Se vacancies and interface engineering modulated bifunctionality prussian blue analogue derivatives for overall water splitting.

It is a challenging task to design and synthesize stable, and high-performance non-precious metals bifunctional catalysts for water-splitting. Herein, the coupling between Se vacancy and interface engineering is highlighted to synthesize a unique CoFeSe hollow nanocubes structure on MXene-modified nickel foam (NF) by in-situ phase transition from bifunctionality prussian blue analogue (PBA) derivatives (VSe-CoFeSe@MXene/NF). DFT theory reveals that the Se vacancy and interface engineering modulate the surface electronic structure and optimize the surface adsorption energy of the intermediates. Experimental data also confirm that the as-prepared CoFeSe@MF catalyst exhibits advanced electrocatalytic properties, 283 mV (OER) and 67 mV (HER) are required to drive the current density of 10 mA cm-2. Notably, it is assembled into a two-electrode system for integral water decomposition, which only requires a low cell potential of 1.57 V at current of 10 mA cm-2, together with excellent durability for 48 h. The strategy is expected to provide a new direction for the design and construction of highly efficient collaborative integrated water decomposition electrocatalysts.

Self-assembled high-entropy Prussian blue analogue nanosheets enabling efficient sodium storage.

High entropy material (HEM) has emerged as an appealing material platform for various applications, and specifically, the electrochemical performances of HEM could be further improved through self-assembled structure design. However, it remains a big challenge to construct such high-entropy self-assemblies primarily due to the compositional complexity. Herein, we propose a bottom-up directional freezing route to self-assemble high-entropy hydrosols into porous nanosheets. Taking Prussian blue analogue (PBA) as an example, the simultaneous coordination-substitution reactions yield stable high-entropy PBA hydrosols. During subsequent directional freezing process, the anisotropic growth of ice crystals could guide the two-dimensional confined assembly of colloidal nanoparticles, resulting in high-entropy PBA nanosheets (HE-PBA NSs). Thanks to the high-entropy and self-assembled structure design, the HE-PBA NSs manifests markedly enhanced sodium storage kinetics and performances in comparison with medium/low entropy nanosheets and high entropy nanoparticles.

Electrolyte Design Enables Stable and Energy-dense Potassium-ion Batteries.

Free from strategically important elements such as lithium, nickel, cobalt, and copper, potassium-ion batteries (PIBs) are heralded as promising low-cost and sustainable electrochemical energy storage systems that complement the existing lithium-ion batteries (LIBs). However, the reported electrochemical performance of PIBs is still suboptimal, especially under practically relevant battery manufacturing conditions. The primary challenge stems from the lack of electrolytes capable of concurrently supporting both the low-voltage anode and high-voltage cathode with satisfactory Coulombic efficiency (CE) and cycling stability. Herein, we report a promising electrolyte that facilitates the commercially mature graphite anode (> 3 mAh cm-2) to achieve an initial CE of 91.14% (with an average cycling CE around 99.94%), fast redox kinetics, and negligible capacity fading for hundreds of cycles. Meanwhile, the electrolyte also demonstrates good compatibility with the 4.4 V (vs. K+/K) high-voltage K2Mn[Fe(CN)6] (KMF) cathode. Consequently, the KMF||graphite full-cell without precycling treatment of both electrodes can provide an average discharge voltage of 3.61 V with a specific energy of 316.5 Wh kg-1-(KMF+graphite), comparable to the LiFePO4||graphite LIBs, and maintain 71.01% capacity retention after 2000 cycles.

Synthesis of Iron-Based Prussian Blue Analogues with Ultralong Cycle Performance in a Novel T-Shaped Collision Microreactor.

Iron based Prussian blue analogues (Fe-PBA) hold significant promise cathode materials for sodium ion batteries due to their low cost and desirable electrochemical properties. However, their practical application is often hindered by the presence of vacancy defects and issues of oxidation that arise during the material preparation process. To overcome these challenges, this study introduces an innovative T-shaped collision microreactor aimed at promoting a uniform concentration field, narrowing the gap between material mixing rate and reaction rate, and providing an oxygen-free environment for the synthesis of Fe-PBA. Employing this microreactor, Fe-PBAs were synthesized with a meticulous approach that led to a material possessing a well-defined morphology and a stoichiometry of Na1.54Fe[Fe(CN)6]0.93. The material exhibited a notable reduction in vacancy defects and minimized oxidation levels. Upon electrochemical evaluation, the Fe-PBA crafted within the microreactor demonstrated an impressive specific capacity of 94.1 mAh/g at a current density of 0.5 C and showcased a long-term cyclability with 72.6% capacity retention over 2000 cycles. Comparative analysis revealed that the structural and electrochemical properties of Fe-PBA prepared in the microreactor outperformed those of samples prepared using traditional reactors. This work provides a new approach for the continuous and stable fabrication of high-performance battery cathode materials.

Coamplified Nanozyme Cocktails for Cascade Reaction-Driven Antioxidant Treatments.

Antioxidant nanozymes are powerful tools to combat oxidative stress, which can be further improved by applying nanozyme mixtures of multiple enzymatic function. Here, cocktails of Prussian blue (PB) nanocubes and copper(II) exchanged ZSM-5 zeolites (CuZ) with enhanced reactive oxygen species (ROS) scavenging activity were developed. Surface functionalization of the particles was performed using polymers to obtain stable colloids, i.e., resistant to aggregation, under a wide range of experimental conditions. The nanozyme cocktails possessed advanced antioxidant properties with multiple enzyme-like functions, catalyzing the decomposition of ROS in cascade reactions. The activity of the mixture far exceeded that of the individual particles, particularly in the peroxidase assay, where an improvement of more than an order of magnitude was observed, pointing to coamplification of the enzymatic activity. In addition, it was revealed that the copper(II) site in the CuZ plays an important role in the decomposition of both superoxide radicals and hydrogen peroxide, as it directly catalyzes the former reaction and acts as cocatalyst in the latter process by boosting the peroxidase activity of the PB nanozyme. The results give important insights into the design of synergistic particle mixtures for the broad-spectrum scavenging of ROS to develop efficient tools for antioxidant treatments in both medical therapies and industrial manufacturing processes.

Enhancing Oxygen Evolution Reaction Performance with rGO/CoNi-Prussian Blue-Derived Oxyhydroxide Nanocomposite Electrocatalyst: A Strategic Synthetic Approach.

Electrochemical water splitting is a promising approach in the development of renewable energy technologies, providing an alternative to fossil fuels. It has attracted considerable attention in recent years. The benchmark materials used in water splitting are precious metals that are expensive and scarce. Therefore, this work proposes a strategic electrochemical synthesis of a reduced graphene oxide and cobalt-nickel hexacyanoferrate (rGO/CoNiHCF)-derived composite (rGO/CoNiPBd-OOH) to achieve optimized OER performance. The optimum rGO/CoNiHCF was fabricated with the Co:Ni precursors in a 3:1 ratio with a ferricyanide solution of pH = 1.0. Using an alkaline electrochemical treatment, the well-distributed globular particles of CoNiHCF over rGO sheets were converted into layered frameworks of metallic (oxy)hydroxide species, giving the final rGO/CoNiPBd-OOH nanocomposite. This nanocomposite presented favorable kinetic activity resulting in a Tafel slope of 33 mV dec-1, while rGO, CoNiPBd-OOH, and RuO2 exhibited slopes of 80, 47, and 51 mV dec-1, respectively. Although the benchmark RuO2 electrocatalyst showed a lower overpotential (240 mV dec-1) at a current density of 10 mA cm-2, the rGO/CoNiPBd-OOH performed well with an overpotential of 346 mV, combined with superior stability compared to CoNiPBd-OOH and RuO2, maintaining a current density of 10 mA cm-2 for 15 h with an overpotential loss of 6.92%. This work successfully presents an "all-electrochemical" synthesis of a rGO/CoNiHCF-derived material with remarkable electrocatalytic activity for OER assisted by a strategic preparation methodology, which helped to understand the influence of synthetic parameters and choose their conditions to achieve the optimum OER performance.

Boosted Electrochemical Hydrogen Evolution Activity via the Core-Shell Heterostructure of Nickel Sulfide Nanoframe-Supported Layered Rhenium Disulfide.

The strategic design of a heterostructure catalyst with a core-shell nanoarchitecture is imperative for enhancing the efficiency of the electrocatalytic hydrogen evolution reaction (HER). Herein, the core-shell catalyst comprising the rhenium disulfide nanosheets was vertically integrated onto a hollow nickel sulfide (NiS@ReS2) via coprecipitation and hydrothermal treatment. The morphology involves the sulfurization of a nickel-based Prussian blue analogue, effectively mitigating the aggregation of ReS2 nanosheets and maximizing the exposed active sites. By the synergistic effect of morphological design and heterostructure formation, the overpotential of NiS@ReS2 is 136 mV at 10 mA cm-2 in an alkaline electrolyte, and the rapid kinetics is confirmed by the small Tafel slope and low charge transfer resistance during the HER process. Moreover, the electrocatalytic durability of NiS@ReS2 is elucidated, and the boosted catalytic activity of NiS@ReS2 is confirmed by density functional theory. This study unveils a promising method for advancing ReS2-based electrocatalysts with potential implications for producing hydrogen.

Photothermal therapy co-localized with CD137 agonism improves survival in an SM1 melanoma model without hepatotoxicity.

Aim: We investigate combining Prussian Blue nanoparticles (PBNPs), as photothermal therapy (PTT) agents, with agonistic CD137 antibodies (αCD137) on a single nanoparticle platform to deliver non-toxic, anti-tumor efficacy in SM1 murine melanoma.Methods: We electrostatically coated PBNPs with αCD137 (αCD137-PBNPs) and quantified their physicochemical characteristics, photothermal and co-stimulatory capabilities. Next, we tested the efficacy and hepatotoxicity of PTT using αCD137-PBNPs (αCD137-PBNP-PTT) in SM1 tumor-bearing mice.Results: The αCD137-PBNPs retained both the photothermal and agonistic properties of the PBNPs and αCD137, respectively. In vivo, SM1 tumor-bearing mice treated with αCD137-PBNP-PTT exhibited a significantly higher survival rate (50%) without hepatotoxicity, compared with control treatments.Conclusion: These data suggest the potential utility of co-localizing PBNP-PTT with αCD137-based agonism as a novel combination nanomedicine.

Photothermal therapy is a strategy to kill cancer cells that uses nanoparticles and lasers to generate heat. Here, we combine photothermal therapy with an immunotherapy that activates the body's T cells, a type of white blood cell, on a single platform, to treat melanoma, a type of skin cancer in a mouse. We find that this novel nanoparticle-based platform significantly improves the survival of mice bearing melanoma, without increasing liver toxicity.

Enhancing tumor photodynamic synergistic therapy efficacy through generation of carbon radicals by Prussian blue nanomedicine.

Significant progress has been achieved in tumor therapies utilizing nano-enzymes which could convert hydrogen peroxide into reactive oxygen species (ROS). However, the ROS generated by these enzymes possess a short half-life and exhibit limited diffusion within cells, making it challenging to inflict substantial damage on major organelles for effective tumor therapy. Therefore, it becomes crucial to develop a novel nanoplatform that could extend radicals half-life. Artesunate (ATS) is a Fe (II)-dependent drug, while the limited availability of iron (II), coupled with the poor aqueous solubility of ATS, limits its application. Here, Prussian blue (PB) was selected as a nano-carrier to release Fe (II), thus constructing a hollow Prussian blue/artesunate/methylene blue (HPB/ATS/MB) nanoplatform. HPB degraded and released iron(III), ATS and MB, under the combined effects of NIR irradiation and the unique tumor microenvironment. Moreover, Fe (III) exploited GSH to formation of Fe (II), disturbing the redox homeostasis of tumor cells and Fe (II) reacted with H2O2 and ATS to generate carbon radicals with a long half-life in situ. Furthermore, MB generates 1O2 under laser irradiation conditions. In vitro and in vivo experiments have demonstrated that the HPB/ATS/MB NPs exhibit a synergistic therapeutic effect through photothermal therapy, photodynamic therapy and radical therapy.

Longevous Protic Hybrid Supercapacitors Using Bimetallic Prussian Blue Analogue/rGO-Based Nanocomposite Against MXene Anode.

MXenes exhibit a unique combination of properties-2D structure, high conductivity, exceptional capacity, and chemical resistance-making them promising candidates for hybrid supercapacitors (HSCs). However, the development of MXene-based HSCs is often hindered by the limited availability of cathode materials that deliver comparable electrochemical performance, especially in protic electrolytes. In this study, this challenge is addressed by introducing a durable protic HSC utilizing a bimetallic Prussian Blue Analogue (PBA) decorated on reduced graphene oxide (rGO) as a nanocomposite cathode paired with a single-layered Ti3C2Tx MXene (SL-MXene) anode. The bimetallic PBA, specifically nickel hexacyanocobaltate (NiHCC), is utilized by virtue of its open and stable structure that facilitates efficient charge storage, leading to enhanced stability and energy storage capabilities. The resulting NiHCC/rGO//SL-MXene cell demonstrates impressive performance, achieving a maximum specific energy of 38.03 Wh kg-1 and a power density of 20 666.67 W kg-1. Remarkably, the NiHCC/rGO//SL-MXene HSC cell also exhibits excellent cycling stability without any loss even after 15 000 cycles while retaining ≈100% coulombic efficiency. This work underscores the potential of bimetallic PBA materials with conductive rGO backbone for overcoming the limitations of current MXene-based protic HSCs, highlighting the significance of this work.

Determination of deoxynivalenol (DON) by a label-free electrochemical immunosensor based on NiFe PBA nanozymes.

Deoxynivalenol (DON) contamination in food products significantly threatens human health, necessitating a reliable and sensitive detection method. This study aims to develop a simple, low-cost, and effective electrochemical immunoassay method for detecting DON based on the nickel­iron bimetallic Prussian blue analog (NiFe PBA). The NiFe PBA nanozymes with high peroxidase-like activity were synthesized using an environmentally friendly chemical precipitation method. In the presence of hydrogen peroxide (H2O2), the current change of thionine oxidation initiated by NiFe PBA nanozymes can be exploited to diagnose DON. Under optimal conditions, the proposed method achieved quantitative detection of DON in the range of 10-107 pg mL-1 with a detection limit of 4.5 pg mL-1 (S/N = 3), demonstrating excellent selectivity, reproducibility, and stability. In addition, the DON immunosensor provides satisfactory results for the detection in real samples, demonstrating the feasibility of the proposed sensor in detecting of DON in such products.

Unveiling the Influence of Water Molecules on the Structural Dynamics of Prussian Blue Analogues.

3D-framework Prussian blue analogues (PBAs) are appealing as a cost-effective, sustainable cathodes for Na-ion batteries. However, the aqueous-based synthesis of PBAs inherently introduces three different forms of water molecules (surface, interstitial and crystal) into the structure. Removal of water molecules causes phase transformation from monoclinic (M) to rhombohedral (R). This work presents the effects of water molecules on the structure before the phase transformation temperature, employing two promising PBA cathodes, Na2Fe[Fe(CN)6]·1.69H2O and Na2Mn[Fe(CN)6]·1.76H2O. Specifically, the water molecules impact the molecular interactions at the local structure and the electrochemical properties. This work has performed calculations on low-vacancy Na2M[Fe(CN)6] PBAs (where M = Mn, Fe, Co, Ni and Cu) to understand the dehydration energy. Employing in situ high-temperature X-ray diffraction and Raman spectroscopy, this work observes that water removal induces negative thermal expansion and stronger interactions between C≡N and Na ions, resulting in biphasic reactions with sluggish kinetics. Additionally, water molecules play a role in maintaining the open 3D tunnels and facilitating a solid-solution like insertion of Na ions. Calculated phonon-Raman spectra provide insights into cyanide group deformations, revealing the interactions between water molecules, alkali-ions, and transition-metal ions. This study enhances the understanding of the relationship among electronic, vibrational, and electrochemical properties.

Interface/Dipole Polarized Antibiotics-Loaded Fe3O4/PB Nanoparticles for Non-Invasive Therapy of Osteomyelitis Under Medical Microwave Irradiation.

Due to their poor light penetration, photothermal therapy and photodynamic therapy are ineffective in treating deep tissue infections, such as osteomyelitis caused by Staphylococcus aureus (S. aureus). Here, a microwave (MW)-responsive magnetic targeting composite system consisting of ferric oxide (Fe3O4)/Prussian blue (PB) nanoparticles, gentamicin (Gent), and biodegradable poly(lactic-co-glycolic acid) (PLGA) is reported. The PLGA/Fe3O4/PB/Gent complex is used in combination with MW thermal therapy (MTT), MW dynamic therapy (MDT), and chemotherapy (CT) to treat acute osteomyelitis infected with S. aureus-infected. The powerful antibacterial effect of the PLGA/Fe3O4/PB/Gent is determined by the synergistic effects of heat and reactive oxygen species (ROS) generation by the Fe3O4/PB nanoparticles under MW irradiation and the effective release of Gent at the infection site via magnetic targeting. The antibacterial mechanism of the PLGA/Fe3O4/PB/Gent under MW irradiation is analyzed using bacterial transcriptome RNA sequencing. The MW heat and ROS reduce the activity of the protein transporters on the bacterial membrane, along with the transport of various ions and the acceleration of phosphate metabolism, which can lead to increased permeability of the bacterial membrane, damage the ribosome and DNA, and accompany the internal protein efflux of the bacteria, thus effectively killing the bacteria.

Polydopamine-coated chondroitin sulfate methacryloyl multifunctional microspheres for wound treatment.

The disappearance of the protective barrier after skin injury leads to the overproduction of reactive oxygen species (ROS) in response to various stimuli. Oxidative stress is one of the most important causes of delayed wound healing, leading to negative outcomes, such as excessive inflammatory response and impaired angiogenesis. In this study, we used microfluidic technology to integrate Prussian blue nanozymes and vascular endothelial growth factor and constructed multifunctional microspheres that improved local oxidative stress. In order to enhance the adhesion of the microspheres on the wound surface and prolong the release of the drug, we coated them with dopamine, ensuring uniform encapsulation on their surface. The microspheres adhered well to the wound surface and promoted wound healing by scavenging ROS, reducing the inflammatory response, and promoting angiogenesis. This strategy of integrating nanozymes and growth factors can have a synergistic effect, which is significant for wound healing.

Targeted delivery of rosuvastatin enhances treatment of hyperhomocysteinemia-induced atherosclerosis using macrophage membrane-coated nanoparticles.

Rosuvastatin (RVS) is an excellent drug with anti-inflammatory and lipid-lowering properties in the academic and medical fields. However, this drug faces a series of challenges when used to treat atherosclerosis caused by hyperhomocysteinemia (HHcy), including high oral dosage, poor targeting, and long-term toxic side effects. In this study, we applied nanotechnology to construct a biomimetic nano-delivery system, macrophage membrane (Møm)-coated RVS-loaded Prussian blue (PB) nanoparticles (MPR NPs), for improving the bioavailability and targeting capacity of RVS, specifically to the plaque lesions associated with HHcy-induced atherosclerosis. In vitro assays demonstrated that MPR NPs effectively inhibited the Toll-like receptor 4 (TLR4)/hypoxia-inducible factor-1α (HIF-1α)/nucleotide-binding and oligomerization domain (NOD)-like receptor thermal protein domain associated protein 3 (NLRP3) signaling pathways, reducing pyroptosis and inflammatory response in macrophages. Additionally, MPR NPs reversed the abnormal distribution of adenosine triphosphate (ATP)-binding cassette transporter A1 (ABCA1)/ATP binding cassette transporter G1 (ABCA1)/ATP binding cassette transporter G1 (ABCG1) caused by HIF-1α, promoting cholesterol efflux and reducing lipid deposition. In vivo studies using apolipoprotein E knockout (ApoE -/-) mice confirmed the strong efficacy of MPR NPs in treating atherosclerosis with favorable biosecurity, and the mechanism behind this efficacy is believed to involve the regulation of serum metabolism and the remodeling of gut microbes. These findings suggest that the synthesis of MPR NPs provides a promising nanosystem for the targeted therapy of HHcy-induced atherosclerosis.

Prussian Blue Analogue-Templated Nanocomposites for Alkali-Ion Batteries: Progress and Perspective.

Lithium-ion batteries (LIBs) have dominated the portable electronic and electrochemical energy markets since their commercialisation, whose high cost and lithium scarcity have prompted the development of other alkali-ion batteries (AIBs) including sodium-ion batteries (SIBs) and potassium-ion batteries (PIBs). Owing to larger ion sizes of Na+ and K+ compared with Li+, nanocomposites with excellent crystallinity orientation and well-developed porosity show unprecedented potential for advanced lithium/sodium/potassium storage. With enticing open rigid framework structures, Prussian blue analogues (PBAs) remain promising self-sacrificial templates for the preparation of various nanocomposites, whose appeal originates from the well-retained porous structures and exceptional electrochemical activities after thermal decomposition. This review focuses on the recent progress of PBA-derived nanocomposites from their fabrication, lithium/sodium/potassium storage mechanism, and applications in AIBs (LIBs, SIBs, and PIBs). To distinguish various PBA derivatives, the working mechanism and applications of PBA-templated metal oxides, metal chalcogenides, metal phosphides, and other nanocomposites are systematically evaluated, facilitating the establishment of a structure-activity correlation for these materials. Based on the fruitful achievements of PBA-derived nanocomposites, perspectives for their future development are envisioned, aiming to narrow down the gap between laboratory study and industrial reality.

Prussian blue nanotechnology in the treatment of spinal cord injury: application and challenges.

Spinal cord injury (SCI) is a serious neurological condition that currently lacks effective treatments, placing a heavy burden on both patients and society. Prussian blue nanoparticles exhibit great potential for treating spinal cord injuries due to their excellent physicochemical properties and biocompatibility. These nanoparticles have strong anti-inflammatory and antioxidant capabilities, effectively scavenge free radicals, and reduce oxidative stress damage to cells. Prussian blue nanotechnology shows broad application potential in drug delivery, bioimaging, cancer therapy, anti-inflammatory and oxidative stress treatment, and biosensors. This article reviewed the potential applications of Prussian blue nanotechnology in treating spinal cord injuries, explored the challenges and solutions associated with its application, and discussed the future prospects of this technology in SCI treatment.

Dislocation Effect Boosting the Electrochemical Properties of Prussian Blue Analogues for 2.6 V High-Voltage Aqueous Zinc-Based Batteries.

Prussian blue analogues (PBAs) have attracted increasing attention in aqueous zinc-based batteries (AZBs) with the advantages of an open framework, adjustable redox potential, and easy synthesis. However, they exhibited a low specific capacity and a poor cycle performance. In this work, crystalline potassium iron hexacyanoferrate (FeHCF) with dislocation was designed and prepared by a poly(vinylpyrrolidone) (PVP) additive. The metastable state provided by PVP would cause an electrostatic interaction between cyanogen and water molecules. The reduced force increases the steric resistance of the water molecules entering the crystal. The low content of crystal water in FeHCF is associated with the formation of dislocation. The dislocation effect effectively improves the electrochemical reactivity and reaction kinetics of FeHCF. Thus, it presents a high reversible capacity of 131 mAh g-1 with a superior capacity retention of 85% after 550 cycles at 0.5 A g-1. When used as a cathode, the AZBs display a high voltage of 2.6 V, a fast charging capability (<5 min), and a satisfactory cycle stability with a capacity retention of 82% after 400 cycles at 0.2 A g-1 in decoupling electrolytes. This work provides an effective strategy for the design of high-performance PBA-based cathodes for 2.6 V AZBs.

Acid-assisted synthesis of core-shell Prussian blue cathode for sodium-ion batteries.

In recent years, core-shell structured Prussian Blue Analogues (PBAs) have been considered as highly promising cathode materials for sodium-ion batteries. Reducing production costs and simplifying the preparation method for core-shell PBAs have also become crucial considerations. This paper presents a novel approach for the first time: by acid-treating the as-synthesized solution from a simple coprecipitation reaction, a high-crystallinity, sodium-rich Mn2+-doped iron hexacyanoferrate (Fe/MnHCF) shell material is self-grown on the surface of manganese hexacyanoferrate (MnHCF). This method significantly improves the electrochemical properties of the MnHCF material. The core-shell structured PBA exhibits excellent cycling performance (with a capacity retention of 95.5 % for 400 cycles at 1 A/g) and high rate performance (134.2mAh/g@10 mA/g, 95.2mAh/g@1 A/g). In this article, we explore the growth mechanism of the high-sodium content, high-crystallinity shell structure and introduce a green chelating agent that is better suited for the crystallization of Mn and Fe-type PBA systems. Our study demonstrates that Mn2+ doping enhances the conductivity of the shell material. Meanwhile, the heterojunction structure of MnHCF@Fe/MnHCF conducive to charge separation and migration. This straightforward synthesis strategy offers a novel approach for fabricating high-performance core-shell structured Prussian Blue Analogue materials.

A Self-Constructed Mg2+/K+ Co-Doped Prussian Blue with Superior Cycling Stability Enabled by Enhanced Coulombic Attraction.

Prussian blue (PB) is regarded as a promising cathode for sodium-ion batteries because of its sustainable precursor elements (e.g., Mn, Fe), easy preparation, and unique framework structure. However, the unstable structure and inherent crystal H2O restrain its practical application. For this purpose, a self-constructed trace Mg2+/K+ co-doped PB prepared via a sea-water-mediated method is proposed to address this problem. The Mg2+/K+ co-doping in the Na sites of PB is permitted by both thermodynamics and kinetics factors when synthesized in sea water. The results reveal that the introduced Mg2+ and K+ are immovable in the PB lattices and can form stronger K‒N and Mg‒N Coulombic attraction to relieve phase transition and element dissolution. Besides, the Mg2+/K+ co-doping can reduce defect and H2O contents. As a result, the PB prepared in sea water exhibits an extremely long cycle life (80.1% retention after 2400 cycles) and superior rate capability (90.4% capacity retention at 20 C relative to that at 0.1 C). To address its practical applications, a sodium salts recycling strategy is proposed to greatly reduce the PB production cost. This work provides a self-constructed Mg2+/K+ co-doped high-performance PB at a low preparation cost for sustainable, large-scale energy storage.