Review
Chemistry, Physical
Xiaofei Zhang, Jianyu Han, Jun Guo, Zhiyong Tang
Summary: Various synthetic methods have been successfully used to prepare nanoscale MOFs, which can improve the utilization of catalytic sites. Despite the rich selection of metal centers and organic molecules in MOFs, challenges exist in their stability under harsh reaction conditions. Efforts have been made to optimize catalytic performance by tuning the chemical environment of active sites in nanoscale MOFs.
Article
Chemistry, Multidisciplinary
Kyle J. Korman, Michael R. Dworzak, Glenn P. A. Yap, Eric D. Bloch
Summary: This paper describes the preparation of a new class of reactive porous solids through straightforward salt metathesis reactions. A porous solid is obtained by reacting the dimethylammonium salt of a magnesium-based porous coordination cage with the chloride salt of [(CrCl)-Cl-II(Me(4)cyclam)](+), with simultaneous removal of dimethylammonium chloride. The porous salt exhibits a Brunauer-Emmett-Teller (BET) surface area of 213 m(2) g(-1) and the chromium(II) cations in the structure are still accessible and reactive, as confirmed by UV-vis spectroscopy. The site-isolated reactive centers show enhanced stability and reactivity compared to dissolved ions.
Review
Chemistry, Multidisciplinary
Qi Wang, Guoxiang Yang, Yangjie Fu, Ningyi Li, Derek Hao, Shengqian Ma
Summary: MOFs have wide applications in catalysis due to their structural advantages, and researchers can customize them and improve catalytic performance through various strategies. Engineering methods include regulating pore size, encapsulating active species, adjusting morphology, and introducing multiple organic functional groups. Challenges for MOFs as green and sustainable catalysts are also discussed for further low-cost and practical applications.
Article
Chemistry, Multidisciplinary
Yangjian Quan, Guangxu Lan, Wenjie Shi, Ziwan Xu, Yingjie Fan, Eric You, Xiaomin Jiang, Cheng Wang, Wenbin Lin
Summary: The study introduced the design of a bifunctional metal-organic layer (MOL) combining a photosensitizer and a hydrogen-transfer catalyst, which efficiently catalyzed acceptorless dehydrogenation reactions of indolines and tetrahydroquinolines, as well as dehydrogenative tandem transformations of indolines with alkenes or aldehydes. With the potential of MOLs in constructing novel multifunctional heterogeneous catalysts demonstrated, this research contributes to the development of catalytic systems for organic transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Wenjie Shi, Lingzhen Zeng, Lingyun Cao, Ying Huang, Cheng Wang, Wenbin Lin
Summary: Reusable solid fluorination reagents and heterogeneous catalysts based on Pd-functionalized two-dimensional metal-organic layers (MOLs) have been developed for efficient fluorination of aromatic compounds, showing potential for late-stage fluorination applications.
Article
Chemistry, Multidisciplinary
Shan-Shan Fu, Qiang-Qiang Yuan, Lihua Ma, Zhi-Ming Zhang, Tong-Bu Lu, Song Guo
Summary: A series of TEMPO@PCN-222 composite photocatalysts were developed by coordinating different amount of 4-carboxy-TEMPO with the secondary building units of PCN-222. Visible-light irradiation enables the transfer of photogenerated holes in the highest occupied molecular orbital of PCN-222 to TEMPO, significantly increasing the photosynthesis of bioactive (iso)quinolones. With an outstanding catalytic stability and substrate tolerance, TEMPO@PCN-222 exhibits a yield of 86.7% for 1-methyl-2-quinolinone, over four times higher than PCN-222 (21.4%). This study provides a new route for constructing composite photocatalysts from abundant starting materials for efficient photosynthesis of high value-added chemicals.
Article
Chemistry, Multidisciplinary
Zhiming Cui, Ting Fan, Liyu Chen, Ruiqi Fang, Chuanmao Li, Yingwei Li
Summary: A solvent assisted ligand exchange-hydrogen reduction strategy was used to selectively encapsulate ultrafine metal nanoparticles (Pd or Pt) within the shallow layers of MOF UiO-67. By controlling the conditions, the particle sizes of the encapsulated nanoparticles and the thickness of the embedded layers can be easily adjusted. Compact encapsulation of nanoparticles within the shallow layers of MOFs can enhance catalytic efficiency and utilization.
SCIENCE CHINA-CHEMISTRY
(2021)
Review
Biochemistry & Molecular Biology
Francisco G. Cirujano, Rafael Luque, Amarajothi Dhakshinamoorthy
Summary: Metal-organic frameworks (MOFs) have become versatile solid materials used in various applications like gas storage, separation, sensors, and catalysis. This review focuses on the use of MOFs as solid catalysts for the Henry reaction, discussing their structural properties and active sites. Comparisons with other solid catalysts in terms of activity and structural stability are made, along with suggestions for future directions in this field.
Article
Chemistry, Multidisciplinary
Xing Liu, Peixin Zhang, Hanting Xiong, Yan Zhang, Ke Wu, Junhui Liu, Rajamani Krishna, Jingwen Chen, Shixia Chen, Zheling Zeng, Shuguang Deng, Jun Wang
Summary: In this study, a novel sulfate-pillared MOF adsorbent (SOFOUR-TEPE-Zn) using the TEPE ligand with dense electronegative pore surfaces is reported for acetylene/carbon dioxide (C2H2/CO2) separation. Compared to the prototype SOFOUR-1-Zn, SOFOUR-TEPE-Zn shows a higher C2H2 uptake and reduced CO2 uptake, leading to a high C2H2/CO2 selectivity. Dynamic breakthrough experiments confirm its application feasibility and good cyclability at various flow rates. The pressure swing adsorption processes reveal a high gas recovery rate and production of high purity C2H2.
ADVANCED MATERIALS
(2023)
Review
Materials Science, Multidisciplinary
Chongxiong Duan, Kuan Liang, Jiahui Lin, Jingjing Li, Libo Li, Le Kang, Yi Yu, Hongxia Xi
Summary: H-MOFs, as a popular class of crystalline porous materials with hierarchical porous structures, have been widely studied in heterogeneous catalysis. They exhibit excellent catalytic activity, selectivity, stability, and recyclability, showing great potential for future research and applications.
SCIENCE CHINA-MATERIALS
(2022)
Article
Chemistry, Physical
Ruixue Zhang, Yan Chen, Muhua Ding, Jie Zhao
Summary: This review provides a comprehensive summary of seminal heterogenized Cu-catalyzed homogenous catalysis reported over the last decade, highlighting the potential and synthetic perspectives of heterogeneous copper catalysis in both academic and industry.
Article
Chemistry, Physical
Nuria Martin, Francisco G. Cirujano
Summary: The direct synthesis of amides from carboxylic acids and amines is of great importance in fine chemistry, drug synthesis, and protein construction in living organisms. The use of heterogeneous catalysts is preferred due to their advantages in terms of easy isolation, recovery, and recycling. This article reviews the most relevant reported heterogeneous catalysts for direct amide bond formation, focusing on their physicochemical properties, catalytic performance, and understanding of the reaction mechanism. The types of active sites incorporated on the solid catalyst surface, their interplay with the support material, and key properties such as surface area and pore size are thoroughly discussed.
CATALYSIS COMMUNICATIONS
(2022)
Review
Materials Science, Multidisciplinary
Huifeng Wang, Chao Zhang, Baoxia Dong, Dichang Zhong, Tongbu Lu
Summary: Metal-organic layers (MOLs) have attracted significant attention in materials science due to their unique characteristics. Over the past decade, there has been rapid development in the synthesis and applications of MOLs. This review presents the latest research advances on MOLs, including the two preparation approaches, applications in gas separation, catalysis, energy catalysis and conversion, and chemical sensors, as well as future opportunities and challenges.
SCIENCE CHINA-MATERIALS
(2023)
Review
Chemistry, Multidisciplinary
Haowu Wang, Fengbin Zheng, Guangxin Xue, Yinglong Wang, Guodong Li, Zhiyong Tang
Summary: This review summarizes recent advances in HoMOFs and their composites for heterogeneous catalysis, including the synthetic strategies for various HoMOFs and their structures when combined with other materials for composite formation.
SCIENCE CHINA-CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Harsh Vardhan, Abdullah M. Al-Enizi, Ayman Nafady, Yanxiong Pan, Zhongyu Yang, Humberto R. Gutierrez, Xiaolong Han, Shengqian Ma
Summary: The exponential growth in the field of covalent-organic frameworks (COFs) is attributed to the direct correlation between designing principles and desired properties. The comparison of catalytic activity between single-pore and dual-pore COFs is crucial for establishing a structure-function relationship. By synthesizing imine-linked dual-pore COFs with controllable bipyridine content, this study demonstrates efficient catalytic active sites for selective functionalization of sp(2)C-H bonds to C-X (X = Br, Cl) or C-O bonds. The comparison between palladium decorated dual-pore frameworks and single-pore imine-linked Pd(II) @ Py-2,2'-BPyDC framework provides insights into the relationship between catalytic activity and core properties of rationally designed frameworks.
Review
Chemistry, Multidisciplinary
Hengyu Lin, Yihao Yang, Yu-Chuan Hsu, Jiaqi Zhang, Claire Welton, Ibukun Afolabi, Marshal Loo, Hong-Cai Zhou
Summary: As water scarcity becomes a global issue, hygroscopic materials are seen as a significant solution. This review focuses on the recent development of hygroscopic materials, including traditional ones, crystalline frameworks, polymers, and composites. The similarities between water harvesting and carbon capture suggest a future challenge of simultaneously addressing both issues, with an emphasis on metal-organic frameworks and their water stability and uptake. Recent advances in understanding the effects of moisture on CO2 adsorption are also reviewed.
ADVANCED MATERIALS
(2023)
Article
Biochemistry & Molecular Biology
Xuran Ji, Zhijie Shen, Wenping Xu, Shimiao Yao, Lian Xiong, Hairong Zhang, Hongcai Zhou, Xuefang Chen, Xinde Chen
Summary: Nonpolar hyper-cross-linked adsorption resins (HCARs) were synthesized and applied to decolorize molasses. The results showed that the surface area and pore volume of the resin significantly increased after the alkylation reaction. The HCARs achieved a decolorization rate of 74% and exhibited stable recycling performance.
APPLIED BIOCHEMISTRY AND BIOTECHNOLOGY
(2023)
Article
Nanoscience & Nanotechnology
Liefeng Hu, Chuxiao Xiong, Jun-Jie Zou, Junrong Chen, Hengyu Lin, Scott J. Dalgarno, Hong-Cai Zhou, Jian Tian
Summary: This study developed a novel chemiluminescence-photodynamic therapy (PDT) nanosystem by integrating an oxygen-supplying protein (hemoglobin, Hb) and a luminescent donor (luminol, Lum) into hierarchically engineered mesoporous porphyrinic metal-organic framework (MOF) nanoparticles. The system activated luminescence through chemiluminescence resonance energy transfer and produced reactive oxygen species for cancer cell killing, resulting in an excellent anticancer activity both in vitro and in vivo. This self-illuminating, oxygen-self-supplying nanosystem integrates essential components of PDT and holds great potential for selective phototherapy of deep-seated cancer.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Multidisciplinary
Jiang-Pei Yuan, Zong-Jie Guan, Heng-Yu Lin, Bing Yan, Kang-Kai Liu, Hong-Cai Zhou, Yu Fang
Summary: Mimicking the active site and substrate binding cavity of enzymes, PCCs can achieve specificity in catalytic reactions. PCC-6-M (M = Zn/Ni/Co) exhibit distinct catalytic activities, which are significant for studying the regulation of ROS generation by supramolecular catalysts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Kun-Yu Wang, Jiaqi Zhang, Yu-Chuan Hsu, Hengyu Lin, Zongsu Han, Jiandong Pang, Zhentao Yang, Rong-Ran Liang, Wei Shi, Hong-Cai Zhou
Summary: Enzymatic catalysis has attracted interest from chemists due to its efficiency and selectivity, but the complexity and vulnerability of enzymes limit their application potential. Metal-organic frameworks (MOFs) integrate the structure and active sites of natural enzymes into porous solids, providing bioinspired heterogeneous catalysts with superior stability and customizable structures. This review comprehensively summarizes the advances of bioinspired MOFs for catalysis, discusses the design principles of various MOF-based catalysts, and explores their utility in different reactions. The advantages of MOFs as enzyme mimetics are highlighted, and potential solutions to current challenges in MOF catalysis are discussed.
Article
Chemistry, Inorganic & Nuclear
Simin Sheybani, Muhammad Abbas, Hamid R. Firouzi, Zhifeng Xiao, Hong-Cai Zhou, Kenneth J. Balkus Jr
Summary: A new fluoro-bridged rare-earth (RE) metal-organic framework was synthesized through the transformation of a dimeric complex with the bridging linker 1,3,5-tris(4-carboxyphenyl)benzene (H3BTB). The rare-earth metal ions Ho3+ and Gd3+ were also found to remove fluorine from other organo-fluorine compounds, resulting in the new fluorobridged RE-MOFs.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Wenmiao Chen, Zhi Wang, Qi Wang, Khaoula El-Yanboui, Kui Tan, Heather M. Barkholtz, Di-Jia Liu, Peiyu Cai, Liang Feng, Youcong Li, Jun-Sheng Qin, Shuai Yuan, Di Sun, Hong-Cai Zhou
Summary: In this study, the structural evolution of trinuclear [FexM3-x(mu 3-O)] cluster-based metal-organic frameworks (MOFs) (PCN-250, M = Ni2+, Co2+, Zn2+, Mg2+) was examined during thermal activation using in situ variable-temperature single-crystal X-ray diffraction. The formation of open metal sites and the transformation of Fe3+ coordination geometries from octahedron to square pyramid were observed. The metal site structures were confirmed by X-ray absorption and infrared spectroscopy.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Biochemical Research Methods
Zongsu Han, Kunyu Wang, Hong-Cai Zhou, Peng Cheng, Wei Shi
Summary: Luminescent sensing materials are favored in environmental analysis due to their high selectivity, excellent sensitivity, and rapid response to targeted analytes. Metal-organic frameworks (MOFs) with multiple luminescent centers have been synthesized to optimize selectivity for analytes of interest. This approach can accelerate the discovery of advanced sensing materials for practical applications.
Review
Chemistry, Inorganic & Nuclear
Weidong Fan, Kun-Yu Wang, Claire Welton, Liang Feng, Xiaokang Wang, Xiuping Liu, Yue Li, Zixi Kang, Hong-Cai Zhou, Rongming Wang, Daofeng Sun
Summary: This article systematically summarizes the construction and properties of aluminum metal-organic frameworks (MOFs), and discusses their applications in various fields. By studying the MOFs constructed by aluminum ions (Al3+), it was found that they have advantages such as low toxicity, abundant reserves, low cost, and sustainability. Aluminum MOFs have attracted much attention due to their diverse structures and functions, high physicochemical stability, and wide applications in many scientific and engineering fields.
COORDINATION CHEMISTRY REVIEWS
(2023)
Article
Chemistry, Inorganic & Nuclear
Vladimir I. Bakhmutov, Douglas W. Elliott, Hengyu Lin, Hong-Cai Zhou
Summary: A layered crystalline phosphate, alpha-Sn(HPO4)2 center dot H2O, treated with CD3OD was characterized by solid-state NMR techniques. Surprisingly, deuterated hydronium ions were found on the surface of the material instead of intercalated methanol. This phenomenon was confirmed by 13C NMR and GC-MS studies, indicating the formation of deuterated dimethyl ether from the dehydration of methanol-d4.
INORGANICA CHIMICA ACTA
(2023)
Article
Chemistry, Multidisciplinary
Hui-Hui He, Jiang-Pei Yuan, Pei-Yu Cai, Kun-Yu Wang, Liang Feng, Angelo Kirchon, Ji Li, Liang-Liang Zhang, Hong-Cai Zhou, Yu Fang
Summary: One of the challenges in multicomponent metal-organic frameworks (MOFs) is to achieve selective product formation by finely tuning their active centers. In this study, a technique called cluster labilization was used to create hierarchically porous MOF composites with hollow structures and adjustable active centers. By partially replacing zirconium with cerium in the hexanuclear clusters of UiO-66, unevenly distributed yolk-shell structures (YSS) were formed, which can be further transformed into single-shell hollow structures (SSHS) or double-shell hollow structures (DSHS) through acid treatment or annealing. These structures exhibit tunable catalytic activity, reversed selectivity, and high stability in tandem reactions and photoreactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Engineering, Chemical
Shanshan Shang, Chao Yang, Yuanmeng Tian, Zeyu Tao, Mallory Smith, Hongyan Zhang, Lin Zhang, Liangchun Li, Qinfen Gu, Hong-Cai Zhou, Yong Sik Ok, Jin Shang
Summary: Selective adsorption using porous materials is a promising approach to removing ambient nitrogen dioxide (NO2). In this study, multivariate porphyrin-based metal-organic frameworks (MTV-PMOFs Al-PMOF(NixCoy)) with atomically dispersed Ni/Co dual-metal centers were designed as adsorbents capable of synergistically boosting NO2 adsorption capability and retaining the evolved NO. This work provides new perspectives for the development of adsorption-based technology for mitigating ambient NO2 pollution and managing other corrosive and toxic gases.
SEPARATION AND PURIFICATION TECHNOLOGY
(2023)
Article
Chemistry, Physical
Vladimir I. Bakhmutov, Douglas W. Elliott, Nattamai Bhuvanesh, Hong-Cai Zhou
Summary: The study of a layered crystalline Sn(IV) phosphate using solid-state NMR revealed that the 31P T1 relaxation of phosphate groups, which depends on spinning rate, is controlled by limited spin diffusion to paramagnetic ions identified by EPR. The spin-diffusion constant, D(SD), was estimated to be 2.04 10-14 cm2s 1. This conclusion was further supported by 31P T1 time measurements in zirconium phosphate 1-1, which also contain paramagnetic ions, and in the diamagnetic compound (NH4)2HPO4.
SOLID STATE NUCLEAR MAGNETIC RESONANCE
(2023)
Article
Chemistry, Inorganic & Nuclear
Muhammad Abbas, Amanda M. Maceda, Zhifeng Xiao, Hong-Cai Zhou, Kenneth J. Balkus
Summary: A new mixed linker metal-organic framework (MOF), CuMOF-Bipy, has been synthesized using a copper-based MOF and 2,2'-bipyridine. The crystal structure of CuMOF-Bipy consists of a stacked two-dimensional framework with one-dimensional sinusoidal channels. CuMOF-Bipy shows selective diffusion of CO2 but not N-2.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Physical
John Pellessier, Xiangtao Gong, Boyang Li, Jiaqi Zhang, Yang Gang, Kirk Hambleton, Chinmoy Podder, Zhongjia Gao, Hongcai Zhou, Guofeng Wang, Heng Pan, Ying Li
Summary: A solvent-free processing method was developed to improve the production of multi-carbon (C2+) products in the electrochemical CO2 reduction reaction. By coating commercial Cu nanoparticles with a porous nanocoating of polytetrafluoroethylene (PTFE), a large interfacial surface area was created, facilitating the transport of CO2 and leading to significantly higher C2+ product selectivity of the Cu catalysts.
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
