二维金属-有机框架纳米片用作高效液相色谱手性固定相研究

采用溶剂热法合成出一种二维金属-有机框架纳米片Co-NH_(2)-BDC,将(1S)-(+)-10-樟脑磺酰氯衍生到Co-NH_(2)-BDC上,制备了手性材料Co-NH_(2)-BDC-(1S)-(+)-10-樟脑磺酰氯,并对Co-NH_(2)-BDC和手性材料Co-NH_(2)-BDC-(1S)-(+)-10-樟脑磺酰氯进行了表征。通过“网包法”制备了手性固定相,用于高效液相色谱(HPLC)对其拆分能力进行考察。Co-NH_(2)-BDC-(1S)-(+)-10-樟脑磺酰氯色谱柱共拆分了26种外消旋体和5种苯系位置异构体,且大部分手性化合物的分离效果较好,达到基线分离。该色谱柱在不同进样量和柱温下具有良好的分离能力和较好的重复性,说明Co-NH_(2)-BDC-(1S)-(+)-10-樟脑磺酰氯所制备的HPLC手性固定相分离效果良好,具有较好的应用前景。

微乳液法调控纳米Cu-MOF形貌的实验教学案例

通过微乳液法调控Cu-MOF的形貌,对其制备条件进行优化,得到各种不同形貌的Cu-MOF材料。为了开发材料化学实验与时俱进的教学案例,探究环己烷的用量、反应时间、反应温度等条件对Cu-MOF形貌的影响,从而优化实验细节以满足实验教学案例的要求,使得到的Cu-MOF材料具有重复性好、成本低廉、可行性高的优点。通过本实验教学案例,能够使学生掌握调控纳米MOFs形貌的技能。

超薄Sm-MOF纳米片的合成及可见光催化降解芥子气模拟剂性能

超薄金属-有机框架材料(MOFs)纳米片具有高密度、易暴露的表面活性位点、较短的底物/产物扩散路径等特点,是性能优异的异相催化剂.本文以光活性有机配体(H_(4)TBAPy)和镧系金属离子Sm^(3+)构筑光活性超薄MOFs纳米片,以苯甲酸作为调节剂,利用微波法快速合成了Sm-TBAPy二维纳米片.利用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射(XRD)、紫外-可见漫反射光谱(UV-Vis DRS)、傅里叶变换红外光谱(FTIR)和氮气吸附-脱附等手段表征了Sm-TBAPy二维纳米片的形貌、结构和组成.所合成的Sm-TBAPy为单分散二维纳米片,宽度约为200 nm,厚度约为12 nm,BET比表面为163 m^(2)/g,禁带宽度为2.62 eV.Sm-TBAPy二维纳米片在室温、氧气氛围和可见光照射条件下,可将芥子气模拟剂[2-氯乙基乙基硫醚(CEES)]高效、高选择性氧化成亚砜产物CEESO,且催化剂经过4次循环使用仍保持较高的催化性能.结合电子顺磁共振波谱,提出了Sm-TBAPy二维纳米片可见光催化氧化CEES的催化机理.

Highly Sensitive Detection of Strontium Ions Using Metal-Organic Frameworks Functionalized Solid-state Nanochannels

Strontium-90,a highly radioactive isotope,accumulates within the food chain and skeletal structure,posing significant risks to human health.There is a critical need for a sensitive detection strategy for Strontium-90 in complex environmental samples.Here,solid-state nanochannels,modified with metal-organic frameworks(MOF)and specific aptamers,were engineered for highly sensitive detection of strontium ion(Sr^(2+)).The synergistic effect between the reduced effective diameter of the nanochannels due to MOF and the specific binding of Sr^(2+) by aptamers amplifies the difference in ionic current signals,enhancing detection sensitivity significantly.The MOF-modified nanochannels exhibit highly sensitive detection of Sr^(2+),with a limit of detection(LOD)being 0.03 nmol·L^(-1),whereas the LOD for anodized aluminum oxide(AAO)without the modified MOF nanosheets is only 1000 nmol·L^(-1).These findings indicate that the LOD of Sr^(2+) detected by the MOF-modified nanochannels is approximately 33,000 times higher than that by the nanochannels without MOF modification.Additionally,the highly reliable detection of Sr^(2+) in various water samples was achieved,with a recovery rate ranging from 94.00%to 118.70%.This study provides valuable insights into the rapidly advancing field of advanced nanochannel-based sensors and their diverse applications for analyzing complex samples,including environmental contaminant detection,food analysis,medical diagnostics,and more.

Hierarchically porous S-scheme CdS/UiO-66 photocatalyst for efficient 4-nitroaniline reduction

Unveiling the pore-size performance of metal organic frameworks(MOFs)is imperative for controllable design of sophisticated catalysts.Herein,UiO-66 with distinct macropores and mesopores were intentionally created and served as substrates to create advanced CdS/UiO-66 catalysts.The pore size impacted the spatial distribution of CdS nanoparticles(NPs):CdS tended to deposit on the external surface of mesoporous UiO-66,but spontaneously penetrated into the large cavity of macroporous UiO-66 nanocage.Normalized to unit amount of CdS,the photocatalytic reaction constant of macroporous CdS/UiO-66 over 4-nitroaniline reduction was~3 folds of that of mesoporous counterpart,and outperformed many other reported state-of-art CdS-based catalysts.A confinement effect of CdS NPs within UiO-66 cage could respond for its high activity,which could shorten the electron-transport distance of NPs-MOFs-reactant,and protect the active CdS NPs from photocorrosion.The finding here provides a straightforward paradigm and mechanism to rationally fabricate advance NPs/MOFs for diverse applications.

Non-derivatized metal-organic framework nanosheets for water electrolysis:Fundamentals,regulation strategies and recent advances

Water splitting powered by clean electricity is a sustainable and promising approach to produce green hydrogen.Currently,noble metal(e.g.Iridium,Ruthenium,Platinum)-based catalysts are most widely used for water splitting electrolysis.However,noble metal-based catalysts often suffer from multiple disadvantages,including high cost,low selectivity and poor durability.The emergence of metal-organic framework nanosheets(MOFNSs)attracts significant attention due to their unique advantages.Here,a concise,yet comprehensive and critical,review of recent advances in the field of MOFNSs is provided.This review explains the fundamental oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)catalytic mechanisms as well as key characterization techniques for the structure-activity relationship study are discussed.Moreover,it discusses efficient design strategies and the brief research advances of MOFNSs in HER,OER,and bifunctional electrocatalysis,along with some challenges and opportunities.

Metal‐organic framework‐derived multifunctional photocatalysts

Metal‐organic framework(MOF)‐derived nanomaterials have attracted widespread attention,because the excellent features,such as high surface area,porosity and tunable properties are inherited from MOFs.Moreover,the derivatives avoid the poor conductivity and stability of MOFs.MOF‐derived nanomaterials can easily be regulated by a specific selection of metal nodes and organic linkers,resulting in multifunctionality in photocatalysis.MOF derivatives can be used not only as semiconductor photocatalysts,but also as co‐catalysts for photocatalytic hydrogen evolution,CO_(2) reduction,pollutants degradation,etc.This review focuses on the multifunctional applications of MOF derivatives in the field of photocatalysis.The researches in recent years are analyzed and summarized from the aspects of preparation,modification and application of MOF derivatives.At the end of the review,the development and challenges of MOF derivatives applied in photocatalysis in the future are put forward,in order to provide more references for further research in this field and bring new inspiration.

Solid-state synthesis of MoS2 nanorod from molybdenum-organic framework for efficient hydrogen evolution reaction

MoS2 is a promising candidate for catalyzing hydrogen evolution reaction (HER) due to its low cost and high activity. However, the poor conductivity and the stack of active sites of bulk MoS2 hinder its application. Herein, a new facile solid-state synthesis strategy was developed to fabricate MoS2 nanorods by one-step pyrolysis of molybdenum-organic framework (Mo-MOF) in the presence of thiourea. The obtained MoS2 keeps the Mo-MOF nanorod structure with more active sites, while the residual carbon left in the nanorod enhances the conductivity. The as-prepared MoS2 nanorods exhibit superior stability and excellent activity towards HER with a small onset potential of 96 mV and a low Tafel slope of 93 mV decade^-1.