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Electron microscopy is a key characterization technique for nanoscale systems, and electron microscopy images are typically recorded and analyzed in terms of the morphology of the objects under study in static mode. The emerging current trend is to analyze the dynamic behavior at the nanoscale observed during electron microscopy measurements. In this work, the study of the stability of MOF structures with different compositions and topologies under conditions of an electron microscope experiment revealed an unusual dynamic behavior of M NPs formed due to the electron-beam-induced transformation of specific frameworks. The transition to the liquid phase led to spatial movement, rapid sintering, and an increase in the M NPs size within seconds. In the case of copper nanoparticles, instantaneous sublimation was observed. The dynamic behavior of Co NPs was analyzed with a computational framework combining deep learning and classic computer vision techniques. The present study for the first time revealed unique information about the stability of a variety of MOFs under an electron beam and the dynamic behavior of the formed M NPs. The formation of Fe, Ni, Cu, and Co NPs was observed from a molecular framework with a specific subsequent behavior - a stable form for Fe, excessive dynamics for Co, and sublimation/condensation for Cu. Two important outcomes of the present study should be mentioned: (i) electron microscopy investigations of MOF samples should be made with care, as decomposition under an electron beam may lead to incorrect results and the appearance of "phantom" nanoparticles; and (ii) MOFs represent an excellent model for fundamental studies of molecular-to-nano transitions in situ in video mode, including a number of dynamic transformations.
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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 catalysisâeasier 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.
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Automated computational analysis of nanoparticles is the key approach urgently required to achieve further progress in catalysis, the development of new nanoscale materials, and applications. Analysis of nanoscale objects on the surface relies heavily on scanning electron microscopy (SEM) as the experimental analytic method, allowing direct observation of nanoscale structures and morphology. One of the important examples of such objects is palladium on carbon catalysts, allowing access to various chemical reactions in laboratories and industry. SEM images of Pd/C catalysts show a large number of nanoparticles that are usually analyzed manually. Manual analysis of a statistically significant number of nanoparticles is a tedious and highly time-consuming task that is impossible to perform in a reasonable amount of time for practically needed large amounts of samples. This work provides a comprehensive comparison of various computer vision methods for the detection of metal nanoparticles. In addition, multiple new types of data representations were developed, and their applicability in practice was assessed.
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The interaction between diphenylacetylene and dichlorophenylphosphine under various conditions is a simple method for the preparation of pentaphenylphosphole derivatives exhibiting fluorescence properties. Depending on the electronic state of the various centers of the phospholic structure, it was possible to obtain molecules with fluorescence, as in the blue area for 1,2,3,4,5-pentaphenyl-2,5-dihydro-phosphole-1-oxide (H2PPPO), in the yellow area for 1,2,3,4,5-pentaphenylphosphole-1-oxide (PPPO) and in the cyan area for 1,2,3,4,5-pentaphenylphosphole (PPP). The effect of the structure and π-conjugation on the optical properties of these compounds was studied using PPP derivatives as examples. Unusual changes in the optical properties of PPP derivatives in solution and in the crystalline state are explained. In the case of agglomeration of PPPO and PPP molecules, the effect of aggregation-induced emission (AIE) was observed to have weak fluorescence in solution and strong fluorescence in the aggregated state. However, for H2PPPO, the AIE effect remains mild. With the help of experimental studies, supported by theoretical calculations, the main mechanism of the optical properties of pentaphenylphosphole derivatives has been revealed. It was observed that the intramolecular motions of PPPO and PPP are more limited in the solid state than the motions of H2PPPO, which is associated with less conjugation of the phenyl rotors of H2PPPO. The analysis of the structure and distribution of electron density showed why hydrogenation of the phosphole ring leads to a sharp change in the optical properties of pentaphenylphosphole derivatives, while the oxidation of phosphorus does not lead to the disappearance of the AIE effect and to a lesser extent affects the change in the fluorescence wavelength. Thus, it was shown how the regulation of various structural features of the phospholic ring helps to control the optical properties of such compounds.
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Homogeneous catalysis is typically considered "well-defined" 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 109 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.
Assuntos
Aprendizado Profundo , Nanopartículas Metálicas , Carbono , Catálise , Nanopartículas Metálicas/química , Paládio/químicaRESUMO
Sparkling drinks such as cola can be considered an affordable and inexpensive starting material consisting of carbohydrates and sulfur- and nitrogen-containing organic substances in phosphoric acid, which makes them an excellent precursor for the production of heteroatom-doped carbon materials. In this study, heteroatom-doped carbon materials were successfully prepared in a quick and simple manner using direct carbonization of regular cola and diet cola. The low content of carbon in diet cola allowed reaching a higher level of phosphorus in the prepared carbon material, as well as obtaining additional doping with nitrogen and sulfur due to the presence of sweeteners and caffeine. Effects of carbon support doping with phosphorus, nitrogen and sulfur, as well as of changes in textural properties by ball milling, on the catalytic activity of palladium catalysts were investigated in the Suzuki-Miyaura and Mizoroki-Heck reactions. Contributions of the heteroatom doping and specific surface area of the carbon supports to the increased activity of supported catalysts were discussed. Additionally, the possibility of these reactions to proceed in 40% potable ethanol was studied. Moreover, transformation of various palladium particles (complexes and nanoparticles) in the reaction medium was detected by mass spectrometry and transmission electron microscopy, which evidenced the formation of a cocktail of catalysts in a commercial 40% ethanol/water solution.
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Smoothness/defectiveness of the carbon material surface is a key issue for many applications, spanning from electronics to reinforced materials, adsorbents and catalysis. Several surface defects cannot be observed with conventional analytic techniques, thus requiring the development of a new imaging approach. Here, we evaluate a convenient method for mapping such "hidden" defects on the surface of carbon materials using 1-5 nm metal nanoparticles as markers. A direct relationship between the presence of defects and the ordering of nanoparticles was studied experimentally and modeled using quantum chemistry calculations and Monte Carlo simulations. An automated pipeline for analyzing microscopic images is described: the degree of smoothness of experimental images was determined by a classification neural network, and then the images were searched for specific types of defects using a segmentation neural network. An informative set of features was generated from both networks: high-dimensional embeddings of image patches and statics of defect distribution.
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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.
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Development of sustainable catalysts for synthetic transformations is one of the most challenging and demanding goals. The high prices of precious metals and the unavoidable leaching of toxic metal species leading to environmental contamination make the transition metal-free catalytic systems especially important. Here we demonstrate that carbene active centers localized on carbon atoms at the zigzag edge of graphene represent an alternative platform for efficient catalytic carbon-carbon bond formation in the synthesis of benzene. The studied acetylene trimerization reaction is an efficient atom-economic route to build an aromatic ring-a step ubiquitously important in organic synthesis and industrial applications. Computational modeling of the reaction mechanism reveals a principal role of the reversible spin density oscillations that govern the overall catalytic cycle, facilitate the product formation, and regenerate the catalytically active centers. Dynamic π-electron interactions in 2D carbon systems open new opportunities in the field of carbocatalysis, unachievable by means of transition metal-catalyzed transformations. The theoretical findings are confirmed experimentally by generating key moieties of the carbon catalyst and performing the acetylene conversion to benzene.
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In recent years, the application of microwave (MW) irradiation has played an increasingly important role in the synthesis and development of high performance nanoscale catalytic systems. However, the interaction of microwave irradiation with solid catalytic materials and nanosized structures remains a poorly studied topic. In this paper we carried out a systematic study of changes in morphology under the influence of microwave irradiation on nanoscale particles of various metals and composite particles, including oxides, carbides, and neat metal systems. All systems were studied in the native solid form without a solvent added. Intensive absorption of microwave radiation was observed for many samples, which in turn resulted in strong heating of the samples and changes in their chemical structure and morphology. A comparison of two very popular catalytic materials-metal particles (M) and supported metal on carbon (M/C) systems-revealed a principal difference in their behavior under microwave irradiation. The presence of carbon support influences the heating mechanism; the interaction of substances with the support during the heating is largely determined by heat transfer from the carbon. Etching of the carbon surface, involving the formation of trenches and pits on the surface of the carbon support, were observed for various types of the investigated nanoparticles.
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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).