Autonomous Reaction Network Exploration in Homogeneous and Heterogeneous Catalysis

Autonomous computations that rely on automated reaction network elucidation algorithms may pave the way to make computational catalysis on a par with experimental research in the field. Several advantages of this approach are key to catalysis: (i) automation allows one to consider orders of magnitude more structures in a systematic and open-ended fashion than what would be accessible by manual inspection. Eventually, full resolution in terms of structural varieties and conformations as well as with respect to the type and number of potentially important elementary reaction steps (including decomposition reactions that determine turnover numbers) may be achieved. (ii) Fast electronic structure methods with uncertainty quantification warrant high efficiency and reliability in order to not only deliver results quickly, but also to allow for predictive work. (iii) A high degree of autonomy reduces the amount of manual human work, processing errors, and human bias. Although being inherently unbiased, it is still steerable with respect to specific regions of an emerging network and with respect to the addition of new reactant species. This allows for a high fidelity of the formalization of some catalytic process and for surprising in silico discoveries. In this work, we first review the state of the art in computational catalysis to embed autonomous explorations into the general field from which it draws its ingredients. We then elaborate on the specific conceptual issues that arise in the context of autonomous computational procedures, some of which we discuss at an example catalytic system. Graphical Abstract

Механизм термической ионизации уротропина на поверхности интерметаллида NaAu-=SUB=-x-=/SUB=-

Thermal ionization of methenamine (C6H12N4) on the surface of the NaAux intermetallic compound has been studied. It has been established that the processes of decomposition, desorption and ionization of adsorbed compounds, thermally stimulated on the surface, proceed due to the accumulation of energy at the degrees of freedom of the adsorption complex, including the adsorbed compound and a solid, by the mechanism of monomolecular decomposition reactions. In this case, the decomposition of the adsorption complex is accompanied by the desorption of ions that are not in thermal equilibrium with the solid. The uniformity of the temperature dependences of the ion current and their distribution over two groups allowed us to conclude that ions are desorbed from the surface, which correspond to the decays of individual adsorbed molecules, as well as the decays of dimers formed on the surface. The decay of methenamine molecules during thermal ionization occurs in the same way as their decay in vacuum during electron ionization, which indicates the preservation of the bulk structure of methenamine molecules during adsorption and a significant lifetime of the excited state of compounds on NaAux.

EXPRESS METHOD FOR CALCULATING THE SPECIFIC HEAT OF EXPLOSIVE TRANSFORMATION OF CHNO CONDENSED EXPLOSIVES

Разработан экспресс-метод расчета теплоты взрыва СаHbNcOdконденсированных взрывчатых веществ с различным кислородным балансом от резко отрицательного до положительного. Предложенный метод использует минимальный набор входных данных, состоящих из элементного состава, плотности энтальпий образований исходного взрывчатого вещества и его продуктов детонации. Расчет теплоты взрыва основывается на корреляционной связи между минимальной и максимальной теплотами взрыва с плотностью высокоэнергетического соединения. В статье подробно приведены реакции разложения взрывчатых веществ для случаев с минимальной и максимальными теплотами взрыва. Проведены расчеты теплоты взрыва по новому способу и методу Пепекина по представленной в статье базы взрывчатых веществ, а также приведены результаты сравнения, которые показали большую точность (в 2,3 раза) предложенного метода. An express method has been developed for calculating the explosion heat of cahbncod condensed explosives with different oxygen balance from sharply negative to positive. The proposed method uses a minimal set of input data consisting of the elemental composition, enthalpy density of the formations of the initial explosive and its detonation products. The calculation of the heat of explosion is based on the correlation between the minimum and maximum heat of explosion with the density of a high-energy compound. The article describes in detail the decomposition reactions of explosives for cases with minimum and maximum explosion heats. Calculations of the heat of explosion according to the new method and the pepekin method are carried out according to the explosives database presented in the article, and comparison results are also presented, which showed a better accuracy (2.3 times) of the proposed method.

Selective Anticancer and Antimicrobial Metallodrugs Based on Gold(III) Dithiocarbamate Complexes

New dithiocarbamate cycloaurated complexes have been synthesized and their physicochemical and in vitro antitumor properties have been evaluated. All the performed studies highlighted good transport through the blood and biodistribution, according to the balance between the properties of hydrophilicity/lipophilicity and the binding of moderate strength to the BSA protein. Furthermore, none of the complexes exhibited reduction or decomposition reactions, presenting excellent physiological stability. The in vitro cytotoxic effect was evaluated on human colon cancer cell line Caco-2/TC7, and the complexes showed great antiproliferative activity and excellent selectivity, as much less effect was detected on normal Caco-2/TC7 cells. Most of the complexes exhibit antiproliferative activity that was better than or similar to auranofin, and at least nine times better than that of cisplatin. Its action mechanism is still under discussion since no evidence of cell cycle arrest was found, but an antioxidant role was shown for some of the selective complexes. All complexes were also tested as antimicrobial drugs, exhibiting good activity towards S. aureus and E. coli. bacteria and C. albicans and C. neoformans fungi.

Study on Vacuum Roasting Pretreatment of Carbonaceous Gold Concentrates Based on Nonoxidation Technology

Carbonaceous gold ores are difficult to treat because of the “preg-robbing” by carbonaceous matters and locking by minerals. Roasting is the most commonly used method that is useful in dealing with carbonaceous gold ores. In this study, flotation gold concentrates containing sulfides and carbonaceous matters were investigated to ascertain the reaction process and the matters’ transformation characteristics in different temperatures by vacuum roasting pretreatment. Calcine and volatile condensates were characterized with several techniques. In the process of vacuum roasting, the main chemical reactions were decomposition reaction and carbothermic reduction reactions of sulfide ores, carbothermic reduction reactions of SiO2, and thermal decomposition reactions of organic carbon. The bad effects of “preg-robbing” by carbonaceous matters were greatly weakened by the thermal decomposition and carbothermal reduction. The gold locking minerals were mainly removed by reduction reactions. The sulfides were removed in ways that did not produce SO2. The removal of sulfur and carbonaceous matters during the vacuum roasting process was 95.83% and 65.38%, respectively. Direct cyanidation of the calcine extracted from 2.13% to 88.37% of the gold content with a vacuum degree of 10 Pa and roasting from 25°C to 1,200°C for 30 min.

Effect of Impurities Control on the Crystallization and Densification of Polymer-Derived SiC Fibers

The polymer-derived SiC fibers are mainly used as reinforcing materials for ceramic matrix composites (CMCs) because of their excellent mechanical properties at high temperature. However, decomposition reactions such as release of SiO and CO gases and the formation of pores proceed above 1400 °C because of impurities introduced during the curing process. In this study, polycrystalline SiC fibers were fabricated by applying iodine-curing method and using controlled pyrolysis conditions to investigate crystallization and densification behavior. Oxygen and iodine impurities in amorphous SiC fibers were reduced without pores by diffusion and release to the fiber surface depending on the pyrolysis time. In addition, the reduction of the impurity content had a positive effect on the densification and crystallization of polymer-derived SiC fibers without a sintering aid above the sintering temperature. Consequently, dense Si-Al-C-O polycrystalline fibers containing β-SiC crystal grains of 50~100 nm were easily fabricated through the blending method and controlled pyrolysis conditions.

Study on Sulfide Oxidation in a Clay Matrix by the Hyphenated Method

The requirement of a ceramic product with high technical and aesthetic performance makes it necessary to select and control raw materials to avoid losses caused by low-quality products. Many defects have their origin in impurities present in clay minerals such as sulfides and sulfates. It is important to study the oxidation, decomposition, and pyrolysis reactions that affect these minerals and their dependence on environment conditions (humidity and temperature) during the extraction and beneficiation of clay minerals in an open pit mine. The development of hyphenated techniques coupling mass spectrometry with a thermal analysis instrument provides information that is not available from either technique alone, such as decomposition behavior and the determination of emissions with a lower limit of detection. The evolution of sulfur dioxide from the oxidation of different sulfides provides information on the in situ oxidation and decomposition reactions that happen when a thermal treatment is applied. The results obtained show important differences in the reactions that take place in sulfides when they are stored under different environmental conditions. Specifically, the general tendency is that the sulfurs stored under high relative humidity show a decrease in the intensity of the emission as well as changes in the onset of the peak emission.

A Computational Comparison of Ether and Ester Electrolyte Stability on a Ca Metal Anode

Ca-ion batteries (CIBs) have the potential to provide inexpensive energy storage, but their realization is impeded by the lack of suitable electrolytes. Motivated by recent experimental progress, we perform ab initio molecular dynamics simulations to investigate early decomposition reactions at the anode-electrolyte interface. By examining different combinations of solvent—tetrahydrofuran (THF) or ethylene carbonate (EC)—and salt—Ca(BH4)2, Ca(BF4)2, Ca(BCl4)2, and Ca(ClO4)2—we identify a variety of behavioral trends between electrolyte solutions. Next, we perform a separate trajectory with pure THF and gradually increased negative charge; despite an addition of -32e, no THF decomposition is detected. Charge analysis reveals that in a reductive environment, THF distributes excess charge evenly across its hydrocarbon backbone, while EC concentrates charge on its ester oxygens and carbonyl carbon, resulting in decomposition. Graphs of charge vs. time for both solvents reveal that EC decomposition products can be reduced by up to five electrons, while those of THF are limited to a single electron. Ultimately, we find Ca(BH4)2 and THF to be the most stable solution investigated herein, corroborating experimental evidence of its suitability as a CIB electrolyte.

Studying the effect of monochrome light on the photocatalytic activity of tungsten oxide

The paper presents studies of the photocatalytic activity of tungsten oxide nanopowder agglomerates under the action of monochrome light in the decomposition reactions of an organic pollutant (methylene blue). It is determined that the radiation of 470 nm (blue) provides the highest values of the rate constant of phototransformation of methylene blue