Antifungal Potential of Transition Metal Hexacyanoferrates against Fungal Diseases of Mushroom

Ferrocyanides of Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) were synthesized and characterized by IR spectra, magnetic susceptibility, thermal gravimetric analysis, elemental analysis and X ray diffraction studies. Antimicrobial potential of these complexes have been evaluated. Antifungal screening of these complexes has been carried out against Mycogone perniciosa and Verticillium fungicola causing wet and dry bubble diseases of button mushroom respectively. Nickel ferrocyanide has been found to be most effective against Mycogone perniciosa with 60% inhibitory effect while cadmium ferrocyanide has exhibited significant potential of 85% against Verticillium fungicola.

High Fe^(LS)(C)electrochemical activity of an iron hexacyanoferrate cathode boosts superior sodium ion storage

Sodium iron hexacyanoferrate(FeHCF)is one of the most promising cathode materials for sodium-ion batteries(SIBs)due to its low cost theoretical capacity.However,the low electrochemical activity of Fe^(LS)(C)in FeHCF drags down its practical capacity and potential plateau.Herein,FeHCF with high Fe^(LS)(C)electrochemical activity(C-FeHCF)is synthesized via a facile citric acid-assisted solvothermal method.As the cathode of SIBs,C-FeHCF shows superior cycling stability(ca.87.3%capacity retention for 1000 cycles at 10 C)and outstanding rate performance(ca.68.5%capacity retention at 50 C).Importantly,the contribution of Fe^(LS)(C)to the whole capacity was quantitatively analyzed via combining dQ/dV and discharge curve for the first time,and the index reaches 44.53%for C-FeHCF,close to the theoretical value.In-situ X-ray diffraction proves the structure stability of C-FeHCF during charge-discharge process,ensuring its superior cycling performance.Furthermore,the application feasibility of the C-FeHCF cathode in quasi-solid SIBs is also evaluated.The quasi-solid SIBs with the C-FeHCF cathode exhibit excellent electrochemical performance,delivering an initial discharge capacity of 106.5 mAh g^(−1) at 5 C and high capacity retention of 89.8%over 1200 cycles.This work opens new insights into the design and development of advanced cathode materials for SIBs and the beyond.

Switching Optimally Balanced Fe-N Interaction Enables Extremely Stable Energy Storage

The interaction between electrode materials and charge carriers is one of the central issues dominating underlying energy storage mechanisms.To address the notoriously significant volume changes accompanying intercalation or formation of alloy/compounds,we aim to introduce and utilize a weak,reversible Fe-N interaction during the(de)intercalation of ammonium ions(NH_(4)^(+))within iron(Ⅲ)hexacyanoferrate(FeHCF),inspired by manipulating the electrostatic adsorption between N and Fe in the early stages of ammonia synthesis(Bosch-Harber Process,Chemical Engineering)and steel nitriding processes(Metal Industry).Such strategy of switching well-balanced Fe-N interaction is confirmed in between the nitrogen of ammonium ions and highspin Fe in FeHCF,as observed by using X-ray absorption spectroscopy.The resulting material provided an extremely stable energy storage(58 mAh g^(-1) after 10000 cycles at current density of 1 A g^(-1))as well as high-rate performance(23.6 mAh g^(-1) at current density of 10 A g^(-1)).

聚丙烯腈-亚铁氰化钾钴/钛球形复合吸附剂制备及其对Cs^+的吸附性能研究

本文合成了聚丙烯腈-亚铁氰化钾钴/钛球形复合吸附剂(PAN-KCoCF和PAN-KTiCF),通过静态吸附实验,研究了接触时间、pH值、竞争离子、Cs+初始浓度等对PAN-KCoCF和PAN-KTiCF吸附Cs+效果的影响,分析了吸附过程的反应动力学和吸附等温线,并用扫描电镜(SEM)、傅里叶红外光谱(FT-IR)、X射线衍射仪(XRD)等对吸附剂进行了分析。结果表明,PAN-KCoCF和PAN-KTiCF对Cs+的吸附平衡时间均为16h,随着pH值的增加,PAN-KTiCF对Cs+的吸附量先快速增大,随后趋于平缓,而PAN-KCoCF对Cs+的吸附量几乎不变,溶液中含K+、Na+、NH+4、Ca2+或Mg2+等竞争离子时,PAN-KCoCF相比PAN-KTiCF对Cs+的选择性更高;PAN-KCoCF和PAN-KTiCF对Cs+的吸附动力学行为可用准二级动力学方程来描述,表面吸附为动力学控制的主要步骤;吸附过程符合Langmuir等温吸附模型,为单分子层吸附,PAN-KCoCF和PAN-KTiCF对Cs+的饱和吸附量分别可达128.370、278.552mg/g。

Prussian blue and its analogues as advanced supercapacitor electrodes

Remarkable attention has been directed to Prussian blue(PB) and its analogues(PBA) as one of the most widely used metal-organic frameworks(MOFs) especially in the field of energy storage devices due to their fabulous features such as 3D open framework, high surface area, controllable distribution of pores and the low cost. Nevertheless, their depressed conductivity causes some insulation when being used as an electrode for supercapacitors leading to be restricted in further applications particularly the electronics. To the best of our knowledge, our review aimed primarily to give a total picture of the research that was done on utilizing PB and PBA for fabricating the electrodes of supercapacitor, studying their synthesis approaches in addition to the hybridization with other materials such as graphene, CNTs and conducting polymer. It also addresses the transformation of PB or PBA into other interesting nanostructures such as oxides, sulfides, and bicomponent of graphitic carbon nitride/metal oxides, as well. Furthermore,It exhibits various avenues for overcoming their disadvantages of bad cycle life, retention rate and not achieving the desired values of energy/power densities opening the door for enlarging the number of researches on their application as supercapacitors.

Post-Synthetic and In Situ Vacancy Repairing of Iron Hexacyanoferrate Toward Highly Stable Cathodes for Sodium-Ion Batteries

Iron hexacyanoferrate(FeHCF)is a promising cathode material for sodium-ion batteries.However,FeHCF always suffers from a poor cycling stability,which is closely related to the abundant vacancy defects in its framework.Herein,post-synthetic and in-situ vacancy repairing strategies are proposed for the synthesis of highquality FeHCF in a highly concentrated Na_(4)Fe(CN)_(6) solution.Both the post-synthetic and in-situ vacancy repaired FeHCF products(FeHCF-P and FeHCF-I)show the significant decrease in the number of vacancy defects and the reinforced structure,which can suppress the side reactions and activate the capacity from low-spin Fe in FeHCF.In particular,FeHCF-P delivers a reversible discharge capacity of 131 mAh g^(−1) at 1 C and remains 109 mAh g^(−1) after 500 cycles,with a capacity retention of 83%.FeHCF-I can deliver a high discharge capacity of 158.5 mAh g^(−1) at 1 C.Even at 10 C,the FeHCF-I electrode still maintains a discharge specific capacity of 103 mAh g^(−1) and retains 75% after 800 cycles.This work provides a new vacancy repairing strategy for the solution synthesis of high-quality FeHCF.

Hydrogen Bond-Assisted Ultra-Stable and Fast Aqueous NH_(4)^(+)Storage

Aqueous ammonium ion batteries are regarded as eco-friendly and sustainable energy storage systems.And applicable host for NH_(4)^(+)in aqueous solution is always in the process of development.On the basis of density functional theory calcula-tions,the excellent performance of NH_(4)^(+)insertion in Prussian blue analogues(PBAs)is proposed,especially for copper hexacyanoferrate(CuHCF).In this work,we prove the outstanding cycling and rate performance of CuHCF via electrochemical analyses,delivering no capacity fading during ultra-long cycles of 3000 times and high capacity retention of 93.6%at 50 C.One of main contributions to superior performance from highly reversible redox reaction and structural change is verified during the ammoniation/de-ammoniation progresses.More importantly,we propose the NH_(4)^(+)diffusion mechanism in CuHCF based on con-tinuous formation and fracture of hydrogen bonds from a joint theoretical and experimental study,which is another essential reason for rapid charge transfer and superior NH_(4)^(+)storage.Lastly,a full cell by coupling CuHCF cathode and polyaniline anode is constructed to explore the practical application of CuHCF.In brief,the outstanding aqueous NH_(4)^(+)storage in cubic PBAs creates a blueprint for fast and sustainable energy storage.

Advanced metal–organic frameworks for aqueous sodium-ion rechargeable batteries

Inexpensive and abundant sodium resources make energy storage systems using sodium chemistry promising replacements for typical lithium-ion rechargeable batteries(LIBs).Fortuitously,aqueous sodium-ion rechargeable batteries(ASIBs),which operate in aqueous electrolytes,are cheaper,safer,and more ionically conductive than batteries that operate in conventional organic electrolytes;furthermore,they are suitable for grid-scale energy storage applications.As electrode materials for storing Na~+ ions in ASIBs,a variety of multifunctional metal-organic frameworks(MOFs) have demonstrated great potential in terms of having porous 3 D crystal structures,compatibility with aqueous solutions,long cycle lives(≥1000 cycles),and ease of synthesis.The present review describes MOF-derived technologies for the successful application of MOFs to ASIBs and suggests future challenges in this area of research based on the current understanding.

镍铁氰化物纳米粒子的合成及其多相催化无溶剂条件下苯甲醇氧化的潜能(英文)

Nickel hexacyanoferrate nanoparticles were synthesized and characterized using elemental analysis, thermal analysis, infrared spectroscopy, and X-ray diffraction. A FE-SEM image of the nickel hexacyanoferrate showed that it consists of nearly spherical particles with sizes ranging from 30 to 70 nm. The synthesized material was found to be a heterogeneous catalyst useful for the solvent-free oxidation of benzyl alcohol with H2O2 as an oxidant. A 36% conversion of benzyl alcohol to benzaldehyde was achieved under optimized reaction conditions using specific parameters such as the amount of catalyst, the temperature, the benzyl alcohol to H2O2 molar ratio, and the reaction time.

In-Situ Microscopic FTIR Spectroelectrochemistry of Ascorbic Acid in Poly(ethylene glycol)/LiClO_4 Electrolyte Paste and in the Presence of Dispersed Cobalt Hexacyanoferrate Microcrystalline Powder

In-situ microscopic FTIR spectroelectrochemical technique(MFTIRs) was applied to studying the electrochemical oxidation of ascorbic acid(AA) in poly(ethylene glycol)(PEG) paste at a 100 μm diameter Pt disk electrode. Using this technique, the catalytic ability of cobalt hexacyanoferrate(CoHCF) microcrystalline toward AA oxidation was also studied. It was found that the dispersed CoHCF powder in the PEG paste can generate well shaped thin layer cyclic voltammetric waves with the peak height proportional to the scan rate, corresponding to the Fe centered redox reactions. This oxidation step catalyzed the AA oxidation. Also, this pasted CoHCF powder generated well resolved in situ MFTIRs spectra, by which a chemical interaction between CC bond of AA ring and CoHCF lattice was revealed. A corresponding surface docking mechanism for the catalytic reaction has been proposed.

Mechanistic Study and Kinetic Determination of Cu(Ⅱ) by the Catalytic Kinetic Spectrophotometric Method

A highly sensitive and selective catalytic kinetic spectrophotometric method for the determination of Cu(Ⅱ) is proposed. It is based on the catalytic effect of Cu(Ⅱ) on the oxidation of glutathione(GSH) by potassium hexacyanoferrate(Ⅲ) in acidic medium at 25.0℃. The reaction is monitored spectrophotometrically by measuring the decrease in absorbance of oxidant at 420 nm using the fix-time method. Under the optimum conditions, the proposed method allows the determination of Cu(Ⅱ) in a range of 0-35.0 ng m L^(-1) with good precision and accuracy and the limit of detection is down to 0.04 ng m L^(-1). The relative standard deviation(RSD) is 1.02%. The reaction orders with respect to each reagent are found to be 1, 1/2, and 1/2 for potassium hexacyanoferrate(Ⅲ), glutathione and Cu(Ⅱ) respectively. On the basis of these values, the rate equation is obtained and the possible mechanism is established. Moreover, few anions and cations can interfere with the determination of Cu(Ⅱ). The new proposed method can be successfully used to the determination of Cu(Ⅱ) in fresh water samples and seawater samples. It is found that the proposed method has fairly good selectivity, high sensitivity, good repeatability, simplicity and rapidity.

Characterization of porous cobalt hexacyanoferrate and activated carbon electrodes under dynamic polarization conditions in a sodium-ion pseudocapacitor

We report here the activated carbon and cobalt hexacyanoferrate composite,which is applied as the electrode materials in symmetric supercapacitors containing a 1.0 M Na_(2)SO_(4) aqueous electrolyte.This novel material combines high specific surface area and electrochemical stability of activated carbon with the redox properties of cobalt hexacyanoferrate,resulting in maximum specific capacitance of 329 F g^(-1) with large voltage working window of 2.0 V.Electrochemical studies indicated that cobalt hexacyanoferrate introduces important pseudocapacitive properties accounting for the overall charge-storage process,especially when I<0.5 A g^(-1).At lower gravimetric currents(e.g.,0.05 A g^(-1))and up to 1.0 V,the presence of cobalt hexacyanoferrate improves the specific energy for more than 300%.In addition,to better understanding the energy storage process we also provided a careful investigation of the electrode materials under dynamic polarization conditions using the in situ Raman spectroscopy and synchrotron light Xray diffraction techniques.Interesting complementary findings were obtained in these studies.We believe that this novel electrode material is promising for applications regarding the energy-storage process in pseudocapacitors with long lifespan properties.

Chemically Modified Carbon Paste Electrode for Determination of Cesium Ion by Potentiometric Method

A new chemically modified carbon paste electrode for cesium(I) ion determination based on potassium zinc hexacyan-oferrate (PZHCF) as an ionophore was prepared. The electrode exhibits a Nernstian response for Cs(I) ions over a wide concentration range from 1 × 10-6 to 1 × 10-1 mol·L-1 with a slope of 58 ± 0.5 mV·decade-1. It has a response time of about 35 s and can be used for a period of 3 months with good reproducibility. Detection limit obtained in the optimal conditions was 3 × 10-7 mol·L-1. The potentiometric response is independent of the pH of the solution in the pH range 4.0 - 8.0. The electrode possesses the advantages of low resistance, fast response over a variety of other cations. The proposed electrode is applied as a sensor for the determination of Cs(I) ion concentration in different samples solutions. The results showed a good correlation with the data obtained by atomic absorption spectrometric method.

MnHCF/MnO_2 Core-shell Nanostructures as Cathode Material for Supercapacitors with High Energy Density

A nanocomposite of manganese dioxide coated manganese hexacyanoferrate was synthesized by a facile co-precipitation method and tested as active electrode material for an electrochemical supercapacitor. A way called "Deep electro-oxidation" was used to generate manganese dioxide coated layer for stabilizing the electrode material. The structure and ingredient of the resulting MnHCF/MnO2 composites were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and X-ray Photoelectron Spectroscopy. Electrochemical testing showed a capacitance of 225.6 F/g at a sweep rate of 5 mV/s within a voltage range of 1.3 V, and high energy density of 37.2 Wh/kg at a current density of 0.5 A/g in galvanostatic charge/discharge cycling. It is suggested that the two different components, manganese hexacyanoferrate core and manganese dioxide shell, lead to an integrated electrochemical behavior, and an enhanced capacitor. The electrochemical testing and corresponding XPS analysis also demonstrated that the manganese coordinated by cyanide groups via nitrogen atoms in MnHCF did not get involved in the charge storage process during potential cycles.

Low-strain binary hexacyanoferrate nanocuboids with concentration-gradient structure towards fast and durable energy storage

The exploration of low-strain and high-performance electrode is a crucial issue for aqueous potassiumion battery(AKIB).Herein,a novel potassium mediated iron/manganese binary hexacyanoferrate nanocuboid,i.e.,K_(x)Fe_(y)Mn_(1-y)[Fe(CN)_(6)]·nH_(2)O(KFeMnHCF)nanocuboid,with the concentration-gradient(CG)structure is designed as a high-performance cathode for AKIB.Internal the CG-KFeMnHCF nanocuboids,the manganese content gradually decreases from the interior to the surface and the iron content changes reverse,resulting in the concentration-gradient structure.Both experimental and finite element simulation(FEA)results demonstrate the lower internal stress and better mechanical characteristics of CG structured nanocuboid than the homogenous structured one upon ion intercalation/deintercalation processes.Meanwhile,the electrochemical testing and theoretical calculation(DFT)results disclose the substitution of Fe to Mn in the KMnHCF crystal results in the enhanced electronic conductivity,potassium migration and electrochemical kinetics.Taken both advantages from the well-designed architecture and optimized crystal structure,the CG-KFeMnHCF achieves the superior rate capability and ultrahigh stability in aqueous potassium ion system.In particular,the CG-KFe_(0.31)Mn_(0.69)HCF achieves the best comprehensive properties among all the samples.The full AKIBs based on CG-KFe_(0.31)Mn_(0.69)HCF cathode achieves the high energy density(83 Wh kg^(-1)),superior power density,high capacity retention(83%)over high-rate long-term cycles,good adaptation to a wide temperature range(-20 to 40℃)and high reliability even under outside deformations.Therefore,this work not only provides a new clue to design the highperformance cathode,but also promotes the applications of AKIBs for diverse electronics and wide working environments.

Enhanced stability and rate performance of zinc-doped cobalt hexacyanoferrate (CoZnHCF) by the limited crystal growth and reduced distortion

Cobalt hexacyanoferrate (CoHCF) is a potential cathode for aqueous Na-ion batteries due to its high theoretical specific capacity (170 m Ah g^(-1));however,its lower rate capability and cyclability limit its applications.Structural distortion at a weak N-coordinated crystal field during cycling disintegrates Co,yielding an irreversible reaction.Different Zn amounts ranging 0–1 were added to the Co site to suppress the structural irreversibility of CoHCF,yielding Co_(1-x)Zn_(x)HCF powder;this Zn (x≤0.09) addition reduced the powder’s dimension because the lower four coordination of Zn–N,not the six coordination of Co–N,limits the powder growth.Simultaneously,a small lattice parameter and interaxial angle (~90°) are obtained,implying that a narrower Co_(1-x)Zn_(x)HCF inner structure is formed to accommodate Na ions.Moreover,the electronic conductivity of Co_(1-x)Zn_(x)HCF gradually increased within 0–0.09 range.A smaller particle size with a high surface area leads to a near-surface-limited redox process,similar to a capacitive reaction.Both the surface-limited reaction and electronic conductivity enhances the reversibility due to the smaller charge transfer resistance at the electrode/electrolyte interface caused by Zn addition.Replacing redox-active Co with non-active Zn amount of 0.07 (Co_(1-x)Zn_(x)HCF) slightly reduces the specific capacity from 127 to 119 mAh g^(-1)at 0.1 A g^(-1)due to the shrunken Co charging sites.Rate performance is enhanced by compromising the capacity and reduced distortion,resulting in 81%retention at a 20-times-faster charging rate.Notably,the Co_(1-x)Zn_(x)HCF sample exhibited the good stability while preserving 74%of the initial capacity at 0.5 A g^(-1)after 200 cycles.

Electrochemical oxidation of polyethylene glycol in electroplating solution using paraffin composite copper hexacyanoferrate modified (PCCHM) anode

Electrochemical oxidation of polyethylene glycol(PEG) in an acidic(pH 0.18 to 0.42) and high ionic strength electroplating solution was investigated. The electroplating solution is a major source of wastewater in the printing wiring board industry. A paraffin composite copper hexacyanoferrate modified(PCCHM) electrode was used as the anode and a bare graphite electrode was used as the cathode. The changes in PEG and total organic carbon(TOC) concentrations during the course of the reaction were monitored. The efficiency of the PCCHM anode was compared with bare graphite anode and it was found that the former showed significant electrocatalytic property for PEG and TOC removal. Chlorides present in the solution were found to contribute significantly in the overall organic removal process. Short chain organic compounds like acetic acid, oxalic acid, formic acid and ethylene glycol formed during electrolysis were identified by HPLC method. Anode surface area and applied current density were found to influence the electro-oxidation process, in which the former was found to be dominating. Investigations of the kinetics for the present electrochemical reaction suggested that the two stage first-order kinetic model provides a much better representation of the overall mechanism of the process if compared to the generalized kinetic model.

In-situ FTIR Spectroelectrochemical Study of Chromium Hexacyanoferrate on Glassy Carbon Electrode

Chromium hexacyanoferrate (CrHCF) modified grassy carbon electrode (GC) in different electrolytes was studied by cyclic voltammetry and in situ FTIR spectroelectrochemistry. The results indicate that the behavior of CrHCF firm can be understood in term of two structures: Cr1/3Cr(III)Fe(II)(CN), and MCr(III)Fe(II)(CN)(6). Besides,the film exists in amorphous state: the outer layer is porous film, while the inner layer is relatively compact. According to the electrochemical reaction of CrHCF, the lattice can contract and expand with the cations' diffusion.

Rocking-chair ammonium ion battery with high rate and long-cycle life

Aqueous rechargeable ammonium-ion batteries(AIBs)have drew considerable attention because of their capacity for high rates,low cost,and high safety.However,developing desired electrodes requiring stable structure in the aqueous fast ammoniation/de-ammoniation becomes urgent.Herein,an ammonium ion full battery using Cu_(3)[Fe(CN)_(6)]_(2)(CuHCF)acting to be a cathode and barium vanadate(BVO)acting to be an anode is described.Its excellent electrochemical behavior of Prussian blue analogs and the perfectly matched lattice structure of NH_(4)^(+)is expected.And the open structure of vanadium compounds satisfies the fast ammoniation/de-ammoniation of NH4+is also achieved.As a result of these synergistic effects,the BVO//CuHCF full cell retains 80.5 percent of its capacity following 1000 cycling.These achievements provide new ideas for developing low-cost and long-life AIBs.

Cu-substituted nickel hexacyanoferrate with tunable reaction potentials for superior ammonium ion storage

In this work,a variety of Cu_(x)Ni_(2-x)Fe(CN)_(6)(x=0,0.4,0.8,1.2,1.6,2)cathodes for ammonium ion batteries are prepared and their electrochemical performances are investigated.During the introduction of copper in nickel hexacyanoferrate,the electrochemical performance varies without changing the structure of nickel hexacyanoferrate.The increase of Cu content in nickel hexacyanoferrate leads to the enhancement of reaction potential and capacity.Electrochemical results suggest that the substitution of Cu for Ni has a positive effect on improving the cycling stability and rate capacity of nickel hexacyanoferrate when x in Cu_(x)Ni_(2-x)Fe(CN)_(6)is less than 0.4.Therefore,Cu_(0.4)Ni_(1.6)Fe(CN)_(6)exhibits the best cycling per-formance(capacity retention of 97.54%at 0.3 C)and the highest rate capacity(41.4 mAh g^(-1)at 10 C)in Cu_(x)Ni_(2-x)Fe(CN)_(6).Additionally,the X-ray diffraction(XRD)and X-ray photoelectron spectroscopy(XPS)tests also reveal that the structural evolution of Cu_(0.4)Ni_(1.6)Fe(CN)_(6)is highly reversible upon NH_(4)^(+)storage.Therefore,this work proposes a candidate material for ammoniumion batteries and offers a novel avenue for adjusting the operating potential of the material.