碱性电解液中K3[Fe(CN)6]在锌阳极上的自发还原和吸附延长锌镍电池的循环寿命

采用K₃[Fe(CN)₆]作为锌镍电池的电解液添加剂,克服了锌阳极的变形。此外,通过一系列实验设计和表征,探索了电解液中金属锌与K₃[Fe(CN)₆]的反应机理。通过XRD (X-ray diffraction)和XPS (X-ray photo-electron spectroscopy)测试,我们发现金属锌在KOH水溶液中能够与K₃[Fe(CN)₆]反应,将[Fe(CN)₆]^3–还原为[Fe(CN)₆]⁴⁻。添加K₃[Fe(CN)₆]的锌镍电池实现了更长的循环寿命,比不添加K₃[Fe(CN)₆]的锌镍电池长3倍以上。在相同循环次数下,改性电解质中锌阳极循环不仅形状变化较小,而且没有出现“死”锌现象,电极添加剂和粘结剂也没有发生偏析。此外,不同于一般的有机添加剂,K₃[Fe(CN)₆]的加入不仅不会增大电极的极化,还能够提高锌镍电池的放电容量和倍率性能。因此,考虑到这一改性策略有着较高的可行性和较低的成本,K₃[Fe(CN)₆]添加剂在锌镍电池的实际应用中具有极大的推广潜力。     

金属-超分子聚合物的合成及其多色电致变色器件

本文合成了一种多齿配体化合物——1,4-双(2,2′:6′,2′′-三联吡啶-4′-基)苯及其Fe/Ru金属-超分子聚合物——Poly Fe和Poly Ru,同时以喷涂在ITO导电玻璃上的Fe/Ru金属-超分子聚合物膜为工作电极、0.1 mol/L Li Cl O4水溶液为电解质,并添加K_3Fe(CN)_6为电化学互补材料,制作了系列电致变色器件.由Poly Fe和Poly Ru的组合,可以得到从Poly Fe的蓝紫色渐变到Poly Ru橙红色的彩色薄膜及其多色电致变色器件,器件响应速度快(2 s),褪色电压0.9~1.2 V,着色电压0 V,最大光学对比度约57%.添加K_3Fe(CN)_6后,器件的寿命得到极大提高.     

过渡金属配合物阴离子嵌人聚吡咯膜电极的表征

采用电化学聚合方法在水溶液中制备出Fe(CN)_6~(4-)嵌入的聚吡咯膜修饰电极, 电极具有稳定的Fe(CN)_6~(4-)/Fe(CN)_6~(3-)电化学响应, 其氧化、还原电位与电解质溶液中H~+浓度有关。借助XPS、IR和ESR方法对聚合物膜结构进行表征, 探讨嵌入物种Fe(CN)_6~(n-)和聚吡咯之间的相互作用, 提出一种可能的轨道相互作用模式。     

K4[Fe(CN)6]作为氰源在氰基化反应中的应用**

过渡金属催化氰基化反应成为合成芳基腈化物的重要手段之一。2004年,无毒、廉价的K4[Fe(CN)6]首次被用来代替传统的KCN、NaCN及CuCN等作为氰源用于芳基卤代物的氰基化反应。K4[Fe(CN)6]作为氰源时无需复杂的预处理,其6个氰根均可参与反应。该反应为氰基化反应开创了一个新的研究方向,迅速得到了众多研究者的青睐。K4[Fe(CN)6]用于氰基化反应的研究也得到了较快的发展。本文主要综述了近年来K4[Fe(CN)6]作为氰源用于卤代芳烃和芳基氟代磺酸酯的氰基化反应。主要介绍了在钯催化剂和铜催化剂作用下,以K4[Fe(CN)6]为氰源的氰基化反应在配体、反应介质和底物适用范围等方面的研究成果。     

快速检测中药材中黄曲霉毒素B1的电化学生物传感器

结合新型纳米传感膜材料,以黄曲霉毒素Bl(AFBl)单克隆抗体为生物识别元件,通过考察AFB1与抗体之间的相互作用对测试底液中[Fe(CN)6]3-/[Fe(CN)6]4-([Fe(CN)6]3-/4-)氧化还原体系的影响,构建了一种可用于中药材中AFB1快速检测的电化学生物传感器.在最佳条件下,对AFB1浓度的线性响...     

A Study on Thermal Decomposition of K_3[Fe(CN)_6] and KFe[Fe(CN)_6] in Helium

K3 [Fe(CN)6] and KFe[Fe(CN)6] are classical coordination compounds. However, the mechanism of decomposition reactions has not been well expounded. The gas products of thermal decomposition were examined by gas chroma tography (GC) , and the structure of the solid products by Mossbauer spectroscopy(MS) and X-ray diffraction(XRD). The findings are explained in terms of the theory of coordination chemistry and a decomposition mechanism is proposed in this study. On the basis of various experimental results, the first stage of the decomposition of K3[Fe(CN)6] in He was found to be the evolution of(CN)2 resulting in the reduction of Fe(Ⅲ)12K3 [Fe(CN)6]→9K4[Fe(CN)6] + Fe2 [Fe(CN)6] + 6 ( CN )For KFe [Fe(CN) 6 ], the first stage of decomposition man be represented as6KFe[Fe(CN)6]→3K2Fe[Fe(CN)6] + 2Fe2[Fe(CN)6 + 3(CN)2At higher temperatures, the decomposition of both K3[Fe(CN)6) andKFe[Fe(CN)6] to form KCN and Fe2C was accomplished by the release of(CN)2 and N2.     

基于石墨烯-甲苯胺蓝复合物癌胚抗原电化学免疫传感器

研究了在PBS缓冲介质中,一种检测癌胚抗原的新型免标记电化学免疫传感器的制备及应用,石墨烯与甲苯胺蓝复合物饰于玻碳电极表面,通过循环伏安法对修饰的电极进行表征.基于以[Fe(CN)6]3-/4-为氧化还原探针,癌胚抗原抗体反应引起[ Fe(CN)6] 3-/4-探针的电流响应的变化,来实现癌胚抗原的检测,癌胚抗原的浓度...     

铁氰化钾-Fe(Ⅲ)分光光度法测定盐酸氯丙嗪

建立了以铁氰化钾-Fe(Ⅲ)体系测定盐酸氯丙嗪的新方法.研究表明,盐酸氯丙嗪可以使Fe(Ⅲ)还原为Fe(Ⅱ),还原生成的Fe(Ⅱ)可以与K3[Fe(CN)6]反应生成可溶性普鲁士蓝KFe[Fe(CN)6].盐酸氯丙嗪的质量浓度在0.21-32.00μg/mL范围内与吸光度呈现良好线性关系,线性回归方程A=0.01854+0.07652p(μg/mL),相关系数R=0.9992,摩尔吸光系数ε=2.5×10(4)·L·mol-1·cm-1,检出限0.12μg/mL.方法用于测定药物和血清中盐酸氯丙嗪含量,回收率为98.1%～101.3%.     

基于纳米银/碳纳米纤维复合材料的增强效应电化学测定多贝斯

将银纳米粒子(AgNPs)电沉积在碳纳米纤维(CNFs)修饰玻碳电极表面制备纳米银/碳纳米纤维修饰玻碳电极(AgNPs/CNFs/GCE).采用扫描电镜考察其表面形态,在K3[Fe(CN)6]-K4[Fe(CN)6]体系中用循环伏安法和电化学阻抗法研究AgNPs/CNFs/GCE的电化学行为.采用循环伏安法和方波伏安法...     

基于铁氰化钾选择性氧化间接光度法同时测定药剂中半胱氨酸和胱氨酸

K3[Fe(CN)6]作为一种高选择性的弱氧化剂,能氧化半胱氨酸而不能氧化胱氨酸。利用半胱氨酸分子中的巯基(-SH)可将K3[Fe(CN)6]还原为K4[Fe(CN)6],K4[Fe(CN)6]与Fe Cl3反应生成在730 nm处有最大吸收的可溶性蓝色物质KFe[Fe(CN)6],通过测定蓝色物质的吸光度,可间接测定半胱氨酸的含量,从而建立了准确、快速测定半胱氨酸和胱氨酸的新方法,对反应底物、显色剂和分析途径等条件进行优化。结果表明:铁氰化钾作底物,三氯化铁作显色剂间接光度法效果更好,半胱氨酸质量浓度在0~80μmol·L-1范围内与A呈良好的线性关系,线性回归方程为A=0.0180+0.0084C(μmol·L-1),线性相关系数r=0.9999,表观摩尔吸收系数ε=0.84×104L/(mol·cm)。方法用于实际药品中半胱氨酸和胱氨酸含量测定,结果与标示量基本一致。     

碱性电解液中K3[Fe(CN)6]在锌阳极上的自发还原和吸附延长锌镍电池的循环寿命

In view of the continuously worsening environmental problems, fossil fuels will not be able to support the development of human life in the future. Hence, it is of great importance to work on the efficient utilization of cleaner energy resources. In this case, cheap, reliable, and eco-friendly grid-scale energy storage systems can play a key role in optimizing our energy usage. When compared with lithium-ion and lead-acid batteries, the excellent safety, environmental benignity, and low toxicity of aqueous Zn-based batteries make them competitive in the context of large-scale energy storage. Among the various Zn-based batteries, due to a high open-circuit voltage and excellent rate performance, Zn-Ni batteries have great potential in practical applications. Nevertheless, the intrinsic obstacles associated with the use of Zn anodes in alkaline electrolytes, such as dendrite, shape change, passivation, and corrosion, limit their commercial application. Hence, we have focused our current efforts on inhibiting the corrosion and dissolution of Zn species. Based on a previous study from our research group, the failure of the Zn-Ni battery was caused by the shape change of the Zn anode, which stemmed from the dissolution of Zn and uneven current distribution on the anode. Therefore, for the current study, we selected K₃[Fe(CN)₆] as an electrolyte additive that would help minimize the corrosion and dissolution of the Zn anode. In the alkaline electrolyte, [Fe(CN)₆]^3– was reduced to [Fe(CN)₆]^4– by the metallic Zn present in the Zn-Ni battery. Owing to its low solubility in the electrolyte, K₄[Fe(CN)₆] adhered to the active Zn anode, thereby inhibiting the aggregation and corrosion of Zn. Ultimately, the shape change of the anode was effectively eliminated, which improved the cycling life of the Zn-Ni battery by more than three times (i.e., from 124 cycles to more than 423 cycles). As for capacity retention, the Zn-Ni battery with the pristine electrolyte only exhibited 40% capacity retention after 85 cycles, while the Zn-Ni battery with the modified electrolyte (i.e., containing K₃[Fe(CN)₆]) showed 72% capacity retention. Moreover, unlike conventional organic additives that increase electrode polarization, the addition of K₃[Fe(CN)₆] not only significantly reduced the charge-transfer resistance in a simplified three-electrode system, but also improved the discharge capacity and rate performance of the Zn-Ni battery. Importantly, considering that this strategy was easy to achieve and minimized additional costs, K₃[Fe(CN)₆], as an electrolyte additive with almost no negative effect, has tremendous potential in commercial Zn-Ni batteries.     

电化学法改性阳极对MFC性能的影响

采用不同质量分数的NH_4NO_3和(NH_4)_2S_2O_8溶液作为电解液,对双室微生物燃料电池的阳极炭布进行改性。以餐厨废水作为阳极底物,以K_3[Fe(CN)_6]和NaCl混合溶液为阴极液,考察不同电解液改性阳极条件下微生物燃料电池的产电性能及污水处理效果。结果表明,采用NH_4NO_3或(NH_4)_2S_2O_8改性炭布作为阳极的微生物燃料电池的发电性能和水处理效果均有改善。其中,采用质量分数为4%的(NH_4)_2S_2O_8溶液作为阳极改性电解液时,微生物燃料电池系统的产电性能达到最佳,其稳态电流密度约为60 m A/m~2,COD去除率约为42.5%。     

微生物燃料电池处理餐饮废水及同步发电性能研究

针对食堂餐饮废水,建立微生物燃料电池实验系统,研究微生物燃料电池废水处理与同步发电性能。首先使用Fe(NO3)3溶液作为阴极电解液进行实验,证明餐饮废水生物降解及产电的可行性;分别采用NaCl溶液和K3[Fe(CN)6]溶液作为阴极电解液进行对比实验,研究不同运行环境下微生物燃料电池的发电性能和污水净化效果。结果表明,采用NaCl溶液和K3[Fe(CN)6]溶液作为阴极电解液时的COD去除率分别是30%和22%左右,平均电流密度分别为5.6和5.2mA/m2。在污水稀释比为2∶1、NaCl电解液浓度为0.4mol/L的情况下,微生物燃料电池系统的发电性能和净水效果达到最佳状态,稳态电流密度为8.8mA/m2,COD去除率为33.3%。     

Radiation chemical formation and precipitation of Turnbull blue from Fe(III)-oxalate

The radiation chemical analogue of the light induced formation of Turnbull blue, K[Fe(II)Fe(III)(CN)₆], from K₃[Fe(III)(oxalate)₃] and K₃[Fe(III)(CN)₆] was investigated by pulse radiolysis. The kinetic analysis revealed a two-step process: after a pseudo-first order reaction an autocatalytic formation of Turnbull blue takes place. The rate coefficient of the first step is k₈=1.42×10⁵ M⁻¹ s⁻¹. The incubation time of precipitation was also determined.     

铁氰根桥联的一维链状大环配位聚合物的合成及结构

配位聚合物的合成、结构和性质研究近年来引起了人们极大的兴趣 ,已成为配位化学最活跃的研究领域之一 .由于 [Fe( CN) 6 ]3- 和 [Fe( CN) 6 ]4- 离子本身具有丰富的配位特性 ,可与金属离子及其配合物形成一维链状、二维网状和三维立体结构的配位聚合物 [1～ 5] ,铁氰根和亚铁氰根桥联的配位聚合物的研究成为其中的研究热点之一 .此外 ,铁氰根和亚铁氰根桥联的配位聚合物具有较高的铁磁相变温度[6～ 8] ,是一类具有较好应用前景的分子磁体 .但是 ,以金属大环配合物作为结构单元与 [Fe( CN) 6 ]3-和 [Fe( CN) 6 ]4-离子形成的配位聚合物…     

[(Me3Sn)2(Me3Sb)M(CN)6]∞ (M = Fe, Ru): Neuartige Organo-Sn/Sb-Polymere von besonderer chemischer und thermischer stabilität

The thermally (decomp. temp. 300°C) and completely air stable, novel coordination polymers [(Me₃Sn^IV)₂(Me₃Sb^V)M^II(CN)₆]_∞ with M = Fe and Ru can be prepared by co-precipitation from aqueous solutions of Me₃SnCl, Me₃SbBr₂ and K₄[(M(CN)₆], or, alternatively, by the ion-exchange-like reaction of the polymers [A(Me₃Sn)₃M(CN)₆]_∞ (A⁺ = Et₄N⁺, Cp₂Co⁺, Me₃Sn⁺ etc.) with Me₃SbBr₂. IR-spectroscopic findings suggest a statistical distribution of quasi-octahedral M(CN-Sn··)_6-x(CNSb ··)_x building blocks (with x = 0–6) within a three-dimensional network.     

Self-assembly of an Unprecedented Cynao-bridged One-dimensional 4f-3d Complex[Eu(DMF)4(H2O)2Cr(CN)6] H2O

Recently, there has been considerable interest in cyano-bridged lanthanide(Ⅲ) hexacyanometalate(Ⅲ) complexes LnM(CN)₆·nH₂O (M=Fe, Cr and Co) because of their potential as catalytic, semiconductive, and magnetic materials.^[1-8] In this study, we employed N,N-dimethylformamide (DMF) as a hybrid ligand to construct a bimetallic complex[Eu(DMF)₄(H₂O)₂Cr(CN)₆]·H₂O. It was synthesized as yellow crystals by the self-assembly of anhydrous EuCl₃ and (Bu₄N)₃[Cr(CN)₆] in MeOH and DMF. Single-crystal X-ray diffraction analysis shows that it consists of a cyano-bridged chain structure. The Eu atom is eight-coordinate with a distorted bicapped square antiprism geometry. Six oxygen atoms of two water molecules and four DMF molecules and two nitrogen atoms of the bridging CN ligands are bound to Eu with the Eu-O distance ranging from 2.368(7) to 2.447(8) Å. The bridging cyanides coordinate to the Europium(Ⅲ) ion[N(l)-Eu=2.543(9) Å and N(3)-EuA=2.543(8) Å] in a bent fashion with the bond angles of 164.0(9) for C(1)-N(1)-Nd and 155.1(7)。for C(3)-N(3)-EuA (A denotes the symmetry transformation:-x+l,y-l/2,-z+3/2). Each Cr(CN)₆ coordinates to two Eu(Ⅲ) ions using two cis cyanide ligands, while each Eu(DMF)₄(H₂O)₂ group connects two Cr(CN)₆ moieties in a cis fashion, giving rise to an unprecedented chain structure. Crystal data:monoclinic, space group P2₁/c, a=13.151(2), b=12.905(2), c=19.186(2) Å, β=109.70(1)°, V=3065.5(7) ų,Z=4, ρ_obs=1.531 Mg m^-3, S=1.024,R1=0.0540, R_w=0.1616.     

Reductive nitrosylation of tetraoxometallates—XVII. Molybdate-hydroxylamine-cyanide reaction, and synthesis and characterization of K2[Mo(NO)(CN)5] and (NMe4)2[Mo(NO)(CN)4]

A reaction condition is established which determines the nature of the products in the molybdate-hydroxylamine-cyanide reaction. With hydroxylamine always used in excess, it is the hydroxyl ion concentration of the reaction mixture which plays a vital role in determining whether K₄[Mo(NO)(CN)₅] or K₂[Mo(NO)(CN)₅] is obtained exclusively. The latter product is hereby reported for the first time. Its powder diffractogram being typical of a cubic system, a gross structural characterization has been made possible. The former under aqueous, aerobic conditions yields a new product, (NMe₄)₂[Mo(NO)(CN)₄].