通过等体积浸渍法制备了金属有机骨架材料MIL-53(Al)(MIL:Materials of Institut Lavoisier)负载纳米Pd催化剂.采用X射线衍射(XRD)、透射电子显微镜(TEM)和X射线光电子能谱(XPS)等手段对催化剂的结构进行了表征.催化剂在反应前后XRD衍...通过等体积浸渍法制备了金属有机骨架材料MIL-53(Al)(MIL:Materials of Institut Lavoisier)负载纳米Pd催化剂.采用X射线衍射(XRD)、透射电子显微镜(TEM)和X射线光电子能谱(XPS)等手段对催化剂的结构进行了表征.催化剂在反应前后XRD衍射峰保持不变,说明载体MIL-53(Al)具有良好的稳定性.采用TEM对催化剂进行表征,结果表明,MIL-53(Al)的多孔晶体结构有助于形成高度分散的纳米Pd颗粒,样品2.7%(w)Pd/MIL-53中Pd颗粒的平均粒径为2.21 nm.该催化剂在CO氧化反应中表现出较高的催化活性,115°C达到完全转化.同时催化剂可循环使用,多次反应后催化活性和催化剂结构都保持稳定.展开更多
采用溶剂法合成了热稳定性高的金属有机骨架材料MIL-53(Al)(MIL:Materials of Institut Lavoisier),用此材料为载体负载钴催化剂用于CO的催化氧化反应,并与Al2O3负载的钴催化剂进行了对比.采用热重-差热扫描量热(TG-DSC)、傅里叶变换红...采用溶剂法合成了热稳定性高的金属有机骨架材料MIL-53(Al)(MIL:Materials of Institut Lavoisier),用此材料为载体负载钴催化剂用于CO的催化氧化反应,并与Al2O3负载的钴催化剂进行了对比.采用热重-差热扫描量热(TG-DSC)、傅里叶变换红外(FTIR)光谱、X射线衍射(XRD)、N2物理吸附-脱附、透射电子显微镜(TEM)、氢气程序升温还原(H2-TPR)等方法对催化剂的结构性质进行了表征.TG和N2物理吸附-脱附结果表明,载体MIL-53(Al)有好的稳定性和高的比表面积;XRD以及TEM结果表明Co/MIL-53(Al)上负载的Co3O4颗粒粒径(平均约为5.03 nm)明显小于Al2O3上Co3O4颗粒粒径(平均约为7.83 nm).MIL-53(Al)的三维多孔结构中分布均匀的位点能很好地分散固定Co3O4颗粒,高度分散的Co3O4颗粒有利于CO的催化氧化反应.H2-TPR实验发现Co/MIL(Al)催化剂的还原温度低于Co/Al2O3催化剂的还原温度,低的还原温度表现为高的催化氧化活性.CO催化氧化结果表明,MIL-53(Al)负载钴催化剂的催化活性明显高于Al2O3负载钴催化剂,MIL-53(Al)负载钴催化剂在160°C时使CO氧化的转化率达到98%,到180°C时CO则完全转化,催化剂的结构在催化反应过程中保持稳定.展开更多
A postsynthetic modification method was used to prepare salicylaldehyde functionalized metal-organicframeworks through the nucleophilic addition of salicylaldehyde with the amine group present in the frameworks ofNH2-...A postsynthetic modification method was used to prepare salicylaldehyde functionalized metal-organicframeworks through the nucleophilic addition of salicylaldehyde with the amine group present in the frameworks ofNH2-MIL-53（A1）. Hydroxyl groups were successfully grafted onto NI-I2-MIL-53（A1）, and imine groups were formed.Importantly, these hydroxyl and imine groups of the resulting NH2-MIL-53（A1）-SA can be used as the anchoringgroup to stabilise Au^3＋ ions and Au^0 nanoparticles（NPs）. By doing this, Au^3＋ ions and Au^0 NPs were successfully en-capsulated in the cages of NH2-MIL-53（A1） by a simple impregnation method. The resulting gold functionalizedNH2-MIL-53（AI） showed good catalytic activities in the one-pot synthesis of structurally divergent propargylaminesby three-component coupling reactions of aldehydes, amines and alkynes. Various aromatic/aliphatic aldehydes, aro-matic alkynes, and piperidine were able to undergo three-component coupling on NH2-MIL-53（A1）-Au. In addition,the catalyst NH2-M/L-53（A/）-Au was recovered easily by centrifugation and reused up to four times. Thus, it can beused for the environmentally friendly synthesis ofpropargylamines.展开更多
For all-solid-state lithium batteries(ASSLBs),polymer-blended solid composite electrolytes(SCEs)have drawn wide interest owing to their significance in improving the interfacial solid-solid contacts and inhibiting the...For all-solid-state lithium batteries(ASSLBs),polymer-blended solid composite electrolytes(SCEs)have drawn wide interest owing to their significance in improving the interfacial solid-solid contacts and inhibiting the growth of lithium dendrites.In this work,SCEs based on PVDF-HFP/PMMA matrix containing MOFs(NH2-MIL-53(Al))and LiTFSI were designed and synthesized employing an easy solution casting method.The synthesized samples were examined by XRD,SEM,EDS,and electrochemical tests.It was found that MPP-2 SCE not only has excellent ionic conductivity at 60℃ of 5.54×10^(−4) S cm^(−1),but also exhibits superior interfacial compatibility in Li||Li symmetric batteries,which can constantly cycle for about 800 h at 0.1 mA cm^(−2) with no short-circuiting.The assembled Li|MPP-2|LiFePO4 cell exhibited a first discharge specific capacity of up to 157.1 mAh g^(−1) at 60℃ and 0.2 C.This work may help to further advance the progress of ASSLBs in the future.展开更多
基金The project was supported by the National Natural Science Foundation of China(21073235,21173270,21177160)National High-Tech Research and Development Program of China(863)(2013AA061902)~~
文摘通过等体积浸渍法制备了金属有机骨架材料MIL-53(Al)(MIL:Materials of Institut Lavoisier)负载纳米Pd催化剂.采用X射线衍射(XRD)、透射电子显微镜(TEM)和X射线光电子能谱(XPS)等手段对催化剂的结构进行了表征.催化剂在反应前后XRD衍射峰保持不变,说明载体MIL-53(Al)具有良好的稳定性.采用TEM对催化剂进行表征,结果表明,MIL-53(Al)的多孔晶体结构有助于形成高度分散的纳米Pd颗粒,样品2.7%(w)Pd/MIL-53中Pd颗粒的平均粒径为2.21 nm.该催化剂在CO氧化反应中表现出较高的催化活性,115°C达到完全转化.同时催化剂可循环使用,多次反应后催化活性和催化剂结构都保持稳定.
文摘A postsynthetic modification method was used to prepare salicylaldehyde functionalized metal-organicframeworks through the nucleophilic addition of salicylaldehyde with the amine group present in the frameworks ofNH2-MIL-53（A1）. Hydroxyl groups were successfully grafted onto NI-I2-MIL-53（A1）, and imine groups were formed.Importantly, these hydroxyl and imine groups of the resulting NH2-MIL-53（A1）-SA can be used as the anchoringgroup to stabilise Au^3＋ ions and Au^0 nanoparticles（NPs）. By doing this, Au^3＋ ions and Au^0 NPs were successfully en-capsulated in the cages of NH2-MIL-53（A1） by a simple impregnation method. The resulting gold functionalizedNH2-MIL-53（AI） showed good catalytic activities in the one-pot synthesis of structurally divergent propargylaminesby three-component coupling reactions of aldehydes, amines and alkynes. Various aromatic/aliphatic aldehydes, aro-matic alkynes, and piperidine were able to undergo three-component coupling on NH2-MIL-53（A1）-Au. In addition,the catalyst NH2-M/L-53（A/）-Au was recovered easily by centrifugation and reused up to four times. Thus, it can beused for the environmentally friendly synthesis ofpropargylamines.
基金supported by National Natural Science Foundation of China(grant Nos.21701083,22179054)The Ministry of Science and Technology of the People's Republic of China(grant No.G2023014022L)Jiangsu Provincial Key Research and Development Program(grant No.BZ2023010).
文摘For all-solid-state lithium batteries(ASSLBs),polymer-blended solid composite electrolytes(SCEs)have drawn wide interest owing to their significance in improving the interfacial solid-solid contacts and inhibiting the growth of lithium dendrites.In this work,SCEs based on PVDF-HFP/PMMA matrix containing MOFs(NH2-MIL-53(Al))and LiTFSI were designed and synthesized employing an easy solution casting method.The synthesized samples were examined by XRD,SEM,EDS,and electrochemical tests.It was found that MPP-2 SCE not only has excellent ionic conductivity at 60℃ of 5.54×10^(−4) S cm^(−1),but also exhibits superior interfacial compatibility in Li||Li symmetric batteries,which can constantly cycle for about 800 h at 0.1 mA cm^(−2) with no short-circuiting.The assembled Li|MPP-2|LiFePO4 cell exhibited a first discharge specific capacity of up to 157.1 mAh g^(−1) at 60℃ and 0.2 C.This work may help to further advance the progress of ASSLBs in the future.
