连续共价有机框架筛分复合膜及全钒电池性能

设计了应用于全钒液流电池的尺寸筛分效应共价有机框架/聚醚砜(COF/PES)复合膜,利用纳米片的有序交错堆叠在聚醚砜支撑层上构建了具有均匀埃米级离子传输通道的连续COF分离层。连续COF层的规整刚性骨架赋予了膜极低的溶胀比,有序的埃米级孔道(有效孔径约为0.6 nm)对氢/钒离子具有精确的尺寸筛分作用。COF/PES筛分复合膜的钒渗透率仅有0.61×10^-8 cm^-2·s^-1,质子/钒离子选择性为Nafion 212的4.0倍。电流密度为80 mA·cm^-2下复合膜的能量效率达到82.9%,优于Nafion 212(81.2%)。100 mA·cm^-2下的长循环测试中,复合膜电池容量保持率相比于Nafion 212电池提高了16.2%,表明连续COF/PES筛分复合膜在全钒液流电池中具有广阔的应用前景。     

连续共价有机框架筛分复合膜及全钒电池性能

设计了应用于全钒液流电池的尺寸筛分效应共价有机框架/聚醚砜(COF/PES)复合膜,利用纳米片的有序交错堆叠在聚醚砜支撑层上构建了具有均匀埃米级离子传输通道的连续COF分离层。连续COF层的规整刚性骨架赋予了膜极低的溶胀比,有序的埃米级孔道(有效孔径约为0.6 nm)对氢/钒离子具有精确的尺寸筛分作用。COF/PES筛分复合膜的钒渗透率仅有0.61×10^-8 cm^-2·s^-1,质子/钒离子选择性为Nafion 212的4.0倍。电流密度为80 mA·cm^-2下复合膜的能量效率达到82.9%,优于Nafion 212(81.2%)。100 mA·cm^-2下的长循环测试中,复合膜电池容量保持率相比于Nafion 212电池提高了16.2%,表明连续COF/PES筛分复合膜在全钒液流电池中具有广阔的应用前景。     

共价有机框架材料的制备及对染料吸附性能的研究

利用溶剂热法合成了一种二维的共价有机框架（DMTP-TAPB COF）材料。通过X射线衍射仪（XRD）、扫描电子显微镜（SEM）和热重分析仪（TGA）对合成材料的结构、形貌和性能进行了详细的研究。然后研究了制备的共价有机框架材料对于靛蓝胭脂红染料（IC）的吸附能力,考察了不同吸附时间、不同p H和不同靛蓝胭脂红的初始浓度对吸附性能的影响。实验结果表明,制备的二维共价有机框架材料具有良好的结晶度和均匀的形貌。同时,DMTP-TAPB COF对靛蓝胭脂红具有较高的吸附能力（330.5 mg/g）和移除效率（84.5%）,吸附过程符合准二级动力学方程和Langmuir吸附模型。该研究表明共价有机框架材料作为污染物的吸附剂具有广阔的应用前景。     

High surface area benzimidazole based porous covalent organic framework for removal of methylene blue from aqueous solutions

In this study, a highly thermally stable benzimidazole based covalent organic framework (bCOF) was synthesized by the reaction of perlin‐tetracarboxylic anhydride, 5‐aminoisophthalic acid and diaminobenzidine in polyphosphoric acid medium. The synthesized porous bCOF was identified by different techniques. From CO₂ adsorption, the micropore surface area of the bCOF was found to be 856 m² g^?1; this synthesized bCOF has a widespread netting construction, and it has various porosity. The TGA results displayed the high thermal strength of the synthesized bCOF. After characterization, the bCOF was used for the removal of methylene blue from aqueous solution, and the essential parameters such as pH of the solution, contact time and initial concentration were assessed. The maximum adsorption capacity of the bCOF for removal of methylene blue was 63.29 mg g^?1 after only 40 min contact time at a pH of 6. Two kinetics and adsorption models were used for interpretation, and the outcomes showed that the pseudo‐second‐order and Langmuir models respectively were better fitted to the results. According to the results, the novel bCOF can be applied to remove methylene blue from aqueous solution. © 2020 Society of Chemical Industry     

Metal phosphonate-derived cobalt/nickel phosphide@N-doped carbon hybrids as efficient bifunctional oxygen electrodes for Zn−air batteries

The exploration of efficient bifunctional electrocatalysts for oxygen reduction reaction and oxygen evolution reaction is pivotal for the development of rechargeable metal–air batteries. Transition metal phosphides are emerging as promising catalyst candidates because of their superb activity and low cost. Herein, a novel metal phosphonate-derived cobalt/nickel phosphide@N-doped carbon hybrid was developed by a carbothermal reduction of cobalt/nickel phosphonate hybrids with different Co/Ni molar ratios. The metal phosphonate derivation method achieved an intimately coupled interaction between metal phosphides and a heteroatom-doped carbon substrate. The resultant Co₂P/Ni₃P@NC-0.2 enables an impressive electrocatalytic oxygen reduction reaction activity, comparable with those of state-of-the-art Pt/C catalysts in terms of onset potential (0.88 V), 4e^‒ selectivity, methanol tolerance, and long-term durability. Moreover, remarkable oxygen evolution reaction activity was also observed in alkaline conditions. The high activity is ascribed to the N-doping, abundant accessible catalytic active sites, and the synergistic effect among the components. This work not only describes a high-efficiency electrocatalyst for both oxygen reduction reaction and oxygen evolution reaction, but also highlights the application of metal phosphonate hybrids in fabricating metal phosphides with tunable structures, which is of great significance in the energy conversion field.     

Heterometallic cluster-based organic frameworks as highly active electrocatalysts for oxygen reduction and oxygen evolution reaction: a density functional theory study

Recently, metal–organic frameworks are one of the potential catalytic materials for electrocatalytic applications. The oxygen reduction reaction and oxygen evolution reaction catalytic activities of heterometallic cluster-based organic frameworks are investigated using density functional theory. Firstly, the catalytic activities of heterometallic clusters are investigated. Among all heterometallic clusters, Fe₂Mn–Mn has a minimum overpotential of 0.35 V for oxygen reduction reaction, and Fe₂Co–Co possesses the smallest overpotential of 0.32 V for oxygen evolution reaction, respectively 100 and 50 mV lower than those of Pt(111) and RuO₂(110) catalysts. The analysis of the potential gap of Fe₂M clusters indicates that Fe₂Mn, Fe₂Co, and Fe₂Ni clusters possess good bifunctional catalytic activity. Additionally, the catalytic activity of Fe₂Mn and Fe₂Co connected through 3,3′,5,5′-azobenzenetetracarboxylate linker to form Fe₂M–PCN–Fe₂M is explored. Compared with Fe₂Mn–PCN–Fe₂Mn, Fe₂Co–PCN–Fe₂Co, and isolated Fe₂M clusters, the mixed-metal Fe₂Co–PCN–Fe₂Mn possesses excellent bifunctional catalytic activity, and the values of potential gap on the Mn and Co sites of Fe₂Co–PCN–Fe₂Mn are 0.69 and 0.70 V, respectively. Furthermore, the analysis of the electron structure indicates that constructing a mixed-metal cluster can efficiently enhance the electronic properties of the catalyst. In conclusion, the mixed-metal cluster strategy provides a new approach to further design and synthesize high-efficiency bifunctional electrocatalysts.