Review
Chemistry, Multidisciplinary
Ana Sousa-Castillo, Andrea Marino-Lopez, Begona Puertolas, Miguel A. Correa-Duarte
Summary: Bioorthogonal chemistry has provided a powerful tool for performing biocompatible chemospecific reactions in living systems, particularly in the areas of genetic encoding systems, bioimaging, and cancer therapy. This Minireview focuses on recent advances in the use of heterogeneous catalysts for bioorthogonal reactions, discussing the synthetic strategies of Pd-, Au-, and Cu-based materials, their applications in activating caged fluorophores and prodrugs, and the potential of using external stimuli for targeted drug release in diseased tissues. The review also highlights future directions and challenges in this emerging field.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Multidisciplinary Sciences
Terry Z. H. Gani, Zachariah J. Berkson, Ran Zhu, Jong Hun Kang, John R. Di Iorio, Ka Wing Chan, Daniel F. Consoli, Sohel K. Shaikh, Christophe Coperet, Yuriy Roman-Leshkov
Summary: The authors identify a dynamic site renewal and decay cycle, mediated by proton transfers involving proximal BrOnsted acidic OH groups, which operates concurrently with the Chauvin cycle and could address roadblocks associated with industrial metathesis processes. This cycle can be manipulated using small quantities of promoter olefins to drastically increase steady-state propylene metathesis rates, with negligible promoter consumption, showing potential applicability to other reactions. The increase in activity and reduction of operating temperature requirements were also observed on MoOx/SiO2 catalysts, indicating the broad scope of this strategy in addressing major challenges in industrial metathesis processes.
Article
Chemistry, Multidisciplinary
Yuki Saito, Shu Kobayashi
Summary: The application of heterogeneous catalysts in continuous-flow enantioselective hydroacylation reactions was studied. Catalysts were prepared by mixing supports and rhodium complexes, and showed excellent activity and enantioselectivity. Under optimized conditions, the catalysts exhibited high turnover numbers and could be applied to various substrates. Furthermore, sequential-flow reactions with other heterogeneous catalysts were demonstrated for the synthesis of biologically active molecules and functional materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Polymer Science
Eduard Karakhanov, Anton Maximov, Anna Zolotukhina
Summary: This article reviews the recent advances and applications of dendritic catalysis in the past two decades, with a focus on heterogeneous dendrimer-based catalysts. Three main approaches to synthesizing immobilized heterogeneous dendrimer-based catalysts are considered, and magnetically separable dendritic catalysts are also discussed. These dendritic catalysts can be stored as powders and easily separated from the reaction medium, maintaining efficiency similar to homogeneous dendritic catalysts.
Review
Chemistry, Multidisciplinary
Lifei Lian, Huaiying Zhang, Sai An, Wei Chen, Yu-Fei Song
Summary: POMs, as a class of discrete anionic metal-oxygen clusters with tunable structure, exhibit super strong Bransted acidity, high proton mobility, and thermal stability, making them potential green alternatives to conventional homogeneous acid catalysts. Through design strategies such as functionalized cations, covalent interactions, non-precious metal support, and porous polymer framework, POMs-based heterogeneous catalysts have shown excellent catalytic performance in specific acid-catalyzed reactions.
SCIENCE CHINA-CHEMISTRY
(2021)
Review
Chemistry, Physical
Ekaterina V. Pokochueva, Dudari B. Burueva, Oleg G. Salnikov, Igor V. Koptyug
Summary: HET-PHIP has attracted significant research attention in recent years, showing major prospects for applications in biomedical MRI and industrial catalytic studies, despite the current need for further improvement in NMR signal enhancements.
Article
Chemistry, Physical
Kristian Knemeyer, Jan Dirk Epping, Frederik Ruether, Christian Schulz, Benjamin Frank, Philipp Mueller, Raoul Naumann d'Alnoncourt, Matthias Driess, Frank Rosowski
Summary: The application of atomic layer deposition (ALD) in synthesizing catalysts can reveal the relationships between catalyst performance and properties, which is crucial for studying catalytic conversion processes.
Review
Chemistry, Multidisciplinary
Yang Chen, Jian Lin, Qin Pan, Xu Liu, Tianyi Ma, Xiaodong Wang
Summary: Dual-atom catalysts (DACs) have become a new frontier in heterogeneous catalysis due to their unique intrinsic properties. The synergy between dual atoms provides flexible active sites, promising to enhance performance and even catalyze more complex reactions. However, precisely regulating active site structure and uncovering dual-atom metal interaction remain grand challenges.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Multidisciplinary Sciences
Yanyan Zhao, Sheng Dai, Ke R. Yang, Sufeng Cao, Kelly L. Materna, Hannah M. C. Lant, Li Cheng Kao, Xuefei Feng, Jinghua Guo, Gary W. Brudvig, Maria Flytzani-Stephanopoulos, Victor S. Batista, Xiaoqing Pan, Dunwei Wang
Summary: Atomically dispersed catalysts have shown high activity for selective oxidation of carbon monoxide with excess hydrogen, but their stability is not ideal. This study demonstrates that introducing a structural component to minimize the diffusion of the active metal center significantly improves stability without compromising activity. By using a dinuclear iridium heterogeneous catalyst as a study platform, two types of oxygen species, interfacial and bridge, are identified to work together for both activity and stability. This work provides important insights into the synergistic effect between the active metal center and the supporting substrate, with potential broad applications for atomically dispersed catalysts.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2023)
Article
Chemistry, Physical
David Tetour, Tomas Paska, Veronika Makova, Barbora Nikendey Holubova, Jana Karpiskova, Michal Rezanka, Jiri Brus, Jana Hodacova
Summary: Two hybrid organosilica materials containing bis-cinchonine-phthalazine bridging organic unit were synthesized and used as heterogenized ligands in catalysis of enantioselective Sharpless alkene dihydroxylation. The nanostructured material exhibited higher enantioselectivities than the bulk material and could be used at least five times without loss of enantioselectivity.
JOURNAL OF CATALYSIS
(2021)
Article
Chemistry, Physical
Oleg G. Salnikov, Dudari B. Burueva, Larisa M. Kovtunova, Valerii I. Bukhtiyarov, Kirill V. Kovtunov, Igor V. Koptyug
Summary: In this study, the mechanism of methylenecyclobutane hydrogenation over titania-supported Rh, Pt, and Pd catalysts was investigated using parahydrogen-induced polarization (PHIP) technique. It was found that the reaction leads to the formation of a mixture of cyclic, linear, and branched compounds, and the temperature has a significant influence on the product composition.
Article
Chemistry, Multidisciplinary
Bon Seung Goo, Kyungrok Ham, Yeji Han, Seunghoon Lee, Hayoon Jung, Yongmin Kwon, Youngmin Kim, Jong Wook Hong, Sang Woo Han
Summary: This study successfully decouples the activity of the edge and {110}-plane atoms of Pd NCs by comparing the catalytic behaviors of edge-covered Pd NCs with pristine Pd NCs, providing a new method for more precise examination of the surface properties of various NC catalysts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Bon Seung Goo, Kyungrok Ham, Yeji Han, Seunghoon Lee, Hayoon Jung, Yongmin Kwon, Youngmin Kim, Jong Wook Hong, Sang Woo Han
Summary: This study developed a novel approach to investigate the intrinsic catalytic reactivity of edge and terrace atoms in nanocrystal catalysts. By comparing the catalytic behaviors of edge-covered Pd NCs with those of pristine Pd NCs, researchers successfully decoupled the activity of edge and {110}-plane atoms.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
R. Tyler Mertens, Charles E. Greif, James T. Coogle, Gilles Berger, Sean Parkin, Mark D. Watson, Samuel G. Awuah
Summary: This study reports the development of a gold-catalyzed cross coupling reaction without oxidants, which can form biaryls without homocoupling of aryl halides. The study unveils the critical role of unsymmetrical tricoordinate Au(I) catalysts in this transformation.
JOURNAL OF CATALYSIS
(2022)
Review
Chemistry, Multidisciplinary
Qian Qian Hao, Zhen Zhang, Ya Mao, Kai Xue Wang
Summary: Li-CO2 batteries have attracted extensive attention for their high energy density and utilization of CO2, but their practical application is limited by inferior electrochemical performance. Developing efficient electrocatalysts is crucial for enhancing the performance of Li-CO2 batteries.
Article
Chemistry, Physical
Christopher D. Evans, Jonathan K. Bartley, Stuart H. Taylor, Graham J. Hutchings, Simon A. Kondrat
Summary: Exceptional selectivity of LaMnO3 supported Au catalysts for the oxidation of glycerol to tartronic acid is reported. The choice of metal nanoparticle influences the selectivity of the catalysts.
Article
Chemistry, Physical
Sabrina Ballauri, Enrico Sartoretti, Min Hu, Carmine D'Agostino, Zijuan Ge, Liang Wu, Chiara Novara, Fabrizio Giorgis, Marco Piumetti, Debora Fino, Nunzio Russo, Samir Bensaid
Summary: This study presents an improved design for Pd/Ce-Pr catalysts, showing that the PdO-PrOx interaction in materials with high praseodymium content results in lower activity, while a limited amount of Pr in ceria can lead to a more active catalyst. The simultaneous presence of Pd in its reduced and oxidized forms is a key factor for high activity, and the higher hydrophobicity of the sample significantly reduces the H2O inhibition effect typical of Pd-based materials.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2023)
Review
Chemistry, Multidisciplinary
Nicholas F. Dummer, David J. Willock, Qian He, Mark J. Howard, Richard J. Lewis, Guodong Qi, Stuart H. Taylor, Jun Xu, Don Bethell, Christopher J. Kiely, Graham J. Hutchings
Summary: The direct transformation of methane to methanol at a larger scale remains challenging due to the low reactivity of methane. This review examines several promising routes to methanol and evaluates the performance targets necessary for process development. It provides critical perspectives on future operation and discusses the emergence of active heterogeneous catalysts and their reaction mechanisms.
Article
Chemistry, Physical
Parag M. M. Shah, Liam A. Bailey, Stuart H. Taylor
Summary: A series of ceria-manganese mixed metal oxide catalysts with different Ce:Mn ratios were prepared by coprecipitation, and their capabilities for total oxidation of propane and naphthalene were evaluated. The catalyst with a higher manganese content showed the highest activity, specifically Ce0.25Mn0.75Ox. Characterization techniques revealed that the high activity of Ce0.25Mn0.75Ox was attributed to the formation of phase-separated Mn-substituted ceria and Mn2O3 phases. The catalyst preparation technique also played a significant role, as the mechanochemical and urea catalysts exhibited greater activity than the carbonate coprecipitated catalyst.
Article
Nanoscience & Nanotechnology
Graziano Di Carmine, Costanza Leonardi, Luke Forster, Min Hu, Daniel Lee, Christopher M. A. Parlett, Olga Bortolini, Mark A. Isaacs, Alessandro Massi, Carmine D'Agostino
Summary: The alcoholysis of furfuryl alcohol in SBA-15-pr-SO3H catalysts with different pore sizes was studied. Results showed that changes in pore size have a significant effect on catalyst activity and durability, with larger-pore-size catalysts deactivating more rapidly. The presence of SO3H groups on the external surface and reduced pore clogging were identified as factors contributing to the increased reusability of smaller-pore-size catalysts.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Physical
Heng Liu, Xue Jia, Ang Cao, Li Wei, Carmine D'agostino, Hao Li
Summary: By using surface Pourbaix analysis, this study reveals that the surface state of transition metal X-ide catalysts can be different from their pristine forms under electrochemical conditions, due to water dissociation or generation. This suggests the need to consider the surface state under reaction conditions in order to accurately identify and analyze active sites of these catalysts.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Parag M. M. Shah, Liam A. A. Bailey, David J. J. Morgan, Stuart H. H. Taylor
Summary: Iron-manganese mixed metal oxide catalysts with different Fe:Mn ratios were synthesized and evaluated for total propane oxidation. The Fe0.50Mn0.50Ox catalyst showed the highest activity due to increased surface area and the formation of a Mn2O3 phase. The choice of precipitating agent was found to affect the activity, with the hydroxide-precipitated catalysts generally being more active.
Article
Chemistry, Physical
Run Zou, Sarayute Chansai, Shaojun Xu, Bing An, Shima Zainal, Yangtao Zhou, Ruojia Xin, Pan Gao, Guangjin Hou, Carmine D'Agostino, Stuart M. Holmes, Christopher Hardacre, Yilai Jiao, Xiaolei Fan
Summary: Stabilisation of metal species using hydroxyl-rich dealuminated zeolites is a promising method for catalysis. The presence of abundant hydroxyl groups on dealuminated zeolites stabilises highly active metal-oxygen species and improves the activity and anti-coking ability of the catalyst.
Article
Chemistry, Multidisciplinary
Chengxu Zhu, Carmine D'Agostino, Sam P. de Visser
Summary: The study demonstrates how CO2 and H-2 can be reacted to produce methanol and highlights the crucial steps in the reaction mechanism. Calculations predict that the reaction proceeds through three cycles, requiring high pressure to overcome H-2 cleavage, and the ligand scaffold plays an important role in the reaction mechanism.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Meshal Aljohani, Helen Daly, Lan Lan, Aristarchos Mavridis, Matthew Lindley, Sarah J. Haigh, Carmine D'Agostino, Xiaolei Fan, Christopher Hardacre
Summary: H-2 production from photoreforming of organosolv lignin is lower compared to that from cellulose, but can be enhanced by cycling the catalyst.
Article
Chemistry, Multidisciplinary
Heng Liu, Di Zhang, Stuart M. Holmes, Carmine D'Agostino, Hao Li
Summary: The anion exchange membrane fuel cell (AEMFC) offers a promising way for the broad application of earth-abundant element based catalysts in alkaline media. Recent studies found that zirconium nitride (ZrN) exhibits superior activity in the alkaline oxygen reduction reaction (ORR), even surpassing that of Pt. This study proposes a new theoretical framework to understand the ORR mechanism of ZrN and applies it to other transition metal nitrites. The findings provide insights for the rational design of transition metal nitrides for alkaline ORR.
Article
Chemistry, Physical
Atika Muhammad, Chengxu Zhu, Xiao Yu, Graziano Di Carmine, Hannah Wood, Paola Carbone, Sam P. de Visser, Christopher Hardacre, Carmine D'Agostino
Summary: Heterogenisation of homogeneous catalysts onto solid supports is a potential strategy for recyclable and reuseable catalysis. However, immobilised catalysts usually exhibit lower activity compared to their homogeneous counterparts. In this study, the influence of support and solvent on the catalytic activity of heterogenised catalysts in the H-transfer reduction of propionaldehyde was investigated. The results showed that the choice of support does not significantly affect catalytic activity, but solvents with high affinity for the catalyst surface or solvation effects that hinder access to active sites result in lower activity. Molecular dynamics simulations provided insights into the solvation effects involved in the reactions, which play a crucial role in determining the catalytic behavior. The activity of the heterogenised catalysts was found to be comparable to the homogeneous catalysts, indicating that immobilisation of the homogeneous catalyst onto solid supports is a viable and effective strategy for this type of reaction.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Review
Chemistry, Multidisciplinary
Umar C. Abubakar, Yash Bansod, Luke Forster, Vincenzo Spallina, Carmine D'Agostino
Summary: Acrylic acid, an essential chemical used in various industries, is currently produced from petroleum-based feedstocks, which is unsustainable for achieving net zero carbon emissions. Waste glycerol generated from biodiesel production has been proposed as an alternative feedstock. However, commercial-scale adoption faces challenges in converting glycerol to acrylic acid. This review discusses different conversion routes and their recent developments, highlighting the potential of biochemical conversion for its environmental benefits and thermocatalytic conversion for higher yields.
REACTION CHEMISTRY & ENGINEERING
(2023)
Article
Chemistry, Physical
Carmine D'Agostino, Valentina Preziosi, Giuseppina Caiazza, Maria Vittoria Maiorino, Einar Fridjonsson, Stefano Guido
Summary: Emulsions are widely used in various consumer products and studying their microscopic behavior is challenging. This study investigates the effect of surfactant concentration on the microstructure and diffusion within water-in-oil emulsion systems using low-field pulsed-field gradient (PFG) NMR and optical imaging. The results show that high surfactant concentration leads to smaller droplets and restricted diffusion near the droplet boundaries, while decreasing surfactant concentration results in larger droplets and less pronounced diffusion components.
Article
Chemistry, Physical
Riccardo Bacchiocchi, Alessia Ventimiglia, Andrea Canciani, Giorgia Peroni, Tommaso Tabanelli, Stefania Albonetti, Nikolaos Dimitratos, Ivan Rivalta, Shima Zainal, Luke Forster, Carmine D'Agostino, Fabrizio Cavani
Summary: This study investigates the continuous-flow, gas-phase, catalytic transfer hydrogenation of methyl levulinate and ethanol over zirconia catalysts. The effect of two different crystalline phases on catalyst performance is examined through catalyst characterization and computational and NMR studies, revealing the structure-activity relationship of the catalytic process.
JOURNAL OF CATALYSIS
(2023)