MOFs/PEI混合基质膜的制备及CO_(2)分离性能研究

二氧化碳的分离和捕获对可持续发展具有重要意义。聚醚酰亚胺(PEI)具有优异的耐溶剂、耐高温、选择性高等优势,然而CO_(2)渗透性能低成为限制其进一步发展的关键瓶颈。通过引入2种三维MOFs颗粒[UIO-66和MIL^(-1)01(Cr)]及2种二维MOFs纳米片[CuBDC和Zn2(bim)4]制备了4种MOFs/PEI混合基质膜(MMMs),对膜的物理化学性质及CO_(2)分离性能展开深入研究。结果表明MOFs的引入大幅提高了PEI膜的CO_(2)扩散系数及分离性能,并改善了PEI膜的抗CO_(2)塑化性能。同时,相比三维MOFs颗粒,二维CuBDC纳米片与PEI表现出更高的相容性,其填料含量为20%时MMMs的CO_(2)渗透通量相比纯PEI膜提高了3.5倍,其CO_(2)/CH4选择性提高了2.2倍。以二维MOFs纳米片为功能性填料制备混合基质膜用于CO_(2)分离是一种有效的策略。

Single-atom Pd anchored in the porphyrin-center of ultrathin 2D-MOFs as the active center to enhance photocatalytic hydrogen-evolution and NO-removal

Single-atom catalysts were widely used to treat atmospheric pollution and alleviate energy crises through photocatalysis.However,how to prevent the aggregation of single atoms during the preparation and catalytic processes remained a great challenge.Herein,a novel ultrathin two-dimensional porphyrin-based single-atom photocatalyst Ti-MOF(abbreviated as TMPd)obtained through a simple hydrothermal synthesis strategy was used for photocatalytic hydrogen evolution and NO removal,in which the singleatom Pd tightly anchored in the center of porphyrin to ensure single-atom Pd stable existence.Compared with most reported MOFs-based photocatalysts,the TMPd showed an excellent hydrogen evolution rate(1.32 mmol g^(-1)h^(-1))and the NO removal efficiency(62%)under visible light irradiation.Aberrationcorrected high-angle annular dark-field scanning transmission electron microscope(HAADF-STEM)and synchrotron-radiation-based X-ray absorption fine-structure spectroscopy(XAFS)proved that pd in TMPd existed in an isolated state,and the atomic force microscope(AFM)proved the ultrathin morphology of TMPd.DFT calculations had demonstrated that single-atom Pd could serve as the active center and more effectively achieve electron transfer,indicating that single-atom Pd played a vital role in photocatalytic hydrogen evolution.In addition,a possible photocatalytic pathway of NO removal was proposed based on ESR and in-situ infrared spectra,in which the catalysts anchored with single-atom Pd could produce more active substances and more effectively oxidize NO to NO_(2)^(-)or NO_(3)^(-).The results suggested that coordinating single-atom metal species as the active site in the center of porphyrin could be a feasible strategy to obtain various ultrathin porphyrin-based single-atom photocatalysts to acquire excellent photocatalytic performance further.

Construction of 2D Zn‐MOF/BiVO_(4)S‐scheme heterojunction for efficient photocatalytic CO_(2) conversion under visible light irradiation

The construction of S‐scheme heterojunction photocatalysts has been regarded as an effective avenue to facilitate the conversion of solar energy to fuel.However,there are still considerable challenges with regard to efficient charge transfer,the abundance of catalytic sites,and extended light absorption.Herein,an S‐scheme heterojunction of 2D/2D zinc porphyrin‐based metal‐organic frameworks/BiVO_(4)nanosheets(Zn‐MOF/BVON)was fabricated for efficient photocatalytic CO_(2)conversion.The optimal one shows a 22‐fold photoactivity enhancement when compared to the previously reported BiVO4 nanoflake(ca.15 nm),and even exhibits~2‐time improvement than the traditional g‐C3N4/BiVO4 heterojunction.The excellent photoactivities are ascribed to the strengthened S‐scheme charge transfer and separation,promoted CO_(2)activation by the well‐dispersed metal nodes Zn_(2)(COO)_(4)in the Zn‐MOF,and extended visible light response range based on the results of the electrochemical reduction,electron paramagnetic resonance,and in‐situ diffuse reflectance infrared Fourier transform spectroscopy.The dimension‐matched Zn‐MOF/BVON S‐scheme heterojunction endowed with highly efficient charge separation and abundant catalytic active sites contributed to the superior CO2 conversion.This study offers a facile strategy for constructing S‐scheme heterojunctions involving porphyrin‐based MOFs for solar fuel production.

Size engineering of 2D MOF nanosheets for enhanced photodynamic antimicrobial therapy

Although porphyrin-based metal-organic frameworks(MOFs)have been widely explored as photosensitizers for photodynamic therapy,how the size will affect the light-induced catalytic activity for generation of reactive oxygen species(ROS)still remain unclear.Herein,we first report the size-controlled synthesis of two-dimensional(2D)porphyrin-based PCN-134 MOF nanosheets by a two-step solvothermal method to explore the size effect on its PDT performance,thus yielding enhanced photodynamic antimicrobial therapy.By simply controlling the reaction temperature in the synthesis process,the bulk PCN-134 crystal,large PCN-134(L-PCN-134)nanosheets with a lateral size of 2–3μm and thickness of 33.2–37.5 nm and small PCN-134 nanosheets(S-PCN-134)with a lateral size of 160–180 nm and thickness of 9.1–9.7 nm were successfully prepared.Interestingly,the S-PCN-134 nanosheets exhibit much higher photodynamic activity for ROS generation than that of the bulk 3D PCN-134 crystal and L-PCN-134 nanosheets under a660 nm laser irradiation,suggesting that the photodynamic activity of PCN-134 MOF increases when the size reduces.Therefore,the S-PCN-134 nanosheets show much enhanced performance when used as a photosensitizer for photodynamic antimicrobial activity and wound healing.

Ultrathin two-dimensional porphyrinic metal-organic framework nanosheets induced by the axial aryl substituent

Ultrathin two-dimensional metal-organic framework nanosheets have emerged as a promising kind of heterogeneous catalysts. Herein, we report a new kind of 2D porphyrinic metal-organic framework nanosheets of Rh2-PCN-222, which was prepared from the self-assembly of the metalloporphyrin ligand Rh(TCPP)(DCB)(TCPP = 5,10,15,20-tetrakis(4-methoxycarbonylphenyl)porphyrin;DCB = 3,4-dichlorobenzene) and ZrCl_(4) in the presence of two kinds of monocarboxylic acids as the modulating reagent. The thickness of Rh2-PCN-222 nanosheets was characterized by atomic force microscopy(AFM)and determined to be 5.4-9.6 nm. It was found that the axial aryl dichlorophenyl substituent, which controlled the anisotropic growth of MOFs, was essential for the formation of nanosheets. Catalytic results showed that Rh2-PCN-222 nanosheets were efficient for CO_(2) transformation.

Thermal expansion-quench of nickel metal-organic framework into nanosheets for efficient visible light CO_(2) reduction

Metal-organic framework nanosheets (MOF NNs) offer potential opportunities for many applications,but an efficient strategy for the scalable preparation of few-layered two-dimensional (2D) MOF NNs are still a major challenge.Herein,we present an efficient top-down method for the synthesis of the Ni-BDC(Ni_(2)(OH)_(2)(1,4-BDC);1,4-BDC=1,4-benzenedicarboxylate) nanosheets utilizing a novel thermal expansionquench method of the flowerlike bulky MOFs in liquid N2.The obtained Ni-BDC nanosheets exhibit significantly enhanced photocatalytic performance of reductive CO_(2)deoxygenation (7.0μmol h^(-1)mg^(-1)) under visible light illumination compared with the bulky MOFs,due to much higher surface area for CO_(2)adsorption,more abundant active sites exposed and stronger electron transport ability of the nanosheets.More importantly,this synthetic strategy can be extended to fabricate other MOF nanosheets which also exhibit significantly improved performance for deoxygenative CO_(2)reduction compared to their bulky counterparts.This work may provide a guideline for preparing other 2D layered photocatalysts materials to realize energy conversion applications.

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.

Emerging porous nanosheets:From fundamental synthesis to promising applications

Metal-organic framework(MOF)nanosheets and covalent organic framework(COF)nanosheets as emerging porous materials nanosheets have captured increasing attention owing to their attractive properties originating from the advantages of large lateral size,ultrathin thickness,tailorable physiochemical environment,flexibility and highly accessible active sites on surface,and the applications of them have been explored in a wide range of fields.Although MOF and COF nanosheets own many similar properties,their applications in various fields show significant differences,probably due to their different compositions and bonding modes.Hence,we summarize the recent progress of MOF and COF nanosheets by comparative analysis on their advantages and limitations in synthesis and applications,providing a more profound and full-scale perspective for researchers or beginners to understand this field.Herein,the categories of preparation methods of MOF and COF nanosheets are firstly discussed,including top-down and bottom-up methods.Secondly,the applications of MOF and COF nanosheets for separation,catalysis,sensing and energy storage are summarized.Finally,based on current achievements,we put forward our personal insights into the challenges and outlooks on the synthesis,characterizations,and promising applications for future research of MOF and COF nanosheets.

2-D/2-D heterostructured biomimetic enzyme by interfacial assembling Mn_(3)(PO_(4))_(2) and MXene as a flexible platform for realtime sensitive sensing cell superoxide

It is critical for fabricating flexible biosensors with both high sensitivity and good selectivity to realize real-time monitoring superoxide anion(O_(2)^(·−)),a specific reactive oxygen species that plays critical roles in various biological processes.This work delicately designs a Mn_(3)(PO_(4))_(2)/MXene heterostructured biomimetic enzyme by assembling two-dimensional(2-D)Mn_(3)(PO_(4))_(2) nanosheets with biomimetic activity and 2-D MXene nanosheets with high conductivity and abundant functional groups.The 2-D nature of the two components with strong interfacial interaction synergistically enables the heterostructure an excellent flexibility with retained 100%of the response when to reach a bending angle up to 180°,and 96%of the response after 100 bending/relaxing cycles.It is found that the surface charge state of the heterostructure promotes the adsorption of O_(2)^(·−),while the high-energy active site improves electrochemical oxidation of O_(2)^(·−).The Mn_(3)(PO_(4))_(2)/MXene as a sensing platform towards O2•−achieves a high sensitivity of 64.93µA·µM^(−1)·cm^(−2),a wide detection range of 5.75 nM to 25.93µM,and a low detection limit of 1.63 nM.Finally,the flexible heterostructured sensing platform realizes real-time monitoring of O_(2)^(·−)in live cell assays,offering a promising flexible biosensor towards exploring various biological processes.

Dimensional reduction enhances photocatalytic carbon dioxide reduction performance of metal-organic frameworks

Metal-organic frameworks(MOFs)have shown significant potential as photocatalysts.It has been widely assumed that all catalytic active sites within MOFs are functional in photocatalytic reactions but for a three-dimensional MOF,whether the internal catalytic active sites can effectively absorb light and actively contribute to photocatalytic reactions remains to be explored.In this context,we synthesized a two-dimensional nanosheet MOF(2D-MOF)and a three-dimensional bulk MOF(3D-MOF)composed of Zr^(6) clusters and tetracarboxylic porphyrin(TCPP)by the approach described in the literature.Re(bpy)(CO)^(3)Cl(bpy=2,2’-bipyridine),which has remarkable CO_(2) photoreduction ability,was introduced to the two MOFs to create two new photocatalysts 2D-MOF-Re and 3D-MOF-Re,respectively.Photocatalytic CO_(2) reduction experiments show that based on the equal number of catalytic active sites,the CO turnover number(TON)of 2D-MOF-Re reaches 27.8 in 6 h,which is 50 times that of 3D-MOF-Re.The result shows that certain catalytic active sites inside the bulk MOF are inactive due to the inability to absorb light.This study illuminates the potential of the dimensional reduction approach in the design of photocatalysts to exploit the capabilities fully.