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Journal articles on the topic 'Porus Framework'

Author: Grafiati

Published: 6 September 2023

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1

Mizutani, Yoichiro, Masateru Hattori, Masahiko Okuyama, Toshihiro Kasuga, and Masayuki Nogami. "Preparation of Porous Composites with a Porous Framework Using Hydroxyapatite Whiskers and Poly(L-Lactic Acid) Short Fibers." Key Engineering Materials 309-311 (May 2006): 1079–82. http://dx.doi.org/10.4028/www.scientific.net/kem.309-311.1079.

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A new type of porous composite with a porous framework was prepared using a mixture of hydroxyapatite whiskers (W-HA) and poly(L-lactic acid) short fibers (F-PLLA) by a particle-leaching technique. The material, composed of a porous framework with interconnecting pore of >1 µm, has large-sized pores of about 200 µm. The large-sized pores were formed by leaching sucrose granules. The porosity can be controlled in the range from 60 to 85 % by the sucrose content. The small-sized pores in the framework formed due to the poor densification of the W-HAs / F-PLLAs mixture. The pore distribution in the framework can be controlled by the compressing pressure without change in the distribution of large-sized pores.

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2

Alves Brito-Neto, Jose Geraldo, Taku Matsuzaka, Yosuke Saito, and Masanori Hayase. "Porous Metal Frameworks on Silicon Substrates." Advances in Science and Technology 54 (September 2008): 416–21. http://dx.doi.org/10.4028/www.scientific.net/ast.54.416.

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In this work, we describe the use of porous Si as a base material for the production of porous metal layers by a galvanic displacement reaction. We have applied this process for the production of porous Pt, Au, Ru and Pd layers. By adding HF to the reaction bath, we achieve a virtually complete displacement of Si by the metal. We have worked with porous Si samples of different morphologies, obtained on differently doped Si substrates, and studied the influence of the chemical nature of the metal precursor on the morphology of the porous metal layer produced. The samples were studied by SEM with EDS, BET analysis, and voltammetry. Porous metal layers comprising random agglomerates of spherical particles with diameters between 50 and 100 nm are usually obtained, while the original porous Si samples show arrays of straight pores. With Au, using its ethylenediamine complex, the original straight pore morphology could be preserved.

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3

Wang, Sue-Lein. "Mesoporous Metal Phosphites with 3D Crystalline Frameworks." Acta Crystallographica Section A Foundations and Advances 70, a1 (August 5, 2014): C1119. http://dx.doi.org/10.1107/s2053273314088809.

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The synthesis of crystalline porous solids is of great importance in the area of materials chemistry. Naturally occurring zeolites are mostly crystalline; however, they possess pores/channels that only allow small species smaller than 1 nm in diameter to pass through. One exception is the mineral cacoxenite, containing 36-membered ring (36R) channels that allow guest species of up to 1.41 nm in diameter to pass through. In the past, much effort has been devoted to the development of zeolitic materials. Even though multi-faceted design strategies were utilized, the discovery of larger inorganic channels was often accidental. Compared with amorphous mesoporous silicates that contain synthetically tunable pores, zeolitic crystalline structures lack rational synthesis routes. In general, molecular templating leads to crystalline frameworks whereas organized assemblies that are able to produce much larger pores lead to noncrystalline frameworks. Synthetic methods that generate crystallinity from both discrete and organized templates represent a viable design strategy for the development of crystalline porous inorganic frameworks spanning both the micro and the meso regimes. We show by integrating templating mechanisms for both zeolites and mesoporous silica in a single system, the channel size for gallium zincophosphites can be tuned systematically up to 64R and 72R. With apertures of 3.5 nm, the new compounds represent the first non-disordered structures for mesoporous solids. Through the use of long straight-chain alkyl monoamines as templates, three common building blocks are induced that repeatedly self assemble into two isotypic porous frameworks with the ability to increasingly enlarge channel size. The rational design of crystalline porous metal oxides is achieved for the first time. A general formula was derived to predict new members with even larger channels along with their individual space group symmetry.

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4

Li, Pei-Zhou, Jie Su, Jie Liang, Jia Liu, Yuanyuan Zhang, Hongzhong Chen, and Yanli Zhao. "A highly porous metal–organic framework for large organic molecule capture and chromatographic separation." Chemical Communications 53, no. 24 (2017): 3434–37. http://dx.doi.org/10.1039/c7cc01063j.

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5

Zharkov, Evgeny. "Post-Normal Times Laboratory." Philosophy. Journal of the Higher School of Economics V, no. 4 (December 31, 2021): 65–77. http://dx.doi.org/10.17323/2587-8719-2021-4-65-77.

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Nowadays, for science as a type of activity and a socio-cultural institution, the question of the boundaries of its own agency is extremely relevant. Various global challenges (energy, climate, pandemics, security, etc.) are in tune with the challenges for the very concept of science, for its norms and values. In a discussion article, V.N. Porus and V.A. Bazhanov discuss aspects of the political agency of post-normal science (J. Ravetz, S. Funtowicz) — a type of science that claims to go beyond normal science (T. Kuhn) as a process simple and definite solution of problems within the framework of the prevailing paradigms. This article discusses aspects of the political subjectivity of science in the language of locations, the most important of which is the laboratory, understood in broad socio-cultural and socio-epistemic aspects. With the involvement of historical and scientific (atomic-nuclear problem) and modern situational cases (COVID-19), the problems of the relationship between “scientific” and “political” in the location of the expanded laboratory are considered. In the extended laboratory, the situational realization of the political agency of science is carried out. It is emphasized that science has not yet acquired the status of an independent and full-fledged political agency, and the corresponding institutionalization. The political agency of science is specific and episodic. Loaded with complexity and uncertainty modernity is considered by a number of authors at the present time as a post-normal times. It is noted that in the light of the post-normal nature of modernity while striving for political subjectivity, science (at the level of a multitude of participating actors) should not change its “personal ontology” (responsibility for the truth), which is difficult to achieve without an appeal to the virtue of wisdom.

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6

Li, Xiao-Hui, Yi-Wei Liu, Shu-Mei Liu, Shuang Wang, Li Xu, Zhong Zhang, Fang Luo, Ying Lu, and Shu-Xia Liu. "A gel-like/freeze-drying strategy to construct hierarchically porous polyoxometalate-based metal–organic framework catalysts." Journal of Materials Chemistry A 6, no. 11 (2018): 4678–85. http://dx.doi.org/10.1039/c7ta10334d.

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7

Wang, Zi, and Zhongyu Hou. "Room-temperature fabrication of a three-dimensional porous silicon framework inspired by a polymer foaming process." Chemical Communications 53, no. 63 (2017): 8858–61. http://dx.doi.org/10.1039/c7cc04309k.

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8

Park, Seung-Keun, Jin-Sung Park, and Yun Chan Kang. "Selenium-infiltrated metal–organic framework-derived porous carbon nanofibers comprising interconnected bimodal pores for Li–Se batteries with high capacity and rate performance." Journal of Materials Chemistry A 6, no. 3 (2018): 1028–36. http://dx.doi.org/10.1039/c7ta09676c.

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9

Lee, Seonghwan, Seok Jeong, Junmo Seong, Jaewoong Lim, Amitosh Sharma, Somi Won, Dohyun Moon, Seung Bin Baek, and Myoung Soo Lah. "Solvent-mediated framework flexibility of interdigitated 2D layered metal–organic frameworks." Materials Chemistry Frontiers 5, no. 9 (2021): 3621–27. http://dx.doi.org/10.1039/d1qm00251a.

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The 2D framework with guest molecules in the solvent pores shows reversible framework expansion and contraction, whereas the 2D framework without guest molecules does not show framework expansion under the same conditions.

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10

Wang, Zhen, Yan-Qun Liu, Yu-Hang Zhao, Qing-Pu Zhang, Yu-Ling Sun, Bin-Bin Yang, Jian-Hua Bu, and Chun Zhang. "Highly covalent molecular cage based porous organic polymer: pore size control and pore property enhancement." RSC Advances 12, no. 26 (2022): 16486–90. http://dx.doi.org/10.1039/d2ra02343a.

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11

Wang, Zhen, Yan-Qun Liu, Yu-Hang Zhao, Qing-Pu Zhang, Yu-Ling Sun, Bin-Bin Yang, Jian-Hua Bu, and Chun Zhang. "Highly covalent molecular cage based porous organic polymer: pore size control and pore property enhancement." RSC Advances 12, no. 26 (2022): 16486–90. http://dx.doi.org/10.1039/d2ra02343a.

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12

Han, Shao Wei, Wei Min Wang, Zheng Yi Fu, and Hao Wang. "Preparation of Titanium Diboride Reticulated Porous Ceramics." Key Engineering Materials 368-372 (February 2008): 964–66. http://dx.doi.org/10.4028/www.scientific.net/kem.368-372.964.

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Using a reticulated polyurethane sponge with interconnected pores as primal framework and immersing into TiB2 slurry consisting of Ni and Mo as sintering additives, a porous TiB2 ceramics with high porosity and interconnected pores was prepared by immersing and high temperature sintering process. The rheology of TiB2 slurry which used silica sol as a binder was studied. The optimum condition of the slurry suitable for impregnating the polyurethane sponge was obtained. The flexural strength of the porous reticulated TiB2 ceramics can reach 1 MPa.

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13

Tanaka, Daisuke, and Susumu Kitagawa. "Captured Molecules in Coordination Frameworks." MRS Bulletin 32, no. 7 (July 2007): 540–43. http://dx.doi.org/10.1557/mrs2007.103.

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In recent years, a new class of porous materials based on a combination of organic components and metal centers has emerged, namely, microporous coordination polymers (MCPs), in which the chemical properties as well as the pore dimensions affect the incorporation of “guest” molecules within the pores. In this article, we describe the ability of MCPs to store gas molecules, which is ascribed to framework regularity and high porosity, and the unique capacity of certain MCPs to capture molecules selectively by well-defined interactions with organic functional groups.

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14

Yang, Lu, Yong Dou, Zhen Zhou, Daopeng Zhang, and Suna Wang. "A Versatile Porous Silver-Coordinated Material for the Heterogeneous Catalysis of Chemical Conversion with Propargylic Alcohols and CO2." Nanomaterials 9, no. 11 (November 5, 2019): 1566. http://dx.doi.org/10.3390/nano9111566.

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The efficient transformation of carbon dioxide into useful chemical feedstock is of great significance, attracting intense research interest. The widely studied porous-coordinated polymers possess large pores to adsorb guest molecules and further allow the contact and to transfer the substrate molecule within their microenvironment. Here we present the synthesis of a silver-based metal-organic frameworks (MOFs) material with a three-dimensional structure by incorporating a tetraphenyl-ethylene moiety as the four-point connected node via the solvothermal method. This polymer exhibits as an efficient heterogeneous catalyst for the carboxylative cyclization of CO2 to α-methylene cyclic carbonates in excellent yields. Moreover, the introduction of silver (Ag (I)) chains in this framework shows the specific alkynophilicity to activate C≡C bonds in propargylic alcohols to greatly accelerate the efficient conversion, and the large pores in the catalyst exhibit a size-selective catalytic performance.

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15

Raptopoulou, Catherine P. "Metal-Organic Frameworks: Synthetic Methods and Potential Applications." Materials 14, no. 2 (January 9, 2021): 310. http://dx.doi.org/10.3390/ma14020310.

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Metal-organic frameworks represent a porous class of materials that are build up from metal ions or oligonuclear metallic complexes and organic ligands. They can be considered as sub-class of coordination polymers and can be extended into one-dimension, two-dimensions, and three-dimensions. Depending on the size of the pores, MOFs are divided into nanoporous, mesoporous, and macroporous items. The latter two are usually amorphous. MOFs display high porosity, a large specific surface area, and high thermal stability due to the presence of coordination bonds. The pores can incorporate neutral molecules, such as solvent molecules, anions, and cations, depending on the overall charge of the MOF, gas molecules, and biomolecules. The structural diversity of the framework and the multifunctionality of the pores render this class of materials as candidates for a plethora of environmental and biomedical applications and also as catalysts, sensors, piezo/ferroelectric, thermoelectric, and magnetic materials. In the present review, the synthetic methods reported in the literature for preparing MOFs and their derived materials, and their potential applications in environment, energy, and biomedicine are discussed.

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16

Raptopoulou, Catherine P. "Metal-Organic Frameworks: Synthetic Methods and Potential Applications." Materials 14, no. 2 (January 9, 2021): 310. http://dx.doi.org/10.3390/ma14020310.

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Metal-organic frameworks represent a porous class of materials that are build up from metal ions or oligonuclear metallic complexes and organic ligands. They can be considered as sub-class of coordination polymers and can be extended into one-dimension, two-dimensions, and three-dimensions. Depending on the size of the pores, MOFs are divided into nanoporous, mesoporous, and macroporous items. The latter two are usually amorphous. MOFs display high porosity, a large specific surface area, and high thermal stability due to the presence of coordination bonds. The pores can incorporate neutral molecules, such as solvent molecules, anions, and cations, depending on the overall charge of the MOF, gas molecules, and biomolecules. The structural diversity of the framework and the multifunctionality of the pores render this class of materials as candidates for a plethora of environmental and biomedical applications and also as catalysts, sensors, piezo/ferroelectric, thermoelectric, and magnetic materials. In the present review, the synthetic methods reported in the literature for preparing MOFs and their derived materials, and their potential applications in environment, energy, and biomedicine are discussed.

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17

Williams, Teresa E., Daniela Ushizima, Chenhui Zhu, André Anders, Delia J. Milliron, and Brett A. Helms. "Nearest-neighbour nanocrystal bonding dictates framework stability or collapse in colloidal nanocrystal frameworks." Chemical Communications 53, no. 35 (2017): 4853–56. http://dx.doi.org/10.1039/c6cc10183f.

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18

Yun, Jonghyeok, Hong Rim Shin, Eun-Seo Won, and Jong-Won Lee. "Li Metal Storage in Porous Carbon Frameworks: Effect of Li–Substrate Interaction." ECS Meeting Abstracts MA2022-01, no. 4 (July 7, 2022): 529. http://dx.doi.org/10.1149/ma2022-014529mtgabs.

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Lithium-metal electrodes are of particular interest for next-generation rechargeable batteries because of their high specific capacity and low redox potential. Therefore, Li-metal-based batteries may afford higher energy densities than commercially available Li-ion batteries with graphite anodes. However, various bottlenecks have hampered the commercial development of these batteries, including uncontrolled Li dendrite formation and huge volume changes during cycling. Consequently, Li-metal batteries suffer from low Coulombic efficiency and poor cycling stability. In recent years, there has been extensive research on the design and construction of three-dimensional (3D) porous electrodes that can host metallic Li. However, the low pore utilization and uneven Li plating remain crucial issues. This can be understood in terms of electronic and ionic transport through the framework electrode. The carbon frameworks exhibit high electronic conductance; however, large resistance to Li+ migration in the electrolytes of internal and interparticle pores inhibits the penetration of Li+ deep into the electrode. In this work, we demonstrate that a strong interaction between Li and a lithiophilic nanolayer on a substrate plays a critical role in enhancing pore utilization in carbon framework electrodes. As a model architecture, we examine a Li storage process in a framework electrode consisting of porous carbon derived from metal-organic frameworks (MOFs) and a galvanically displaced Ag layer on a Cu substrate (Cu@Ag). The electrochemical experiments combined with operando XRD measurements and microstructural characterizations suggest that a lithiophilic Ag on the Cu substrate preferentially reacts with Li+ to form Li x Ag during the initial stage of Li plating. This Li x Ag phase acts as a seed that can regulate the subsequent Li plating, promoting confined Li storage in the carbon framework electrode while suppressing top plating. Because of these advantages, the MOF-C framework electrode on Cu@Ag exhibits better cycling stability (>250 cycles) than the MOF-C framework electrode on Cu (140cycles). However, when the thickness of the MOF-C framework is increased to 90 μm, the diffraction peak for Ag remains dominant throughout Li plating-stripping, and the formation of Li x Ag alloys is not clearly detectable in the diffraction patterns, suggesting that only a limited amount of Ag is involved in the alloying reaction with Li+. Based on the computational studies, the efficacy of lithiophilic layers toward improving pore utilization is discussed in terms of the kinetic competition between Li+ transport through porous channels and the interfacial reaction of Li+ with the substrate. This study conveys an important message that the Li-substrate interaction plays a vital role in promoting the confined Li storage; hence, it should be considered a key design factor for porous carbon frameworks with high capacity and long cycle lifetime. References Yun, H. R. Shin, E.-S. Won, H. C. Kang, J.-W. Lee, Confined Li metal storage in porous carbon frameworks promoted by strong Li-substrate interaction, Chem. Eng. J. 430 (2022) 132897. Jin, Y. Ye, Y. Niu, Y. Xu, H. Jin, J. Wang, Z. Sun, A. Cao, X. Wu, Y. Luo, H. Ji, L. J. Wan, Solid-solution-based metal alloy phase for highly reversible lithium metal anode, J. Am. Chem. Soc. 142 (2020) 8818–8826. Kim, J. Lee, J. Yun, S.H. Choi, S.A. Han, J. Moon, J.H. Kim, J.-W. Lee, M.-S. Park, Functionality of dual-phase lithium storage in a porous carbon host for lithium-metal anode, Adv. Funct. Mater. 30 (2020) 1910538.

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19

Maji, Tapas Kumar, and Susumu Kitagawa. "Chemistry of porous coordination polymers." Pure and Applied Chemistry 79, no. 12 (January 1, 2007): 2155–77. http://dx.doi.org/10.1351/pac200779122155.

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Remarkable advances in the recent development of porous compounds based upon coordination polymers have paved the way toward functional chemistry having potential applications such as gas storage, separation, and catalysis. From the synthetic point of view, the advantage is a designable framework, which can readily be constructed from building blocks, the so-called bottom-up assembly. Compared with conventional porous materials such as zeolites and activated carbons, porous inorganic-organic hybrid frameworks have higher potential for adsorption of small molecules because of their designability with respect to the coordination geometry around the central metal ion as well as size and probable multifunctionality of bridging organic ligands. Although rigidity and robustness of porous framework with different degree of adsorption are the most studied properties of metal-organic coordination frameworks, there are few studies on dynamic porous frameworks, which could open up a new dimension in materials chemistry.

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20

Zhang, An-An, Xiyue Cheng, Xu He, Wei Liu, Shuiquan Deng, Rong Cao, and Tian-Fu Liu. "Harnessing Electrostatic Interactions for Enhanced Conductivity in Metal-Organic Frameworks." Research 2021 (October 21, 2021): 1–11. http://dx.doi.org/10.34133/2021/9874273.

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The poor electrical conductivity of metal-organic frameworks (MOFs) has been a stumbling block for its applications in many important fields. Therefore, exploring a simple and effective strategy to regulate the conductivity of MOFs is highly desired. Herein, anionic guest molecules are incorporated inside the pores of a cationic MOF (PFC-8), which increases its conductivity by five orders of magnitude while maintaining the original porosity. In contrast, the same operation in an isoreticular neutral framework (PFC-9) does not bring such a significant change. Theoretical studies reveal that the guest molecules, stabilized inside pores through electrostatic interaction, play the role of electron donors as do in semiconductors, bringing in an analogous n-type semiconductor mechanism for electron conduction. Therefore, we demonstrate that harnessing electrostatic interaction provides a new way to regulate the conductivity of MOFs without necessarily altering the original porous structure. This strategy would greatly broaden MOFs’ application potential in electronic and optoelectronic technologies.

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21

Lin, C., C. Xiao, and Z. Shen. "Nano pores evolution in hydroxyapatite microsphere during spark plasma sintering." Science of Sintering 43, no. 1 (2011): 39–46. http://dx.doi.org/10.2298/sos1101039l.

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Micron-spherical granules of hydroxyapatite (HAp) nanoparticles were prepared by powder granulation methods. Through subsequent sintering, porous HAp microspheres with tailored pore and grain framework structures were obtained. Detailed microstructure investigation by SEM and TEM revealed the correlation of the pore structure and the necking strength with the sintering profiles that determine the coalescence features of the nanoparticles. The partially sintered porous HAp microspheres containing more than 50% porosity consisting of pores and grains both in nano-scale are active in inducing the precipitation of HAp in simulated body fluid. The nano-porous HAp microspheres with an extensive surface and interconnecting pores thus demonstrate the potential of stimulating the formation of collagen and bone and the integration with the newly formed bones during physiological bone remodeling.

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22

Smithenry, Dennis W., Scott R. Wilson, Shirley Nakagaki, and Kenneth S. Suslick. "Sorption and catalysis by robust microporous metalloporphyrin framework solids." Journal of Porphyrins and Phthalocyanines 21, no. 12 (December 2017): 857–69. http://dx.doi.org/10.1142/s1088424617500791.

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Two isostructural metalloporphyrin framework solids have been synthesized. Both frameworks contains manganese(III) metal complexes of trans-dicarboxylateporphyrins whose peripheralcarboxylates coordinate the edges of tetrahedral Zn4O[Formula: see text] clusters; the two metalloporphyrins explored are Mn(III) and Co(II). The cubic interpenetrated frameworks have 72% free volume and 4 × 7 Å averaged size pores. The evacuated frameworks are robust and retain a structure open to the sorption of substrates with medium polarity. The manganese porphyrin framework catalyzes the hydroxylation of cyclic and linear alkanes with iodosylbenzene as oxidant in a size- and polarity-selective manner. In addition, the catalysis was found to occur within the pores, making this a rare case of porphyrin framework solid with interior catalysis.

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23

Barsukova, Marina, Evgeny Dudko, Denis Samsonenko, Konstantin Kovalenko, Alexey Ryadun, Aleksandr Sapianik, and Vladimir Fedin. "Influence of Substituents in Terephthalate Linker on the Structure of MOFs Obtained from Presynthesized Heterometallic Complex." Inorganics 9, no. 1 (January 2, 2021): 4. http://dx.doi.org/10.3390/inorganics9010004.

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The synthesis of new porous materials with desired properties is a challenging task. It becomes especially difficult if you need to combine several metals in one framework to obtain a heterometallic node. The use of presynthesized complexes for obtaining of new heterometallic metal–organic frameworks could be essential to solve the problem of tailored synthesis. In our study we use presynthesized heterometallic pivalate complex [Li2Zn2(piv)6(py)2] to obtain new MOFs with heterometallic core as a node of the framework. We are managed to obtain four new heterometallic MOFs: [H2N(CH3)2]2[Li2Zn2(bdc)4]·CH3CN·DMF (1), [Li2Zn2(H2Br2-bdc)(Br2-bdc)3]·2DMF (2), [H2N(CH3)2][LiZn2(ndc)3]·CH3CN (3) and [{Li2Zn2(dmf)(py)2}{LiZn(dmf)2}2 (NO2-bdc)6]·5DMF (4). Moreover three of them contain starting tetranuclear core {Li2Zn2} and saves its geometry. We also demonstrate the influence of substituent in terephthalate ring on preservation of tetranuclear core. For compound 1 it was shown that luminescence of the framework could be quenched when nitrobenzene is included in the pores.

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24

Boldyreva, O. Yu. "The propagation of surface waves in a cylindrical cavity in a saturated porous medium." Proceedings of the Mavlyutov Institute of Mechanics 5 (2007): 107–12. http://dx.doi.org/10.21662/uim2007.1.010.

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The frequency dependencies of velocity and attenuation of waves propagating along the fluid-filled cylindrical cavity in a saturated porous medium are investigated. The study is made in the framework of two velocity, two stress model of the porous medium, taking into account the non-stationary forces of interphase interaction. On the boundary between the fluid and the porous medium two types of boundary conditions, i.e. open and closed pores, are considered. It is found that the most significant impact on the velocity and attenuation of the primary acoustic mode in a cylindrical waveguide in a porous medium has a permeability of the porous medium

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25

Kim, Hyunwoo, Nayeong Kim, and Jungki Ryu. "Porous framework-based hybrid materials for solar-to-chemical energy conversion: from powder photocatalysts to photoelectrodes." Inorganic Chemistry Frontiers 8, no. 17 (2021): 4107–48. http://dx.doi.org/10.1039/d1qi00543j.

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26

Carrington, Elliot J., Iñigo J. Vitórica-Yrezábal, and Lee Brammer. "Crystallographic studies of gas sorption in metal–organic frameworks." Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials 70, no. 3 (May 24, 2014): 404–22. http://dx.doi.org/10.1107/s2052520614009834.

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Metal–organic frameworks (MOFs) are a class of porous crystalline materials of modular design. One of the primary applications of these materials is in the adsorption and separation of gases, with potential benefits to the energy, transport and medical sectors.In situcrystallography of MOFs under gas atmospheres has enabled the behaviour of the frameworks under gas loading to be investigated and has established the precise location of adsorbed gas molecules in a significant number of MOFs. This article reviews progress in such crystallographic studies, which has taken place over the past decade, but has its origins in earlier studies of zeolites, clathratesetc. The review considers studies by single-crystal or powder diffraction using either X-rays or neutrons. Features of MOFs that strongly affect gas sorption behaviour are discussed in the context ofin situcrystallographic studies, specifically framework flexibility, and the presence of (organic) functional groups and unsaturated (open) metal sites within pores that can form specific interactions with gas molecules.

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27

Plonka, Anna, Debasis Banerjee, William Woerner, and John Parise. "In situ studies of gas sorption in porous networks." Acta Crystallographica Section A Foundations and Advances 70, a1 (August 5, 2014): C1468. http://dx.doi.org/10.1107/s2053273314085313.

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Selective gas separation is one of the key properties exploited in industrial processes utilizing porous materials. The crystal structure of the native and activated frameworks, along with those of ion exchanged and otherwise modified variants, provide the basis for rational development of gas-selective nanoporous solids. In situ scattering studies of gas-loaded materials provide an understanding of the nature of interactions between sorbed gas and pore surface, which can be vital to development of reliable interatomic potentials, used simulating adsorption behavior. We find that simultaneous observation of the Differential Scanning Calorimetry coupled with x-ray diffraction (DSC-XRD) measurements is a particularly powerful tool 1, 2. The powder diffraction pattern can be monitored for changes, such as framework collapse, as porous materials are heated and activated. Apart from monitoring structural changes, thermal responses accompanying dynamic exposure to gases at variable humidity, and as the temperature is varied, provides a reliable tool in order to screen for new and potentially selective porous materials. The DSC signal provides a reliable means to determine the enthalpy of interaction between framework and gas, and there is experimental evidence this signal may distinguish between gas interactions with bare metal sites in the activated framework and other gas-framework interactions. Studies where the enthalpy of interaction and X-ray scattering from low angle peaks, which are most sensitive to the filling and evacuation of pores of the porous materials are monitored, can be coupled with varying the nature of the gas and the relative humidity. These studies are conveniently carried out with a modified gas manifold interfaced to a slightly modified Rigaku corporation DSC-XRD, which allows studies from about 150 – 600 K. Illustrative examples of the use of this laboratory based equipment, which provide the underpinnings of detailed single crystal studies of gas-loaded materials, include studies of porous calcium based coordination network (CaSDB, SDB: 4,4' - sulfonyldibenzoate), which is selective for CO2, even in the presence of high relative humidity (RH). Recent results from a series of materials studied in the home laboratory and at synchrotron sources will be presented.

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28

Liu, Bo, Ya-Hui Jiang, Zhi-Sen Li, Lei Hou, and Yao-Yu Wang. "Selective CO2 adsorption in a microporous metal–organic framework with suitable pore sizes and open metal sites." Inorganic Chemistry Frontiers 2, no. 6 (2015): 550–57. http://dx.doi.org/10.1039/c5qi00025d.

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A new microporous framework was constructed from uncommon ternary SBUs with a rare (5,5,5)-connected topology, which contains pores of suitable sizes and a high polarity porous system, exhibits a higher uptake capacity for CO₂ and is highly selective for CO₂ over N₂ and CH₄ gases.

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29

Ebrahim, Asma, Mohsen Ghali, and Ahmed Abd El-Moneim. "Enhancing Thermoelectric Properties of Conductive Polymers Using Zr-Metal-Organic Frameworks Composite Materials." Materials Science Forum 1053 (February 17, 2022): 104–8. http://dx.doi.org/10.4028/p-5w654u.

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Controlling the polymerization of polypyrrole (Ppy) in presence of Zr-based metal organic-framework (Zr-MOFs) using sodium dodecyl sulphonate (SDS) as a dopant, leads to the formation of a new class of thermoelectric materials based on conducting polymer and highly porous MOFs with enhanced properties for energy production applications. The polymerization of polypyrrole in the Zr-Fumerate pores leads to the formation of homogenously coated MOF-spheres with high crystalinity and a high degree of improvement in many electrical properties such as conductivity and carrier mobility. The figure shows the movement of the electrons from the hot to the cold side in the aligned polymer inside the MOF pores.

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Cui, Fengjuan, Qingfang Deng, and Li Sun. "Prussian blue modified metal–organic framework MIL-101(Fe) with intrinsic peroxidase-like catalytic activity as a colorimetric biosensing platform." RSC Advances 5, no. 119 (2015): 98215–21. http://dx.doi.org/10.1039/c5ra18589k.

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Nanosized porous PB/MIL-101(Fe) was facilely prepared by growing Prussian blue (PB) on MIL-101(Fe). It has more active sites and pores for peroxidase substrates and gives a simple, sensitive colorimetric assay to detect H₂O₂and glucose.

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Su, Hongmin, Yang Zhou, Tao Huang, and Fuxing Sun. "Study on Gas Sorption and Iodine Uptake of a Metal-Organic Framework Based on Curcumin." Molecules 28, no. 13 (July 6, 2023): 5237. http://dx.doi.org/10.3390/molecules28135237.

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Medi-MOF-1 is a highly porous Metal-Organic framework (MOF) constructed from Zn(II) and curcumin. The obtained crystal was characterized using powder X-ray diffraction (PXRD) and scanning electron microscopy (SEM). A micrometer-sized crystal with similar morphology was successfully obtained using the solvothermal method. Thanks to its high surface area, good stability, and abound pores, the as-synthesized medi-MOF-1 could be used as a functional porous material to adsorb different gases (H2, CO2, CH4, and N2) and iodine (I2). The activated sample exhibited a high I2 adsorption ability of 1.936 g g–1 at room temperature via vapor diffusion. Meanwhile, the adsorbed I2 could be released slowly in ethanol, confirming the potential application for I2 adsorption.

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32

Somsri, Supattra, Naoto Kuwamura, Tatsuhiro Kojima, Nobuto Yoshinari, and Takumi Konno. "Self-assembly of cyclic hexamers of γ-cyclodextrin in a metallosupramolecular framework with d-penicillamine." Chemical Science 11, no. 34 (2020): 9246–53. http://dx.doi.org/10.1039/d0sc03925j.

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The complex anions with d-penicillamine are organized into a 3D porous framework that allows the inclusion of γ-CD. The inclusion is accompanied by the 3D-to-2D transformation of porous frameworks so as to accept cyclic hexamers of γ-CD.

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Zhang, Shiji, Danqing Liu, and Guangtong Wang. "Covalent Organic Frameworks for Chemical and Biological Sensing." Molecules 27, no. 8 (April 18, 2022): 2586. http://dx.doi.org/10.3390/molecules27082586.

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Covalent organic frameworks (COFs) are a class of crystalline porous organic polymers with polygonal porosity and highly ordered structures. The most prominent feature of the COFs is their excellent crystallinity and highly ordered modifiable one-dimensional pores. Since the first report of them in 2005, COFs with various structures were successfully synthesized and their applications in a wide range of fields including gas storage, pollution removal, catalysis, and optoelectronics explored. In the meantime, COFs also exhibited good performance in chemical and biological sensing, because their highly ordered modifiable pores allowed the selective adsorption of the analytes, and the interaction between the analytes and the COFs’ skeletons may lead to a detectable change in the optical or electrical properties of the COFs. In this review, we firstly demonstrate the basic principles of COFs-based chemical and biological sensing, then briefly summarize the applications of COFs in sensing some substances of practical value, including some gases, ions, organic compounds, and biomolecules. Finally, we discuss the trends and the challenges of COFs-based chemical and biological sensing.

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34

Arici, Mürsel, Tuğba Alp Arici, Hakan Demiral, Murat Taş, and Okan Zafer Yeşilel. "A porous Zn(ii)-coordination polymer based on a tetracarboxylic acid exhibiting selective CO2 adsorption and iodine uptake." Dalton Transactions 49, no. 31 (2020): 10824–31. http://dx.doi.org/10.1039/d0dt01875a.

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A 3D porous Zn(ii)-coordination polymer with a sqc5381 net adsorbed selectively CO₂ over N₂ and CH₄ at 273 K and also 19.99% and 30.26% iodine in solution and vapor phase. X-ray result and Raman spectra showed iodine units in the pores of framework.

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35

Vaidhyanathan, Ramanathan, Isaac Martens, Jian-Bin Lin, Simon S. Iremonger, and George K. H. Shimizu. "Larger pores via shorter pillars in flexible layer coordination networks." Canadian Journal of Chemistry 94, no. 4 (April 2016): 449–52. http://dx.doi.org/10.1139/cjc-2015-0391.

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Metal organic frameworks are porous coordination networks that offer tunable structures via modular synthetic routes. It is well established that zinc 3-amino-1,2,4-triazolate (ATz) forms structures with cationic layers. These layers can be pillared by anions to generate pores. We present three new Zn2(ATz)2(A) structures with A = 1,4-benzenedicarboxylate (BDC) pillars, 2-amino-1,4-benzene-dicarboxylate (BDC-NH2) and 2-methyl-1,4-benzenedicarboxylate (BDC-Me) to give the CALF-24 series of metal organic frameworks. Initially, these compounds were prepared to assess their CO2 capture ability and these data are presented. More significantly, comparing these and published ZnATz relatives, primarily from the group of X.M. Chen, we propose that, for layered systems with some flexibility in their bonding, larger pores actually result by pillaring with shorter linkers. While this may seem counterintuitive, a rationale is offered as borne out by the library of existing data. This offers a general concept for making porous materials based on the rigidity of the building units.

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Yuan, Yao, Xiaoyu Chen, Xing Zhang, Zumin Wang, and Ranbo Yu. "A MOF-derived CuCo(O)@ carbon–nitrogen framework as an efficient synergistic catalyst for the hydrolysis of ammonia borane." Inorganic Chemistry Frontiers 7, no. 10 (2020): 2043–49. http://dx.doi.org/10.1039/d0qi00023j.

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Shimizu, George, and Benjamin Gelfand. "Designing Proton Conducting Metal Organic Frameworks." Acta Crystallographica Section A Foundations and Advances 70, a1 (August 5, 2014): C1121. http://dx.doi.org/10.1107/s2053273314088780.

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Metal organic frameworks (MOFs) or porous coordination polymers (PCPs) represent a tunable molecular scaffolding that can be adjusted for a breadth of applications. This presentation will concern our efforts towards tailoring MOFs towards making new proton conductors ultimately for fuel cells. A major hurdle in these technologies is an electrolyte capable of conducting protons above 100°C. Higher operating temperatures will enhance electrode kinetics and decrease electrode poisoning among several critical operational benefits. In contrast to the macromolecular approaches typically employed towards these electrolytes, we have used a MOF strategy to generate crystalline networks with acidic pores. These MOFs present options to address higher temperature conduction,1 conduction over 10-2 Scm-1,2 and water stability.3 The emphasis in the talk will concern routes to designing these systems and subsequent challenges in their characterization.

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Gándara, Felipe, Hiroyasu Furukawa, Zhang Yue-Biao, Juncong Jiang, Wendy Queen, Matthew Hudson, and Omar Yaghi. "Synthesis, structure and water sorption in Zr metal-organic frameworks." Acta Crystallographica Section A Foundations and Advances 70, a1 (August 5, 2014): C1240. http://dx.doi.org/10.1107/s2053273314087592.

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Metal-organic frameworks (MOFs) based on zirconium secondary building units (SBUs) have proven to have great thermal and chemical stability,[1,2] which make them ideal for their use in different applications. We have prepared a series of six new MOFs made from the Zr6O4(OH)4(-CO2)nsecondary building units (n = 6, 8, 10, or 12) and variously shaped carboxyl organic linkers to make extended porous frameworks, with the aim of studying their performance as water adsorbents. Thus, we have evaluated the water adsorption properties of these new MOFs and other reported porous materials to identify the compounds with the most promising materials for use in applications such as thermal batteries or delivery of drinking water in remote areas. An X-ray single-crystal and a powder neutron diffraction study reveal the position of the water adsorption sites in one of the best performing materials, and highlight the importance of the intermolecular interactions between adsorbed water molecules within the pores.

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Cherevko, Anton I., Igor A. Nikovskiy, Yulia V. Nelyubina, Kirill M. Skupov, Nikolay N. Efimov, and Valentin V. Novikov. "3D-Printed Porous Magnetic Carbon Materials Derived from Metal–Organic Frameworks." Polymers 13, no. 22 (November 10, 2021): 3881. http://dx.doi.org/10.3390/polym13223881.

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Here we report new porous carbon materials obtained by 3D printing from photopolymer compositions with zinc- and nickel-based metal–organic frameworks, ZIF-8 and Ni-BTC, followed by high-temperature pyrolysis. The pyrolyzed materials that retain the shapes of complex objects contain pores, which were produced by boiling zinc and magnetic nickel particles. The two thus provided functionalities—large specific surface area and ferromagnetism—that pave the way towards creating heterogenous catalysts that can be easily removed from reaction mixtures in industrial catalytic processes.

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40

Dalabaev, Umurdin. "Flow Simulation in a combined Region." E3S Web of Conferences 264 (2021): 01016. http://dx.doi.org/10.1051/e3sconf/202126401016.

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The article deals with the flow in a complex area. The composition of this region consists of a porous medium through the pores of which the liquid moves and a zone without a porous framework (free zone). The flow is modeled using an interpenetrating heterogeneous model. In the one-dimensional case, an analytical solution is obtained. This solution is compared with the solution learned by the move node method. An analysis is made with experimental data with a Brinkman layer. A numerical solution of a two-dimensional problem is also obtained.

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Mínguez Espallargas, Guillermo, Mónica Giménez-Marqués, Néstor Calvo Galve, and Eugenio Coronado. "Responsive magnetic coordination polymers: effects of gas sorption." Acta Crystallographica Section A Foundations and Advances 70, a1 (August 5, 2014): C905. http://dx.doi.org/10.1107/s2053273314090949.

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Responsive materials for which physical or chemical properties can be tuned by applying an external stimulus are attracting considerable interest in view of their potential applications as chemical switches or molecular sensors [1]. A major source of such materials is provided by the so-called metal-organic frameworks (MOFs), in which physisorption of guest molecules, located in the pores, can cause subtle changes which affect the magnetic properties. Here we present two different approaches to modify the magnetic properties through gas sorption. First, we show that the chemisorption of gaseous HCl molecules by a non-porous one-dimensional coordination polymer instigates drastic modifications in the magnetic properties of the material, switching from strong antiferromagnets to ferromagnets upon gas sorption [2]. These conversions result from profound structural changes, involving cleavage and formation of covalent bonds caused by the removal/addition of ligands from the framework itself, but with no disruption of crystallinity. In a different approach, we present a family of FeII coordination polymers which shows spin-crossover behaviour and selectively sorbs CO2 over N2 [3]. Despite the lack of permanent channels, these non-porous coordination polymers trap CO2 gas molecules into the internal cavities due to the flexible and dynamic nature of the framework. One CO2 molecule is incorporated in each internal cavity of the crystalline material, as unequivocally demonstrated by structural determination after CO2 loading. This physisorption shifts the spin transition producing an increase in the transition temperature of 9 K (see Figure).

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Rocío-Bautista, Taima-Mancera, Pasán, and Pino. "Metal-Organic Frameworks in Green Analytical Chemistry." Separations 6, no. 3 (June 27, 2019): 33. http://dx.doi.org/10.3390/separations6030033.

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Metal-organic frameworks (MOFs) are porous hybrid materials composed of metal ions and organic linkers, characterized by their crystallinity and by the highest known surface areas. MOFs structures present accessible cages, tunnels and modifiable pores, together with adequate mechanical and thermal stability. Their outstanding properties have led to their recognition as revolutionary materials in recent years. Analytical chemistry has also benefited from the potential of MOF applications. MOFs succeed as sorbent materials in extraction and microextraction procedures, as sensors, and as stationary or pseudo-stationary phases in chromatographic systems. To date, around 100 different MOFs form part of those analytical applications. This review intends to give an overview on the use of MOFs in analytical chemistry in recent years (2017–2019) within the framework of green analytical chemistry requirements, with a particular emphasis on possible toxicity issues of neat MOFs and trends to ensure green approaches in their preparation.

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43

Filinchuk, Yaroslav, Nikolay Tumanov, Voraksmy Ban, Hyunchul Oh, Michael Hirscher, Bo Richter, Torben Jensen, et al. "Unprecedented adsorption of molecular hydrogen in the porous hydride framework." Acta Crystallographica Section A Foundations and Advances 70, a1 (August 5, 2014): C1473. http://dx.doi.org/10.1107/s205327331408526x.

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"Recently the first porous hydride, gamma-Mg(BH4)2, featuring so-called ""borohydride framework"" and capable to store reversibly guest species was discovered [1]. This example clearly shows that the covalently bound hydride anions, such as borohydride, can act as directional ligands, capable to form molecular and polynuclear complexes, as well as framework structures typically occurring in classical coordination chemistry. Various small molecules are reversibly absorbed in gamma-Mg(BH4)2. In this work we show that molecular hydrogen and nitrogen have different adsorption sites in gamma-Mg(BH4)2, leading to different capacities on saturation and to different H2 and N2 BET areas. Only up to 0.66 N2 molecules are adsorbed per Mg atom, but the saturation capacity is double for the smaller hydrogen molecule. Moreover, at higher pressures, the second hydride phase forms with unprecedented hydrogen content of ~22 weight % (!). The density of hydrogen adsorbed into the pores is much higher than in liquid hydrogen, having no analogues among other porous systems. On the technical side, we will illustrate how in-situ diffraction at neutron and synchrotron sources allows to follow adsorption isobars, aiming for extraction of isosteric heats of adsorption directly from diffraction data, as well as for clarifying the microscopic mechanisms in terms of guest-host and guest-guest interactions."

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44

Derakhshandeh, Parviz Gohari, Sara Abednatanzi, Karen Leus, Jan Janczak, Rik Van Deun, Pascal Van Der Voort, and Kristof Van Hecke. "Ce(III)-Based Frameworks: From 1D Chain to 3D Porous Metal–Organic Framework." Crystal Growth & Design 19, no. 12 (October 24, 2019): 7096–105. http://dx.doi.org/10.1021/acs.cgd.9b00949.

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45

Abazari, Reza, Soheila Sanati, Ali Morsali, Alexandra M. Z. Slawin, Cameron L. Carpenter-Warren, Wei Chen, and Anmin Zheng. "Ultrafast post-synthetic modification of a pillared cobalt(ii)-based metal–organic framework via sulfurization of its pores for high-performance supercapacitors." Journal of Materials Chemistry A 7, no. 19 (2019): 11953–66. http://dx.doi.org/10.1039/c9ta01628g.

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In this study, a fast and simple technique (2 min) has been developed to modify the pores of a novel micro-porous, amide-functionalized Co(ii)-based MOF [Co(oba)₂(bpfb)₄](DMF)₂, TMU-61, (H₂oba = 4,4′-oxybis(benzoic acid) and bpfb = N,N′-bis-(4-pyridylformamide)-1,4-benzenediamine).

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46

Liang, Rong-Ran, Shu-Yan Jiang, Ru-Han A, and Xin Zhao. "Two-dimensional covalent organic frameworks with hierarchical porosity." Chemical Society Reviews 49, no. 12 (2020): 3920–51. http://dx.doi.org/10.1039/d0cs00049c.

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This review highlights the state-of-the-art progress achieved in two-dimensional covalent organic frameworks (COFs) with hierarchical porosity, an emerging class of COFs constructed by integrating different types of pores into one framework.

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47

Hanikel, Nikita, Xiaokun Pei, Saumil Chheda, Hao Lyu, WooSeok Jeong, Joachim Sauer, Laura Gagliardi, and Omar M. Yaghi. "Evolution of water structures in metal-organic frameworks for improved atmospheric water harvesting." Science 374, no. 6566 (October 22, 2021): 454–59. http://dx.doi.org/10.1126/science.abj0890.

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Designing water uptake Although the locations of water molecules in some porous materials have been determined with diffraction techniques, determining the filling sequence of water sites has been challenging. Hanikel et al . used single-crystal x-ray diffraction to locate all of the water molecules in pores of the metal-organic framework MOF-303 at different water loadings (see the Perspective by Öhrström and Amombo Noa). They used this information on the water molecule adsorption sequence to modify the linkers of this MOF and control the water-harvesting properties from humid air for different temperature regimes. —PDS

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48

Parkinson, Bruce Alan, John Hoberg, Katie Li-Oakey, and Phuoc Duong. "Selective Ion Sieving and Disorder in Membranes Constructed from Two-Dimensional Covalent Organic Frameworks." ECS Meeting Abstracts MA2022-01, no. 47 (July 7, 2022): 1987. http://dx.doi.org/10.1149/ma2022-01471987mtgabs.

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Two-dimensional covalent organic frameworks (2D-COFs) have been of increasing interest in the past decade due to their potentially ordered porous structures. One of the most common routes to these polymers relies on Schiff-base chemistry, i.e. the condensation reaction between a carbonyl and an amine. However, the judicious choice of these two building blocks is critical given that many COF forming reactions can lead to an inherent disorder if such a pathway is available. Examples of disorder in 2D-COFs due to both inherent growth mechanisms and reaction pathways will be given and their influence on ion sieving membranes will be discussed. A 2D-COF with negatively charged carboxylated pores, where disorder is minimized, has been shown to be highly charge and size selective for ion conductivity for a series of tetraalkyl ammonium cations. Progress on membranes for desalinization and small ion separations such as Li ion separation from brines using negatively charged, positively charged and zwitterion pores will also be presented.

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Hawxwell, Samuel M., Guillermo Mínguez Espallargas, Darren Bradshaw, Matthew J. Rosseinsky, Timothy J. Prior, Alastair J. Florence, Jacco van de Streek, and Lee Brammer. "Ligand flexibility and framework rearrangement in a new family of porous metal–organic frameworks." Chem. Commun., no. 15 (2007): 1532–34. http://dx.doi.org/10.1039/b618796j.

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50

Dincă, Mircea, and Jeffrey R. Long. "Introduction: Porous Framework Chemistry." Chemical Reviews 120, no. 16 (August 26, 2020): 8037–38. http://dx.doi.org/10.1021/acs.chemrev.0c00836.

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