Review
Chemistry, Applied
Hai-Yang Cheng, Tao Wang
Summary: Covalent organic frameworks (COFs) built upon dynamic covalent chemistry have great potential in catalytic organic synthesis, with researchers exploring their applications in various reactions. While COFs as heterogeneous organic catalysts bring benefits, they also present new challenges that require further research and discussion.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Physical
Xenia Tarrach, Jingzhou Yang, Mohammad Soleiman-Beigi, Silvia Diez-Gonzalez
Summary: In this work, an air-stable and easily accessible copper(I) complex was developed as a catalyst for the deuteration of mono-substituted alkynes. The reactions were conducted in common solvents and in the presence of air, resulting in excellent incorporation of deuterium into various functionalized alkynes.
Article
Materials Science, Multidisciplinary
Syed Shoaib Ahmad Shah, Muhammad Sufyan Javed, Tayyaba Najam, Muhammad Altaf Nazir, Aziz ur Rehman, Abdul Rauf, Manzar Sohail, Francis Verpoort, Shu-Juan Bao
Summary: This article provides a comprehensive explanation of the designed fabrication of COFs for heterogeneous catalysis and discusses the advantageous features of COFs as catalysts. It also highlights the active sites in COFs and presents future perspectives and challenges.
Article
Nanoscience & Nanotechnology
Chidharth Krishnaraj, Himanshu Sekhar Jena, Kuber Singh Rawat, Johannes Schmidt, Karen Leus, Veronique Van Speybroeck, Pascal Van Der Voort
Summary: This study synthesized and compared the performance of 2D imine COFs as catalysts, finding that Pd@TTA-DFB COF exhibited fast reactivity but low stability, Pd@TTA-DFP COF had the highest stability but slowest reactivity, and Pd@TTA-TBD COF showed the best overall performance. Experimental and computational results indicated that the reduction from Pd(II) to Pd(0) is a key step in determining the catalytic activity of COFs.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Review
Chemistry, Multidisciplinary
Hui Chen, Himanshu Sekhar Jena, Xiao Feng, Karen Leus, Pascal Van der Voort
Summary: This Review provides a comprehensive and systematic overview of the application of covalent organic frameworks (COFs) as photocatalysts for organic transformations. It covers the photophysical properties, characterization methods, general photocatalytic mechanism, advantages, and strategies to improve the efficiency of COF-based photocatalysts. It also analyzes advanced examples and discusses the challenges and prospects in the field.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(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, Multidisciplinary
Shaofeng Huang, Ji Yong Choi, Qiucheng Xu, Yinghua Jin, Jihye Park, Wei Zhang
Summary: Two covalent organic frameworks, MC-COF-1 and MC-COF-2, consisting of carbazolylene-ethynylene shape-persistent macrocycles with azine or imine linkages, were synthesized via imine condensation. The 2D frameworks are fully conjugated, imparting semiconducting properties, and exhibit high porosity with aligned porous channels. The frameworks can be doped with I-2 to enable electrical conductivity and have switchable electrical properties between conducting and insulating states.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Inorganic & Nuclear
Jintu Francis Kurisingal, Hyojin Kim, Jong Hyeak Choe, Chang Seop Hong
Summary: This article reviews recent progress in the design, synthesis, and catalytic mechanisms of COF-based functional materials for CO2 utilization reactions. It discusses various CO2 utilization reactions, such as photo/electrocatalytic CO2 reduction, cycloaddition, carboxylation, and hydrogenation, and evaluates the application of different types of COFs. The challenges and prospects of COF-based catalysts for CO2 utilization are highlighted.
COORDINATION CHEMISTRY REVIEWS
(2022)
Article
Materials Science, Multidisciplinary
Saeid Asghari, Iraj Mohammadpoor-Baltork, Hassan Sabzyan, Shahram Tangestaninejad, Majid Moghadam, Valiollah Mirkhani, Forouz Rastegari
Summary: This paper presents a study on the synthesis and applications of an amine-linked COF (IR-COF) with excellent catalytic performance and acid sensing capabilities. The IR-COF can efficiently catalyze the synthesis of tetrahydro-4H-chromenes and exhibits immediate color change upon exposure to hydrochloric acid.
APPLIED MATERIALS TODAY
(2023)
Review
Chemistry, Inorganic & Nuclear
Guang-Bo Wang, Ke-Hui Xie, Hai-Peng Xu, Yan-Jing Wang, Fei Zhao, Yan Geng, Yu -Bin Dong
Summary: Light-involved catalysis, especially photocatalysis and photothermal catalysis, is a promising alternative to traditional thermocatalysis. Highly efficient photocatalysts are crucial for the development of light-mediated catalysis. Covalent organic frameworks (COFs) are crystalline molecular solids with designable structures, light-harvesting, and semiconducting properties. The recent development of COFs has brought opportunities for visible-light induced organic transformations. This review comprehensively summarizes and discusses the applications of COFs in selective light-initiated organic transformations, provides an overview of COF-based photocatalysts, and discusses the limitations, challenges, and future perspectives of COF photocatalysis and photothermal catalysis.
COORDINATION CHEMISTRY REVIEWS
(2022)
Article
Chemistry, Multidisciplinary
Bang Hou, Shi Yang, Kuiwei Yang, Xing Han, Xianhui Tang, Yan Liu, Jianwen Jiang, Yong Cui
Summary: Three-dimensional covalent organic frameworks (COFs) with well-defined porous channels have been shown to induce chiral molecular catalysts from non-enantioselective to highly enantioselective in catalyzing organic transformations. By condensing compounds derived from enantiopure BINOL, chiral COFs with highly interpenetrated diamondoid frameworks were prepared. The COF catalyst provides preferential secondary interactions between the substrate and framework to induce enantioselectivities that are not achievable in homogeneous systems.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Huijie Qiao, Liting Yang, Xiubei Yang, Jialin Wang, Ya Chen, Lin Zhang, Wuxuan Sun, Lipeng Zhai, Liwei Mi
Summary: Two new covalent organic frameworks (COFs) were synthesized and successfully applied as efficient photocatalysts for the synthesis of thiophosphinates. One of the COFs exhibited better catalytic activity and recycling capacity, demonstrating the potential of COFs as robust platforms for efficient heterogeneous photocatalysts in organic transformations.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Review
Chemistry, Multidisciplinary
Hao Zhang, Lan-Lan Lou, Kai Yu, Shuangxi Liu
Summary: Asymmetric catalysis is essential due to the increasing demand for optically pure substances. Metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) show great potential for heterogeneous asymmetric catalysis. The unique properties of MOFs and COFs make them highly active and enantioselective for a wide range of asymmetric catalytic organic transformations.
Article
Chemistry, Physical
Chaonan Jin, Ning Li, En Lin, Xuepeng Chen, Ting Wang, Yan Wang, Mingfang Yang, Wansheng Liu, Jiangyue Yu, Zhenjie Zhang, Yao Chen
Summary: This study developed a photoenzymatic platform for asymmetric catalysis by immobilizing wheat germ lipase (WGL) onto rationally designed photocatalytic porphyrinic covalent organic frameworks (COFs). The WGL@COFs photobiocatalysts demonstrated high enzymatic activity and good operational stability, and exhibited excellent performance for an enantioselective Mannich reaction under visible light irradiation. This work provides a general and efficient strategy for fabricating photobiocatalysts that enable highly efficient photoenzymatic asymmetric catalysis using COFs as photocatalytic platforms for enzyme immobilization.
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.
Article
Chemistry, Physical
Haojie Li, Bingke Yang, Zhen Yao, Xuetao Wang, Kaiming Shen, Mengjie Liu
Summary: This study systematically investigates the influence of metal and nonmetal element doping on the photochemical properties of g-C3N4 for efficient catalytic AB hydrogen production. It provides a design method for high performance bifunctional catalysts of photocatalysis and metal catalysis. The results show that both non-metals (B, P) and metals (Ru, Ni) have efficient regulatory effects on the band structure of g-C3N4, resulting in a reduced band gap and improved hydrogen production. The study offers a theoretical method for the coupling of metal catalysis/photocatalysis ammonia borane to produce hydrogen.
MOLECULAR CATALYSIS
(2024)
Article
Chemistry, Physical
Shrouq Mujahed, Davide Gandolfo, Luigi Vaccaro, Evgueni Kirillov, Dmitri Gelman
Summary: In this study, a high-valent Ru(IV) bifunctional catalyst was successfully applied for the hydrosilylation of various functional groups. The high-valent hydride complexes showed high chemoselectivity and affinity towards reducing polar bonds. The scope, limitations, and plausible mechanism of the reaction were described.
MOLECULAR CATALYSIS
(2024)
Article
Chemistry, Physical
Yongzhen Peng, Kongchen Xia, Qi Wu
Summary: In this study, we report an engineered cyclohexanone monooxygenase that can be used for the asymmetric synthesis of chiral alpha-deuterated carbonyl compounds via enantioselective reductive dehalogenation. The engineered enzyme exhibits good chemoselectivity, stereoselectivity, and d-incorporation, making it a promising method for the synthesis of deuterated drugs.
MOLECULAR CATALYSIS
(2024)
Article
Chemistry, Physical
Qi Yang, Ruixuan Xu, Hongqi Nie, Qilong Yan, Jun Liu, Jiuyu Chen, Yunlan Sun
Summary: The adsorption and decomposition processes of ammonium perchlorate (AP) on pure-Al and Al2O3/Al surfaces were investigated using density functional theory. The results showed that the pure-Al surface is more conducive to the decomposition of AP and the activation of NH3, while the Al2O3/Al surface promotes the disengagement of H and NH3 decomposition.
MOLECULAR CATALYSIS
(2024)
Article
Chemistry, Physical
Yudong Hu, Guochao Xu, Ye Ni
Summary: This study identified a novel phenylalanine dehydrogenase (QtPDH) with high catalytic efficiency and thermal stability, making it a promising biocatalyst for industrial production of bulky aromatic primary amines. QtPDH exhibited a broader substrate specificity and significantly longer half-life compared to BbPDH.
MOLECULAR CATALYSIS
(2024)
Article
Chemistry, Physical
Weiling Zhao, Zhiling Huang, Hui Shen, Xianglong Li, Shaofen Zhao, Bo Xie, Shengjie Xia
Summary: This study investigated the effects of metal doping and crystal plane selection on the CO2 adsorption properties of MgO using density functional theory (DFT) methods. The results showed that the appropriate crystal plane and metal doping can improve the adsorption properties of MgO on CO2. The influence of different crystal planes and metal dopants on CO2 adsorption properties varied significantly. The research provides some references for experimental studies on CO2 adsorption by MgO by combining the dual modification of crystal plane and doped metal.
MOLECULAR CATALYSIS
(2024)
Article
Chemistry, Physical
Jie Zhang, Jinwei Chen, Zongbo Shi, Junyu Zhao, Runsheng Zhuo, Ruilin Wang
Summary: In this study, a double-layered silicalite-1 support with high specific surface area was synthesized, and a magnesium modification strategy was adopted to improve the catalytic activity and stability of the zinc-based catalyst. The modified catalyst showed enhanced propylene selectivity and anti-coking property.
MOLECULAR CATALYSIS
(2024)
Article
Chemistry, Physical
Pei-Sen Gao, Chang-Wang Pan, Cheng Liu, Wen -Tong Chen
Summary: Asymmetric electrocatalysis offers a unique approach to obtain enantioenriched molecules that are difficult to obtain through conventional methods. This study developed a novel bifunctional electrocatalyst, enabling the oxidative kinetic resolution of chiral 1,4-diols and gamma-lactones. The work demonstrates the potential of bifunctional electrocatalysis for asymmetric synthetic methods and its importance in the development of novel electrocatalytic methods.
MOLECULAR CATALYSIS
(2024)
Article
Chemistry, Physical
Qinzhe Lin, Xuanjin Lv, Xianming Zeng, Mengning Zhong, Qiyun Wu, Huilin Ren, Shenpeng Xu, Wentian Chen, Wenting Du, Jun Li
Summary: The catalytic efficiency of engineered IRED M5 was found to be relatively low when tasked with a bulky amine substrate. Rational design led to the mutants M203V and F260A, with F260A exhibiting a substantial improvement in conversion and stereoselectivity. The study revealed the potential molecular mechanisms underlying the effect of F260A and M203V on catalytic performance.
MOLECULAR CATALYSIS
(2024)
Article
Chemistry, Physical
Zhishuai Wang, Fengyun Su, Hailong Cao, Mengzhen Tian, Xiang Li, Haiquan Xie, Xiaoli Jin, Zhengdao Li, Xin Ying Kong
Summary: In this study, the efficiency of photocatalytic CO2 reduction was significantly enhanced by incorporating nickel oxide onto niobium pentoxide. The resulting catalyst showed remarkable methane and carbon monoxide production improvements.
MOLECULAR CATALYSIS
(2024)
Article
Chemistry, Physical
A. Yu. Sidorenko, Yu. M. Kurban, T. V. Khalimonyuk, I. V. Il'ina, N. S. Li-Zhulanov, O. S. Patrusheva, V. V. Goltsova, M. P. Bei, Zh. V. Ihnatovich, J. Warna, K. P. Volcho, N. F. Salakhutdinov, D. Yu. Murzin, V. E. Agabekov
Summary: This study provides a comprehensive investigation into the catalytic condensation of renewable 3-carene with formaldehyde for the one-step preparation of terpenoid trans-4-hydroxymethyl-2-carene. Various acids and alumino-silicates were found to catalyze the reaction, but the selectivity to the desired product was limited. Phosphoric acid showed the highest selectivity, and an excess of formaldehyde or catalyst loading significantly increased the yield of the target product. Water presence also led to increased selectivity. Additionally, a detailed mechanism for the 3-carene condensation with formaldehyde was proposed and confirmed through kinetic modeling.
MOLECULAR CATALYSIS
(2024)
Article
Chemistry, Physical
Meng-Yu Rong, Jing Nie, Shen Li, Jun-An Ma
Summary: We synthesized a new class of chiral quaternary ammonium salts and used them as catalysts in phase-transfer catalytic asymmetric alkylation. By employing these catalysts, we obtained a series of chiral fluorinated aromatic alpha-amino acid derivatives with high yields and enantioselectivities.
MOLECULAR CATALYSIS
(2024)
Article
Chemistry, Physical
Zhaozhou Wei, Guangtao Wei, Huixian Che, Deyuan Xiong, Linye Zhang, Ruihua Xue, Yalin Tang, Xuanli Lu
Summary: This study demonstrates that small-sized graphite crystallite and highly defective carbon-based catalysts can increase the -SO3H density of the catalysts and modulate their surface electronic properties, leading to improved efficiency in the alpha-pinene hydration reaction. The reduction of graphite crystallite size is considered a critical step in enhancing the selectivity of alpha-terpineol.
MOLECULAR CATALYSIS
(2024)
Article
Chemistry, Physical
Kempanna S. Kanakikodi, Nagendra Kulal, K. S. Subramanya, M. S. Puneethkumar, Bhavana B. Kulkarni, Ganapati Shanbhag, Sanjeev P. Maradur
Summary: An effective and highly selective protocol for synthesizing asymmetric organic carbonates using dimethyl carbonate (DMC) as a reactant and solvent has been developed. The performance of CeO2 nanostructures with different morphologies in the carbonate interchange reaction (CIR) of alcohols was investigated, and the CeO2 nano-catalyst with rod morphology exhibited the highest oxygen vacancy and remarkable enhancement in conversion. The CeO2 characterization data revealed that the exposed active sites, defect density, coordination state of surface atoms, and reducibility of the catalytic materials are the contributing factors to its high catalytic activity. CeO2 can be easily recovered and reused for multiple cycles.
MOLECULAR CATALYSIS
(2024)
Article
Chemistry, Physical
Yanzhao Gao, Xianglei Meng, Shiqi Huang, Hui Wu, Liantao Jiang, Yu Zhou, Yuting Song, Yanyan Diao
Summary: Gamma alumina modified with alkaline earth metal shows improved catalytic performance for hydrogenation reactions. Pd catalysts supported by Al2O3 and Mg-modified Al2O3 were synthesized and their structure, composition, and surface acidity were investigated. The results showed that Pd/MgO-Al2O3-2 catalyst exhibited the best catalytic performance due to its metallic state palladium and weak acid sites.
MOLECULAR CATALYSIS
(2024)