Review
Engineering, Environmental
Shuxing Bai, Ankang Jia, Jialu Song, Shuang Cao, Ning Wang, Xia Liu
Summary: This article summarizes the catalytic mechanism of hydrogen production from formic acid decomposition (FAD) using heterogeneous catalysts. It thoroughly discusses the optimization of FAD performance based on metal, support, and treatment, and proposes a rational design and precise construction approach for efficient catalytic structures.
CHEMICAL ENGINEERING JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Tahani A. C. A. Bayrakdar, Camille Lescot
Summary: A simple Rh-based catalyst has been developed for the carbene transfer reaction of methyl diazoacetate (MDA) and various substrates under heterogeneous flow conditions. Two different methods for heterogenizing the catalyst in a column reactor have been successfully applied. The catalyst exhibited high activity and selectivity for functionalizing different X-H (X=O, S, Si, CH2) bonds and for cyclopropenation under mild continuous flow conditions. Catalyst recycling experiments showed that up to 5 catalytic cycles could be achieved for the carbene O-H insertion reaction, and a sequential transformation of different substrates with up to 10 consecutive runs per reactor was achieved without any loss in catalytic activity, allowing the production of compound families.
Article
Chemistry, Organic
D. N. Gorbunov, M. V. Nenasheva, R. P. Matsukevich, M. V. Terenina, Yu. S. Kardasheva, E. A. Karakhanov
Summary: A phosphine-containing porous polymer (TPDB) and its rhodium-based catalyst have been successfully synthesized, showing good catalytic activity in model reactions. Experimental results demonstrate that the catalyst can be reused multiple times with consistent activity.
PETROLEUM CHEMISTRY
(2021)
Article
Chemistry, Physical
Max Deimling, Shravan R. Kousik, Karina Abitaev, Wolfgang Frey, Thomas Sottmann, Kaloian Koynov, Sabine Laschat, Petia Atanasova
Summary: The study used macro-mesoporous silica inverse opal films as a model system to investigate the molecular infiltration behavior of a probe molecule. The results showed homogeneous tracer distribution in the SiO2-IO films and attachment to both transport and mesopores.
Review
Engineering, Environmental
Mengzhu Li, Weinan Yin, Junan Pan, Yanwei Zhu, Ning Sun, Xinyu Zhang, Yingtong Wan, Zhongzhong Luo, Lanhua Yi, Longlu Wang
Summary: Hydrogen spillover, a phenomenon of active species migration, has received considerable attention in recent years. It not only participates in catalytic reactions as reactants, but also induces support to form defects or phase transitions, thereby adjusting the energy band and improving catalytic performance. As a result, hydrogen spillover has broad potential applications in heterogeneous catalysis and hydrogen production. However, there is still a lack of clear summary on the reaction mechanism and important applications of hydrogen spillover. This review focuses on the recent progress of hydrogen spillover, including different types, structural models, and applications, aiming to provide new ideas for the design and application of hydrogen spillover.
CHEMICAL ENGINEERING JOURNAL
(2023)
Article
Chemistry, Physical
Carlos Lizandara-Pueyo, Xinyuan Fan, Carles Ayats, Miquel A. Pericas
Summary: This study involved the controlled synthesis of calcium carbonate particles surface-functionalized with azido groups, followed by copper-catalyzed alkyne-azide cycloaddition reactions to prepare novel catalytic materials. The immobilized catalyst demonstrated high selectivity and efficiency in catalyzing Michael addition reactions of aldehydes, with the added advantage of being reusable and adaptable to continuous-flow operation for increased productivity.
JOURNAL OF CATALYSIS
(2021)
Article
Chemistry, Analytical
Oleg G. Salnikov, Ivan A. Trofimov, Andrey N. Pravdivtsev, Kolja Them, Jan-Bernd Hoevener, Eduard Y. Chekmenev, Igor V. Koptyug
Summary: This research demonstrates the utility of using RASER to amplify nuclear magnetic resonance (NMR) signals of solute and solvent molecules in the liquid state. The study shows that parahydrogen-induced RASER can enhance nuclear spin polarization of protons and heteronuclei in a wide range of molecules. The experimental results are supported by control experiments and spin dynamics simulations. The enhanced NMR sensitivity achieved through RASER can have significant applications in mixture analysis, metabolomics, and structure determination.
ANALYTICAL CHEMISTRY
(2022)
Article
Chemistry, Physical
Maria Paula de Souza Rodrigues, Andre H. B. Dourado, Leonardo de O. Cutolo, Luanna S. Parreira, Tiago Vinicius Alves, Thomas J. A. Slater, Sarah J. Haigh, Pedro H. C. Camargo, Susana Ines Cordoba de Torresi
Summary: The study presents a mechanism for enhancing the hydrogen evolution reaction (HER) performance using gold-rhodium core-shell nanoflowers (Au@Rh NFs), demonstrating how LSPR excitation from Au NPs can improve the catalytic properties of Rh. This offers insights into optimizing catalytic performance for future applications.
Article
Chemistry, Multidisciplinary
Matthew R. Gyton, Cameron G. Royle, Simon K. Beaumont, Simon B. Duckett, Andrew S. Weller
Summary: The heterogeneous solid-gas reactions of crystals of [Rh(L-2)(propene)][BAr4F] with H-2 and different alkenes and alkynes were investigated using gas-phase NMR spectroscopy. The study provides insights into catalytic pairwise para-H-2 transfer, molecular-level changes in the crystalline catalyst, and the production of high-quality gas-phase spectra. The results reveal the formation of dimeric [Rh(L-2)(H)(mu-H)](2)[BAr4F](2) upon reaction with H-2 and the conversion of NMR silent para-H-2 to NMR active ortho isomer. The hydrogenation of propene and other alkenes and alkynes showed high levels of initial polarization and strong PHIP effects.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Engineering, Chemical
Yani Guan, Donovan Chaffart, Guihua Liu, Zhaoyang Tan, Dongsheng Zhang, Yanji Wang, Jingde Li, Luis Ricardez-Sandoval
Summary: The recent application of machine learning in the development of new heterogeneous catalysts has shown significant progress in establishing relationships between material properties and catalytic performance, improving efficiency in design and screening guidelines. However, accurate prediction of high-performance catalysts still presents challenges.
CHEMICAL ENGINEERING SCIENCE
(2022)
Article
Chemistry, Physical
Jun Hee Jang, Insoo Ro, Phillip Christopher, Mahdi M. Abu-Omar
Summary: A bifunctional Pt-ReOx/C heterogeneous catalyst was used to achieve the one-step conversion of mucic acid to adipates with high yield using isopropanol as solvent and reductant. The catalyst is reusable and demonstrated a broad substrate scope for various diols, showcasing its potential for multifunctional catalysis in biomass-derived molecule valorization.
Article
Chemistry, Multidisciplinary
Yuting Li, Yu Tang, Franklin (Feng) Tao
Summary: This article reports a new supported catalyst, Rh-1/P25, consisting of singly dispersed Rh-1 atoms anchored on TiO2 (P25) nanoparticles. The Rh-1/P25 catalyst exhibits high activity for C-N coupling and demonstrates selectivity of higher than 90% for producing tertiary amines in six hydroaminoalkylation reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Physical
Calum T. J. Ferguson, Kai A. Zhang
Summary: The combination of classical polymers with photocatalytic small molecules has yielded a class of recyclable photocatalytic materials that are inexpensive, easy to produce, and versatile in functionality and physical features. These materials can be easily tuned for specific application requirements, enabling a broad range of visible-light-mediated photoredox reactions.
Article
Chemistry, Multidisciplinary
Emmett D. Goodman, Arun S. Asundi, Adam S. Hoffman, Karen C. Bustillo, Jonathan F. Stebbins, Simon R. Bare, Stacey F. Bent, Matteo Cargnello
Summary: The study demonstrates the importance of electronic and geometric interactions between active and support phases in heterogeneous catalysts, focusing on the challenging study of metal-support interactions. By utilizing ALD and colloidal nanocrystal synthesis methods, catalysts with sub-nanometer precision of active and support phases were prepared, allowing for detailed examination of metal-support interactions. The research highlights the significant impact of coverage and structure of Al2O3 at the Pd/Al2O3 interface on catalytic activity, with even a single monolayer of alumina contributing to a tenfold increase in reaction rate.
ADVANCED MATERIALS
(2021)
Article
Chemistry, Physical
Weiyu Wang, Qiang Wang, Jun Xu, Feng Deng
Summary: Parahydrogen-induced polarization (PHIP) is a technique that can increase the NMR sensitivity by several orders. It is a powerful tool to characterize catalyst properties and elucidate reaction mechanisms. In this Perspective, the heterogeneous PHIP (HET-PHIP) technique and its application in catalytic hydrogenation are comprehensively reviewed. The fundamentals of HET-PHIP are introduced and its ability to provide information about catalyst morphology and electronic properties is discussed. The mechanistic understanding of catalytic hydrogenations using HET-PHIP is also discussed.
Editorial Material
Physics, Atomic, Molecular & Chemical
Daniel Abergel, Gerd Buntkowsky, Konstantin L. Ivanov, Perunthiruthy K. Madhu
APPLIED MAGNETIC RESONANCE
(2021)
Article
Chemistry, Multidisciplinary
Laurynas Dagys, Vytautas Klimavicius, Martin Brodrecht, Gerd Buntkowsky, Vytautas Balevicius
Summary: The study investigated cross-polarization with magic-angle spinning (CP MAS) kinetics between remote spins in various selected materials, aiming to understand the thermal equilibration pathways and determine the fractal dimensions. The results suggest that different compounds exhibit distinct fractal dimensions, with thermal equilibration mediated primarily through strong interatomic/intramolecular vibrations and high proton mobility along H-bonds.
JOURNAL OF PHYSICS AND CHEMISTRY OF SOLIDS
(2021)
Article
Multidisciplinary Sciences
Stephan Knecht, John W. Blanchard, Danila Barskiy, Eleonora Cavallari, Laurynas Dagys, Erik Van Dyke, Maksim Tsukanov, Bea Bliemel, Kerstin Muennemann, Silvio Aime, Francesca Reineri, Malcolm H. Levitt, Gerd Buntkowsky, Alexander Pines, Peter Bluemler, Dmitry Budker, James Eills
Summary: This study discusses the techniques of hyperpolarizing fumarate using dissolution dynamic nuclear polarization and parahydrogen-induced polarization, as well as the method of purifying pure solid fumarate from impurities through acid precipitation.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2021)
Article
Physics, Atomic, Molecular & Chemical
Laura Wienands, Franziska Theiss, James Eills, Lorenz Roesler, Stephan Knecht, Gerd Buntkowsky
Summary: Parahydrogen-induced polarization is a hyperpolarization method that enhances nuclear magnetic resonance signals through chemical reactions involving the para spin isomer of hydrogen gas. This method allows for biomolecules to be hyperpolarized for real-time in vivo metabolic imaging. Current research on the efficient hyperpolarization of fumarate has not been thoroughly investigated, leading to inconsistencies in chosen reaction conditions in previous work seeking higher reaction rates and yields.
APPLIED MAGNETIC RESONANCE
(2022)
Article
Thermodynamics
Markus M. Hoffmann, Joseph D. Kealy, Torsten Gutmann, Gerd Buntkowsky
Summary: The study investigated the physical properties of polyethylene glycol (PEG) and its binary mixtures, finding a linear relationship between temperature and density, while viscosity and self-diffusion coefficients followed the Arrhenius law. Calculated molar volumes largely agreed with measured values, viscosities were mostly within a few percent, and self-diffusion coefficients were generally within 20% of measurement uncertainty.
JOURNAL OF CHEMICAL AND ENGINEERING DATA
(2022)
Review
Biochemistry & Molecular Biology
Mateusz Wozny, Adam Mames, Tomasz Ratajczyk
Summary: This article presents the recent developments in the synthesis and properties of new triptycenes, and compares them with earlier pivotal works. The focus of the research includes new synthesis methods and regioselective synthesis of highly sterically demanding systems, as well as the application of triptycenes in catalysis. Additionally, the article discusses the relationship between triptycene structures and their properties, as well as their unique properties and molecular interactions in the liquid and solid states.
Article
Biochemistry & Molecular Biology
Kristina Kristinaityte, Mateusz Urbanczyk, Adam Mames, Mariusz Pietrzak, Tomasz Ratajczyk
Summary: Anthracenes are important in chemistry and materials sciences for their unique structure and reactivity. Photodimerization of anthracenes can lead to novel photoresponsive materials. This study utilized NMR spectroscopy to investigate the photodimerization of two anthracenes, showing differences in reaction rates when studied separately or in a mixture. Additionally, the study of mixtures provided insight into relative reactivity and improved understanding of the photodimerization processes for potential applications in material sciences.
Article
Biochemistry & Molecular Biology
Nargiz B. Asanbaeva, Larisa Yu Gurskaya, Yuliya F. Polienko, Tatyana Rybalova, Maxim S. Kazantsev, Alexey A. Dmitriev, Nina P. Gritsan, Nadia Haro-Mares, Torsten Gutmann, Gerd Buntkowsky, Evgeny Tretyakov, Elena G. Bagryanskaya
Summary: This study investigates the feasibility of using ferrocene-substituted 1,3-diazetidine-2,4-diimine couplers as DNP agents. The results show that the spiro-substituted nitroxyl biradicals have a higher DNP gain compared to the methyl-substituted biradicals. The difference in temperature dependence of the EPR spectra is explained using DFT calculations. The effects of nucleophiles and substituents on the ring-opening reaction and the influence of ring opening on the exchange interaction are also examined.
Article
Chemistry, Multidisciplinary
Kristina Kristinaityte, Adam Mames, Mariusz Pietrzak, Franz F. Westermair, Wagner Silva, Ruth M. Gschwind, Tomasz Ratajczyk, Mateusz Urbanczyk
Summary: Comprehensive real-time in situ monitoring of chemical processes is essential for a deep understanding and efficient design of chemicals and materials. This work demonstrates the simultaneous utilization of two novel time-resolved NMR methods, allowing the follow-up of diffusion coefficient and monitoring of specific products with excellent resolution. By employing both methods and comparing their results, the validation of the second method is unequivocally achieved.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
Markus M. Hoffmann, Matthew D. Too, Nathaniel A. Paddock, Robin Horstmann, Sebastian Kloth, Michael Vogel, Gerd Buntkowsky
Summary: In this study, molecular dynamics simulations were performed to investigate polyethylene glycol (PEG)200. Force fields for describing ethylene glycol oligomers were tested and adjusted to improve the agreement with experimental properties. The simulations revealed that PEG200 is a random mixture of its ethylene glycol oligomer components.
JOURNAL OF PHYSICAL CHEMISTRY B
(2023)
Article
Chemistry, Physical
Sonja C. Doeller, Torsten Gutmann, Markus Hoffmann, Gerd Buntkowsky
Summary: This study investigates the behavior of four different commercially available polarizing agents using 1-octanol as the analyte. By establishing a relative method to compare the direct and indirect polarization transfer pathways, it is possible to directly compare the polarization efficacy for different radicals and different parts of the 1-octanol molecule. The results highlight the importance of hydrophilicity in the polarization transfer process.
SOLID STATE NUCLEAR MAGNETIC RESONANCE
(2022)
Article
Biochemistry & Molecular Biology
Nargiz B. B. Asanbaeva, Sergey A. A. Dobrynin, Denis A. A. Morozov, Nadia Haro-Mares, Torsten Gutmann, Gerd Buntkowsky, Elena G. G. Bagryanskaya
Summary: This paper reports on the DNP efficiency at a high magnetic field for two water-soluble biradicals resistant to reducing media. The radicals were obtained in the form of quaternary ammonium salts to achieve water solubility. The influence of hyperfine interaction and exchange interaction on the DNP effect was determined through EPR spectroscopy.
Article
Chemistry, Multidisciplinary
Adam Mames, Sylwia Jopa, Mariusz Pietrzak, Tomasz Ratajczyk
Summary: Signal Amplification by Reversible Exchange (SABRE) and hydrogenable Parahydrogen Induced Polarization (hPHIP) can enhance weak NMR signals, expanding the range of NMR applications. Using an N-heterocyclic carbene Ir-based catalyst, simultaneous SABRE and hPHIP was achieved for a compound with an N-donor site and an acetylene triple bond. The interplay between SABRE and hPHIP can be manipulated, with the hPHIP effect almost completely suppressed while stable SABRE is observed in subsequent consecutive experiments. These results have the potential to increase the number of parahydrogen hyperpolarizable molecules.
