Magnetic stir bars are routinely used by every chemist doing synthetic or catalytic transformations in solution. Each bar lasts for months or years, as the regular PTFE (polytetrafluoroethylene) coating is believed to be highly durable, inert, and resistant to multiple washings and cleanings. By using electron microscopy, we found out quite unexpectedly that the surface of magnetic stir bars is susceptible to microscale destruction and forms various types of defects. These microscopic defects effectively trap and accumulate trace amounts of active components from reaction mixtures, most notably metal species. Trapped in surface defects, the impurities escape elimination by washing and cleaning, thus remaining on the surface. FE-SEM/EDX analysis shows that the surface of used stir bars is littered with contaminants representing a variety of metals (Pd, Pt, Au, Fe, Co, Cr, etc.). ESI-MS monitoring corroborates the transfer of the trace metal species to reaction mixtures, while chemical tests indicate their significant catalytic activity. A theoretical DFT study reveals a remarkably high binding energy of metal atoms to the PTFE surface, especially in cases of local mechanical disruption or chemical influence. A plausible mechanism of PTFE surface contamination is suggested, and the results show that metal contamination of reusable polymercoated labware is greatly underestimated. The present study suggests that corresponding control experiments with an unused stir bar (to avoid misinterpretations due to the influence of contamination of magnetic stir bars) are a "must do" for reporting high-performance catalytic reactions, reactions with low catalyst loadings, metal-catalyst-free reactions, and mechanistic studies.
In the present study state-of-the-art experimental techniques involving ultra high resolution SEM/STEM microscopy (1 Å resolution), high brilliance X-ray absorption spectroscopy and theoretical calculations on truly nanoscale systems were utilized to reveal the role of carbon centers in the formation and nature of Pd/C catalytic materials.
Microwave irradiation of Ni, Co, Cu, Ag, and Pt metal salts supported on graphite and charcoal revealed a series of carbon surface modification processes that varied depending on the conditions used (inert atmosphere, vacuum, or air) and the nature of metal salt. Carbon materials, routinely used to prepare supported metal catalysts and traditionally considered to be innocent on this stage, were found to actively change under the studied conditions: etching and pitting of the carbon surface by metal particles as well as growth of carbon nanotubes were experimentally observed by FE-SEM analysis. Catalyst preparation under microwave irradiation led to the formation of complex metal/carbon structures with significant changes in carbon morphology. These findings are of great value in developing an understanding of how M/C catalysts form and evolve and will help to design a new generation of efficient and stable catalysts. The energy surfaces of carbon support modification processes were studied with theoretical calculations at the density functional level. The energy surface of the multistage process of carbon nanotube formation from an etched graphene sheet was calculated for various types of carbon centers. These calculations indicated that interconversion of graphene layers and single wall carbon nanotubes is possible when cycloparaphenylene rings act as building units.
A facile direct deposition approach for the preparation of recyclable Pd/C catalysts simply by stirring a solution of tris(dibenzylideneacetone)dipalladium(0) with a suitable carbon material was evaluated. An extraordinarily rapid catalyst preparation procedure (<5 min) under mild conditions and its excellent performance in cross‐coupling and hydrogenation reactions were demonstrated. The key point for catalyst design is the direct deposition of Pd0 centers onto the highly accessible surface area and the avoidance of ill‐defined PdII/Pd0 states.
An approach to the spatially localized characterization of supported catalysts over a reaction course is proposed. It consists of a combination of scanning, transmission, and high-resolution scanning transmission electron microscopy to determine metal particles from arrays of surface nanoparticles to individual nanoparticles and individual atoms. The study of the evolution of specific metal catalyst particles at different scale levels over time, particularly before and after the cross-coupling catalytic reaction, made it possible to approach the concept of 4D catalysis–tracking the positions of catalytic centers in space (3D) over time (+1D). The dynamic behavior of individual palladium atoms and nanoparticles in cross-coupling reactions was recorded with nanometer accuracy via the precise localization of catalytic centers. Single atoms of palladium leach out into solution from the support under the action of the catalytic system, where they exhibit extremely high catalytic activity compared to surface metal nanoparticles. Monoatomic centers, which make up only approximately 1% of palladium in the Pd/C system, provide more than 99% of the catalytic activity. The remaining palladium nanoparticles changed their shape and could move over the surface of the support, which was recorded by processing images of the array of nanoparticles with a neural network and aligning them using automatically detected keypoints. The study reveals a novel opportunity for single-atom catalysiseasier detachment (capture) from (on) the carbon support surface is the origin of superior catalytic activity, rather than the operation of single atomic catalytic centers on the surface of the support, as is typically assumed.
Homogeneous catalysis is typically considered "welldefined" from the standpoint of catalyst structure unambiguity. In contrast, heterogeneous nanocatalysis often falls into the realm of "poorly defined" systems. Supported catalysts are difficult to characterize due to their heterogeneity, variety of morphologies, and large size at the nanoscale. Furthermore, an assortment of active metal nanoparticles examined on the support are negligible compared to those in the bulk catalyst used. To solve these challenges, we studied individual particles of the supported catalyst. We made a significant step forward to fully characterize individual catalyst particles. Combining a nanomanipulation technique inside a field-emission scanning electron microscope with neural network analysis of selected individual particles unexpectedly revealed important aspects of activity for widespread and commercially important Pd/C catalysts. The proposed approach unleashed an unprecedented turnover number of 10 9 attributed to individual palladium on a nanoglobular carbon particle. Offered in the present study is the Totally Defined Catalysis concept that has tremendous potential for the mechanistic research and development of high-performance catalysts.
Metal on carbon catalysts (M/C) are ubiquitously used in modern research and industry to carry out a variety of chemical transformations. Stable metal-support frameworks and inertness of the carbon materials are usually taken for granted in these very useful catalytic systems. Initially, the present study was aimed to increase the efficiency of Pd/C and Pt/C catalytic systems under microwave and conventional heating. Interestingly, a dynamic behavior of the metal nanoparticles was revealed, and a series of carbon support transformations occurred during the thermal treatments of the catalysts. Microwave and thermal heating of the M/C catalysts resulted in substantial transformations of the carbon supports via the formation of pits, trenches, nanofibers, and nanowalls. Detailed studies with field-emission scanning electron microscopy were carried out involving statistical averaging over large surface areas. The effects of the dynamic behaviors of the supported metal particles on the catalytic activities of the synthetically useful Mizoroki-Heck and Suzuki-Miyaura reactions were demonstrated. Revealed dynamic behavior and modification of the carbon support due to microwave treatment were observed in a number of M/C systems (M = Pd, Pt, Ni, Co, Cu, Fe, and Au).
A unique ordering effect has been observed in functional catalytic nanoscale materials. Instead of randomly arranged binding to the catalyst surface, metal nanoparticles show spatially ordered behavior resulting in formation of geometrical patterns. Understanding of such nanoscale materials and analysis of corresponding microscopy images will never be comprehensive without appropriate reference datasets. Here we describe the first dataset of electron microscopy images comprising individual nanoparticles which undergo ordering on a surface towards the formation of geometrical patterns. The dataset developed in this study spans three levels of nanoscale organization: (i) individual nanoparticles (1-5 nm) and arrays of nanoparticles (5-20 nm), (ii) ordering effects (20-200 nm) and (iii) complex patterns (from nm to μm scales). The described dataset for the first time provides a possibility for the development of machine learning algorithms to study the unique phenomena of nanoparticles ordering and hierarchical organization.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.