Prussian Blue Derivatives Research Articles

Fabrication of carbon fibers doped with Prussian blue derivative composites for enhanced electromagnetic wave absorption

Fabrication of carbon fibers doped with Prussian blue derivative composites for enhanced electromagnetic wave absorption

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.

Effects of Nanocomposite Derivatives of Ni-Fe, Ni-Co, Ni-Co-Fe Prussian Blue Analogues on the Thermal Decomposition Performance of Nitrocellulose.

The incorporation of nanomaterials generated from Prussian blue (PB) derivatives has emerged as a promising strategy to significantly improve the properties of energetic materials. In this study, we comprehensively investigated the influence of nanomaterials derived from PB on the thermal decomposition characteristics of energetic materials. To achieve this goal, we prepared nanomaterials using coprecipitation and heat treatment methods with PB derivatives as catalysts. Advanced techniques such as X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Brunauer-Emmett-Teller (BET) analysis for specific surface area and pore size, and X-ray photoelectron spectroscopy were employed to thoroughly characterize these nanomaterials. Differential scanning calorimetry was used to assess the thermal behavior of nitrocellulose (NC), and the relevant kinetic parameters were determined through thermal decomposition kinetics calculations and analysis. This work revealed the influence of catalysts on the NC decomposition process and provided comprehensive insights into the effect of integrating nanomaterials derived from PB derivatives on the thermal decomposition performance of NC. The results of this work demonstrated the possibility of using nanomaterials generated from PB derivatives as effective catalysts to enhance the thermal decomposition characteristics of NC, offering interesting opportunities for their application in the field of high-energy materials.

Tuning the morphology and pyrolysis process of rare-earth Gd-doped prussian blue derivatives for electromagnetic wave absorption and anti-corrosion performance

Prussian blue analogs (PBA) derivatives have been researched extensively as electromagnetic wave (EMW) absorbers. However, the metallic components are typically transition-metal elements, which results in limited potential for optimization of their EMW absorbing performance. In this work, GdCo-PBA derivates with different carbon nanotubes (CNTs) morphologies and phase compositions were synthesized via tuning the pyrolysis rate and the dielectric loss capability can be tuned. As a result, the R-GdN/Co@CNTs achieved the minimum reflection loss (RLmin) of −36.74 dB@1.7 mm and the maximum effective absorption bandwidth (EAB) of 5.61 GHz @ 2.0 mm due to the combined effect of the interconnected CNTs conduction network and the GdN phase in optimizing the impedance matching and enhancing the dielectric loss. Meanwhile, the radar cross section (RCS) simulation and electrochemical corrosion tests confirmed that GdCo-PBA derivatives can significantly reduce RCS values of 28.6 dBm2 @ 15° and possessed satisfied anti-corrosion properties with a corrosion current density of 2.06 × 10−5 A/cm2 and polarization resistance of 2.57 × 104 Ω, which displayed significant potential for practical applications in extreme marine environments. This work presents a strategy for synthesizing lanthanide PBA derivates with the EMW absorbing and anti-corrosion properties.

Stable Ammonium-Ion Batteries in Diluted Electrolyte By Manipulation of H-Bonding Network Via Ethylene Glycol

Aqueous rechargeable batteries (ARB) arose considerable interest for stationary energy storage due to low cost, inherent safety, and environmental friendliness.[1] Besides aqueous lithium-ion batteries, various kinds of aqueous batteries have been proposed, utilizing relatively inexpensive charge carriers either based on metal (Na+, K+, Ca2+, Mg2+, Zn2+, Al3+, etc.) or non-metal cations (H3O+, NH4 + etc.).[2] Among non-metallic ion batteries, aqueous ammonium-ion batteries (AAIBs) distinguish themselves by working in near neutral or mild acidic environment, refraining from severe electrode corrosion.[3] However, like other ARB systems, the energy density of AAIBs is limited by the narrow electrochemical stability window of the aqueous electrolyte. In addition, NH4 + ions hydrolyse in water resulting in decreased pH of the electrolyte which promotes the hydrogen evolution reaction (HER).[3] This means that increasing salt concentration may not be an effective strategy to enlarge the stability window of the electrolyte. In fact, according to a previous report, the cathodic stability of 25 m ammonium acetate (NH4Ac) is even slightly inferior than that of 1 M NH4Ac.[4] Developing alternative strategies to inhibit HER in diluted electrolytes is of uttermost importance.In diluted aqueous electrolytes, the continuous and complicated H bond network among water molecules favours fast ionic motion but also causes severe HER. Here, we propose ethylene glycol (EG) as electrolyte component to manipulate the H bond structure in diluted (1 m) NH4Ac solutions. FTIR results are used to study the H-bonding network as function of the EG:water ratio. The diluted aqueous electrolyte containing EG show no freezing point and wider electrochemical window. As a proof-of-concept, full cells composed of Prussian blue derivatives, PTCDI anode, and 1 m NH4Ac with the addition of EG are tested to verify the effectiveness of EG during battery operation. Improved cycling performance and higher coulombic efficiencies are demonstrated compared to those including 1 m NH4Ac in water.

Polymorphic cerium-based Prussian blue derivatives with in situ growing CNT/Co heterojunctions for enhanced microwave absorption via polarization and magnetization

Polymorphic cerium-based Prussian blue derivatives with in situ growing CNT/Co heterojunctions for enhanced microwave absorption via polarization and magnetization

Graphene-like structure of bio-carbon with CoFe Prussian blue derivative composites for enhanced microwave absorption

Traditional carbon materials such as graphene are often applied in the field of electromagnetic wave (EMW) absorption but they have unbalanced impedance matching and high conductivity. Bio-carbon with graphene-like structure derived from apples has many advantages over graphene: it can be prepared in large quantities and the abundant heteroatoms present in the lattice can provide many polarization phenomena. Herein, Prussian blue analogue (PBA) as a source of magnetic component was combined with bio-carbon or reduced graphene oxide (rGO) to study the EMW absorption properties. The fabricated BC/CFC-12-7 displayed performance with a minimum reflection loss (RLmin) of −72.57 dB and a wide effective absorption bandwidth (EAB) of 5.25 GHz with an ultra-thin and nearly equal matching thickness at 1.61 mm. The results show that the good EMW absorption property of bio-carbon composites comes from good conduction loss, large relaxation polarization loss especially from pyridinic-N, and better impedance matching. The optimized radar cross section is found to be –33.55 dB m2 in the far-field condition using CST. This work explored the advantages of bio-carbon as a novel EMW absorbing material compared with graphene and provided ideas for realizing high-performance EMW absorbing materials in the future.

Two Birds with One Stone: Broadband Electromagnetic Wave Absorption and Anticorrosion Performance in 2-18GHz for Prussian Blue Analog Derivatives Aimed for Practical Applications.

Nowadays, the exploration of electromagnetic (EM) wave absorbers with anticorrosion to improve the survivability and environmental adaptability of military targets in the harsh environments is becoming an attractive and unavoidable challenge. Herein, through modulation of the metal composition in the precursors, the core@shell structure Prussian blue analog-derived NiCo@C, CoFe@C, NiFe@C, and NiCoFe@C are obtained with excellent EM wave absorption performance. As for NiCoFe@C, ascribed to the coupling effect of the dual magnetic alloy, a minimum reflection loss (RL) of -47.6dB and an effective absorption bandwidthof 5.83GHz are realized, which cover the whole Ku-band. Meanwhile, four absorbers display the lower corrosion current density (10-4 -10-6 A cm-2 ) and larger polarization resistance (104 -106 Ω) under acid, neutral, and alkaline corrosion conditions over uninterrupted 30 days. Furthermore, due to the spatial barrier effect and the passivation effect of the graphitic carbon shell , the continuous salt spray test has little effect on RL performance and inconspicuously changes the surface morphologies of coating, demonstrating its excellent bifunctional performance. This work lays the foundation for the development of metal-organic frameworks-derived materials with both anticorrosion and EM wave absorption performance.

Rational designing carbon nanotubes incorporated oxygen vacancy-enriched bimetallic (Ni, Co) oxide nanocages for high-performance hybrid supercapacitor

NiCo bimetallic oxide with low cost and high theoretical capacity is the candidate for high-performance supercapacitor electrodes, but the low conductivity and short cycle life of oxides have hindered their development. Herein, we designed a novel strategy for the fabrication of carbon nanotubes (CNT) incorporated oxygen vacancy (OV) NixCo1-xO nanocages for high performance supercapacitor. The existing oxygen vacancy in OV-NixCo1-xO nanocage changes the electronic environment on the crystal surface and provides more active sites, leading to the enhanced electrical conductivity together with CNT and capture capability for OH–. This CNT/OV-NixCo1-xO composite achieves high capacitance of 1400.7 F g−1 at the current density of 1 A g−1. When assembled a hybrid supercapacitor device of CNT/OV-NixCo1-xO//activated carbon, it exhibits an excellent energy density of 52.7 Wh kg−1 at a power density of 800 W kg−1. Besides, the device exhibited a capacity retention of 85.7 % over up to 10,000 cycles. This work provides a feasible strategy for surface vacancy regulation of Prussian blue derivatives used in high performance supercapacitor.

Prospective Sustainability Screening of Sodium‐Ion Battery Cathode Materials

AbstractSodium‐ion batteries (SIB) are considered as a promising alternative to overcome existing sustainability challenges related to Lithium‐ion batteries (LIB), such as the use of critical and expensive materials with high environmental impacts. In contrast to established LIBs, SIBs are an emerging technology in an early stage of development where a challenge is to identify the most promising and sustainable cathode active materials (CAM) for further research and potential commercialization. Thus, a comprehensive and flexible CAM screening method is developed, providing a fast and comprehensive overview of potential sustainability hotspots for supporting cathode material selection. 42 different SIB cathodes are screened and benchmarked against eight state‐of‐the‐art LIB‐cathodes. Potential impacts are quantified for the following categories: i) Cost as ten‐year average; ii) Criticality, based on existing raw material criticality indicators, and iii) the life cycle carbon footprint. The results reveal that energy density is one of the most important factors in all three categories, determining the overall material demand. Most SIB CAM shows a very promising performance, obtaining better results than the LIB benchmark. Especially the Prussian Blue derivatives and the manganese‐based layered oxides seem to be interesting candidates under the given prospective screening framework.

Rough porous N-doped graphene fibers modified with Fe-based Prussian blue analog derivative for wide-band electromagnetic wave absorption

With the rapid development of wireless communication technology, human living environments are being polluted by a large number of electromagnetic waves (EWs), and EWs absorption materials play an important role in exploring green living spaces. Carbon matrix composites derived from metalorganic frameworks (MOFs) are a new kind of EWs absorbing material with great application prospect. However, obtaining efficient absorbent with low filling rates and wide absorption bands remains a challenge. Here, we designed one-dimensional rough, and porous N-doped graphene fibers (N-GFs) that were assembled from two-dimensional graphene sheets with surfaces modified using a Fe-based Prussian blue analog (PBA) derivative. The rough porous structure optimized impedance matching characteristics of the absorber by introducing air gaps while the PBA particles improved N-GF electromagnetic parameters of N-GFs, increasing EWs absorption. The results showed optimal EWs absorption in the synthesized Fe-based PBA/N-GFs after annealing at 600 °C. At a filling rate of 10 wt%, the EWs absorption bandwidth could reach 8.19 GHz when the matching thickness was 2.1 mm; this covers most of the X radar frequency band and the entire Ku radar frequency band. The Fe-based PBA/N-GFs have a special microstructure and excellent EWs absorption properties, which provide inspiration for further exploration of graphene-based absorbing materials.

An integrated optimization of composition and pore structure boosting electrocatalytic oxygen evolution of Prussian blue analogue derivatives

Exploring efficient and low-cost electrocatalysts for oxygen evolution reaction (OER) is of great importance for renewable energy-related systems. Prussian blue analogues (PBAs) are considered as promising precursors to derive advanced heteroatom-doped carbonaceous materials. However, the pyrolysis treatment usually results in an inevitable aggregation of active sites as well as the reduction of specific surface area, apart from the uncontrollable composition and morphology. Herein, we develop a straightforward synthetic protocol for fabricating highly-active OER electrocatalysts of Co7Fe3, Co, N-codoped carbon (Co7Fe3/Co@NC) by annealing trimetallic CoZnFe-PBA precursors. The surface modification of cobalt species over ZnFe-PBA effectively tailors the active composition for as-derived products, whereas Zn volatilization at a high temperature not only promotes the dispersion of active sites but also fabricates the formation of an intriguing hierarchical structure with multimodal porosity and high specific surface area. The integrated advantages of multinary composition and fabulous pore structure endow the elegantly-designed Co7Fe3/Co@NC with a remarkable catalytic performance towards OER in alkaline electrolyte, as evidenced by an overpotential of 290 mV without iR-correction at a current density of 10 mA cm−2 and impressive long-term durability. The present synthetic strategy offers valuable insights for developing highly-efficient PBAs-derived electrocatalysts with compositional multiplicity and interesting pore texture.

A peroxidase-like nanoenzyme based on strontium(II)-ion-exchanged Prussian blue analogue derivative SrCoO3/Co3O4 nanospheres and carbon quantum dots for the colorimetric detection of tigecycline in river water

In this work, for the first time, we derived a composite of perovskite oxide SrCoO3 and Co3O4 by annealing the Prussian blue analogue exchanged with strontium ions and modified with carbon quantum dots (CQDs). Its peroxidase-like catalytic activity was explored. The peroxidase-like activity was mainly evaluated by the rate of the chromogenic reaction. When H2O2 was present in the reaction system, the colorless substrate 3,3′,5,5′-tetramethylbenzidine (TMB) was oxidized into a blue product (oxTMB), and this was monitored by UV–vis absorption spectrum. Among them, the SrCoO3 and CQDs not only promoted the generation of superoxide anion radicals (O2−•) and electron-hole pairs (h+) in the reaction system, but also accelerated the electron transfer between the substrate TMB and H2O2. Therefore, the peroxidase-like catalytic activity of the reaction system was significantly improved. Moreover, the complexation of tigecycline (TGC) and CQDs@SrCoO3/Co3O4 composite enhanced the peroxidase-like catalytic activity of the reaction system. Based on this, using TGC and TMB as template molecules, a molecularly imprinted colorimetric sensor for detecting TGC was constructed. The absorbance difference of the reaction system was linear with the TGC concentration in the range of 0.02–6.0 μM, and the detection limit was 4.46 nM. Furthermore, the proposed sensor had high selectivity and applied to the detection of TGC in Pearl River water.

Understanding the Catalytic Selectivity of Cobalt Hexacyanoferrate toward Oxygen Evolution in Seawater Electrolysis

Hydrogen is a most desirable solar energy storage medium. It provides reliable, scalable, and long-term energy storage, while helping in the decarbonization of the energy cycle. Such a storage medium is required for further deployment of photovoltaics, either for their inclusion into transportation and heavy industries or for supporting renewable grid management. The most accessible hydrogen source is water. However, fresh water is a scarce resource, while seawater is abundant worldwide. A major drawback of seawater electrolysis comes from chloride oxidation competing with the oxygen evolution reaction (OER). This may produce toxic products such as chlorine and also limits the hydrogen energy efficiency of the overall process. Thus, selective catalysts toward the OER are of strong technological interest. Here we report the electrocatalytic activity of heterogeneous cobalt hexacyanoferrate toward seawater oxidation. Combining experimental and computational studies, we highlight the great difficulty in obtaining such selectivity and its main mechanistic descriptors. This Prussian blue derivative is an excellent and robust OER electrocatalyst, but unfortunately, it is not selective enough toward the OER in the presence of Cl– anions. Faradaic efficiencies above 30% toward Cl2 were observed during untreated seawater bulk electrolysis.

Regulating pyrolysis strategy to construct CNTs-linked porous cubic Prussian blue analogue derivatives for lightweight and broadband microwave absorption

Metal-organic framework (MOFs) derived carbon-based nanocomposites are considered as a class of new microwave absorption materials with great application potential. However, it remains a challenge to obtain high-efficiency absorbers based on MOFs with lower filling ratio and wider effective absorption band. In addition, it is difficult to construct uniform interconnection networks of carbon nanotubes (CNTs) in situ on the surface of MOFs derivatives by simple method. Here, we innovatively combined the pyrolysis laws of Co-based Prussian blue analogue (PBA) with the mechanisms of CNTs synthesis catalyzed by Co nanoparticles, and prepared CNTs-linked cubic porous PBA derivative (CoCN@CNT) through a designed pyrolysis process. Results show that when a temperature plateau was added and the final pyrolysis temperature was controlled to 700 ℃, the obtained sample has a unique morphology and the best microwave absorption performance. When the filling ratio is only 20%, it could exhibit an ultra-wideband effective absorption of 6.35 GHz with a matching thickness of 2.5 mm, covering the entire Ku radar band. This work provides theoretical support for the controllable growth of metal-catalyzed CNTs, as well as novel insights for the design and facile synthesis of high-performance micro-nano-scale microwave absorbers.

Magnetic Prussian Blue derivative like absorbent cages for an efficient thallium removal

Environmental thallium concentration has been increasing due to anthropogenic events making the development of Tl(I) adsorbents an area of interest for materials science researchers. This report proposes a new composite based on a Prussian Blue derivative and magnetite nanoparticles for thallium(I) removal. Additionally, extensively characterization by FTIR-ATR, TGA, XRD, TEM/SEM, XPS, BET, and Magnetization were performed. The Tl(I) removal capacity from simulated wastewater was evaluated as well as the influence of different experimental conditions. The maximum experimental sorption capacity was 117 mg of Tl(I) per gram of composite after 21 h of interaction. The Tl-loaded composite was recovered by means of magnet achieving a final Tl concentration in the medium 28 times lower than the permitted limit for wastewaters. The removal process is independent of the pH with slight interferences of typical ions contained in wastewaters of the mining industry. The sorbent is reusable with non-significative variations of the thallium sorption capacity allowing to recover 97% of removed thallium under KCl solution desorption treatment. Moreover, the magnetic composite showed potentialities for multiple metals adsorption, like Cu and Pb removal. The main mechanism involved in the separation of Tl(I) is a K–Tl ionic exchange described by a pseudo-second-order and intra-particle diffusion kinetics. Herein, a new sorbent material easy to prepare, low-cost, reusable and eco-friendly is presented for effective magnetic thallium removal and recovery from wastewaters.

Cobalt Hexacyanoferrate as a Selective and High Current Density Formate Oxidation Electrocatalyst

Herein we report the selectivity, stability, and electrochemical characterization of cobalt hexacyanoferrate, the Co–Fe Prussian Blue derivative (CoFePB), as a formate/formic acid oxidation electro...

Microstructural Changes of Prussian Blue Derivatives during Cycling in Zinc‐Containing Electrolytes

AbstractThe reversible electrochemical insertion of zinc into host materials has been shown to be very promising for large‐scale energy storage applications. In particular, copper hexacyanoferrate (CuHCF) and its derivatives from the Prussian Blue family enable a fast and reversible (de‐)insertion of zinc ions when operated in a zinc‐based aqueous electrolyte. In this work, the effect of the concentration of a zinc sulfate‐containing aqueous neutral solution on the aging of CuHCF and copper‐zinc hexacyanoferrate mixture (CuZnHCF) was studied. The electrochemical and morphological analysis revealed the occurrence of a phase change during the materials aging. Such phase transformation induced morphological changes, different from the ones formed when the materials were cycled in lower electrolyte concentration. In the case of CuZnHCF, the occurrence of a spike‐shaped morphology upon cycling, which appears to be electrochemically inactive, caused a faster capacity fading.

Spontaneous Magnetization and Optical Activity in the Chiral Series {(L-proline)nV[Cr(CN)6]x} (0 < n < 3)

The incorporation of the natural amino acid L-proline in the synthesis to vanadium-chromium Prussian blue derivatives results in materials exhibiting magnetic ordering including chiral magnetic centers. Although the amorphous nature of these materials makes difficult to assess the structural features of these proline-containing compounds, magnetic and spectroscopic data confirms their multifunctionality. They exhibit high-temperature magnetic ordering (Tc < 255 K) and a circular dichroic signal, representing the molecule-based chiral magnets with the highest ordering temperatures reported to date. In addition, the presence of chiral L-proline (or D-proline) has additional benefits, including higher redox stability and the appearance of magnetic hysteresis. The latter was not observed in the parent compounds, the series of room temperature molecule-based magnets V[Cr(CN)6]x.

Prussian Blue Derivatives: Hierarchical Assembly of Prussian Blue Derivatives for Superior Oxygen Evolution Reaction (Adv. Funct. Mater. 45/2019)

Prussian Blue Derivatives: Hierarchical Assembly of Prussian Blue Derivatives for Superior Oxygen Evolution Reaction (Adv. Funct. Mater. 45/2019)