普鲁士蓝及普鲁士蓝类化合物材料在钠离子电池中的研究进展

近年来,普鲁士蓝(PB)及普鲁士蓝类化合物(PBAs)用于钠离子电池电极材料方面的研究逐渐深入.作为金属有机框架(MOFs)材料,PB及PBAs是具有可调控的化学组成和物理性质的简单配位聚合物.PB及PBAs可直接作为高性能钠离子电池正极材料,也可以通过与其他材料复合用于钠离子电池正极;此外,利用PB及PBAs作为前驱体制备各类具有纳米结构的金属化合物(如金属氧化物、金属硫化物、金属硒化物和金属磷化物等)及金属化合物复合材料,并用于钠离子电池负极.本文简要介绍了PB、PBAs和以它们为前驱体制备的金属化合物及复合材料在钠离子存储方面的应用研究进展.     

亚铁氰化锌对放射性废水中铜离子的吸附研究

采用共沉淀法制备了一种普鲁士蓝类似物——亚铁氰化锌(KZnFC),通过X射线荧光分析仪(XRF)和X射线衍射仪(XRD)表征分析,确定样品化学组成式为K1.11Zn1.53Fe(CN)6。采用静态吸附研究了亚铁氰化锌在不同吸附时间、用量、pH值、铜离子初始质量浓度条件下对模拟放射性废水硫酸铜溶液中铜离子的吸附影响,并通过透射电镜(TEM)和穆斯堡尔谱分析对吸附机理进行了初步探讨。实验结果表明:亚铁氰化锌对Cu2+在用量为100mg、pH值为4~7、室温等条件下,2h内去除率可达89.23%,吸附量可达121.86mg/g。KZnFC对Cu2+吸附前后的穆斯堡尔谱表明,此吸附过程主要是KZnFC中的K+同溶液中Cu2+进行离子交换反应。亚铁氰化锌对铜离子的吸附过程符合Freundlich吸附等温模型。     

普鲁士蓝/生物炭材料的制备及其氨氮吸附机理

以氮、磷污染物导致的水体富营养化问题在我国普遍存在。本研究将普鲁士蓝与改性生物炭相结合,得到普鲁士蓝/生物炭复合材料。通过多种表征手段研究了复合材料的形貌及结构并通过模拟废水测试了其吸附性能。结果表明,复合材料在pH8时达到最佳吸附效果,氨氮去除率在95%以上,最大吸附量为24.4mg/g,比未改性生物碳提高101.3%。对复合材料吸附机理的研究表明,复合材料通过普鲁士蓝对氨氮的配位作用对多组分污水中氨氮实现了选择性吸附。此外,复合材料在外加H₂O₂溶液的条件下可形成芬顿氧化体系,能实现同步催化降解有机污染物和促进氨氮的吸附,因此有望在多组分富营养化污水治理中投入实际应用。     

高纯石墨对铯吸附性能的研究

通过4种类型高纯石墨的吸铯试验,研究了不同结构的高纯石墨吸附铯后的变化情况及原因。在此基础上,提出了作为铯束管吸铯剂的高纯石墨,需要有良好的吸铯性能和加工性能以及高的机械强度。比较分析发现其中一种高纯石墨可以满足铯束管的要求。     

沙柳基磁性多孔炭的制备及其吸附亚甲基蓝性能研究

采用水热法原位改性沙柳生物炭制备磁性多孔炭复合材料,利用SEM、XRD、FT-IR、XPS和BET分别对多孔炭的形貌、结构表征,并研究磁性多孔炭吸附去除废水中亚甲基蓝性能.系列表征分析结果表明磁性复合材料表面疏松多孔,比表面积为63.01 m2/g,含有-COOH、-OH等丰富的官能团.在亚甲基蓝初始质量浓度为50 m...     

改性丝瓜络对铜离子吸附的研究

在柠檬酸溶液中,以硫酸氢钠为催化剂,通过酯化反应制备了改性丝瓜络重金属离子吸附剂。研究了不同温度下其对Cu(Ⅱ)的静态吸附性能,测定了不同温度下的吸附曲线,并通过SEM及XRD对碱处理前后的丝瓜络进行了表征。结果表明,改性丝瓜络在不同温度下的吸附过程符合一级动力学模型;SEM分析表明碱处理后表面有明显的沟壑;XRD分析显示碱处理后丝瓜络结晶度降低了13.4%。     

Co-Fe普鲁士蓝/多壁碳纳米管复合材料的超电容性能

Co-Fe普鲁士蓝(CoPBA)是目前被广泛研究的超级电容器正极材料,其比电容高循环性能好,但低导电性和较差的倍率性能限制了其在超级电容器中的应用。为了提高CoPBA的导电性和电化学性能,本文以Co-glycerate为前驱体,采用牺牲模板法制备了Co-Fe普鲁士蓝/多壁碳纳米管(CoPBA/MWCNT)复合材料,利用XRD、SEM和FTIR等对复合材料的结构和形貌进行表征,使用电化学工作站在三电极体系和非对称超级电容器中测定了复合材料的电化学性能。实验结果表明：采用牺牲模板法成功合成出形貌较好的球状复合材料,以中性溶液Na₂SO₄为电解液,测得在1 A/g的电流密度下复合材料的质量比电容达到391.5 F/g。在10 A/g的高电流密度下比电容达到312.6 F/g,为1 A/g时的79.8%。利用软件模拟得出电荷转移电阻由3.9Ω降低到1.1Ω。以CoPBA/MWCNT为正极,以活性炭为负极制成非对称电容器,在功率密度为1 092 W/kg时能量密度可达39.5 Wh/kg, 5 000次循环后容量保持率为85.2%。采用牺牲模板法制备的...     

疏浚底泥活化吸附剂的制备及其吸附铜离子研究

通过"碱溶-活化-水热"三者联用在低于100℃,制备出从微孔到大孔的宽范围粒径分布,表面富集合氧基团、孔隙发达的多孔吸附剂.将其用于水体铜离子的吸附,最佳吸附时间为180min;吸附剂在弱酸至碱性条件下的吸附能力较强.当铜离子溶液pH接近中性时,该吸附剂对铜离子的去除率达98.97％.铜离子溶液pH大于6时,几乎可全部...     

Co类普鲁士蓝/多壁碳纳米管纳米复合材料的制备及其超电容性能

Co类普鲁士蓝（CoPBA）作为令人瞩目的超级电容器阳极材料拥有高比容量和优异的循环稳定性,但较差的电子导电性限制了其倍率性能。利用ZIF-67作为前驱体合成了Co类普鲁士蓝/多壁碳纳米管（CoPBA/MWCNT）复合材料,并使用XRD、SEM和TEM对材料的结构和形貌进行表征。在三电极体系中,测得CoPBA/MWCNT电极在电流密度为1 A·g^-1时电容提高到312 F·g^-1。制备的CoPBA/MWCNT电极有利于提高材料电导率和机械稳定性,从而获得更高的电化学性能。将CoPBA/MWCNT正极和活性炭（AC）负极组装为非对称电池,测得5 000圈循环后容量保留率为83.1%,循环稳定性优异。     

普鲁士蓝基HClO荧光纳米探针及其对肿瘤细胞的特异性检测（英文）

次氯酸(HClO)是一种活性氧(ROS),在许多生理和病理过程中起着至关重要的作用。然而,过量的HClO会导致组织损伤、动脉粥样硬化、神经退行性疾病甚至癌症。因此,实时检测肿瘤细胞中HCl O对于探索HClO在肿瘤进展以及免疫治疗中的作用具有重要意义。与目前常用的工艺复杂、水溶性差的有机分子探针不同,本工作简单地将异硫氰酸荧光素(FITC)与中空介孔普鲁士蓝纳米粒子(HMPB)相结合,构建了一种新型的无机亲水荧光纳米探针。由于内滤光效应,HMPB中FITC的荧光有一定程度的猝灭,但通过Fe²⁺-ClO^–氧化还原反应可恢复荧光。体外条件下,加入HClO后, FITC在发射峰(520 nm)处荧光逐渐增强, HClO在5×10^–6～50×10^–6 mol/L范围内呈良好的线性关系,检出限为2.01×10^–6mol/L。此外,在细胞水平上,该纳米探针对癌细胞中的HClO显示出良好的特异检测能力,且灵敏度高。     

Highly Crystalline Prussian Blue for Kinetics Enhanced Potassium Storage

Prussian blue analogs (PBAs) are promising cathode materials for potassium-ion batteries (KIBs) owing to their large open framework structure. As the K⁺ migration rate and storage sites rely highly on the periodic lattice arrangement, it is rather important to guarantee the high crystallinity of PBAs. Herein, highly crystalline K₂Fe[Fe(CN)₆] (KFeHCF-E) is synthesized by coprecipitation, adopting the ethylenediaminetetraacetic acid dipotassium salt as a chelating agent. As a result, an excellent rate capability and ultra-long lifespan (5000 cycles at 100 mA g⁻¹ with 61.3% capacity maintenance) are achieved when tested in KIBs. The highest K⁺ migration rate of 10⁻⁹ cm² s⁻¹ in the bulk phase is determined by the galvanostatic intermittent titration technique. Remarkably, the robust lattice structure and reversible solid-phase K⁺ storage mechanism of KFeHCF-E are proved by in situ XRD. This work offers a simple crystallinity optimization method for developing high-performance PBAs cathode materials in advanced KIBs.     

Oriented Assembled Prussian Blue Analogue Framework for Confined Catalytic Decomposition of Ammonium Perchlorate

The design of highly dispersed active sites of hollow materials and unique contact behavior with the components to be catalyzed provide infinite possibilities for exploring the limits of catalyst capacity. In this study, the synthesis strategy of highly open 3-dimensional frame structure Prussian blue analogues (CoFe-PBA) was explored through structure self-transformation, which was jointly guided by template mediated epitaxial growth, restricted assembly and directional assembly. Additionally, good application prospect of CoFe-PBA as combustion catalyst was discussed. The results show that unexpected thermal decomposition behavior can be achieved by limiting AP(ammonium perchlorate) to the framework of CoFe-PBA. The high temperature decomposition stage of AP can be advanced to 283.6 °C and the weight loss rate can reach 390.03% min⁻¹. In-situ monitoring shows that CoFe-PBA can accelerate the formation of NO and NO₂. The calculation of reaction kinetics proved that catalytic process was realized by increasing the nucleation factor. On this basis, the catalytic mechanism of CoFe-PBA on the thermal decomposition of AP was discussed, and the possible interaction process between AP and CoFe-PBA during heating was proposed. At the same time, another interesting functional behavior to prevent AP from caking was discussed.     

Reflective and Complementary Transmissive All-Printed Electrochromic Displays Based on Prussian Blue

By combining the electrochromic (EC) properties of Prussian blue (PB) and poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS), complementary EC displays manufactured by slot-die coating and screen printing on flexible plastic substrates are reported. Various display designs have been realized, resulting in displays operating in either transmissive or reflective mode. For the transmission mode displays, the color contrast is enhanced by the complementary switching of the two EC electrodes PB and PEDOT:PSS. Both electrodes are either exhibiting a concurrent colorless or blue appearance. For the displays operating in reflection mode, a white opaque electrolyte is used in conjunction with the EC properties of PB, resulting in a display device switching between a fully white state and a blue-colored state. The developments of the different device architectures, that either operate in reflection or transmission mode, demonstrate a scalable manufacturing approach of all-printed EC displays that may be used in a large variety of Internet of Things applications.     

Hollow Structures Based on Prussian Blue and Its Analogs for Electrochemical Energy Storage and Conversion

Due to their special structural characteristics, hollow structures grant fascinating physicochemical properties and widespread applications, especially in electrochemical energy storage and conversion. Recently, the research of Prussian blue (PB) and its analog (PBA) related nanomaterials has emerged and has drawn considerable attention because of their low cost, facile preparation, intrinsic open framework, and tunable composition. Here, the recent progress in the study of PB‐ and PBA‐based hollow structures for electrochemical energy storage and conversion are summarized and discussed. First, some remarkable examples in the synthesis of hollow structures from PB‐ and PBA‐based materials are illustrated in terms of the structural architectures, i.e., closed single‐shelled hollow structures, open hollow structures, and complex hollow structures. Thereafter, their applications as potential electrode materials for lithium‐/sodium‐ion batteries, hybrid supercapacitors, and electrocatalysis are demonstrated. Finally, the current achievements in this field together with the limits and urgent challenges are summarized. Some perspectives on the potential solutions and possible future trends are also provided.     

Enabling Superior Sodium Capture for Efficient Water Desalination by a Tubular Polyaniline Decorated with Prussian Blue Nanocrystals

The application of electrochemical energy storage materials to capacitive deionization (CDI), a low-cost and energy-efficient technology for brackish water desalination, has recently been proven effective in solving problems of traditional CDI electrodes, i.e., low desalination capacity and incompatibility in high salinity water. However, Faradaic electrode materials suffer from slow salt removal rate and short lifetime, which restrict their practical usage. Herein, a simple strategy is demonstrated for a novel tubular-structured electrode, i.e., polyaniline (PANI)-tube-decorated with Prussian blue (PB) nanocrystals (PB/PANI composite). This composite successfully combines characteristics of two traditional Faradaic materials, and achieves high performance for CDI. Benefiting from unique structure and rationally designed composition, the obtained PB/PANI exhibits superior performance with a large desalination capacity (133.3 mg g⁻¹ at 100 mA g⁻¹), and ultrahigh salt-removal rate (0.49 mg g⁻¹ s⁻¹ at 2 A g⁻¹). The synergistic effect, interfacial enhancement, and desalination mechanism of PB/PANI are also revealed through in situ characterization and theoretical calculations. Particularly, a concept for recovery of the energy applied to CDI process is demonstrated. This work provides a facile strategy for design of PB-based composites, which motivates the development of advanced materials toward high-performance CDI applications.     

Chemical Properties,Structural Properties,and Energy Storage Applications of Prussian Blue Analogues

Prussian blue analogues (PBAs, A₂T[M(CN)₆], A = Li, K, Na; T = Fe, Co, Ni, Mn, Cu, etc.; M = Fe, Mn, Co, etc.) are a large family of materials with an open framework structure. In recent years, they have been intensively investigated as active materials in the field of energy conversion and storage, such as for alkaline‐ion batteries (lithium‐ion, LIBs; sodium‐ion, NIB; and potassium‐ion, KIBs), and as electrochemical catalysts. Nevertheless, few review papers have focused on the intrinsic chemical and structural properties of Prussian blue (PB) and its analogues. In this Review, a comprehensive insight into the PBAs in terms of their structural and chemical properties, and the effects of these properties on their materials synthesis and corresponding performance is provided.     

A Heterostructure Coupling of Bioinspired,Adhesive Polydopamine,and Porous Prussian Blue Nanocubics as Cathode for High‐Performance Sodium‐Ion Battery

Prussian blue (PB) and its analogues are recognized as promising cathodes for rechargeable batteries intended for application in low‐cost and large‐scale electric energy storage. With respect to PB cathodes, however, their intrinsic crystal regularity, vacancies, and coordinated water will lead to low specific capacity and poor rate performance, impeding their application. Herein, nanocubic porous Na_xFeFe(CN)₆ coated with polydopamine (PDA) as a coupling layer to improve its electrochemical performance is reported, inspired by the excellent adhesive property of PDA. As a cathode for sodium‐ion batteries, the Na_xFeFe(CN)₆ electrode coupled with PDA delivers a reversible capacity of 93.8 mA h g^?1 after 500 cycles at 0.2 A g^?1, and a discharge capacity of 72.6 mA h g^?1 at 5.0 A g^?1. The sodium storage mechanism of this Na_xFeFe(CN)₆ coupled with PDA is revealed via in situ Raman spectroscopy. The first‐principles computational results indicate that Fe^II sites in PB prefer to couple with the robust PDA layer to stabilize the PB structure. Moreover, the sodium‐ion migration in the PB structure is enhanced after coating with PDA, thus improving the sodium storage properties. Both experiments and computational simulations present guidelines for the rational design of nanomaterials as electrodes for energy storage devices.     

水系钠离子电池普鲁士蓝正极材料的制备与电化学性能研究

普鲁士蓝(PB)是一种金属有机骨架配合物, 作为正极材料在水系钠离子电池中有广泛的应用前景。本文采用单一源法制备PB, 系统研究了反应温度、反应时间以及盐酸浓度对PB形貌结构和电化学性能的影响。研究结果表明, 升高反应温度能提高PB结晶性和循环稳定性, 以80 ℃合成的PB为正极材料组装的电池在100圈充放电循环后容量保持率为93.9%。延长反应时间可以使PB粒径增大, 但是反应时间超过6 h后PB粒径基本保持不变。延长反应时间有利于提高循环性能, 10 h所合成PB组装的电池在100圈充放电循环后容量保持率可以达到90%。提高盐酸浓度会改变PB的表面形貌, 同时改善电化学性能。盐酸浓度为0.20 mol/L时, 所得PB组装的电池经过100个循环后, 比容量仍有67.5 mAh/g。本研究可以为制备高性能PB基水系钠离子电池提供理论和实验指导。     

Copper-Enriched Prussian Blue Nanomedicine for In Situ Disulfiram Toxification and Photothermal Antitumor Amplification

In situ toxification of less toxic substance for the generation of effective anticarcinogens at the specific tumor tissue has been a novel paradigm for combating cancer. Significant efforts have been recently dedicated to turning clinical-approved drugs into anticancer agents in specific tumor microenvironment by chemical reactions. Herein, a hollow mesoporous Prussian blue (HMPB)-based therapeutic nanoplatform, denoted as DSF@PVP/Cu-HMPB, is constructed by encapsulating alcohol-abuse drug disulfiram (DSF) into the copper-enriched and polyvinylpyrrolidone (PVP)-decorated HMPB nanoparticles to achieve in situ chemical reaction-activated and hyperthermia-amplified chemotherapy of DSF. Upon tumor accumulation of DSF@PVP/Cu-HMPB, the endogenous mild acidity in tumor condition triggers the biodegradation of the HMPB nanoparticle and the concurrent co-releases of DSF and Cu²⁺, thus forming cytotoxic bis(N,N-diethyl dithiocarbamato)copper(II) complexes (CuL₂) via DSF-Cu²⁺ chelating reaction. Moreover, by the intrinsic photothermal-conversion effect of PVP/Cu-HMPBs, the anticancer effect of DSF is augmented by the hyperthermia generated upon near-infrared irradiation, thus inducing remarkable cell apoptosis in vitro and tumor elimination in vivo on both subcutaneous and orthotopic tumor-bearing models. This strategy of in situ drug transition by chemical chelation reaction and photothermal-augmentation provides a promising paradigm for designing novel cancer-therapeutic nanoplatforms.