Article
Chemistry, Physical
Vishakha Kaushik, Hardik L. Kagdada, Dheeraj K. Singh, Sachin Pathak
Summary: The study explores hybrid SERS substrates prepared by coating silver nanoparticles on graphene layers, utilizing both chemical and electromagnetic enhancement mechanisms for remarkable SERS intensities. The experiment and theory demonstrate substantial enhancement in electronic and vibrational properties of graphene fragments through interactions with small silver clusters, leading to enhanced G-band intensity. This research contributes to the understanding of mechanisms and the development of high-performance SERS substrates for sensing applications.
APPLIED SURFACE SCIENCE
(2022)
Review
Chemistry, Multidisciplinary
Shahar Dery, Barak Friedman, Hadar Shema, Elad Gross
Summary: The recent development of high spatial resolution microscopy and spectroscopy tools has allowed for the analysis of reactions in (electro)catalysts at previously unattainable resolution and sensitivity. These studies have revealed that catalysts are more heterogeneous than expected, with variations in active sites leading to differences in reaction mechanisms. This review highlights recent insights gained from high spatial resolution studies, including the detection of reactivity in single particles or molecular catalysts and the analysis of catalyst distribution and accessibility on overall reactivity. It is emphasized that the integration of spectroscopy and microscopy measurements under realistic reaction conditions is essential for bridging the gap between model systems and real-world catalysis research.
Article
Chemistry, Physical
Pratibha L. Gai, Edward D. Boyes
Summary: Real-time in situ visualization and analysis of gas-solid catalyst reactions are crucial for understanding the relationship between dynamic catalyst atomic structure and function. Single atom processes and reaction mechanisms are believed to be important in catalytic reactions, but are not well understood under extreme reaction conditions like gas and temperature.
JOURNAL OF MATERIALS CHEMISTRY A
(2022)
Article
Materials Science, Ceramics
Kelvin Y. Xie, Qirong Yang, Christopher J. Marvel, Mo-Rigen He, Jerry C. LaSalvia, Martin P. Harmer, Chawon Hwang, Richard A. Haber, Kevin J. Hemker
Summary: This paper reviews the progressive understanding of amorphization in three successive generations of boron carbide, comparing the susceptibility of amorphization in each generation and elucidating the fundamental mechanisms that explain the reduction in amorphization for B-rich and B/Si codoped boron carbides. Future research directions to further deepen the understanding of stress-induced amorphization of boron carbide are also discussed.
JOURNAL OF THE AMERICAN CERAMIC SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Aleksandr Kryshtal, Sergiy Bogatyrenko, Olha Khshanovska
Summary: In this study, the melting kinetics of a single Sn nanoparticle was investigated using in situ transmission electron microscopy heating techniques. It was found that a few-monolayer-thick disordered phase nucleated at the surface of the Sn particle at a temperature 25°C below the melting point and grew into the solid core with increasing temperature until the whole particle became liquid. The disordered overlayer was revealed to be a quasi-liquid with a density intermediate between that of solid and liquid Sn.
Article
Geochemistry & Geophysics
Tomoki Taguchi, Yui Kouketsu, Yohei Igami, Tomoyuki Kobayashi, Akira Miyake
Summary: The study reveals the presence of abundant small-sized coesite inclusions in garnet-rich layers from the Italian Western Alps, potentially filling the gap between predicted and observed abundances of coesite worldwide. The results indicate that coesite-derived quartz pseudomorphs are not typical structures in ultrahigh-pressure metamorphic rocks, and the minuscule coesite in many rocks may be overlooked.
EARTH AND PLANETARY SCIENCE LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Kevin M. Roccapriore, Shin-Hum Cho, Andrew R. Lupini, Delia J. Milliron, Sergei Kalinin
Summary: The spatial confinement of matter in functional nanostructures has positioned them at the forefront of nanoscience, serving as playgrounds for exotic physics and quantum phenomena as well as finding applications in various fields. Through modern synthesis processes and precise sculpting, the plasmonic response of nanoparticles can be effectively modified, offering a wide range of possibilities for nanophotonic design.
Article
Engineering, Mechanical
Peng-Han Lu, De-Gang Xie, Bo-Yu Liu, Fei Ai, Zhao-Rui Zhang, Ming-Shang Jin, Xiao Feng Zhang, En Ma, Ju Li, Zhi-Wei Shan
Summary: The translational and rotational motion of solid matter is typically driven by external physical forces, but catalytic palladium nanoparticles were observed to undergo self-propelled, peristalsis-like motion on a substrate under an oxygen atmosphere within an environmental transmission electron microscope. This peristaltic crystal migration with shape oscillation is mediated by profuse surface diffusion and chemical driving forces from palladium-catalyzed gaseous oxidation of a carbonaceous layer, revealing emergent behavior in an energy-metabolizing nano-system.
EXTREME MECHANICS LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Maria Fernanda Moyano-Arocutipa, Jacquelyne Y. Zarria-Romero, Melissa Ysabel Huertas-Chambilla, Noemi-Raquel Checca-Huaman, Jose Pino, Edson C. Passamani, Amaya Arencibia, Juan A. Ramos-Guivar
Summary: Controlled-size maghemite (gamma-Fe2O3) nanoparticles (NPs) were functionalized with zeolite 5A and cetyltrimethylammonium bromide (CTAB) by the co-precipitation method. The magnetic remediation properties of the nanomaterials were characterized, and acute toxicity tests were conducted on Daphnia magna to assess their impact. The nanohybrids showed higher toxicity compared to bare gamma-Fe2O3 NPs and caused significant physiological changes and malformations in the organisms.
CRYSTAL GROWTH & DESIGN
(2023)
Review
Physics, Condensed Matter
See Wee Chee, Thomas Lunkenbein, Robert Schloegl, Beatriz Roldan Cuenya
Summary: This article reviews the latest technology of in situ and operando electron microscopy (EM) studies of heterogeneous catalysts in gas and liquid environments during reactions. The importance of heterogeneous catalysts in efficient production of chemicals/fuels on an industrial scale and their role in ensuring a sustainable future for society is highlighted. The challenges and future directions in experimentally applying these techniques, as well as the critical discussion of spatially-resolved operando measurements and available experimental setups, are addressed.
JOURNAL OF PHYSICS-CONDENSED MATTER
(2021)
Article
Multidisciplinary Sciences
Jaianth Vijayakumar, Tatiana M. Savchenko, David M. Bracher, Gunnar Lumbeeck, Armand Beche, Jo Verbeeck, Stefan Vajda, Frithjof Nolting, C. A. F. Vaz, Armin Kleibert
Summary: This paper provides a detailed understanding of the oxidation process of cobalt nanoparticles and evaluates the development of models for metal oxidation and magnetic phenomena at the nanoscale. Understanding the chemical reactivity and magnetism of 3d transition metal nanoparticles is essential for applications in spintronics and catalysis.
NATURE COMMUNICATIONS
(2023)
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.
Article
Materials Science, Ceramics
H. Plaisantin, J. Danet, I. Berdoyes, G. Laduye, A. Desenfant, G. Chollon
Summary: Chemical vapor deposited SiC coatings were examined using X-ray diffraction, Raman microspectroscopy, and transmission electron microscopy. Different (micro)structures were observed based on specific preparation conditions, showing varying levels of disorder. The coatings exhibited a columnar morphology with a preferred orientation and a faulted cubic structure.
JOURNAL OF THE EUROPEAN CERAMIC SOCIETY
(2023)
Article
Materials Science, Ceramics
Shanshan Xu, Ce Zheng, Yichun Bi, Qingping Mao, Hailong Qin, Yiming Qin, Xiaoqiang Li
Summary: Amosic-3 SiC/SiC composites were irradiated with 6 MeV Si ions at 300 degrees C to doses of 13 and 55 dpa, resulting in the loss of amorphous carbon packets and the growth of SiC grains. A mechanism based on grain growth theory was proposed to explain the relationship between carbon packet loss and SiC grain growth, with evidence from TEM images supporting the proposed mechanism.
JOURNAL OF THE EUROPEAN CERAMIC SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Mei Wang, Asher C. Leff, Yue Li, Taylor J. Woehl
Summary: This study successfully demonstrated the in situ controlled synthesis of alloyed AuCu nanocrystals under LP-TEM, while maintaining the molecular structure of metal thiolate complexes. The research revealed that polymer capping ligands not only have known functions during LP-TEM synthesis, but also prevent copper oxidation and facilitate the formation of prenucleation cluster intermediates.
Article
Multidisciplinary Sciences
Iris C. ten Have, Josepha J. G. Kromwijk, Matteo Monai, Davide Ferri, Ellen B. Sterk, Florian Meirer, Bert M. Weckhuysen
Summary: Converting CO2 into valuable chemicals and fuels is a promising tool for environmental and industrial purposes. This study introduces a new catalyst consisting of cobalt oxide nanoparticles stabilized on various support oxides, which shows higher selectivity and activity in producing C2+ hydrocarbons through a different reaction mechanism.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Jiangqian Yang, Ying He, Jiang He, Yuanshuai Liu, Huawei Geng, Shaohua Chen, Lu Lin, Meng Liu, Tiehong Chen, Qike Jiang, Bert M. Weckhuysen, Wenhao Luo, Zhijie Wu
Summary: This study successfully encapsulated nanoscale Ru clusters within high-aluminum ZSM-5 zeolite, which is of great significance for the rational design and development of zeolitic bifunctional catalysts.
Article
Chemistry, Physical
S. H. van Vreeswijk, M. Monai, R. Oord, J. E. Schmidt, E. T. C. Vogt, J. D. Poplawsky, B. M. Weckhuysen
Summary: In this study, the nano-scale coking behavior of zeolite SSZ-13 was investigated using atom probe tomography (APT), revealing its similarity to silicoaluminophosphate and difference compared to previously studied zeolite ZSM-5.
CATALYSIS SCIENCE & TECHNOLOGY
(2022)
Review
Chemistry, Multidisciplinary
Charlotte Vogt, Bert M. Weckhuysen
Summary: Catalysis is essential in chemistry, enabling the production of various goods and facilitating the shift towards a renewable and circular society. This article explores the concept of active sites in catalysis, discussing different approaches and comparing catalytic concepts from enzymatic and homogeneous catalysis. It highlights the challenge of defining active sites in solid catalysts and emphasizes the need to tailor their functioning according to different parameters.
NATURE REVIEWS CHEMISTRY
(2022)
Article
Multidisciplinary Sciences
Koen W. Bossers, Laurens D. B. Mandemaker, Nikolaos Nikolopoulos, Yuanshuai Liu, Marcus Rohnke, Peter de Peinder, Bas J. P. Terlingen, Felix Walther, Joren M. Dorresteijn, Thomas Hartman, Bert M. Weckhuysen
Summary: The study introduces a spherical cap Ziegler-type catalyst model system to bridge the morphology gap between planar model systems and industrially relevant spherical catalyst particles. The combination of this model system and advanced micro-spectroscopy tools enables high-throughput screening of catalyst functions with industrially relevant morphologies on the nano-scale.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Bas J. P. Terlingen, Tjom Arens, Thomas P. P. van Swieten, Freddy T. T. Rabouw, P. Tim Prins, Michiel M. M. de Beer, Andries Meijerink, Mathieu P. P. Ahr, Eline M. M. Hutter, Coert E. J. van Lare, Bert M. M. Weckhuysen
Summary: In the field of heterogeneous catalysis, the temperature of the reactor or reaction medium is often reported, but it may vary significantly from the temperature of the reactive catalyst. The interplay between catalyst temperature and catalytic performance is not always accurately known. This study uses EuOCl as both a solid catalyst and a thermometer to determine temperature during operation. The results reveal the dynamics of catalyst temperature in relation to reaction conditions and provide insights into heat dissipation mechanisms. This approach of operando catalyst thermometry can enhance understanding of catalyst performance and improve safety in chemical industries.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Correction
Chemistry, Multidisciplinary
Matteo Monai, Marianna Gambino, Sippakorn Wannakao, Bert M. Weckhuysen
CHEMICAL SOCIETY REVIEWS
(2023)
Article
Chemistry, Multidisciplinary
Maximilian J. Werny, Kirsten B. Siebers, Nicolaas H. Friederichs, Coen Hendriksen, Florian Meirer, Bert M. Weckhuysen
Summary: The use of confocal fluorescence microscopy and advanced image processing allows for efficient evaluation of support fragmentation in olefin polymerization catalysts, revealing both intra- and interparticle heterogeneities in the catalyst particles. The observed heterogeneities are primarily attributed to the diverse support structures and metallocene distribution within the catalyst particles. Additionally, a significant number of catalyst particles exhibit limited support fragmentation at the onset of the reaction, potentially impacting the particle size distribution during the early stages of polymerization.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Multidisciplinary Sciences
Guusje Delen, Matteo Monai, Katarina Stanciakova, Bettina Baumgartner, Florian Meirer, Bert M. Weckhuysen
Summary: Researchers have discovered that the sorption and conversion of gaseous molecules on the surface of functional materials preferentially occur on specific undercoordinated high-index surface sites. By combining in situ PiFM with DFT calculations, they have studied the site-specific sorption and conversion of formaldehyde on faceted ZIF-8 microcrystals and observed preferential adsorption on high-index planes. They have also visualized unsaturated nanodomains and found structure sensitive conversion mediated by Lewis acidity on defective ZIF-8 crystals.
NATURE COMMUNICATIONS
(2023)
Editorial Material
Chemistry, Physical
Javier Perez-Ramirez, Bert M. Weckhuysen, Maria E. Southall
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Laurens D. B. Mandemaker, Christia Jabbour, Nikolaos Nikolopoulos, Joren M. Dorresteijn, Miguel Rivera-Torrente, Bert M. Weckhuysen
Summary: The growth mechanisms and molecular phenomena of UiO-67, UU-1, and ZIF-8 metal-organic framework (MOF) films on transparent substrates are studied using transmission-based characterization. UiO-67 follows a Volmer-Weber growth mechanism with assistance from solution-grown seeds. UU-1 exhibits fiber-like morphology and inter-fiber macroporosity, while ZIF-8 shows a similar Volmer-Weber growth mode. CO probe molecule adsorption FT-IR spectroscopy reveals the effects of methanol exposure, with UiO-67 becoming inaccessible to CO, UU-1 undergoing a topotactic transformation, and ZIF-8 remaining stable with impurity removal. This approach opens new possibilities for studying other film materials using transmission-based spectroscopy.
ADVANCED MATERIALS INTERFACES
(2023)
Article
Chemistry, Physical
Thuy T. Le, Wei Qin, Ankur Agarwal, Nikolaos Nikolopoulos, Donglong Fu, Matthew D. Patton, Conan Weiland, Simon R. Bare, Jeremy C. Palmer, Bert M. Weckhuysen, Jeffrey D. Rimer
Summary: This study reveals that the presence of a catalytically inactive siliceous exterior rim on ZSM-5 particles can significantly reduce diffusion limitations, leading to an improved catalyst lifetime. The synthesis of Si-zoned ZSM-5 catalysts improves the diffusion properties of the catalyst. Operando ultraviolet-visible light diffuse reflectance spectroscopy shows a substantial reduction in external coking among Si-zoned samples. Molecular dynamics simulations demonstrate that there are significantly reduced transport limitations in the zoned regions, which contributes to the improved catalyst activity of Si-zoned zeolites compared to ZSM-5 with a homogeneous acid-site distribution.
Article
Chemistry, Multidisciplinary
J. J. Erik Maris, Luke A. Parker, Katarina Stanciakova, Nikolaos Nikolopoulos, Koen M. H. Berendsen, Alfons van Blaaderen, Florian Meirer, Freddy T. Rabouw, Bert M. Weckhuysen
Summary: In this study, we used confocal laser scanning microscopy to investigate the molecular accessibility and diffusion of a small fluorescent dye molecule, resorufin, in the hierarchical, anisotropic pore structure of large zeolite-beta crystals. Our findings revealed that protonated resorufin exhibits strong fluorescence when confined within zeolite micropores, enabling fluorescence microimaging experiments. Through our experiments, we were able to characterize the pore space and quantify the diffusion coefficient in the straight pores of zeolite-beta. We also observed that diffusion is impeded when crossing the boundaries between zeolite subunits.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Florian Zand, Suzanne J. T. Hangx, Christopher J. Spiers, Peter J. van den Brink, James Burns, Matthew G. Boebinger, Jonathan D. Poplawsky, Matteo Monai, Bert M. Weckhuysen
Summary: Understanding and controlling the structure and composition of nanoparticles in supported metal catalysts are crucial for improving chemical processes. Atom probe tomography (APT) is a powerful tool for three-dimensional chemical imaging of materials with nanometer resolution. However, APT has not been used for mesoporous oxide-supported metal catalysts due to sample fracture. In this study, we developed a high-pressure resin impregnation strategy to overcome this issue and successfully applied APT to high-porous supported Pd-Ni catalyst materials active in CO2 hydrogenation. Our results demonstrate the capability of APT to quantitatively assess the size, composition, and metal distribution of nanoparticles in industrial catalysts.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Mark J. J. Mangnus, Vincent R. M. Benning, Bettina Baumgartner, P. Tim Prins, Thomas P. van Swieten, Ayla J. H. Dekker, Alfons van Blaaderen, Bert M. Weckhuysen, Andries Meijerink, Freddy T. Rabouw
Summary: This study investigates the influence of solvent and gas environments on the photoluminescence (PL) properties of lanthanide-doped nanocrystals, and explains the changes in PL spectrum and excited-state lifetimes using energy transfer mediated by molecular vibrations. EVET-mediated quenching holds promise for probing the local chemical environment of nanocrystals dispersed in a liquid or exposed to gaseous molecules.
