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Earth abundant metal‐based heterogeneous catalysts with highly active and at the same time stable isolated metal sites constitute a key factor for the advancement of sustainable and cost‐effective chemical synthesis. In particular, the development of more practical, and durable iron‐based materials is of central interest for organic synthesis, especially for the preparation of chemical products related to life science applications. Here, we report the preparation of Fe‐single atom catalysts (Fe‐SACs) entrapped in N‐doped mesoporous carbon support with unprecedented potential in the preparation of different kinds of amines, which represent privileged class of organic compounds and find increasing application in daily life. The optimal Fe‐SACs allow for the reductive amination of a broad range of aldehydes and ketones with ammonia and amines to produce diverse primary, secondary, and tertiary amines including N‐methylated products as well as drugs, agrochemicals, and other biomolecules (amino acid esters and amides) utilizing green hydrogen. [ABSTRACT FROM AUTHOR]

The development of highly efficient and stable visible-light-driven photocatalysts for the removal of herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) from water is still a challenge. In this work, Bi2MoO6 (BMO) materials with different morphology were successfully prepared via a simple hydrothermal method by altering the solvent. The morphology of the BMO material is mainly influenced by the solvent used in the synthesis (H2O, ethanol, and ethylene glycol or their mixtures) and to a lesser extent by subsequent thermal annealing. BMO with aggregated spheres and nanoplate-like structures hydrothermally synthesized in ethylene glycol (EG) and subsequently calcined at 400 °C (BMO-400 (EG)) showed the highest adsorption capacity and photocatalytic activity compared to other synthesized morphologies. Complete degradation of 2,4-D on BMO upon irradiation with a blue light-emitting diode (LED, λmax = 467 nm) was reached within 150 min, resulting in 2,4-dichlorophenol (2,4-DCP) as the main degradation product. Holes (h+) and superoxide radicals (⋅O2−) are assumed to be the reactive species observed for the rapid conversion of 2,4-D to 2,4-DCP. The addition of H2O2 to the reaction mixture not only accelerates the degradation of 2,4-DCP but also significantly reduces the total organic carbon (TOC) content, indicating that hydroxyl radicals are crucial for the rapid mineralization of 2,4-D. Under optimal conditions, the TOC value was reduced by 84.5% within 180 min using BMO-400 (EG) and H2O2. The improved degradation performance of BMO-400 (EG) can be attributed to its particular morphology leading to lower charge transfer resistance, higher electron–hole separation, and larger specific surface area. [ABSTRACT FROM AUTHOR]

The nature of the support can fundamentally affect the function of a heterogeneous catalyst. For the novel type of isolated metal atom catalysts, sometimes referred to as single‐atom catalysts, systematic correlations are still rare. Here, we report a general finding that Pd on nitride supports (non‐metal and metal nitride) features a higher oxidation state compared to that on oxide supports (non‐metal and metal oxide). Through thorough oxidation state investigations by X‐ray absorption spectroscopy (XAS), X‐ray photoelectron spectroscopy (XPS), CO‐DRIFTS, and density functional theory (DFT) coupled with Bader charge analysis, it is found that Pd atoms prefer to interact with surface hydroxyl group to form a Pd(OH)x species on oxide supports, while on nitride supports, Pd atoms incorporate into the surface structure in the form of Pd−N bonds. Moreover, a correlation was built between the formal oxidation state and computational Bader charge, based on the periodic trend in electronegativity. [ABSTRACT FROM AUTHOR]

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 Gd2O3‐based catalysts at 700 °C using N2O 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 Gd2O3. [ABSTRACT FROM AUTHOR]

Zr-based UiO-66 metal–organic frameworks are ideal platforms for the design and development of heterogeneous single-atom catalysts (SACs) because of their thermal and chemical stability with the presence of structural defects, enabling the introduction of isolated metal atoms. Elucidating the structure–reactivity relationships and understanding reaction mechanisms for these catalysts are crucial for their industrial applications. We focus here on these aspects for a technically important reaction, preferential CO oxidation (PROX) on a UiO-66-supported Cu SAC by following temperature perturbations in catalytic performance in correlation with changes in the electronic and adsorption properties, which are validated by comprehensive DFT computations. In situ DR-UV-VIS, XANES and NAP-XPS measurements indicated an increase of Cu1+-like states and partial reduction of ZrOx nodes with the increase in reaction temperature, which correlated with a decrease in PROX selectivity. Under similar conditions, DRIFTS measurements revealed a decay of COad adsorption on Cu (i.e., COad@Cu1+ species) and a corresponding red-shift under PROX conditions compared to CO oxidation, suggesting reduction-mediated charge transfer at the Cu–ZrOx interface. In contrast to the CO oxidation cycle which commences by CO adsorption on Cu1+-like sites, DFT computations revealed that the H2 oxidation cycle starts with the reaction of H2 with a pre-adsorbed O2 molecule on Cu1+-like sites, resulting in the generation of a H2O molecule and Cu2+-like sites, which are subsequently reduced to Cu1+-like sites through a successive reaction with a second H2 (or CO) molecule. Adsorption configurations and energies of CO and H2O co-adsorption indicated a competitive adsorption phenomenon on Cu species, which depends on the oxidation state of the Cu ion with a preference for CO adsorption on Cu1+-like sites, while H2O exhibits a stronger affinity for Cu2+-like sites. These results are discussed in terms of the reaction mechanism and PROX selectivity in Cu SAC catalysts and present a model for understanding the catalytic phenomena on MOF-supported SACs. [ABSTRACT FROM AUTHOR]

A protocol for efficient N-alkylation of benzamides with alcohols in the presence of cobalt-nanocatalysts is described. Key to the success of this general methodology is the use of highly dispersed cobalt nanoparticles supported on carbon, which are obtained from the pyrolysis of cobalt(II) acetate and o-phenylenediamine as a ligand at suitable temperatures. The catalytic material shows a broad substrate scope and good tolerance to functional groups. Apart from the synthesis of a variety of secondary amides (>45 products), the catalyst allows for the conversion of more challenging aliphatic alcohols and amides, including biobased and macromolecular amides. The practical applicability of the catalyst is underlined by the successful recycling and reusability. [ABSTRACT FROM AUTHOR]

Catalytic hydrogenation and oxidative dehydrogenation of N‐heterocycles to produce tetrahydroquinoline and quinoline derivatives are important reactions of particular importance in the agrochemical and pharmaceutical industries. Herein, we report earth‐abundant cobalt nanoparticles supported on hydroxyapatite (HAP) as an inexpensive and efficient catalyst for the hydrogenation and reverse oxidative dehydrogenation of N‐heterocycles. The optimal nanocatalyst exhibits excellent activity in both reactions for a wide range of substrates including (iso)quinolines, acridine, benzo[h]quinoline, quinoxaline and indole. Reactions proceed under relatively mild conditions without requiring any additives. [ABSTRACT FROM AUTHOR]

Reverse water-gas shift (RWGS) reaction has attracted much attention as a potential approach for CO 2 valorization via the production of synthesis gas, especially over Fe-modified supported Cu catalysts on CeO 2 . However, most studies have focused solely on investigating the RWGS reaction over catalysts with high Cu and Fe loadings, thus leading to an increase in the complexity of the catalytic system and, hence, preventing the gain of any reliable information about the nature of the active sites and reaction mechanism. In this work, a CeO 2 -supported single-atom Cu catalyst modified with iron was synthesized and evaluated for the RWGS reaction. The catalytic results reveal a significant synergistic effect between CuCeO 2 and Fe, demonstrating an activity up to three times higher than the combined catalytic activities of monometallic catalysts (Fe/CeO 2 + CuCeO 2 ) under identical conditions. Various ex situ and in situ/operando techniques are employed to unveil the concealed role of Fe in catalyst activity enhancement. The combined findings from hydrogen temperature-programmed reduction (H 2 -TPR) and operando electron paramagnetic resonance spectroscopy (EPR) reveal that the added Fe predominantly interacts with Cu-containing surface sites, resulting in the stabilization of higher proportions of Cu single sites. Near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) and operando EPR results unveil a synergistic interplay of Fe with Cu-containing sites and CeO x domains, efficiently enhancing both the reoxidation of Cu + in Cu + -O v -Ce 3+ moieties and the reducibility of Ce 4+ in CeO x domains under RWGS conditions. Detailed mechanistic studies reveal that the RWGS reaction predominantly proceeds via the redox mechanism., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Earth abundant metal-based heterogeneous catalysts with highly active and at the same time stable isolated metal sites constitute a key factor for the advancement of sustainable and cost-effective chemical synthesis. In particular, the development of more practical, and durable iron-based materials is of central interest for organic synthesis, especially for the preparation of chemical products related to life science applications. Here, we report the preparation of Fe-single atom catalysts (Fe-SACs) entrapped in N-doped mesoporous carbon support with unprecedented potential in the preparation of different kinds of amines, which represent privileged class of organic compounds and find increasing application in daily life. The optimal Fe-SACs allow for the reductive amination of a broad range of aldehydes and ketones with ammonia and amines to produce diverse primary, secondary, and tertiary amines including N-methylated products as well as drugs, agrochemicals, and other biomolecules (amino acid esters and amides) utilizing green hydrogen., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The nature of the support can fundamentally affect the function of a heterogeneous catalyst. For the novel type of isolated metal atom catalysts, sometimes referred to as single-atom catalysts, systematic correlations are still rare. Here, we report a general finding that Pd on nitride supports (non-metal and metal nitride) features a higher oxidation state compared to that on oxide supports (non-metal and metal oxide). Through thorough oxidation state investigations by X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), CO-DRIFTS, and density functional theory (DFT) coupled with Bader charge analysis, it is found that Pd atoms prefer to interact with surface hydroxyl group to form a Pd(OH) x species on oxide supports, while on nitride supports, Pd atoms incorporate into the surface structure in the form of Pd-N bonds. Moreover, a correlation was built between the formal oxidation state and computational Bader charge, based on the periodic trend in electronegativity., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

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.)

Molecular copper catalysts have emerged as promising candidates for the electrochemical reduction of CO 2 . Notable features of such systems include the ability of Cu to generate C 2+  products and the well-defined active sites that allow for targeted structural tuning. However, the frequently observed in situ formation of Cu nanoclusters has undermined the advantages of the molecular frameworks. It is therefore desirable to develop Cu-based catalysts that retain their molecular structures during electrolysis. In this context, a heterogenized binuclear hydroxo-bridged phenanthroline Cu(II) compound with a short Cu···Cu distance is reported as a simple yet efficient catalyst for electrogeneration of ethylene and other C 2 products. In an aqueous electrolyte, the catalyst demonstrates remarkable performance, with excellent Faradaic efficiency for C 2 products (62%) and minimal H 2 evolution (8%). Furthermore, it exhibits high stability, manifested by no observable degradation during 15 h of continuous electrolysis. The preservation of the atomic distribution of the active sites throughout electrolysis is substantiated through comprehensive characterizations, including X-ray photoelectron and absorption spectroscopy, scanning and transmission electron microscopy, UV-vis spectroscopy, as well as control experiments. These findings establish a solid foundation for further investigations into targeted structural tuning, opening new avenues for enhancing the catalytic performance of Cu-based molecular electrocatalysts., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)