Article
Chemistry, Multidisciplinary
Kira M. Fahy, Mohammad Rasel Mian, Megan C. Wasson, Florencia A. Son, Timur Islamoglu, Omar K. Farha
Summary: This article presents a method of replacing carboxylate linkers with triazolate coordination in MOF-74 via solvent-assisted linker exchange, resulting in the synthesis of the novel NU-250.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Zhichao Shao, Junshuai Chen, Kexin Gao, Qiong Xie, Xiaojing Xue, Shuangyan Zhou, Chao Huang, Liwei Mi, Hongwei Hou
Summary: This paper presents a novel double-helix metal chain organic framework material (ZUT-8) with a network structure, which exhibits high chemical stability and excellent friction power generation performance. The material can effectively prevent metal corrosion and enhance the output performance by enhancing the conjugate effect of the linker.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Kaoru Kioka, Nagi Mizutani, Nobuhiko Hosono, Takashi Uemura
Summary: This paper proposes a design approach using mixed metal-organic frameworks (MOFs) as tunable stationary phases in liquid chromatography (LC). By systematically designing ligands, the pore sizes in the MOFs can be tuned. Columns packed with the MOFs and their mixed-particle/solid-solution stationary phases are prepared and tested for the retention capability of polyethylene glycol (PEG) in LC. The results demonstrate that mixed-linker solid-solution MOFs have higher retention capability compared to pure MOF stationary phases, due to their specific nanostructures.
Article
Chemistry, Physical
Christopher W. Ashling, Lauren K. Macreadie, Thomas J. F. Southern, Yiming Zhang, Lauren N. McHugh, Rachel C. Evans, Stefan Kaskel, Shane G. Telfer, Thomas D. Bennett
Summary: This study focuses on the thermal stability considerations in the formation of metal-organic framework crystal-glass composites (MOF CGCs), and introduces the synthesis of two novel MOF CGCs. The research shows that gas uptake in composites is largely influenced by the a(g)ZIF-62 matrix, indicating that improving the matrix porosity or overcoming a percolation threshold is crucial for enhancing the porosity of MOF CGCs.
JOURNAL OF MATERIALS CHEMISTRY A
(2021)
Article
Electrochemistry
Hongxia Li, Letong Wang, Simeng Yan, Jinliang Chen, Mengmeng Zhang, Rui Zhao, Xiaohui Niu, Kunjie Wang
Summary: A novel metal organic framework structure (Phe-Cu-PTA) was developed for chiral recognition, which can effectively distinguish L-tryptophan and D-tryptophan enantiomers.
ELECTROCHIMICA ACTA
(2022)
Article
Chemistry, Inorganic & Nuclear
Jin-Yang Zheng, Qi-Ming Wang, Feng-Qi Jiang, Yang-Lu Li, Xiao-Xiong Huang, Xiao-Wen Sun, Wen-Wen Dong, Dan Ba, Jun Zhao, Dong-Sheng Li
Summary: Herein, a series of Zr(IV)-MOFs (Zr-(NDC)(x)(SNDC)(1-x)) based on 1,4-naphthalenedicarboxylic acid (H2NDC) and 6-sulfonate-1,4-naphthalenedicarboxylic acid (H3SNDC) were constructed using the postsynthetic ligand exchange process. Functional sulfonic acid groups were anchored in the pores of the MOFs. Among them, Zr-(NDC)(0.3)(SNDC)(0.7) exhibited exceptional proton conductivity of 3.18 x 10(-4) S cm(-1) at 90 degrees C and 98% relative humidity (RH), which was significantly higher than pristine Zr-NDC. This work demonstrates a facile in situ ligand exchange approach for constructing functional group modified MOFs with high proton conductivity.
JOURNAL OF SOLID STATE CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Zhenyu Ji, Yerong Fan, Mingyan Wu, Maochun Hong
Summary: A two-fold interpenetrating pillar-layer microporous material is reported in this study, where the framework transforms into a stable nonporous one after losing guest molecules. The guest-free framework exhibits rare temperature-dependent gate-opening behaviors for C2 gases around room temperature.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Ping Shao, Wei Zhou, Qin-Long Hong, Luocai Yi, Lirong Zheng, Wenjing Wang, Hai-Xia Zhang, Huabin Zhang, Jian Zhang
Summary: Understanding the relationship between structure and composition and the catalytic activity in the electrochemical CO2 reduction reaction is crucial for the design of efficient electrocatalysts. Catalysts featuring Cl-bridged Cu-2 units have been shown to enhance selectivity and activity for C2H4, with neighboring Cu monomers acting as regulators and providing different reaction paths.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Jiangnan Li, Xue Han, Xinchen Kang, Yinlin Chen, Shaojun Xu, Gemma L. Smith, Evan Tillotson, Yongqiang Cheng, Laura J. McCormick McPherson, Simon J. Teat, Svemir Rudic, Anibal J. Ramirez-Cuesta, Sarah J. Haigh, Martin Schroder, Sihai Yang
Summary: This study reports a method of separating propylene and ethylene from propane, ethane, and acetylene using a microporous material, and reveals the mechanism of synergistic host-guest interactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Weichao Xue, Kai Wu, Nianfeng Ouyang, Thierry Brotin, Jonathan R. Nitschke
Summary: The self-assembly of flexible tritopic aniline and 3-substituted 2-formylpyridine subcomponents around iron(II) templates produced a low-spin (Fe4L4)-L-II capsule, while a high-spin (Fe3L2)-L-II sandwich species formed when a sterically hindered 6-methyl-2-formylpyridine was used. The (Fe4L4)-L-II cage was found to have a new structure type with S-4 symmetry, consisting of two mer-Delta and two mer-Delta metal vertices, as confirmed by NMR and X-ray crystallographic analysis. The flexibility of the face-capping ligand allowed the resulting (Fe4L4)-L-II framework to adapt structurally from S-4 to T or C-3 symmetry upon guest binding, and it also displayed negative allosteric cooperativity in binding different guests within its cavity and at the apertures between its faces.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Qinlong Hong, Wenjing Wang, Shumei Chen, Ke Chen, Meng Liu, Hai-Xia Zhang, Jian Zhang
Summary: A novel microporous boron imidazolate framework (BIF-108-Zn) has been reported for efficient separation of ethylene and ethane by integrating organic ligands and extra-framework species as pore partition agents. The structure features high pore volume, reduced pore size, and functionalized pore surface for preferential binding of ethane. Dynamic breakthrough measurements show that BIF-108-Zn can produce polymer-grade ethylene with good regenerability and high stability.
CHEMISTRY OF MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Yan Wei, Miao Chang, Ling-Xia Yun, Meng Qiao, Rong-Kun Liu, Dahuan Liu, Jie-Xin Wang, Jian-Feng Chen
Summary: A facile strategy for highly-efficient activation of MOFs utilizing rotating packed bed is proposed, which can completely activate nine representative MOFs within 2 hours without structural change. Compared with conventional methods, this activation strategy accelerates solvent diffusion and redissolution of residual reactants, significantly shortening the activation time and improving methane storage capacity.
Article
Multidisciplinary Sciences
Seok Jeong, Junmo Seong, Sung Wook Moon, Jaewoong Lim, Seung Bin Baek, Seung Kyu Min, Myoung Soo Lah
Summary: The spatial distribution of mixed building blocks in metal-organic frameworks can be modulated by tuning the reaction temperature, leading to the formation of core-shell and uniform microstructures.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Saiya Fujiwara, Naoto Matsumoto, Koki Nishimura, Nobuo Kimizuka, Kenichiro Tateishi, Tomohiro Uesaka, Nobuhiro Yanai
Summary: Utilizing the induced-fit-type structural transformation of a metal-organic framework (MOF), we demonstrate DNP of guest molecules at around room temperature, resulting in enhanced NMR signal.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Remi Petuya, Samantha Durdy, Dmytro Antypov, Michael W. Gaultois, Neil G. Berry, George R. Darling, Alexandros P. Katsoulidis, Matthew S. Dyer, Matthew J. Rosseinsky
Summary: The structure and guest accessibility of a MOF are determined by the choice of metal and linker. By analyzing experimental three-dimensional MOF structures and studying the chemical properties of the components, we can predict the guest accessibility of a MOF and provide guidance in component selection for exploratory MOF synthesis based on guest accessibility considerations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Nanoscience & Nanotechnology
Hong -Bin Luo, Fang -Ru Lin, Zhi-Yuan Liu, Ya-Ru Kong, Karam B. Idrees, Yangyang Liu, Yang Zou, Omar K. Farha, Xiao-Ming Ren
Summary: In this study, mixed matrix membranes were prepared by incorporating Zr-MOFs into polymer matrices, wherein MOF-808 provides highly active catalytic sites, hydrophilic PVP helps retain water for promoting hydrolytic reaction, and Im serves as a base for catalytic site regeneration. The mixed matrix membranes exhibited excellent catalytic performance for the solid-state hydrolysis of DMNP under high humidity, representing a significant step towards the practical application of Zr-MOFs in chemical protective layers against nerve agents.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Multidisciplinary
Zhihengyu Chen, Gautam D. Stroscio, Jian Liu, Zhiyong Lu, Joseph T. Hupp, Laura Gagliardi, Karena W. Chapman
Summary: In this study, the temperature dependence of the local and long-range structure of metal-organic frameworks (MOFs) based on NU-1000 was investigated using synchrotron X-ray total scattering. It was found that the local distortion of Zr6 nodes was dependent on the stability of the ligands, leading to a negative thermal expansion of the extended framework. A new mechanism for this negative thermal expansion was revealed, which involved an increase in the population of a smaller, distorted node state with increasing temperature. Control of the node distortion allowed for control of the dynamic structure of MOFs.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Bhajan Lal, Karam B. B. Idrees, Haomiao Xie, Courtney S. S. Smoljan, Saman Shafaie, Timur Islamoglu, Omar K. K. Farha
Summary: We report the synthesis of a zinc-based MOF containing a three-dimensional (3D) linker, which shows high thermal stability for the separation of hexane isomers. The incorporation of the 3D linker enhances the structural stability and provides precise pore apertures/channels. This work represents a significant milestone in the construction of stable Zn-based MOFs and the incorporation of 3D linkers for challenging separations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Georgina P. P. Robertson, Sara Mosca, Celia Castillo-Blas, Florencia A. A. Son, Omar K. K. Farha, David A. A. Keen, Simone Anzellini, Thomas D. D. Bennett
Summary: Recent research has shown a shift in focus from crystalline high-porosity metal-organic frameworks (MOFs) to exploring their amorphous counterparts. Applying pressure to a crystalline MOF can lead to amorphization, reducing surface area. Understanding the MOFs' response to pressure is crucial. Three MOFs with varying pore sizes were investigated under high pressure, showing partial crystallinity above 10 GPa. The survival of crystallinity at extreme pressures demonstrates the importance of high-pressure characterization of known structures.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Shujing Hou, Fusheng Liu, Haomiao Xie, Sylvia L. Hanna, Karam B. Idrees, Chenghui Zhang, Xingjie Wang, Yongwei Chen, Peng Li, Omar K. Farha
Summary: This study investigates the structure-modulator relationship in the synthesis of thorium-based MOFs using different modulators and the ligand H4ATC. The results show that formic acid and acetic acid compete with H4ATC to form NU-52 and NU-54, while trifluoroacetic acid and benzoic acid result in NU-53 and NU-55. The identity and amount of modulator play a crucial role in determining the Th-based MOF structures with H4ATC as the coordinated ligand.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Zhiyong Lu, Jiaxin Duan, Hao Tan, Liting Du, Xiang Zhao, Rui Wang, Satoshi Kato, Shilong Yang, Joseph T. Hupp
Summary: By adjusting the linker of a typical zirconium-based MOF (NU-1000), a new isomer with blocked c-pores and large mesopores (ISO-NU-1000) was successfully synthesized. ISO-NU-1000 exhibits excellent water stability, high water vapor uptake capacity, and cycle stability, making it a promising candidate for water-vapor-sorption-based applications.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Wei Gong, Xinfa Chen, Kira M. Fahy, Jinqiao Dong, Yan Liu, Omar K. Farha, Yong Cui
Summary: The interplay of primary organic ligands and inorganic secondary building units has led to the development of metal-organic frameworks (MOFs) in reticular chemistry. This study explores the role of ligand chirality in controlling the synthesis of different MOFs. The findings show that ligand chirality impacts both the structure and function of the MOFs, highlighting its importance in reticular chemistry.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Shengyi Su, Xuhao Zhou, Xinyi Gong, Karam B. Idrees, Kent O. Kirlikovali, Timur Islamoglu, Omar K. Farha, Nathan C. Gianneschi
Summary: In this study, micro-porous synthetic allomelanin (AM) was used as a porous coating on the surface of the MOF material UiO-66. The core-shell structured AM@UiO-66 nanoparticles were successfully prepared through in situ surface-constrained oxidative polymerization. Nitrogen sorption isotherms confirmed that the AM coating did not affect the pore size and porosity of UiO-66. It was demonstrated that by tuning the thickness of the AM coating, the AM@UiO-66 composites exhibited excellent hexane isomer separation selectivity and storage capacity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Chung -Wei Kung, Ken-ichi Otake, Riki J. Drout, Subhadip Goswami, Omar K. Farha, Joseph T. Hupp
Summary: Starting with ferrocyanide ions in acidic aqueous solution, cyano-ferrate(II) species are post-synthetically grafted to the nodes of a mesoporous zirconium-based MOF, NU-1000. The grafting occurs by substitution of cyanide ligands by node-based hydroxo and oxo ligands rather than by substitution of node aqua ligands by cyanide ligands as bridges between Fe(II) and Zr(IV). The installed moieties yield a broad absorption band that is tentatively ascribed to iron-to-zirconium charge transfer. Consistent with Fe(III/II) redox activity, a modest fraction of the installed iron complexes are directly electrochemically addressable.
Article
Engineering, Environmental
John Hegarty, Benjamin Shindel, Daria Sukhareva, Michael L. Barsoum, Omar K. Farha, Vinayak Dravid
Summary: This study investigates the use of new anions in ion-exchange resins for moisture-swing capture of CO2 and compares their performance thermodynamically and kinetically. The findings contribute to the improvement of negative emission technologies and sorbent materials, and provide insights relevant to gas separation.
ENVIRONMENTAL SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Fanrui Sha, Haomiao Xie, Florencia A. Son, Kevin S. Kim, Wei Gong, Shengyi Su, Kaikai Ma, Xiaoliang Wang, Xingjie Wang, Omar K. Farha
Summary: Proteins play important roles in various industries, but their fragility outside of cells limits their potential. Encapsulating proteins in solid materials can enhance their stability, but there is still room for improvement in understanding their interactions with synthetic hosts.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Kaikai Ma, Dahee Jung, John J. Mahle, Sylvia L. Hanna, Timur Islamoglu, Isil Akpinar, Gregory W. Peterson, Omar K. Farha
Summary: Integrating metal-organic frameworks onto textile fibers enables the preparation of solid catalysts for practical protective applications such as the degradation of chemical warfare agents. Multiple variables that affect the catalytic activity and permeability of an MOF-polymer fiber composite have been systematically studied. Activation methods, MOF mass loadings, and MOF particle size are the most crucial parameters that affect the resulting composite.
CELL REPORTS PHYSICAL SCIENCE
(2023)
Review
Chemistry, Multidisciplinary
Zhijie Chen, Kent O. Kirlikovali, Le Shi, Omar K. Farha
Summary: Functional porous metal-organic frameworks (MOFs) have great potential applications in various fields, but their successful implementation depends on their stability. In this article, we summarize the progress in rational design and synthesis of stable and controllable porous MOFs. The reticular synthesis approach allows for the top-down design of stable MOFs with targeted networks and pores. We highlight the synthesis and applications of stable MOFs based on high valent metal ions with carboxylate ligands and low valent metal ions with azolate linkers.
MATERIALS HORIZONS
(2023)
Article
Chemistry, Multidisciplinary
Sylvia L. Hanna, Omar K. Farha
Summary: Uranium, a relatively unexplored element, has rich chemistry and shows promise for various powerful functions such as small molecule activation and photocatalysis. By using metal-organic frameworks (MOFs), researchers have harnessed the properties of uranium and discovered remarkable structures and unique properties not observed in traditional transition metal MOFs. Theoretical calculations have also complemented structure-property studies in uranium MOFs. In this Perspective, the energy-structure-property relationships in U-MOFs are summarized to enable a deeper understanding of chemical phenomena and elevate the field to targeted discovery.
Article
Chemistry, Multidisciplinary
Kaikai Ma, Yuk Ha Cheung, Kent O. Kirlikovali, Xiaoliang Wang, Timur Islamoglu, John H. Xin, Omar K. Farha
Summary: The importance of developing functional materials to protect against chemical and pathogen threats is highlighted by the SARS-CoV-2 pandemic and the misuse of toxic chemical warfare agents. Metal-organic frameworks (MOFs) have emerged as a class of heterogeneous catalysts capable of rapidly detoxifying harmful chemicals and biological hazards. This Account describes the evolution of MOF/fiber composites that effectively capture and deactivate these toxic species, and focuses on key design challenges and considerations.
ACCOUNTS OF MATERIALS RESEARCH
(2023)
