Determining the orderliness of carbon materials with nanoparticle imaging and explainable machine learning.

Carbon materials have paramount importance in various fields of materials science, from electronic devices to industrial catalysts. The properties of these materials are strongly related to the distribution of defects-irregularities in electron density on their surfaces. Different materials have various distributions and quantities of these defects, which can be imaged using a procedure that involves depositing palladium nanoparticles. The resulting scanning electron microscopy (SEM) images can be characterized by a key descriptor-the ordering of nanoparticle positions. This work presents a highly interpretable machine learning approach for distinguishing between materials with ordered and disordered arrangements of defects marked by nanoparticle attachment. The influence of the degree of ordering was experimentally evaluated on the example of catalysis via chemical reactions involving carbon-carbon bond formation. This represents an important step toward automated analysis of SEM images in materials science.

Time-Resolved Formation and Operation Maps of Pd Catalysts Suggest a Key Role of Single Atom Centers in Cross-Coupling.

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 catalysis─easier 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.

Fast evaluation of the safety of chemical reactions using cytotoxicity potentials and bio-Strips.

We introduce new quantitative environmental metrics - "cytotoxicity potentials" - which can be used for the preliminary evaluation of the safety of chemical reactions from the viewpoint of the cytotoxicity of their components. We also elaborate the concept of bio-Profiles to be employed for fast estimation of the potential environmental dangers of chemical processes by (1) including the common cytotoxicity scale for all routes of synthesis of a particular product and (2) proposing a novel, more compact representation of the bio-Profiles themselves in the form of bio-Strips. These improvements allow direct comparisons of various synthetic routes for a particular target product, thus providing faster assessment of the reactions in question from the viewpoint of their "overall cytotoxicity". The advantages of these developments are illustrated by 36 routes of synthesizing 1,1'-biphenyl and 72 routes of synthesizing 4-methoxy-1,1'-biphenyl. The effect of incomplete conversion on bio-Strips and their metrics is also discussed. In addition, we address the impact of the selection of a particular cell line on the evaluation of the reaction safety by comparing the results obtained in three cell lines of various origins.

Yellow to blue switching of fluorescence by the tuning of the pentaphenylphosphole structure: phosphorus electronic state vs. ring conjugation.

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.

Toward Totally Defined Nanocatalysis: Deep Learning Reveals the Extraordinary Activity of Single Pd/C Particles.

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.

How to Make a Cocktail of Palladium Catalysts with Cola and Alcohol: Heteroatom Doping vs. Nanoscale Morphology of Carbon Supports.

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.

Visualization of catalyst dynamics and development of a practical procedure to study complex "cocktail"-type catalytic systems.

The ability to distinguish molecular catalysis from nanoscale catalysis provides a key to success in the field of catalyst development, particularly for the transition to sustainable economies. Complex evolution of catalyst precursors, facilitated by dynamic interconversions and leaching, makes the identification of catalytically active forms an important task, which is sometimes very difficult. We propose a simple method for in situ capturing of nanoparticles with carbon-coated grids directly from reaction mixtures. Application of this method to the Mizoroki-Heck reaction allowed visualization of dynamic changes of the dominant form of palladium particles in the reaction mixtures with homogeneous and heterogeneous catalyst precursors. Changes in the size and shape of the palladium particles reflecting the progress of the catalytic chemical reaction were demonstrated. Detailed computational modeling was carried out to confirm the generality of this approach and its feasibility for different catalytic systems. The computational models revealed strong binding of metal particles to the carbon coating comprising efficient binding sites. The approach was tested for trapping Cr, Co, Ag, Ni, Cu, Pd, Cd, Ir, Ru and Rh nanoparticles from solutions containing micromolar starting concentrations of the metal precursors. The developed approach provides a unique tool for studying intrinsic properties of catalytic systems.

Introducing tox-Profiles of Chemical Reactions.

In this Essay, we present a critical analysis of two common practices in modern chemistry-that is, of using speculations about the "greenness" and "nontoxicity" of developed synthesis procedures and of a priori labelling various compounds derived from natural sources as being environmentally safe. We note that every organic molecule that contains functional groups should be biologically active. Thus, analysis of the particular greenness and the potential environmental impact of a given chemical process should account for the biological activity of all its components in a measureable (rather than empirical) way. We highlight the necessity of clarifying discussions on biological activity and toxicity and propose possible ways of introducing tox-Profiles as a reliable overview of the overall toxicity of chemical reactions.

Solid-State C-S Coupling in Nickel Organochalcogenide Frameworks as a Route to Hierarchical Structure Transfer to Binary Nanomaterials.

In this work, the transfer of the flexible and easily tunable hierarchical structure of nickel organochalcogenides to different binary Ni-based nanomaterials via selective coupling of organic units was developed. We suggested the use of substituted aryl groups in organosulfur ligands (SAr) as traceless structure-inducing units to prepare nanostructured materials. At the first step, it was shown that the slight variation of the type of SAr units and synthetic procedures allowed us to obtain nickel thiolates [Ni(SAr)2]n with diverse morphologies after a self-assembly process in solution. This feature opened the way for the synthesis of different nanomaterials from a single type of precursor using the phenomenon of direct transfer of morphology. This study revealed that various nickel thiolates undergo selective C-S coupling under high-temperature conditions with the formation of highly demanding nanostructured NiS particles and corresponding diaryl sulfides. The in situ oxidation of the formed nickel sulfide in the case of reaction in an air atmosphere provided another type of valuable nanomaterial, nickel oxide. The high selectivity of the transformation allowed the preservation of the initial organochalcogenide morphologies in the resulting products.

2-Carboxyethylgermanium Sesquioxide as A Promising Anode Material for Li-Ion Batteries.

Various forms of germanium and germanium-containing compounds and materials are actively investigated as energy-intensive alternatives to graphite as the anode of lithium-ion batteries. The most accessible form-germanium dioxide-has the structure of a 3D polymer, which accounts for its rapid destruction during cycling, and requires the development of further approaches to the production of nanomaterials and various composites based on it. For the first time, we propose here the strategy of using 2-carboxyethylgermanium sesquioxide ([O1.5 GeCH2 CH2 CO2 H]n , 2-CEGS), in lieu of GeO2 , as a promising, energy-intensive, and stable new source system for building lithium-ion anodes. Due to the presence of the organic substituent, the formed polymer has a 1D or a 2D space organization, which facilitates the reversible penetration of lithium into its structure. 2-CEGS is common and commercially available, completely safe and non-toxic, insoluble in organic solvents (which is important for battery use) but soluble in water (which is convenient for manufacturing diverse materials from it). This paper reports the preparation of micro- (flower-shaped agglomerates of ≈1 µm thick plates) and nanoformed (needle-shaped nanoparticles of ≈500×(50-80) nm) 2-CEGS using methods commonly available in laboratories and industry such as vacuum and freeze-drying of aqueous solutions of 2-CEGS. Lithium half-cell anodes based on 2-CEGS show a capacity of ≈400 mAh g-1 for microforms and up to ≈700 mAh g-1 for nanoforms, which is almost two times higher than the maximal theoretical capacity of graphite. These anodes are stable during the cycling at various rates. The results of DFT simulations suggest that Li atoms form the stable Li2 O with the oxygen atoms of 2-CEGS, and actual charge-discharge cycles involve deoxygenated GeC3 H5 molecules. Thus, C3 chains loosen the anode structure compared to pure Ge, improving its ability to accommodate Li ions.

Evaluation of phytotoxicity and cytotoxicity of industrial catalyst components (Fe, Cu, Ni, Rh and Pd): A case of lethal toxicity of a rhodium salt in terrestrial plants.

Until recently, chemical derivatives of platinum group metals have not been in a systematic direct contact with living organisms. The situation has changed dramatically due to anthropogenic activity, which has led to significant redistribution of these metals in the biosphere. Millions of modern cars are equipped with automotive catalytic converters, which contain rhodium, palladium and platinum as active elements. Everyday usage of catalytic technologies promotes the propagation of catalyst components in the environment. Nevertheless, we still have not accumulated profound information on possible ecotoxic effects of these metal pollutants. In this study, we report a case of an extraordinarily rapid development of lethal toxicity of a rhodium (III) salt in the terrestrial plants Pisum sativum, Lupinus angustifolius and Cucumis sativus. The growth stage, at which the exposure occurred, had a crucial impact on the toxicity manifestation: at earlier stages, RhCl3 killed the plants within 24 h. In contrast, the salt was relatively low-toxic in human fibroblasts. We also address phytotoxicity of other common metal pollutants, such as palladium, iron, nickel and copper, together with their cytotoxicity. None of the tested compounds exhibited phytotoxic effects comparable with that of RhCl3. These results evidence the crucial deficiency in our knowledge on environmental dangers of newly widespread metal pollutants.

High-Performance Synthesis of Phosphorus-Doped Graphene Materials and Stabilization of Phosphoric Micro- and Nanodroplets.

A thermally induced cascade process leading to the formation of stable micro- and nanometer-size phosphoric droplets was developed starting from a molecular precursor. Microwave-induced pyrolysis of 1,2,3,4,5-pentaphenylphosphole oxide proceeded through a series of subsequent transformations involving formation of phosphorus-doped graphene oxide layers, seeding of carbon surface with phosphorus centers, and assembling of stable droplets. A complex nanostructured organization of the material was established in a remarkably short time of 3 min, and the process was performed in a thermally induced manner using microwave irradiation. High stability of the liquid phosphoric structures on the surface of doped graphene oxide over a few-month period was demonstrated, as well as under challenging conditions in organic solvents (chloroform, methylene chloride, or toluene media) and even under sonication. Detailed examination of this material by electron microscopy and a number of analytical methods showed its unique organization at the nanoscale, whereas computational modeling revealed unusually strong binding of phosphorus oxide P4O10 to the graphene surface. The study demonstrates a fascinating opportunity to access a complex nanostructured multicomponent material from a single and easily available molecular precursor.

Improvement of quality of 3D printed objects by elimination of microscopic structural defects in fused deposition modeling.

Additive manufacturing with fused deposition modeling (FDM) is currently optimized for a wide range of research and commercial applications. The major disadvantage of FDM-created products is their low quality and structural defects (porosity), which impose an obstacle to utilizing them in functional prototyping and direct digital manufacturing of objects intended to contact with gases and liquids. This article describes a simple and efficient approach for assessing the quality of 3D printed objects. Using this approach it was shown that the wall permeability of a printed object depends on its geometric shape and is gradually reduced in a following series: cylinder > cube > pyramid > sphere > cone. Filament feed rate, wall geometry and G-code-defined wall structure were found as primary parameters that influence the quality of 3D-printed products. Optimization of these parameters led to an overall increase in quality and improvement of sealing properties. It was demonstrated that high quality of 3D printed objects can be achieved using routinely available printers and standard filaments.