic lead halide perovskites typically consist of an all-inorganic core capped with organic ligands. We hope to find the most suitable ligands for surface passivation that will bring out the best and unique properties of the perovskite, thus broadening its applicability. Furthermore, encapsulation with materials has been proven to be a feasible and effective way to prevent decomposition and improve stability to survive water, light, and heat treatment conditions.

The two problems of low photocatalytic efficiency and poor stability of all-inorganic lead halide perovskites and the proposed solutions were already mainly discussed. As mentioned above, (1) adding dopants to the photocatalytic system can increase the active sites of the photocatalyst to promote adsorption capacity and redox reactions. By introducing appropriate doping metal ions, especially transition metal ions, the E_g of the catalyst can be adjusted, and the recombination of electrons and holes can be suppressed; (2) the construction of heterojunction nanocomposites is considered as an alternative strategy to promote all-inorganic lead halide perovskite photocatalysts. Coupling different types of cocatalysts with all-inorganic lead halide perovskites can induce the separation of photogenerated carriers and maximize the photocatalytic efficiency; (3) the instability problem of all-inorganic lead halide perovskites could be solved. The top priority is to build a protective layer or encapsulate ligands. The existence of a protective layer can isolate the perovskite from the external environment and prevent its interaction.

4 Applications of all-inorganic halide perovskites

Environmental protection and sustainable energy development are two major problems. Green, efficient storage, and renewable solar energy can be achieved using solar radiation to form chemical fuels, which are hydrogen and oxygen (from water splitting) or methane (from CO₂ reduction). The attractive optical properties of all-inorganic halide perovskites (e.g., high absorption coefficient in the UV-visible region, tunable band gap, and high PLQY) make them suitable candidates for solar-driven photocatalytic applications. This section will provide an overview of the current state of development for all-inorganic lead halide perovskites in photocatalytic pollutant degradation, CO₂ reduction, and H₂ evolution.

4.1 Photocatalytic hydrogen production

H₂, as an ideal clean energy source in the 21st century, is considered as an alternative to fossil fuels. Photocatalytic hydrolysis for hydrogen production has potential applications, in which the photocatalyst CsPbX₃ has been widely utilized.^223–225 The balance between photocatalytic activity and stability of CsPbBr₃ is achieved through the rational control of surface ligands. Wang et al. successfully achieved photocatalytic hydrogen evolution by synthesizing CsPbBr₃/Pt–TiO₂ composites.²²⁶ Song et al. prepared the CsPbBr₃@polyaniline, which was stable even in an aqueous solution and had a photocatalytic hydrogen generation efficiency of 4.81 mmol (h⁻¹ g⁻¹).²²⁷ Xiang et al. utilized Zn²⁺-doped CsPbBr₃ nanocrystals to directly reduce hydrogen atoms in water, which exhibited excellent photocatalytic activity and enhanced hydrogen production efficiency.²²⁸ Sun et al. developed a new CsPbBr₃ nanocrystalline coupled NiFe-LDH photocatalyst for high-efficiency photocatalytic CO₂ reduction,²²⁹ and the photocatalyst's optimum electron consumption rate was 39.58 mol g⁻¹ h⁻¹, which was higher than that of pristine NiFe-LDH.

Low-polarity solvents can be utilized to produce stable reaction conditions for photocatalytic hydrogen production. Sun et al. produced 0.8 mol per g hydrogen during 8 hours of simulated solar irradiation using ethyl acetate.²³⁰ In hydrogen halide (HX, X = Br, I) solutions, all-inorganic lead halide perovskites also show high photocatalytic hydrogen generation efficiency, for example, CsPbBr_3−xI_x/Pt exhibited excellent hydrogen production performance with 224 mol h⁻¹ in saturated aqueous HBr solution.²³¹

The attractive optical properties of all-inorganic halide perovskites (e.g., high absorption coefficient in the UV-visible region, tunable E_g, and high PLQY) make them suitable candidates to produce hydrogen. Despite the exciting progress, the field is still in its infancy and there is still much room for development in designing targeted reaction systems, improving the stability and efficiency, and eliminating the toxicity of halide systems in converting solar into chemical energy.

4.2 Photocatalytic reduction of CO₂

CO₂ and other greenhouse gases have been rapidly accumulating in the atmosphere²³² due to mankind's overreliance on fossil fuels, leading to severe and permanent effects on the ecosystem.^233,234 China is supposed to reach a “carbon peak” by 2030,²³⁵ indicating that greenhouse gas emissions play an important role in environmental issues,; thus, photocatalytic reduction of CO₂ is considered the most promising method.^236–239 Due to their outstanding qualities, such as affordability, simplicity of the synthesis method, visible light absorption, high CO₂ adsorption surface area, and adjustable structure, all-inorganic lead halide perovskites have been proved as effective catalysts.^240–246 The all-inorganic lead-halide perovskite materials generate electron–hole pairs by absorbing solar energy, and the generated electrons can reduce CO₂ to high value-added chemicals such as CO,²⁴⁷ CH₄,²⁴⁸ CH₃OH,²⁴⁹ HCHO,²⁵⁰ HCOOH,¹⁹⁶ and C₂H₄.²⁵¹

Hou et al. accomplished CO₂ reduction with CsPbBr₃ quantum dots in ethyl acetate/H₂O solution with reduction product yields of 4.3, 1.5, and 0.1 mol g⁻¹ h⁻¹ for CO, CH₄, and H₂, respectively, where the CO₂ reduction selectivity was approximately 100%²³⁰ (Fig. 6). Currently, the surface modification of CsPbX₃ or the creation of multi-component composites is the most cost-effective and promising solution to several issues with pure CsPbX₃ in the photocatalytic reduction of CO₂. Xu et al. fabricated CsPbBr₃/GO nanocomposites, which showed a CO₂ reduction rate of 23.7 mol h⁻¹ g⁻¹.¹⁷⁶ Additionally, to increase the effectiveness of CO₂ reduction, all-inorganic lead halide perovskites combined with other substances could generate heterojunctions. Wang et al. created a 0D/2D heterojunction photocatalyst with CsPbBr₃/Bi₂WO₆ nanosheets for the photocatalytic reduction of CO₂; the yield was 503 mol g⁻¹, which was 9.5 times greater than that of a single CsPbBr₃.²⁵²

Fig. 6 Solar reduction CO₂ into fuels under 300 W Xe lamp irradiation by CsPbBr₃ quantum dots: 8.5 nm CsPbBr₃ quantum dots (a) and tunable CsPbBr₃ quantum dots with different particle sizes (b).²³⁰

The humidity stability, CO₂ capture capacity, and charge separation efficiency were significantly increased when CsPbBr₃ nanocrystals combined with metal–organic frameworks (MOFs) for the photocatalytic reduction of CO₂.²⁵³ The performance of perovskite nanocrystals can be significantly influenced by the special structure of MOFs. Wan et al. combined CsPbBr₃ and UiO-66(NH₂)²⁵⁴ to create a composite photocatalyst with CsPbBr₃ QDs/UiO-66(NH₂) MOF structure, which was able to convert CO₂ to chemical fuel in a non-aqueous system. The reported photocatalytic reduction of CO₂ by all-inorganic lead halide perovskites is summarized in Table 6.

Table 6 Reported all-inorganic lead halide perovskites photocatalytic reduction of CO₂

No.	Photocatalyst	Solution	Light source	Products and yield (μmol g^−1 h^−1)	Ref.
1	CsPbBr3	Ethyl acetate/water	300 W xenon lamp	CO (4.25)	230
				CH4 (1.5)
				H2 (0.1)
2	CsPbBr3–GO	Ethyl acetate	500 W xenon lamp	CH4 (6.9)	255
3	CsPbBr3/g-C3N4	Acetonitrile/water	300 W xenon lamp	CO (149)	256
4	CsPbBr3/monolayered Ti3C2Tx	Ethyl acetate	300 W xenon lamp	CO (26.32)	257
				CH4 (7.25)
5	CsPbBr3/TiO2	Ethyl acetate	300 W xenon lamp	H2 (5.08)	258
				CO (7.73)
				CH4 (10.12)
6	CsPbBr3@zeolitic imidazolate	CO2 and H2O vapor	100 W xenon lamp	CO (0.67)	253
				CH4 (3.33)
7	Fe–CsPbBr3	Ethyl acetate/water	450 W xenon lamp	CO (3.2)	165
				CH4 (6.1)

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All-inorganic lead halide perovskites are sensitive to water or other polar solvents, resulting in insufficient activity and low selectivity of all-inorganic lead halide perovskites. Therefore, it is considered a feasible method to improve the activity and stability of photocatalytic CO₂ reduction by means of element doping, morphology control, and construction of heterojunctions.

4.3 Contaminant degradation

Many harmful pollutants are emitted into the air, water, and soil as a result of the growth of the industry.^259–261 Photocatalysis is an effective method to degrade pollutants.^262–264 However, the efficiency of photocatalytic degradation of pollutants in water is still limited due to the low efficiency of solar energy utilization and the rapid recombination of photogenerated holes and electrons.^265–269 Among these materials for the photocatalytic degradation of pollutants, all-inorganic lead halide perovskite photocatalysts can efficiently utilize solar energy and have many advantages in terms of efficiency, greenness, and cost.⁶⁰ In particular, the photocatalytic degradation of organic dyes,^270–272 phenols,^273–275 and antibiotics^276–278 in water has generated a lot of interest in all-inorganic lead halide perovskites.

Among the various pollutants, synthetic dyes such as rhodamine B,^279–281 Sudan red III,^282–285 methyl red,^286–288 methyl violet,^289–293 malachite green,^294,295 acid black dye,^296–299 Congo red,³⁰⁰ and methyl orange^301–303 are common. Feng et al. created CsPb(Br_1−xCl_x)₃-Au nanoheterojunction materials,²⁷¹ which were used to decompose Sudan red III pollutants, and the results showed that after 6 hours of visible light exposure, the heterostructures had degraded 71% of Sudan dye. Liu et al. prepared CsPbBr₃ perovskite quantum dots/polymethyl methacrylate composites by ball milling; the degradation rate of rhodamine B by the composites under visible light reached 92.2% within 60 min.³⁰⁴

Besides dyes, the abuse of broad-spectrum antibiotics (ciprofloxacin,^305–307 norfloxacin,^308–311 2-mercaptobenzothiazole,³¹² and tetracycline hydrochloride^313–315) causes harm to ecosystems and poses a threat to human health. Using all-inorganic lead halide perovskites, antibiotics can be successfully removed from water sources. Chen et al. produced all-inorganic CsPbBr₃ calcium titanite quantum dot materials by anti-solvent precipitation,³¹⁶ which was successfully used to remove antibiotic residues from ethanol, showing excellent photocatalytic activity. Zhao et al. synthesized Ag–CsPbBr₃/g-C₃N₄ ternary composites with excellent photocatalytic activity by loading nano-Ag on the surface of CsPbBr₃/bulky g-C₃N₄ composites³¹⁷ (Fig. 7), which were applied to the visible light catalytic degradation of 7-aminocephalosporanic acid; 7%-Ag–CsPbBr₃/g-C₃N₄ composites showed excellent photocatalytic activity, and 92.79% of 7-aminocephalosporanic acid was degraded. The stability and electron–hole separation rate of photocatalytic reactions can generally be improved by the heterostructures. Zhao et al. created type II CsPbCl₃ heterostructures,²⁷⁶ and the catalysts showed excellent photocatalytic performance for the degradation of penicillin–6-aminopenicillins acid. Liu et al. synthesized stable CsPbBr₃–TiO₂ heterojunction, which was applied in the visible light-driven photodegradation of tetracycline hydrochloride;⁵⁶ 80% of tetracycline hydrochloride was degraded in this experiment.

Fig. 7 Possible mechanism diagram for cephalosporin antibiotics degradation with Ag–CsPbBr₃/CN composite under visible light irradiation.³¹⁷

Oxygen activation typically initiates photodegradation reactions by generating reactive oxygen species (such as ·OH and ·O²⁻), which react with the target pollutants. When all-inorganic lead halide perovskites are used as photocatalysts to breakdown organic dyes, some encouraging results have been obtained. All-inorganic lead halide perovskites have attracted great interest due to their excellent optoelectronic properties. Table 7 summarizes the application of all-inorganic lead halide perovskites in the field of photocatalysis, including CO₂ reduction, H₂ evolution, and degradation of pollutants in water. Inspired by natural photosynthesis, artificial photocatalysts that can convert solar energy into useable fuels and chemicals have been extensively studied. The structure of photocatalytic systems has been extensively studied to improve the photocatalytic activity; however, the problems of poor light absorption and conversion efficiency still need to be improved. Researchers are investigating possible strategies to improve the light harvesting and conversion efficiency of efficient photocatalysts. In addition to the effectiveness of the photocatalyst, the environmental friendliness, durability, and recyclability of the materials have also been focused on.

Table 7 Summary of common all-inorganic lead-halide perovskites in terms of synthesis, modification, and application

Application	Sample	Synthesis method	Photocatalytic performance	Stability	Ref.
CO2 reduction	CsPb(Br0.5/Cl0.5)3	Hot injection	Total yield of CO and CH4 up to 875 μmol g^−1 (99% selectivity) (ethyl acetate solution)	The PXRD patterns of CsPb(Br0.5/Cl0.5)3 did not change significantly after photocatalysis	207
	CsPbBr3	Hot injection	CO evolution rate was 204.4 μmol g^−1 h^−1 and (100% selectivity)	Under 35 hours of irradiation, the production of CO increased with the extension of irradiation time	318
	CsPbBr3@SnO2	Solvothermal method and hot-injection	It showed a total production yield of 208.3 μmol g^−1 (192.3 μmol g^−1 for CO, and 16.0 μmol g^−1 for CH4) after 4 h	After four catalytic runs (4 h each). The result showed that no obvious decrease in activity was perceived for CsPbBr3@SnO2	194
	CsPbBr3/MoS2	Ultrasonic method	CO yield of 74.9 μmol g^−1 g^−1 (ethyl acetate solution)	The conversion of CO2 to CO and CH4 decreased slightly by about 3.4% and 9.1%, respectively, after three cycles	319
	CsPbI3/rGO	Hot injection	Formate generation with high selectivity (>90% FEformate) (KHCO3 solution)	Remaining stable in aqueous environments, rGO films provide significant protection for CsPbI3 from the aqueous environment	320
	CsPbBr3/alpha-Fe2O3	LARP	Showed electron consumption rate of 1.42 mmol g^−1 h^−1	The activity can be maintained at 90% after three cycles	206
Wastewater degradation	CsPbBr3	Emulsion and demulsion method	1 mg of catalyst can decompose an MO solution into a colorless solution in 100 min	The photocatalytic activity of CsPbBr3 did not change significantly after two cycles	272
	Ti3C2-MXene/NiO/CsPbI3	Hydrothermal	92.8% degradation of CV dye (15 mg L^−1) achieved in 90 min	After eight consecutive cycles of degradation, the photocatalytic degradation activity of CV dye slightly decreased by 2.9%	321
	CsPbCl3	Facile solution-based technique	Degraded 90% of eosin-B dye in 180 min	Photocatalytic activity did not change after 3 cycles	322
	Co/CsPbCl3	Solvothermal	Degraded 90% of MB dye in 180 min under visible light conditions	After three cycles of experiment, the degradation rate dropped by only 6%	323
	CsPbCl3/CN	Hot injection	The degradation rate of 6-APA was 83.31% in 120 min	The photocatalytic activity did not change significantly after three cycles	276
	CsPbBr3/MOF-808	Mechanochemical method	Cr(VI) reduction rate reached 92%; antibiotic degradation rate reached 97% (120 min)	After three runs, the PXRD patterns, FTIR spectra, and SEM image confirmed the stability of CsPbBr3/MOF-808	324
	CsPbI3/g-C3N4	Ultrasonic method	The degradation rate of RhB was 100% in 80 min (5 mg L^−1)	After four cycles, the degradation efficiency was not reduced	325
	CsPbI3	Hydrothermal method	The degradation rate of methyl violet was 81.7% in 120 min (5 mg L^−1)	After three cycles, the degradation efficiency was slightly reduced	326
H2 production	CsPbBr3@ZIF-8	Ball milling	Exhibited an H2 yield of 19.63 μmol g^−1 after 2.5 h	Photoluminescence intensity remained around 86.7% after 8 weeks	58
	CsPbBr3	Hot injection	Exhibited an H2 evolution rate of 13.3 μmol g^−1 h^−1	Photocatalytic activity did not change significantly after 20 h	57
	CsPbBr3/GO–Pt	Anti-solvent precipitation method	Exhibited an H2 evolution rate of 1060 μmol g^−1 h^−1 with high selectivity (>99%)	The photocatalyst showed no obvious deactivation with consistent H2 after 20 h	191
	CsPbBr3	Hot-injection	The amount of H2 was 132 μmol g^−1 within 4 h	H2 generation with outstanding stability (≥160 h)	223
	Pt@δ-CsPbI3	Solvothermal method	H2 production reached 12.6 mmol g^−1 h^−1	The activity of the material was constant within 24 h	327

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5 Challenges and prospects

All-inorganic lead halide perovskites have made significant progress in the field of photocatalysis. However, the strong ionic character of this substance makes its interior structure less stable. In addition, the existing reports have insufficient research on the growth kinetics of all-inorganic lead halide perovskite in the actual manufacturing process, which makes it difficult to control the formation and leads to low practical application efficiency, mainly due to the following aspects.

(1) The toxicity of lead is the main reason that restricts the actual production and large-scale commercial application of all-inorganic lead halide perovskites. Lead poisoning in humans can result in major health issues such as renal failure, nerve damage, and other disorders even at very low exposure levels.

(2) Due to the inherent ionic nature of all-inorganic lead halide perovskites, the resistance to moisture, oxygen, light, and high temperatures remains a significant challenge, and the perovskite structure is destroyed when exposed to polar solvents or water, which reduces its photocatalytic activity and limits practical application.

(3) The corresponding mechanism of photocatalysis has been extensively studied, but the precise redox pathway is still unknown.

(4) Inorganic lead halide perovskites have weak thermal and light stability and are easily harmed by external stimuli like heat, light, and oxygen.

Future enhancements will mostly focus on the following areas in response to the aforementioned issues.

(1) To reduce the toxicity of inorganic lead halide perovskites, it is necessary to develop efficient and environment-friendly lead-free metal halide perovskites by replacing Pb with other transition metals (such as Sn, Ge, Bi, and Ag). However, the activity of lead-free perovskites will be reduced. Therefore, the development of such lead-free photocatalysts should be combined with several improvement strategies.

(2) To simultaneously maintain high stability and catalytic activity, the A-site is modified with mixed ions. Mixing organic cations and inorganic cations to prepare organic–inorganic hybrid halide perovskites is a promising method. By this way, organic components can be added to improve the photocatalytic activity while retaining the stability of inorganic components. Common hybrid organic cations include FA⁺ and MA⁺; however, the ratio between organic and inorganic ions needs to be further refined.

(3) The development of novel protective layers or ligands to form a core–shell structure should be taken into consideration to address the deficiencies of inorganic perovskite's poor stability. Stable co-catalysts can be developed to form the same structure as various heterojunctions that match the energy bands of inorganic lead halide perovskites.

(4) Photocatalysis can be widely used in various fields. Exploring novel photocatalytic applications, such as (i) removal of organic matter and heavy metals in soil. Inorganic lead halide perovskite catalysts have strong redox capabilities and have broad application prospects in remediating soil organic matter and heavy metals. (ii) Organic synthesis: photocatalytic organic synthesis is an economical and green synthesis method that uses sunlight to drive chemical reactions under mild conditions. Many photoreduction reactions proceed via free radicals or radical ion intermediates. This reactive intermediate can be easily and efficiently generated by visible light. (iii) Environmental monitoring: with the continuous development of the chemical industry, the discharge of various pollutants has led to an increasing demand for the detection of various heavy metals and other pollutants present in waters. Utilizing the luminescent properties of all-inorganic lead halide perovskites is considered a highly sensitive detection method.

In summary, the development of catalysts with excellent catalytic properties is crucial for practical applications. However, how to improve the activity of the catalyst while maintaining the stability of the catalyst requires more research. The problems and challenges encountered so far will motivate researchers to develop more effective perovskite catalysts in the future.

Conflicts of interest

There are no conflicts to declare.

Acknowledgements

This work was supported by Fundamental Research Funds for the Central Universities (2572022BA09), Natural Science Foundation of Heilongjiang Province of China (LH2023D003).

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