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A large number of parts have deep holes, therefore, rotary cutting tools, which represent relatively long and thin columns are used for holemaking. In this article we analyze the behavior of such tools under the influence of an axial compression load, in our case, the axial cutting force Fp , which differs fundamentally from the compression of short tools. Moreover, experience shows that when the cutting force Fp reaches a certain critical value equal to Fkp , a long straight column becomes unstable.

Improving the selectivity in the oxidative coupling of methane to ethane/ethylene poses a significant challenge for commercialization. The required improvements are hampered by the uncertainties associated with the reaction mechanism due to its complexity. Herein, we report about 90 % selectivity to the target products at 11 % methane conversion over Gd 2 O 3 -based catalysts at 700 °C using N 2 O as the oxidant. Sophisticated kinetic studies have suggested the nature of adsorbed oxygen species and their binding strength as key parameters for undesired methane oxidation to carbon oxides. These descriptors can be controlled by a metal oxide promoter for Gd 2 O 3 ., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Knowing the structure of catalytically active species/phases and providing methods for their purposeful generation are two prerequisites for the design of catalysts with desired performance. Herein, we introduce a simple method for precise preparation of supported/bulk catalysts. It utilizes the ability of metal oxides to dissolve and to simultaneously precipitate during their treatment in an aqueous ammonia solution. Applying this method for a conventional VO x -Al 2 O 3 catalyst, the concentration of coordinatively unsaturated Al sites was tuned simply by changing the pH value of the solution. These sites affect the strength of V-O-Al bonds of isolated VO x species and thus the reducibility of the latter. This method is also applicable for controlling the reducibility of bulk catalysts as demonstrated for a CeO 2 -ZrO 2 -Al 2 O 3 system. The application potential of the developed catalysts was confirmed in the oxidative dehydrogenation of ethylbenzene to styrene with CO 2 and in the non-oxidative propane dehydrogenation to propene. Our approach is extendable to the preparation of any metal oxide catalysts dissolvable in an ammonia solution., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The development of selective catalysts for direct conversion of ammonia into nitrous oxide, N 2 O, will circumvent the conventional five-step manufacturing process and enable its wider utilization in oxidation catalysis. Deviating from commonly accepted catalyst design principles for this reaction, reliant on manganese oxide, we herein report an efficient system comprised of isolated chromium atoms (1 wt %) stabilized in the ceria lattice by coprecipitation. The latter, in contrast to a simple impregnation approach, ensures firm metal anchoring and results in stable and selective N 2 O production over 100 h on stream up to 79% N 2 O selectivity at full NH 3 conversion. Raman, electron paramagnetic resonance, and in situ UV-vis spectroscopies reveal that chromium incorporation enhances the density of oxygen vacancies and the rate of their generation and healing. Accordingly, temporal analysis of products, kinetic studies, and atomistic simulations show lattice oxygen of ceria to directly participate in the reaction, establishing the cocatalytic role of the carrier. Coupled with the dynamic restructuring of chromium sites to stabilize intermediates of N 2 O formation, these factors enable catalytic performance on par with or exceeding benchmark systems. These findings demonstrate how nanoscale engineering can elevate a previously overlooked metal into a highly competitive catalyst for selective ammonia oxidation to N 2 O, paving the way toward industrial implementation., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Nitrous oxide, N 2 O, exhibits unique reactivity in oxidation catalysis, but the high manufacturing costs limit its prospective uses. Direct oxidation of ammonia, NH 3 , to N 2 O can ameliorate this issue but its implementation is thwarted by suboptimal catalyst selectivity and stability, and the lack of established structure-performance relationships. Systematic and controlled material nanostructuring offers an innovative approach for advancement in catalyst design. Herein low-valent manganese atoms stabilized on ceria, CeO 2 , are discovered as the first stable catalyst for NH 3 oxidation to N 2 O, exhibiting two-fold higher productivity than the state-of-the-art. Detailed mechanistic, computational and kinetic studies reveal CeO 2 as the mediator of oxygen supply, while undercoordinated manganese species activate O 2 and facilitate N 2 O evolution via NN bond formation between nitroxyl, HNO, intermediates. Synthesis via simple impregnation of a small metal quantity (1 wt%) predominantly generates isolated manganese sites, while full atomic dispersion is achieved upon redispersion of sporadic oxide nanoparticles during reaction, as confirmed by advanced microscopic analysis and electron paramagnetic resonance spectroscopy. Subsequently, manganese speciation is maintained, and no deactivation is observed over 70 h on stream. CeO 2 -supported isolated transition metals emerge as a novel class of materials for N 2 O production, encouraging future studies to evaluate their potential in selective catalytic oxidations at large., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Controlling the precise atomic architecture of supported metals is central to optimizing their catalytic performance, as recently exemplified for nanostructured platinum and ruthenium systems in acetylene hydrochlorination, a key process for vinyl chloride production. This opens the possibility of building on historically established activity correlations. In this study, we derived quantitative activity, selectivity and stability descriptors that account for the metal-dependent speciation and host effects observed in acetylene hydrochlorination. To achieve this, we generated a platform of Au, Pt, Ru, Ir, Rh and Pd single atoms and nanoparticles supported on different types of carbon and assessed their evolution during synthesis and under the relevant reaction conditions. Combining kinetic, transient and chemisorption analyses with modelling, we identified the acetylene adsorption energy as a speciation-sensitive activity descriptor, further determining catalyst selectivity with respect to coke formation. The stability of the different nanostructures is governed by the interplay between single atom-support interactions and chlorine affinity, promoting metal redispersion or agglomeration, respectively., (© 2022. The Author(s), under exclusive licence to Springer Nature Limited.)

Alkali metal promoters have been widely employed for preparation of heterogeneous catalysts used in many industrially important reactions. However, the fundamentals of their effects are usually difficult to access. Herein, we unravel mechanistic and kinetic aspects of the role of alkali metals in CO 2 hydrogenation over Fe-based catalysts through state-of-the-art characterization techniques, spatially resolved steady-state and transient kinetic analyses. The promoters affect electronic properties of iron in iron carbides. These carbide characteristics determine catalyst ability to activate H 2 , CO and CO 2 . The Allen scale electronegativity of alkali metal promoter was successfully correlated with the rates of CO 2 hydrogenation to higher hydrocarbons and CH 4 as well as with the rate constants of individual steps of CO or CO 2 activation. The derived knowledge can be valuable for designing and preparing catalysts applied in other reactions where such promoters are also used., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The production of nitrous oxide, N 2 O, via NH 3 oxidation is not on a practical scale due to the lack of a suitable catalyst. Instead, it is produced via thermal decomposition of NH 4 NO 3 , rendering N 2 O too costly and limiting its prospective uses. Herein, we report CeO 2 -supported Au nanoparticles (2-3 nm) as a highly selective catalyst for low-temperature NH 3 oxidation to N 2 O, exhibiting two orders of magnitude higher space-time yield than the state-of-the-art Mn-Bi/α-Al 2 O 3 and remarkable stability over 70 h on stream. The reaction proceeds via a Mars-van Krevelen mechanism, with the density of interfacial Au δ+ species and the oxygen storage capacity of CeO 2 identified as the key performance descriptors. The latter could be enhanced by cobalt doping, improving the catalytic activity and setting a new benchmark for N 2 O productivity. These findings establish NH 3 oxidation as an efficient process for N 2 O manufacture and facilitate its broader utilization in selective oxidations., (© 2022 Wiley-VCH GmbH.)

Propane dehydrogenation (PDH) to propene is an important alternative to oil-based cracking processes, to produce this industrially important platform chemical 1,2 . The commercial PDH technologies utilizing Cr-containing (refs. 3,4 ) or Pt-containing (refs. 5-8 ) catalysts suffer from the toxicity of Cr(VI) compounds or the need to use ecologically harmful chlorine for catalyst regeneration 9 . Here, we introduce a method for preparation of environmentally compatible supported catalysts based on commercial ZnO. This metal oxide and a support (zeolite or common metal oxide) are used as a physical mixture or in the form of two layers with ZnO as the upstream layer. Supported ZnO x species are in situ formed through a reaction of support OH groups with Zn atoms generated from ZnO upon reductive treatment above 550 °C. Using different complementary characterization methods, we identify the decisive role of defective OH groups for the formation of active ZnO x species. For benchmarking purposes, the developed ZnO-silicalite-1 and an analogue of commercial K-CrO x /Al 2 O 3 were tested in the same setup under industrially relevant conditions at close propane conversion over about 400 h on propane stream. The developed catalyst reveals about three times higher propene productivity at similar propene selectivity., (© 2021. The Author(s).)

Conversion of propane or butanes from natural/shale gas into propene or butenes, which are indispensable for the synthesis of commodity chemicals, is an important environmentally friendly alternative to oil-based cracking processes. Herein, we critically analyse recent developments in the non-oxidative, oxidative, and CO 2 -mediated dehydrogenation of propane and isobutane to the corresponding olefins over metal oxide catalysts. Particular attention is paid to (i) comparing the developed catalysts in terms of their application potential, (ii) structure-activity-selectivity relationships for tailored catalyst design, and (iii) reaction-engineering aspects for improving product selectivity and overall process efficiency. On this basis, possible directions for further research aimed at the development of inexpensive and environmentally friendly catalysts with industrially relevant performance were identified. In addition, we provide general information regarding catalyst preparation and characterization as well as some recommendations for carrying out non-oxidative and CO 2 -mediated dehydrogenation reactions to ensure unambiguous comparison of catalysts developed in different studies.

This paper demonstrates the potential of Eu2O3 and Gd2O3 as catalysts for non-oxidative propane dehydrogenation to propene. They reveal a higher activity than the state-of-the-art bare ZrO2-based catalysts due to the higher intrinsic activity of Gdcus or Eucus in comparison with that of Zrcus (cus = coordinatively unsaturated).

Background: Pathological low-energy (LE) vertebral compression fractures (VFs) are common complications of osteoporosis and predictors of subsequent LE fractures. In 84% of cases, VFs are not reported on chest CT (CCT), which calls for the development of an artificial intelligence-based (AI) assistant that would help radiology specialists to improve the diagnosis of osteoporosis complications and prevent new LE fractures., Aims: To develop an AI model for automated diagnosis of compression fractures of the thoracic spine based on chest CT images., Materials and Methods: Between September 2019 and May 2020 the authors performed a retrospective sampling study of ССТ images. The 160 of results were selected and anonymized. The data was labeled by seven readers. Using the morphometric analysis, the investigators received the following metric data: ventral, medial and dorsal dimensions. This was followed by a semiquantitative assessment of VFs degree. The data was used to develop the Comprise-G AI mode based on CNN, which subsequently measured the size of the vertebral bodies and then calculates the compression degree. The model was evaluated with the ROC curve analysis and by calculating sensitivity and specificity values., Results: Formed data consist of 160 patients (a training group - 100 patients; a test group - 60 patients). The total of 2,066 vertebrae was annotated. When detecting Grade 2 and 3 maximum VFs in patients the Comprise-G model demonstrated sensitivity - 90,7%, specificity - 90,7%, AUC ROC - 0.974 on the 5-FOLD cross-validation data of the training dataset; on the test data - sensitivity - 83,2%, specificity - 90,0%, AUC ROC - 0.956; in vertebrae demonstrated sensitivity - 91,5%, specificity - 95,2%, AUC ROC - 0.981 on the cross-validation data; for the test data sensitivity - 79,3%, specificity - 98,7%, AUC ROC - 0.978., Conclusions: The Comprise-G model demonstrated high diagnostic capabilities in detecting the VFs on CCT images and can be recommended for further validation.

The impact of formaldehyde (HCHO, formed in vehicle exhaust gases by incomplete combustion of fuel) on the performance of a commercial V 2 O 5 -WO 3 /TiO 2 catalyst in NH 3 -SCR of NO x under dry conditions has been analyzed in detail by catalytic tests, in situ FTIR and transient studies using temporal analysis of products (TAP). HCHO reacts preferentially with NH 3 to a formamide (HCONH 2 ) surface intermediate. This deprives NH 3 partly from its desired role as a reducing agent in the SCR and diminishes NO conversion and N 2 selectivity. Between 250 and 400 °C, HCONH 2 decomposes by dehydration (major pathway) and decarbonylation (minor pathway) to liberate toxic HCN and CO, respectively. HCN was proven to be oxidized by lattice oxygen of the catalyst to CO 2 and NO, which enters the NH 3 -SCR reaction.

Au/TiO 2 and Au/SiO 2 catalysts containing 2 wt % Au and different amounts of K or Cs were tested for alcohol synthesis from CO 2 , H 2 , and C 2 H 4 /C 3 H 6 . 1-Propanol or 1-butanol/isobutanol were obtained in the presence of C 2 H 4 or C 3 H 6 . Higher yields of the corresponding alcohols were obtained over TiO 2 -based catalysts in comparison with their SiO 2 -based counterparts. This is caused by an enhanced ability of the TiO 2 -based catalysts for CO 2 activation, as concluded from in situ fourier-transform infrared (FTIR) spectroscopy and temporal analysis of products (TAP) studies. The synthesized carbonate and formate species adsorbed on the support do not hamper CO 2 conversion into CO and the hydroformylation reaction. The transformation of Au δ+ to active Au 0 sites proceeds during an activation procedure. As reflected by CO adsorption and scanning transmission electron microscopy, the accessible Au 0 sites are influenced by the amount of alkali dopants and the support. FTIR data and TAP tests reveal a very weak interaction of C 2 H 4 with the catalyst, suggesting its quick reaction with CO and H 2 after activation on Au 0 sites to form propanol and propane., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Carbon-supported gold catalysts have the potential to replace the toxic mercuric chloride-based system applied industrially for acetylene hydrochlorination, a key technology for the manufacture of polyvinyl chloride. However, the design of an optimal catalyst is essentially hindered by the difficulties in assessing the nature of the active site. Herein, we present a platform of carbon supported gold nanostructures at a fixed metal loading, ranging from single atoms of tunable oxidation state and coordination to metallic nanoparticles, by varying the structure of functionalised carbons and use of thermal activation. While on activated carbon particle aggregation occurs progressively above 473 K, on nitrogen-doped carbon gold single atoms exhibit outstanding stability up to temperatures of 1073 K and under reaction conditions. By combining steady-state experiments, density functional theory, and transient mechanistic studies, we assess the relation between the metal speciation, electronic properties, and catalytic activity. The results indicate that the activity of gold-based catalysts correlates with the population of Au(i)Cl single atoms and the reaction follows a Langmuir-Hinshelwood mechanism. Strong interaction with HCl and thermodynamically favoured acetylene activation were identified as the key features of the Au(i)Cl sites that endow their superior catalytic performance in comparison to N-stabilised Au(iii) counterparts and gold nanoparticles. Finally, we show that the carrier (activated carbon versus nitrogen-doped carbon) does not affect the catalytic response, but determines the deactivation mechanism (gold particle aggregation and pore blockage, respectively), which opens up different options for the development of stable, high-performance hydrochlorination catalysts.

The promotional effect of H 2 on the oxidation of CO is of topical interest, and there is debate over whether this promotion is due to either thermal or chemical effects. As yet there is no definitive consensus in the literature. Combining spatially resolved mass spectrometry and X-ray absorption spectroscopy (XAS), we observe a specific environment of the active catalyst during CO oxidation, having the same specific local coordination of the Pd in both the absence and presence of H 2 . In combination with Temporal Analysis of Products (TAP), performed under isothermal conditions, a mechanistic insight into the promotional effect of H 2 was found, providing clear evidence of nonthermal effects in the hydrogen-promoted oxidation of carbon monoxide. We have identified that H 2 promotes the Langmuir-Hinshelwood mechanism, and we propose this is linked to the increased interaction of O with the Pd surface in the presence of H 2 . This combination of spatially resolved MS and XAS and TAP studies has provided previously unobserved insights into the nature of this promotional effect., Competing Interests: The authors declare no competing financial interest.

Non-oxidative dehydrogenation of propane to propene is an established large-scale process that, however, faces challenges, particularly in catalyst development; these are the toxicity of chromium compounds, high cost of platinum, and catalyst durability. Herein, we describe the design of unconventional catalysts based on bulk materials with a certain defect structure, for example, ZrO2 promoted with other metal oxides. Comprehensive characterization supports the hypothesis that coordinatively unsaturated Zr cations are the active sites for propane dehydrogenation. Their concentration can be adjusted by varying the kind of ZrO2 promoter and/or supporting tiny amounts of hydrogenation-active metal. Accordingly designed Cu(0.05 wt %)/ZrO2 -La2 O3 showed industrially relevant activity and durability over ca. 240 h on stream in a series of 60 dehydrogenation and oxidative regeneration cycles between 550 and 625 °C., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Catalytic ammonia oxidation over platinum has been studied experimentally from UHV up to atmospheric pressure with polycrystalline Pt and with the Pt single crystal orientations (533), (443), (865), and (100). Density functional theory (DFT) calculations explored the reaction pathways on Pt(111) and Pt(211). It was shown, both in theory and experimentally, that ammonia is activated by adsorbed oxygen, i.e. by O(ad) or by OH(ad). In situ XPS up to 1 mbar showed the existence of NH(x)(x= 0,1,2,3) intermediates on Pt(533). Based on a mechanism of ammonia activation via the interaction with O(ad)/OH(ad) a detailed and a simplified mathematical model were formulated which reproduced the experimental data semiquantitatively. From transient experiments in vacuum performed in a transient analysis of products (TAP) reactor it was concluded that N(2)O is formed by recombination of two NO(ad) species and by a reaction between NO(ad) and NH(x,ad)(x= 0,1,2) fragments. Reaction-induced morphological changes were studied with polycrystalline Pt in the mbar range and with stepped Pt single crystals as model systems in the range 10(-5)-10(-1) mbar.