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, Physical
Yun-Nan Gong, Bi-Zhu Shao, Jian-Hua Mei, Wei Yang, Di-Chang Zhong, Tong-Bu Lu
Summary: This study successfully developed photocatalysts with highly dispersed metal centers on g-C3N4 through a simple synthesis method, with the optimal 25-Co-C3N4 showing excellent performance for CO2 reduction without the need for noble metal catalysts/sensitizers.
Article
Chemistry, Analytical
Xiaojun Hu, Yanjie Huang, Jie Chen, Xiaoyu Zhu, Zhihui Mao, Yindian Wang, Ruhui Hu, Hongxia Chen
Summary: The study successfully achieved the preparation of flower-like catalysts using a calixarene-mediated cascade self-assembly method, which increased catalytic activity and selective recognition by mimicking the dual active sites of heme-protein and FeN5. This enabled effective detection of cancer cells with potential for rapid fabrication of artificial enzymes with effective activity and selectivity.
SENSORS AND ACTUATORS B-CHEMICAL
(2021)
Review
Chemistry, Physical
Amarajothi Dhakshinamoorthy, Eva Montero Lanzuela, Sergio Navalon, Hermenegildo Garcia
Summary: Metal organic frameworks (MOFs) are porous crystalline solids with metal ions and rigid organic linkers, leading to materials with high surface area and pore volume. This article reviews Co-based MOFs for oxidation reactions, comparing their advantages with homogeneous salts in terms of product selectivity and stability. Future developments in this field are discussed in the final section.
Article
Chemistry, Multidisciplinary
Meng-Ting Ming, Yu-Chen Wang, Wei-Xue Tao, Wen-Jie Shi, Di-Chang Zhong, Tong-Bu Lu
Summary: Unlocking the potential of sustainable fuel production through the development of highly efficient CO2 reduction catalysts under visible light irradiation remains an ongoing challenge. Herein, a strategically designed Zr-based metal-organic framework (MOF) photocatalyst, incorporating binuclear cobalt complexes as catalytic sites, achieved an impressive CO yield, outperforming its mononuclear counterpart and showcasing exceptional catalytic capabilities. Experimental findings and Density Functional Theory (DFT) calculations revealed the synergistic catalytic effect between the two Co sites and the heightened light absorption attributed to the incorporation of the amino group. By offering a bioinspired approach to designing efficient dual-atom MOF photocatalysts for CO2 reduction, this study has significant implications for the future of sustainable energy production.
Article
Chemistry, Physical
Qining Wang, Jiaxin Dawn Duan, Timothy Goetjen, Joseph Hupp, Justin Notestein
Summary: In this study, the researchers investigated the effect of changing the Cu:Ni ratio on the reactivity of non-oxidative ethanol dehydrogenation using the Zr-based metal-organic framework (MOF) catalyst support, NU-1000. They found that increasing the Ni2+ concentration significantly reduced the activation energy of the reaction by suppressing the onset of Cu reduction. This study demonstrates the potential of using MOFs as catalyst supports to optimize catalyst compositions and understand their impact on catalytic performances.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Ben Ma, Qi Xia, Deyang Wang, Ji-Kang Jin, Zekun Li, Qiu-Jiang Liang, Meng-Ying Sun, Dongyi Liu, Li-Juan Liu, Hui-Xing Shu, Jun Yang, Dan Li, Jian He
Summary: Visible-light copper photocatalysis has become a viable technology for sustainable synthetic processes. In this study, a metal-organic framework (MOF)-supported copper(I) photocatalyst was developed for iminyl radical-mediated reactions. The heterogenized copper photosensitizer exhibited higher catalytic activity than its homogeneous counterpart due to site isolation. The immobilization of copper species on MOF supports using a hydroxamic acid linker allowed for high recyclability of the heterogeneous catalysts and the preparation of previously unavailable monomeric copper species through post-synthetic modification on MOF surfaces. This study highlights the potential of MOF-based heterogeneous catalytic systems in addressing challenges in synthetic methodologies and mechanistic investigations of transition-metal photoredox catalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Nanoscience & Nanotechnology
Benjamin P. Williams, Wei-Shang Lo, Joseph Morabito, Allison P. Young, Frances Tsung, Chun-Hong Kuo, Joseph M. Palomba, Thomas M. Rayder, Lien-Yang Chou, Brian T. Sneed, Xiao-Yuan Liu, Leo K. Lamontagne, Christopher A. Petroff, Casey N. Brodsky, Jane Yang, Ilektra Andoni, Yang Li, Furui Zhang, Zhehui Li, Sheng-Yu Chen, Connor Gallacher, Banruo Li, Sheng-Yuan Tsung, Ming-Hwa Pu, Chia-Kuang Tsung
Summary: Professor Chia-Kuang (Frank) Tsung's scientific impact lies in his atomic-level design of nanoscale materials for heterogeneous catalysis, focusing on both surface and subsurface approaches. He synthesized controlled nanoparticles to enhance catalysis efficiency and utilized metal-organic frameworks (MOFs) for improving catalyst stability and selectivity. Overall, his work emphasized rational design of nanocrystal surfaces, encapsulation in MOFs, and tuning host-guest interactions to inhibit catalyst degradation.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Chemistry, Inorganic & Nuclear
Rajashree Newar, Wahida Begum, Naved Akhtar, Neha Antil, Manav Chauhan, Ajay Kumar, Poorvi Gupta, Jaideep Malik, Balendra, Kuntal Manna
Summary: A metal-organic framework supported monoligated phosphine-cobalt complex has been developed as an active heterogeneous catalyst for aromatic C-H borylation and alkene hydroboration. The catalyst shows broad substrate scope and excellent functional group tolerance, leading to the synthesis of arene- and alkyl-boronate esters with high yields and selectivity. Notably, the catalyst exhibits high turnover number and can be recycled and reused multiple times.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Fanzhen Lin, Anguo Zhang, Jiapeng Zhang, Lijing Yang, Fengming Zhang, Ran Li, Hua Dong
Summary: Carbon-supported Co catalysts fabricated in this study exhibit excellent catalytic activity for NaBH4 hydrolysis, particularly under alkaline conditions. The good distribution of Co species in the catalysts allows for high metal loading without significant decrease in Co efficiency. This type of Co catalyst shows great promise for controllable hydrogen generation from NaBH4 hydrolysis.
COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
(2021)
Review
Materials Science, Multidisciplinary
Kaiwen Xue, Yan Mo, Baojun Long, Wen Wei, Changsheng Shan, Shaojun Guo, Li Niu
Summary: Single-atom catalysts (SACs) have drawn extensive attention due to their high catalytic activity and selectivity, high utilization of metal atoms, and cost reduction. Ordered porous materials (OPMs) serve as promising carriers for stabilizing single atoms by tuning their geometric and electronic structures through interactions, enhancing the catalytic activity. The development of SACs based on OPMs such as zeolites, metal-organic frameworks, and ordered mesoporous materials has been rapidly advancing, providing opportunities and challenges for developing novel catalysts with superior catalytic performances in the future.
Review
Chemistry, Multidisciplinary
Jiaojiao Fang, Qingqing Chen, Zhi Li, Junjie Mao, Yadong Li
Summary: Single-atom catalysts (SACs) show excellent catalytic activity, high selectivity, and maximum atomic utilization efficiency, but tend to migrate and aggregate under typical reaction conditions. This article summarizes the precise synthesis of SACs and their various heterogeneous catalyses, especially in oxidation and reduction reactions of small organic molecules. The challenges faced by single-atom materials in heterogeneous catalysis are also discussed.
CHEMICAL COMMUNICATIONS
(2023)
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.
Article
Chemistry, Multidisciplinary
Yuanjun Chen, Rui Gao, Shufang Ji, Haijing Li, Kun Tang, Peng Jiang, Haibo Hu, Zedong Zhang, Haigang Hao, Qingyun Qu, Xiao Liang, Wenxing Chen, Juncai Dong, Dingsheng Wang, Yadong Li
Summary: This study demonstrates the correlation between atomic configuration induced electronic density of single-atom Co active sites and oxygen reduction reaction (ORR) performance. The designed and synthesized Co-1-N3PS/HC catalyst shows outstanding ORR activity in alkaline and acidic media, surpassing Pt/C and most non-precious ORR electrocatalysts. Insights from this work promote rational design of efficient catalysts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Aljaz Skrjanc, Dominik Jankovic, Anton Meden, Matjaz Mazaj, Erik Svensson Grape, Martin Gazvoda, Natasa Zabukovec Logar
Summary: This study reports the synthesis of the first Ni-based ZIFs and demonstrates their high potential as heterogeneous catalysts for the Suzuki-Miyaura cross-coupling reaction. The presence and arrangement of the carbonyl functional groups on the imidazole linker play a crucial role in completing the preferred octahedral coordination of nickel, providing a promising platform for the rational design of Ni-based ZIFs for a wide range of catalytic applications.
Article
Chemistry, Multidisciplinary
Rajashree Newar, Naved Akhtar, Neha Antil, Ajay Kumar, Sakshi Shukla, Wahida Begum, Kuntal Manna
Summary: This study presents a strategy to develop eco-friendly asymmetric catalysts using naturally occurring amino acids and earth-abundant metals, resulting in highly active and enantioselective catalysts for hydrosilylation and hydroboration of carbonyl compounds by grafting amino acids within the pores of a metal-organic framework (MOF) and post-synthetic metalation with iron precursor. The MOF-Fe catalyst exhibited high turnover numbers and good recyclability, demonstrating higher activity and enantioselectivity compared to its homogeneous control catalyst due to the formation of robust single-site catalyst in the MOF through site-isolation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Neha Antil, Ajay Kumar, Naved Akhtar, Rajashree Newar, Wahida Begum, Ashutosh Dwivedi, Kuntal Manna
Summary: The study introduces a highly efficient, chemoselective, and reusable nickel hydride catalyst for hydrogenation of nitro and nitrile compounds under mild conditions. The catalyst, based on aluminum metal-organic frameworks, has broad substrate scope and excellent functional group tolerance, and can be recycled at least 10 times. This work highlights the potential of MOF-based single-site earth-abundant metal catalysts for practical and eco-friendly production of chemical feedstocks and biofuels.
Article
Chemistry, Inorganic & Nuclear
Neha Antil, Ajay Kumar, Naved Akhtar, Rajashree Newar, Wahida Begum, Kuntal Manna
Summary: A heterogeneous catalyst based on aluminum metal-organic framework and cobalt(II) hydride was reported for selective and efficient deoxygenation of a wide range of carbonyls and alcohols. The catalyst can be recycled and operates under ambient hydrogen pressure.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Neha Antil, Naved Akhtar, Rajashree Newar, Wahida Begum, Ajay Kumar, Manav Chauhan, Kuntal Manna
Summary: The development of efficient and enantioselective heterogeneous catalysts based on abundant elements and inexpensive ligands is crucial for environmentally friendly and cost-effective production of optically active compounds. This study demonstrates the synthesis of chiral amino alcohol-functionalized metal-organic frameworks as highly enantioselective base-metal catalysts for asymmetric organic transformations.
Article
Chemistry, Inorganic & Nuclear
Rajashree Newar, Wahida Begum, Naved Akhtar, Neha Antil, Manav Chauhan, Ajay Kumar, Poorvi Gupta, Jaideep Malik, Balendra, Kuntal Manna
Summary: A metal-organic framework supported monoligated phosphine-cobalt complex has been developed as an active heterogeneous catalyst for aromatic C-H borylation and alkene hydroboration. The catalyst shows broad substrate scope and excellent functional group tolerance, leading to the synthesis of arene- and alkyl-boronate esters with high yields and selectivity. Notably, the catalyst exhibits high turnover number and can be recycled and reused multiple times.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Neha Antil, Ajay Kumar, Naved Akhtar, Wahida Begum, Manav Chauhan, Rajashree Newar, Manhar Singh Rawat, Kuntal Manna
Summary: This study reports a robust and recyclable single-site cobalt-hydride catalyst based on a porous aluminum metal-organic framework for chemoselective hydrogenation of arenes and tandem hydrogenation-hydrodeoxygenation reactions. The catalyst demonstrated excellent catalytic activity, functional group tolerance, and reusability, highlighting the potential of MOF-supported base-metal catalysts for sustainable and environment-friendly industrial production of chemicals and biofuels.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Neha Antil, Manav Chauhan, Naved Akhtar, Rajashree Newar, Wahida Begum, Jaideep Malik, Kuntal Manna
Summary: This article reports the development of a highly efficient catalyst for the selective oxidation of methane to methanol under mild conditions. The catalyst, a cobalt hydroxide supported by a cerium metal-organic framework, achieves a high methanol yield and selectivity using hydrogen peroxide as the oxidant. Experimental and computational studies provide insights into the active sites and catalytic mechanism of the catalyst.
Article
Chemistry, Inorganic & Nuclear
Rahul Kalita, Wahida Begum, Poorvi Gupta, Manav Chauhan, Naved Akhtar, Rajashree Newar, Kuntal Manna
Summary: This research reports on the synthesis and characterization of an aluminum metal-organic framework node-supported copper(II) chloride catalyst, which efficiently oxidizes alkenes to carbonyl or diol compounds using H2O2 as an oxidizing agent. The catalyst exhibits excellent selectivity and can be recycled, highlighting the importance of MOF-supported metal catalysts for oxidation reactions.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Neha Antil, Manav Chauhan, Naved Akhtar, Rahul Kalita, Kuntal Manna
Summary: The direct conversion of methane to acetic acid in a one-step reaction is a industrially important method. Researchers have discovered that by using a metal-organic framework catalyst with a copper hydroxyl site, methane can be oxidized to acetic acid using molecular oxygen under mild conditions. This study is significant for the design of low-cost and environmentally friendly catalysts for the conversion of methane to acetic acid and other valuable chemicals.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Materials Science, Multidisciplinary
Chandan Bhogendra Jha, Chitrangda Singh, Raunak Varshney, Sweta Singh, Kuntal Manna, Rashi Mathur
Summary: This study synthesizes amino acid-based MOF using l-aspartic acid and calcium, and optimizes the reaction conditions. Despite low porosity and surface area, the Ca-MOF shows high impact on haemostatic property. It has the shortest clotting time and lowest blood loss in a rat-tail amputation model, suggesting its potential as a safe and effective haemostatic agent.
MATERIALS ADVANCES
(2023)
Article
Chemistry, Inorganic & Nuclear
Naved Akhtar, Manav Chauhan, Poorvi Gupta, Neha Antil, Kuntal Manna
Summary: This study presents a practical and environmentally friendly method for the synthesis of formamides through N-formylation of amines using CO2 as a cheap and non-toxic C1-feedstock and hydrosilane reducing agent. The use of a porous metal-organic framework-supported cobalt catalyst allows for efficient and chemoselective mono-N-formylation of a wide range of aliphatic and aromatic amines under mild conditions. The catalyst exhibits good tolerance towards various functional groups and can be recycled multiple times.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Physical
Neha Antil, Manav Chauhan, Naved Akhtar, Rajashree Newar, Wahida Begum, Jaideep Malik, Kuntal Manna
Summary: In this study, a novel Ce-UiO-Co heterogeneous catalyst is reported, which can efficiently convert methane to methanol under mild conditions with high selectivity and yield. The catalyst design is based on a metal-organic framework and involves the formation of an intermediate species in the pores of Ce-UiO-66, enabling the activation and functionalization of methane.
Article
Chemistry, Physical
Rajashree Newar, Rahul Kalita, Naved Akhtar, Neha Antil, Manav Chauhan, Kuntal Manna
Summary: A single-site cobalt(ii) hydride catalyst supported on an aluminum metal-organic framework (DUT-5-CoH) is capable of efficiently transforming amines into the corresponding N-formamides, with high catalytic activity and recyclability.
CATALYSIS SCIENCE & TECHNOLOGY
(2022)
Article
Chemistry, Multidisciplinary
Krishna N. Tripathi, Shashank Singh, Naved Akhtar, Kuntal Manna, Ravi P. Singh
Summary: An unprecedented photochemical platform for efficient site-selective C-H alkylation of the C7 position of the benzocore has been reported using Ru(ii) as a photocatalyst in visible light. The transformation demonstrates broad substrate scope and good functional group compatibility, with insights into the mechanistic details of the reaction provided through controlled experiments and DFT calculations.
CHEMICAL COMMUNICATIONS
(2022)
