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Structure,Property and Application of Prussian Blue and Its Analogues

Li Yan , Mingxin Zheng , Zhenyu Wan , Jinying Yuan

Progress in Chemistry ›› 2026, Vol. 38 ›› Issue (6) : 1025 -1037.

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Progress in Chemistry ›› 2026, Vol. 38 ›› Issue (6) : 1025-1037 DOI: 10.7536/PC20251001
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Structure,Property and Application of Prussian Blue and Its Analogues
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Abstract

Prussian blue and its analogues represent a class of open porous framework transition metal coordination compounds with a long history. They possess distinctive structural features,including a unique three-dimensional metal framework and electronic structure,tunable chemical composition,as well as diverse properties such as excellent photothermal and catalytic performance,good biocompatibility,and multimetal synergistic effects. In recent years,researchers have developed various synthesis methods based on their structure and properties,and have achieved a series of applications across different fields. This has gradually expanded the role of Prussian blue and its analogues from traditional pigments and dyes to versatile functional materials with significant potential in modern domains like catalysis,energy storage,and device fabrication. This review summarizes the brief discovery history and structure of Prussian blue and its analogues,introduces common preparation methods,and highlights their recent applications in diverse fields such as catalysis,energy storage,electrochromics,biomedicine,and environmental remediation. Finally,the challenges and future research prospects for the practical application of them are summarized and prospected.

Contents

1 Introduction

2 Discovery and structure of Prussian blue and its analogs

2.1 Discovery and structural analysis of Prussian blue

2.2 Prussian blue analogues

2.3 Preparation method

3 Progress in the application of Prussian blue and its analogues

3.1 Applications of catalysis

3.2 Applications of energy storage

3.3 Applications of electrochromic materials

3.4 Applications of biomedicine

3.5 Applications of environmental remediation

3.6 Applications of other fields

4 Conclusion and outlook

Graphical abstract

Keywords

prussian blue / prussian blue analogue / multifunctional applications / catalysis / energy storage

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Li Yan, Mingxin Zheng, Zhenyu Wan, Jinying Yuan. Structure,Property and Application of Prussian Blue and Its Analogues. Progress in Chemistry, 2026, 38(6): 1025-1037 DOI:10.7536/PC20251001

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1 Introduction

Prussian blue (PB) was first accidentally synthesized in Berlin, Germany, in the 18th century and is one of the oldest known man-made coordination compounds.[1]. PB consists of ferrous iron (Fe2+) and ferric iron (Fe3+) alternately linked via cyano groups (―C≡N―) to form an open face-centered cubic framework structure, with alkali metal ions and water molecules embedded in the lattice to maintain electrical neutrality.[2]. The deep blue color of PB originates from charge transfer transitions from Fe2+ to Fe3+.[3], and this electronic structure endows it with various unique physicochemical properties, such as effective absorption in the "biological transparency window" (750~950 nm) in the near-infrared region.[4], thereby enabling its application in biomedicine.
After its discovery, Prussian blue was widely used as a pigment in painting and textiles[5]. In the mid-19th century, Herschel and others invented the cyanotype printing process, utilizing the chemical reaction of PB under light exposure to reproduce images[6]. Due to PB's strong affinity for thallium and cesium ions, it is also used to treat thallium and radioactive cesium poisoning[7]. In addition, in 1978, Neff[8]obtained PB thin films on conductive substrates via electrochemical methods and achieved a reversible color change between blue and colorless states of the PB films under applied voltage, realizing an innovative application of PB in electrochromism.
With the gradual deepening of research, scientists discovered that metal ions in the Prussian blue structure can be partially or fully replaced by other transition metals, forming a series of derivatives with similar structures but tunable properties, known as Prussian blue analogues (PBAs). As early as the 18th century, John Brown[9]conducted a series of experiments, replacing iron ions with other metal salts such as silver, mercury, copper, bismuth, and lead, which is considered the first study on Prussian blue analogues. PBAs were already used in the field of industrial catalysis in the 1960s[10-12]. In 1995, Karyakin et al.[13]reported the first generation of amperometric glucose sensors based on Prussian blue, applying them to biosensors for the first time. A few years later, Imanishi et al.[14]embedded lithium into the PBA framework as a cathode for lithium secondary batteries, making the application scenarios of PBAs even more extensive.
In recent years, Prussian blue and its analogs have achieved numerous breakthroughs in synthesis technology, structural design, and applications. Shukla et al.[15]investigated the applications of PB and PBAs in the biomedical field, Zhou et al.[16]analyzed the progress in their applications for lithium-ion and potassium-ion batteries, Han et al.[17]reviewed the challenges and prospects of their applications in photocatalysis. Most of these reviews focus on a single field; this paper will outline the discovery history of Prussian blue and its analogs and introduce their applications in multiple fields in recent years.

2 Discovery and Structure of Prussian Blue and Its Analogs

2.1 Discovery and Structural Analysis of Prussian Blue

In the early 18th century, the German dye maker Diesbach accidentally produced a deep blue precipitate, known as Prussian blue, while preparing pigments due to the mistaken use of potash containing cyanide.[18]. In 1710, Frisch[19]wrote a short article for the "Miscellanea Berolinensia" of the Royal Prussian Society of Sciences, introducing "Berlin blue (Prussian blue)" into scientific literature for the first time, thereby formally bringing Prussian blue into the academic spotlight. Although it was known that some nitrogen-containing organic material was required to synthesize Prussian blue, the synthesis process remained confidential for a long time. It was not until 1724 that Woodward[20]published a method for preparing Prussian blue using dried ox blood, revealing the preparation method for the first time.
After understanding the preparation method, scientists proceeded to analyze the structure of Prussian blue. In 1725, Geoffroy heated Prussian blue, observed the release of ammonia gas, and left behind a coke-like residue.[21]. This discovery indicated that Prussian blue contains nitrogen-containing groups, which generate non-volatile products such as carbon and metal oxides upon thermal decomposition. In 1782, Scheele[22]boiled a mixture of PB and dilute sulfuric acid, obtaining a water-soluble acid, but did not determine its specific composition. It was not until 1815 that Gay-Lussac[23]first identified this acid as hydrocyanic acid and established the cyanide structure of Prussian blue. Limited by the analytical methods of the time, details such as the crystal structure of Prussian blue were not fully resolved.
With the development of modern analytical techniques, methods such as X-ray diffraction have gradually been used to analyze crystal structures. In 1936, Keggin et al.[24]determined the structures of Prussian blue and some related compounds through X-ray diffraction (Figure 1a), clarifying that the chemical formula of Prussian blue is FeIIIRFeII(CN)6, where R represents an alkali metal ion or ammonium ion, and proposing that Prussian blue belongs to the cubic crystal system with lattice parameter a = 10.2 Å. Iron atoms in different oxidation states are arranged at the corners of small cubes, cyanide groups are located on the edges of the small cubes connecting iron atoms, and the centers of alternating small cubes are occupied by alkali metal ions. In 1977, Buser et al.[25]further determined the structure of Prussian blue (Figure 1b), proposing its ideal chemical formula as Fe4[Fe(CN)6]3·xH2O (x = 14~16), with lattice parameter a = 10.166 Å. The basic unit consists of [Fe(CN)6]4- containing Fe(II) connected to Fe(III) via cyanide bridges. Single-crystal X-ray diffraction indicated vacancies at certain positions in the crystal, with the actual space group being Pm3m. It is now generally believed that the structure of Prussian blue can be divided into soluble and insoluble PB (Figure 1c), with the general formula KxFeIII[FeII(CN)6](3+x)/4 or K4xFeIII[FeII(CN)6](3+x). Its structure contains four FeII-CN-FeIII pairs, where the number of potassium ions determines the number of hexacyanometallate complex ions in the structure. In the soluble PB structure, four alkali metal ions alternately occupy the small cube positions, while the insoluble PB structure contains no alkali metal ions.[15].

2.2 Prussian blue analogues

Prussian blue analogues are also a class of coordination compounds with the molecular formula AxM[M'(CN)6]1-y□y·zH2O (0 ≤ x ≤ 2, 0 ≤ y ≤ 1), where: A is an alkali metal ion; M and M' are transition metals, which are connected via C≡N-to form an open framework, thereby accommodating A; □ represents vacancies formed by the partial absence of M'(CN)6units, typically occupied by zeolitic water and coordinated water[16]. Due to differences in the types and proportions of alkali metal ions and transition metals, the properties and crystal systems of PBAs vary, such as monoclinic[26], trigonal[27], cubic[28], tetragonal[29], and hexagonal[30], etc. Compared with traditional Prussian blue, PBAs offer greater tunability in composition and function.
In 2021, Cattermull et al.[31]investigated the six most major structural complexities in PBAs and their impact on material properties, including: octahedral tilting (Figure 2a), where M'(CN)6 octahedral units rotate cooperatively along different directions, reducing overall symmetry and allowing adjustment of pore size and connectivity; A-site sliding (Figure 2b), where alkali metal ions slide from vacancies along a certain direction, generating local strain fields in the lattice; Jahn-Teller distortion (Figure 2c), where octahedra distort when the transition metal is a Jahn-Teller active ion (such as Cu2+), affecting conductivity and magnetism; A-site ion type and proportion (Figure 2d), referring to the type and proportion of alkali metal ions in vacancies, which affect void size and thereby regulate electrode potential; hexacyanometalate vacancies (Figure 2e), which are missing M'(CN)6 units in the framework; these vacancies provide additional free volume and channels, enhancing ion diffusion rates but potentially weakening mechanical strength; framework hydration (Figure 2f), where water molecules fill framework vacancies, causing lattice expansion to stabilize the structure and also promoting proton conductivity. This study systematically analyzed the structural complexity of PBAs and its impact on performance, providing a theoretical basis for the structural design and functional research of PBAs. Currently, PBAs have quite extensive practical applications in multiple fields.

2.3 Preparation method

2.3.1 Precipitation method

The precipitation method is the earliest and most commonly used synthesis method for PB/PBAs, mainly including co-precipitation and assisted precipitation methods.
Co-precipitation is the most common method for preparing PB/PBAs, with its core being the use of a mixed solution containing transition metal ions and ferrocyanide or ferricyanide to generate a precipitate. Generally, using the co-precipitation method requires dropping an MX salt solution (X = Cl-, NO3-, etc.) into an A6-x[M′x(CN)6] solution, allowing M ions to coordinate with [M′x(CN)6], thereby obtaining the desired material[32]. Liang et al.[33]investigated the growth mechanism of PBA particles without modifiers, exploring the growth mechanisms of Co-based PBA and Ni-based PBA at the mesoscale. The study found that Co-based PBA forms mesoscale crystals through the aggregation and annealing of precursor nanoparticles, while Ni-based PBA follows a classic ion deposition growth mechanism, providing guidance for designing mesoscale PBA preparation via co-precipitation. Mosaad et al.[34]directly utilized the co-precipitation method to synthesize PBA with the composition Co0.4[Ni(CN)4]0.2/[Cr(CN)6]0.6through simple steps such as dissolution, mixing, and precipitation, providing highly active materials for electronic device applications. During the precipitation process, changes in the solvent also affect precipitate formation. Recently, Yin[35]et al. proposed a binary solvent (H2O/DMF) co-precipitation strategy, successfully synthesizing hexagonal-phase PBA with high crystallinity and an open structure, where the introduction of DMF played a crucial role in the formation of the hexagonal phase.
The auxiliary precipitation method refers to a technique that regulates the precipitation of metal ions by introducing chelating agents or structures, thereby controlling the crystal structure. Jeong et al.[36]introduced sodium citrate during the preparation of nickel-based PBAs. Through the chelation between sodium citrate and nickel ions, the release of nickel ions was slowed, reducing defects from 40% to 6% and significantly increasing the Na+content, thereby enhancing its electrochemical performance. Zhang et al.[37]enhanced micromixing of reactants using a Y-shaped tube while employing sodium citrate as a chelating agent to regulate precipitation kinetics, synthesizing low-defect iron-based PBAs. The auxiliary precipitation method provides a solution for synthesizing low-defect PBAs.

2.3.2 Solvothermal method

The solvothermal method uses solvents as a medium to synthesize PB/PBAs under high temperature and pressure; these solvents can be divided into aqueous and non-aqueous types. Xie et al.[38]used the hydrothermal method to mix raw materials in an aqueous solution and heat them, thereby producing spherical PB nanoparticles with uniform size. To address the issue of toxic HCN escape that is difficult to avoid in traditional hydrothermal methods, Zhang et al.[39]inspired by using Na2S2O3as a cyanide detoxifier, established an improved synthesis method by introducing Na2S2O3into a single-iron-atom hydrothermal system, synthesizing low-defect, high-sodium-content PBA, which exhibited high capacity and high cycling stability in sodium-ion batteries, providing a green improvement strategy for the hydrothermal method. In addition to the hydrothermal method, solvothermal methods using non-aqueous solvents have also been further studied. Geng et al.[40]used anhydrous ethanol as the solvent and adopted a microwave-assisted solvothermal method to successfully prepare NaFePBA with low crystalline water content (approximately 5 wt%). This material also demonstrated excellent electrochemical performance in sodium-ion batteries, proving the effectiveness of non-aqueous solvothermal methods in enhancing the stability and electrochemical performance of PBAs.

2.3.3 Electrochemical deposition method

Electrochemical deposition refers to a method of depositing PB/PBAs onto a substrate surface to form a thin film through electrolytic reactions. This method allows control over the thickness and uniformity of the PB/PBAs layer and is commonly used for preparing PB/PBAs films or electrode materials. The general process involves applying a voltage to the solution in an electrolytic cell, causing ions to migrate toward the electrodes, where redox reactions occur to generate PB/PBAs.[8]. Lamprecht et al.[41]used electrochemical deposition to directly grow NiFe-PBA films on conductive substrates, forming a uniform and well-crystallized active layer that significantly enhanced the electrochemical performance of the battery. Gilpin et al.[42]used electrochemical deposition to grow PB nanoclusters on a poly(o-aminobenzoic acid) template; this material exhibited significant catalytic activity.

2.3.4 Other methods

With the development of technology, more advanced preparation methods have also been applied to the synthesis of PB/PBAs. Silva et al.[43]developed an oxidative photoprinting synthesis method, utilizing inkjet printing combined with flash lamp sintering to achieve rapid two-step synthesis of PB. This approach first deposits a precursor ink containing K₄[Fe(CN)6] and HCl via inkjet printing, then uses a xenon lamp to trigger the oxidation reaction, thereby producing PB, providing a feasible solution for scalable production. Ouyang et al.[44]adopted an innovative thermally induced in-situ conversion strategy, constructing CoFe-PBA materials encapsulated within an N/S-doped carbon network through directional freezing and high-temperature carbonization. Electrochemical tests demonstrated that this material significantly enhances electron conductivity and ion diffusion rates. Meanwhile, this strategy also avoids the interference of crystalline water and cyanide contamination issues associated with traditional hydrothermal and co-precipitation methods. Wang et al.[45]reported a simple solvent-free mechanochemical strategy, achieving solvent-free solid-state reactions through high-energy ball milling, yielding kilogram-scale K₂Mn[Fe(CN)6] products within 10 minutes, offering new insights for the rapid synthesis of high-quality PBAs.

3 Progress in the Application of Prussian Blue and Its Analogs

With in-depth research on PB and PBAs, recent studies have continuously explored their applications in various fields and achieved significant progress.

3.1 Catalytic Applications

As porous coordination polymers, PB and PBAs possess large specific surface areas, unique porous structures, dispersed metal sites, and stability across a wide pH range, making them potential catalysts for electrocatalysis[46][47], however, their practical application is limited by poor conductivity, making direct use as electrocatalysts difficult; a common modification strategy involves compositing with highly conductive carbon supports to construct continuous pathways. One of their applications is in the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) during electrocatalytic water splitting. To address the issues of insufficient electroactive sites and poor conductivity of PBAs in neutral environments, Yoshimura et al.[48]deposited cobalt-based Prussian blue analogues (Co-PBA) on various graphene-based materials and found that, compared to pure Co-PBA, the polarization curves of all Co-PBA/graphene composite catalysts shifted significantly to the left (Figure 3a), indicating a reduced overpotential required to achieve the same current density, and that the Co2+/Co3+ redox peaks appeared earlier (Figure 3b), proving that nitrogen-doped supports enhance neutral OER activity and conductivity by optimizing interfacial charge transfer. This study provides a new strategy for synthesizing PBA-based catalysts for OER in neutral environments. PBAs themselves are prone to aggregation, leading to a reduction in electroactive sites and consequently decreased conductivity. Xiao et al.[49]developed a highly efficient catalyst, CoFe-PBA@CNFs-TA-10, based on electrospun carbon nanofibers loaded with porous cobalt-iron Prussian blue analogues and etched with tannic acid. By compositing with highly conductive carbon nanofibers, the problem of PBA aggregation was solved, and etching significantly increased active sites, thereby enhancing the catalyst's HER performance (Figure 3c), OER performance (Figure 3d), and conductivity, providing new insights for the design and preparation of metal-organic framework materials in the field of electrocatalysis. In addition, PBAs can also be used for the electrocatalytic oxidation of benzyl alcohol. Singh et al.[50]developed a multi-metallic PBA nanocatalyst, MnFeCoNiCu-PBA, which utilized the synergistic effect of multiple metals to lower the oxidation potential (Figure 3e) and achieved high conversion efficiency in the oxidation of benzyl alcohol (Figure 3f), providing a new strategy for the efficient electrocatalytic oxidation of organic molecules using PBAs.
Due to their unique electronic structures, bandgap structures, and excellent photostability, PB and PBAs can also be applied as photothermal catalysts[17]. Meng et al.[51]developed ten bimetallic PBAs for photocatalytic CO2reduction, demonstrating for the first time that PBAs can serve as efficient heterogeneous catalysts without post-treatment. The study showed that Ni-Co PBA exhibited high selectivity towards CO and good cycling stability (Figure 4a), validating the potential of PBAs in photocatalytic carbon dioxide reduction. Kosasang et al.[52]innovatively utilized mechanical grinding to achieve the vitrification of cobalt-based PBAs (CoHCF) into CoHCF-g, proving that the loss of some cyanide ligands during this process generated more open metal sites, thereby optimizing the material's structure. Compared to crystalline materials, the glassy state improved yield and selectivity under visible light, while selectivity remained stable under UV light (Figure 4b). Recently, Jia et al.[53]reported a novel p-n junction heterostructure catalyst, T-CZ-PBA (SC), obtained via controlled pyrolysis of PBA precursors, which provides highly active sites for the adsorption and activation of CO2and enhances the transport efficiency of photothermal carriers. Among them, T-C3Z1-PBA (SC) simultaneously exhibits high conversion rates and high selectivity (Figure 4c), and demonstrates long-term stability under photothermal conditions (Figure 4d). These series of studies provide new ideas and strategies for catalyst design in the field of PBA-based photothermal catalytic CO2conversion.
In addition, PB and PBAs have also been applied in other types of catalysis. Tran et al.[54]used cubic-phase Zn-Co PBA as a heterogeneous high-efficiency catalyst to catalyze the cycloaddition reaction of CO2with dehydrated glycerol to synthesize glycerol carbonate (Figure 5a), demonstrating high catalytic activity and selectivity; they used amorphous-structure PBA catalyst Zn-Co DMC to catalyze ring-opening copolymerization for synthesizing polycarbonate polyols (Figure 5b). This study provides a low-cost feasible solution for the utilization of CO2. PBAs have also been applied in nitrate reduction for ammonia production. Ye et al.[55]constructed a hierarchical cubic array of iron-cobalt PBA (FeCo PBA HCAs) on carbon fiber cloth via an ion exchange method, and used it to reduce nitrate under neutral electrolyte conditions, achieving efficient ammonia synthesis. Liu et al.[56]found that the Ni(II) sites in the Prussian blue analog NiFe-sc-PBA can be used for highly efficient and selective electro-oxidation of ethylene glycol, exhibiting excellent activity and long-term stability.

3.2 Energy Storage Applications

PB and PBAs have unique advantages in energy storage applications. Compared with other metal-organic framework materials, they possess larger voids capable of accommodating large metal ions, can maintain stability during multiple insertions, and their tunable composition and structure can meet the requirements of different types of batteries[57][58][59].Table 1summarizes some representative PBA-based electrode batteries and their performance.
In the application of sodium-ion batteries, researchers have optimized the performance of PBAs through a series of structural designs. Huang et al.[60]By combining single crystals with a high-entropy strategy, they developed a single-crystal high-entropy material, SC-HEPBA. Its high-entropy nature reduces constraints on Na+during diffusion while suppressing metal dissolution, thereby maintaining structural stability. This material exhibits a high capacity of 115 mAh/g at 100 mA/g and retains 79.6% of its capacity after 1000 cycles. The constructed full cell also demonstrates a high capacity of 109.4 mAh/g and good capacity retention (77.8% after 2000 cycles), validating the enhancement of PBA performance by the high-entropy strategy. Pathak et al.[61]prepared the functional material CoFeHCF by regulating low-spin iron redox, effectively suppressing the hindrance of vacancies and interstitial water to Na+diffusion. Electrochemical tests showed that this material has a high capacity of 160 mAh/g at 10 mA/g and retains 89% of its capacity after 300 cycles at 100 mAh/g, achieving improved PBA performance. Jing et al.[62]employed an "acid-assisted synthesis" strategy to prepare a series of early transition metal-late transition metal-based PBA materials. Among them, FeVO-PBA exhibited superior electrochemical performance, with a high capacity of 148.9 mAh/g at 50 mA/g, high capacity retention after 30,000 cycles, and a wide operating temperature range of -60 to 80 °C. The constructed full cell also achieved a high energy density of 259.7 Wh/kg, providing a new strategy for the design of high-energy sodium-ion batteries. Recently, Zhang et al.[63]found that the capacity decay of Prussian blue analog cathodes mainly stems from irreversible structural damage during cycling, and by introducing Mn2+to modify the material, they improved the cycling stability in cylindrical batteries across a wide temperature range.
Compared to sodium ions, aluminum ions exhibit stronger electrostatic interactions, making them more prone to inducing structural changes that affect battery performance. Similar strategies have also been applied to the modification of aluminum-ion batteries. Liu et al.[64]proposed an entropy regulation strategy to design a medium-entropy material, ME-PBA. By introducing four transition metals (Mn, Co, Ni, Cu) at N coordination sites, they utilized the entropy enhancement effect to stabilize phase transitions during charge-discharge cycles, controlling lattice parameter fluctuations to 1.2%. The material exhibited a capacity of 112.4 mAh/g at a current density of 0.05 A/g and retained 66.9% of its capacity after 10,000 cycles at 1.0 A/g. Shortly thereafter, Du et al.[65]developed a high-entropy PBA material, HEPBA, by incorporating multiple transition metals as an electrode for aqueous aluminum-ion batteries, further optimizing performance. This material minimized lattice volume changes through a lattice breathing effect, delivering a capacity of 79.2 mAh/g at 5.0 A/g and retaining 91.2% after 10,000 cycles, providing a new solution for aqueous aluminum-ion batteries. Beyond entropy regulation strategies, researchers have also achieved optimization of aluminum-ion batteries through strategies such as in situ construction of chemically coupled interfaces[66], synthesis of one-dimensional nanowires[67], and other strategies.
In addition to sodium-ion and aluminum-ion batteries, PBAs are also used in other types of cation batteries. Liu et al.[68]designed and prepared a PBA-based hybrid cathode by introducing MoS₂/carbon fibers, effectively addressing the low theoretical capacity of PBA cathodes, thereby significantly enhancing the specific capacity and cycling stability of potassium-ion batteries. Yang et al.[69]investigated V-PBA-coated M-PBAs (M = Co, Cu, Zn) heterostructured cathode materials based on nucleation rate regulation, finding that they can enhance the capacity of aqueous zinc-ion batteries through multi-metal redox reactions, providing a feasible material application strategy for the development of high-performance aqueous zinc-ion batteries.

3.3 Electrochromic Applications

Electrochromism is a phenomenon where optical properties change due to ion and electron intercalation/deintercalation under an electric field.[70]. PB and PBAs contain variable metal ions and can achieve reversible redox reactions, thereby enabling color switching, making them ideal materials for electrochromic devices. As early as 1978, Neff[8]prepared dense PB films on the surface of platinum foil electrodes and achieved a reversible blue/colorless color-changing process, reporting for the first time the direct electrochemical deposition of PB films on electrodes and their clear redox state-color correspondence. In recent years, PB and PBAs have also seen development in the field of electrochromism.
Smart windows are a class of intelligent devices capable of adjusting their color and light transmittance according to user needs, with PB also applied as a material within them. Liu et al.[71]developed a solar-driven multifunctional electrochromic smart window based on WO3/PB, achieving dynamic control over four modes: initial/bright/cool/dark (Figure 6a). The device is self-powered by integrating dye-sensitized solar cells and retains 88.5% visible light transmittance after 2000 cycles. Tang et al.[72]reported a low-spin Fe-based PB thin film material that achieved selective independent modulation of visible light (VIS) and near-infrared light (NIR) for the first time. The material achieved high optical modulation amplitudes of 76.6%, 79.8%, and 79.6% at 650 nm, 1400 nm, and 2000 nm, respectively, and realized three modes: bright-warm, dark-cool, and colored (Figure 6b), enabling dynamic adjustment of indoor lighting and temperature. In actual production, electrochromic smart windows still face certain challenges due to equipment and cost limitations. Based on this, Tian et al.[73]proposed an efficient preparation strategy assisted by the novel two-dimensional material MXene (composed of transition metal carbides/nitrides/carbonitrides) for in-situ growth, achieving simple and green synthesis of PB thin films. This material enables switching among three modes: initial/warm/cool (Figure 6c), achieving a high optical modulation rate of 65.89% at 713 nm, with almost no attenuation in optical modulation rate after 10,000 cycles.
PB and PBAs are also used in some wearable devices. With technological advancements, electrochromic devices have been applied in the field of military camouflage. Li et al.[74]prepared PB films on flexible gold/nylon 66 substrates using electrodeposition to construct a reflective electrochromic device. This device can achieve reversible switching between sandy yellow and leaf green upon application of an external voltage, simulating desert and oasis environmental colors to realize camouflage (Figure 7a). Meanwhile, the coloring of this device requires only 1.3 s, and bleaching requires only 0.9 s, outperforming similar systems. Besides military applications, PB-based wearable devices can also be used in daily life scenarios. Kim et al.[75]proposed a new strategy for PB micro-printing guided by meniscus assembly, integrating the resulting PB micropatterns into smart contact lenses to construct smart electrochromic (EC) displays with real-time navigation capabilities (Figure 7b). This work provides a scalable microfabrication solution for miniature smart electrochromic displays in AR devices and expands the application potential of PB in flexible electronic devices.
In addition, PB and PBAs have also been used in other devices related to electrochromism. Zhang et al.[76]developed a dynamic electrically controlled fluorescent color-changing device based on the synergistic effect of aggregation-induced emission carbon dots (AIE-CDs) and PB, and applied it to the field of reversible data encryption/decryption (Figure 7c), providing a new strategy for dual-mode anti-counterfeiting technology.

3.4 Biomedical Applications

The cyano groups in PB and PBAs bind tightly to metals, exhibiting excellent biocompatibility and good safety, and can be functionalized through surface modification, thus being widely used in the biomedical field[77].
In the near-infrared region, water, blood, and biological tissues exhibit poor absorption capabilities, whereas PB and PBAs possess strong absorption abilities and can efficiently convert light energy into thermal energy, making them suitable for photothermal therapy (PTT).[4]. Wang et al.[78]assembled Prussian blue nanoparticles (PBNPs) with protonated graphitic carbon nitride C3N4-H+into a nanocomposite PBCN via electrostatic interactions. Under 808 nm laser irradiation, it achieved a photothermal conversion efficiency of 60.1%, superior to other PBNP-based nanocomposites, and demonstrated excellent therapeutic effects in living cells. Hong et al.[79]developed a composite injectable nanomaterial IBC-PB based on PBNPs and bacterial cellulose (BC), which enhanced photothermal performance. In biotoxicity experiments, PBNPs showed only 19% cell viability at a concentration of 2500 μg/mL, whereas the composite material exhibited no significant cytotoxicity, indicating that the composite significantly reduced biological toxicity. Meanwhile, the composite displayed 71.5% tumor toxicity, superior to the 68.5% of PBNPs, suggesting that this material can serve as a highly biocompatible and reproducible PTT agent. Beyond directly inducing toxicity in tumor cells, Sweeney et al.[80]created an in vitro platform based on PBNP photothermal therapy. By activating PBNPs with near-infrared laser, they induced immunogenic cell death in tumor cells in vitro, releasing antigens that, after presentation by dendritic cells, expanded highly active, tumor-specific T cells (Figure 8a). They verified that these T cells possessed stronger tumor cytotoxicity compared to those expanded via traditional lysis methods, providing new insights for the application of PBNPs in the field of PTT.
PBNPs are also a novel type of nanocarrier with good cell permeability, thus being used for drug delivery[81]. To address the issues of poor dispersibility and limited specific surface area of traditional PBNPs, Xie et al.[82]synthesized biotinylated PBNP material PB@Lipo via a strategy of encapsulating PB with liposomes, significantly enhancing the biocompatibility and stability of PBNPs, and utilized it for an anti-inflammatory and collagen-promoting drug delivery platform. Facing the therapeutic difficulties of glioblastoma caused by blood-brain barrier (BBB) limitations and strong invasiveness, Hill et al.[83]developed an exosome-coated nanocarrier based on PBNPs, Exo:PB, leveraging the natural BBB penetration ability and homotypic targeting of exosomes to achieve specific delivery. Guo et al.[84]prepared a PB nanocage using the phase-change material 1-pentadecanol as a gating material and loaded with 5-fluorouracil (5-FU) (Figure 8b), achieving controlled release of 5-FU under near-infrared irradiation, providing a novel carrier for tumor-targeted combination therapy. In addition, researchers have enhanced the delivery and targeted therapeutic capabilities of PB and PBAs through a series of doping and modification methods, such as modifying PBNPs with bacterial membranes, photosensitizers, and triphenylphosphine[85], doping with Mn2+/Ir3+, coating PBNPs with CaCO3and loading indocyanine green[86], and using S-doped NiCuFe-PBA[87], which hold great potential in tumor therapy.
Meanwhile, Prussian blue nanoparticles, with their multiple enzyme activities, have demonstrated significant application potential in the intervention and treatment of various diseases. In Zhang et al.[88]'s study, PBNPs can scavenge reactive oxygen species (ROS) through multi-enzyme-like activities such as peroxidase (POD), catalase (CAT), and superoxide dismutase (SOD) activities, demonstrating the potential of PBNPs as nanozymes to inhibit or alleviate ROS-induced diseases. Voros et al.[89]constructed a papain-functionalized PB nanozyme colloid, preparing a triple enzymatic functional material with POD, SOD, and protease activities. Long et al.[90]developed a novel dextran-sorbitol carboxymethyl ether-modified PB nanozyme for treating myocardial ischemia-reperfusion injury (MIRI). This material not only exhibits enhanced SOD activity but can also passively target damaged myocardial tissue through the enhanced permeability and retention effect, holding significant potential for clinical translation. Recently, Pan et al.[91]loaded α-lipoic acid onto hollow mesoporous PB nanozymes to achieve targeting of tumor cells. This nanozyme comprehensively displays both CAT and POD activities, while the α-lipoic acid structure within it contains disulfide bonds that react with glutathione to disrupt the balance inside tumor cells, promoting their apoptosis and achieving the goal of anti-nasopharyngeal carcinoma treatment.
In addition, PB and PBAs are also used as imaging contrast agents[92][93], biosensors[94][95], etc., demonstrating multifaceted application potential in the biomedical field.

3.5 Environmental Remediation Applications

Due to their open framework structures and internal vacancies, PB and PBAs exhibit strong adsorption capabilities for radionuclides and heavy metal ions, and are commonly used to remove radionuclides and heavy metal ions from water.[96]97]. To improve the efficiency of radioactive wastewater treatment, Yao et al.[98]synthesized tetragonal PB nanorods via a template-free microemulsion solvothermal method, optimizing the adsorption performance for Cs+ and Sr2+. Experiments showed that at 298 K under neutral conditions, the maximum adsorption capacities of PB nanorods for Cs+ and Sr2+ reached 194.26 mg/g and 256.62 mg/g, respectively, surpassing other adsorbents. Addressing the challenge of removing Tl+ from thallium-containing wastewater amidst interference from high concentrations of coexisting ions, Zhang et al.[99]developed a PB-loaded biochar composite material, BC@PB, achieving excellent selectivity by removing over 95% of Tl+ even when the concentrations of coexisting ions such as Na+, Cd2+, and Zn2+ were far higher (1000 times) than that of Tl+. This material also possesses a high adsorption capacity of 9365 μg/g and can remove over 95% of Tl+ within one minute, providing a new pathway for the removal of Tl+ from wastewater. Wahman et al.[100]constructed a detection and removal method for Pb2+ based on PB/SiO2 mesoporous nanocomposites, achieving an optimal adsorption capacity of 190 mg/g for Pb2+ at pH 7.5. With good regeneration capability, this approach offers a viable solution for the highly sensitive detection and green remediation of Pb2+ in the environment.
Meanwhile, the unique chemical composition and structure of PB and PBAs make them potential catalysts for Fenton reactions, thereby enabling the degradation of organic pollutants.[101]. Currently, PB and PBAs have been used for bisphenol S[102], phenol[103], sulfonamides[104], methylene blue[105], azo dyes[106], and ciprofloxacin[107]in the degradation of such organic pollutants, providing new solutions for wastewater treatment.

3.6 Other apps

Beyond the aforementioned applications, PB and PBAs also find use in other fields. Wang et al.[108]developed a near-infrared light-responsive bidirectional shape memory composite by doping citrate-modified PBNPs into a shape memory polyurethane matrix. This material utilizes the photothermal properties of PBNPs to rapidly heat up under illumination, achieving shape recovery and demonstrating repeatable photomechanical jumping behavior. Wei et al.[109]constructed a multi-scale integrated lightweight microwave absorption material via a PBA-assisted assembly strategy, achieving strong dual-band absorption at a low loading of 1.1 wt%, providing new insights for designing lightweight and efficient wave-absorbing materials. PB and PBAs can also be used for spin logic function design[110], triboelectric nanogenerators[111], memristors[112], and other areas, offering diverse application scenarios.

4 Conclusion and Outlook

This article systematically reviews the development history, structure, preparation methods, and multi-field applications of Prussian Blue (PB) and Prussian Blue Analogs (PBAs). As a class of porous open-framework compounds coordinated by transition metals, PB and PBAs possess unique skeleton structures and tunable chemical compositions, demonstrating various advantages in electron transport, photothermal performance, and biocompatibility. After a relatively long research journey, the structures of PB and PBAs have gradually become clear. Their preparation methods have expanded from simple precipitation to solvothermal synthesis, electrochemical deposition, and other techniques, achieving control over particle size, morphology, and vacancies, laying the foundation for further applications and performance improvements. In terms of applications, PB and PBAs exhibit significant multifunctionality. Their reversible valence changes and open channels make them ideal materials for battery electrodes, with practical applications realized in various ion batteries. Their multi-metal sites, vacancy structures, and electronic structures demonstrate excellent activity and selectivity in catalytic fields such as electrocatalysis and photothermal catalysis. Their electrochromic properties have found practical applications in smart windows and wearable devices. Furthermore, their favorable photothermal conversion efficiency, biocompatibility, and adsorption capacity for metal ions enable their use in biomedical scenarios like photothermal therapy and drug delivery, as well as in environmental remediation. These applications collectively indicate that PB and PBAs are a class of materials with multi-faceted application potential.
Compared with other materials, PB and PBAs have both advantages and disadvantages. In terms of catalysis, PB and PBAs can achieve functional design through metal doping and are lower in cost compared to noble metal catalysts and single-atom catalysts; however, their electron conductivity and surface active sites are usually inferior to those of other types of catalysts, so they often need to be compounded with conductive substrates such as graphene to enhance the rate. As electrode materials, the voids in PB and PBAs facilitate the insertion and extraction processes of metal ions, maintaining stability during multiple insertions, and their composition and structure are also tunable; nevertheless, layered metal oxides and conductive carbon materials are superior in electronic conductivity, mechanical stability, and long-term cycle life. Meanwhile, PB and PBAs exhibit better selectivity in adsorption compared to materials like activated carbon and do not require the complex organic ligands of metal-organic frameworks (MOFs), making their synthesis relatively simple; however, their total adsorption capacity, regenerability, and other adsorption properties are inferior to those of adsorbents such as activated carbon, MOFs, and zeolites, requiring compounding with other materials or modification to compensate. Furthermore, in biomedicine, PB and PBAs have demonstrated unique advantages in photothermal therapy, drug delivery, and enzyme activity; but compared to mature biomedical carriers, research on their long-term degradation and metabolism is not yet deep enough, and the potential impact of their coordinated cyano groups on living organisms requires further verification.
Although PB and PBAs have been applied in multiple fields, there are still some limitations and challenges when further scaling up for practical applications. The issue of structural stability is the core challenge restricting their practical application. During battery cycling, irreversible phase transitions, structural degradation, deactivation of redox sites, and dissolution of metal ions occurring in PBAs continuously accumulate, leading to morphological destruction and a continuous decline in capacity.[63]Under different electrolytes or pH levels, the framework of PBAs also undergoes distortion, migration, and deactivation of active sites, which adversely affects their electrochemical performance and catalytic activity, limiting their application in energy storage and catalysis to a certain extent. Meanwhile, the accumulation of PB within living organisms can also cause certain toxic side effects. Although injected PB can be rapidly cleared from the blood, it accumulates in the liver and lungs before being completely excreted; when the accumulated dose reaches a certain level, it affects the metabolic levels of the liver and lungs, triggering mild inflammation.[113]The metabolic pathways of potentially generated free cyanide ions remain unclear, and the associated potential risks limit the clinical application of PB and PBAs to a certain extent. Furthermore, the low electronic conductivity of PB and PBAs restricts their direct application in electrochemistry. In terms of preparation, the use of cyanide raw materials in some methods brings potential environmental issues, and problems such as difficulty in ensuring uniformity and process sensitivity may exist during scale-up production, limiting the practical application of PB and PBAs to a certain extent.
To address the aforementioned limitations, future research can resolve these issues through methods such as structural modification. On one hand, combining PB/PBAs with materials like graphene, carbon nanotubes, and conductive polymers can overcome application constraints caused by their low electronic conductivity; additionally, assistance from external materials can enhance structural stability during cycling, thereby mitigating irreversible phase transitions and site deactivation. On the other hand, further optimization of preparation methods should be pursued to explore green synthesis pathways characterized by low energy consumption, low pollution, and renewable raw materials. By improving preparation processes, scaled industrial production can be gradually achieved, thus promoting the practical application of PB and PBAs. Furthermore, establishing a performance database for PB and PBA materials can facilitate the discovery and optimization of new materials.
In summary, after centuries of exploration and development, PB and PBAs have demonstrated application potential in many aspects, but certain limitations and challenges still exist. In the future, more researchers are needed to continuously optimize and improve them, further exploring and expanding the space for their preparation and application.

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Funding

National Natural Science Foundation of China(52273106)

National Natural Science Foundation of China(52473114)

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