Design of Supported Metal Catalysts and Systems for Propane Dehydrogenation.

Propane dehydrogenation (PDH) is currently an approach for the production of propylene with high industrial importance, especially in the context of the shale gas revolution and the growing global demands for propylene and downstream commodity chemicals. In this Perspective article, we comprehensively summarize the recent advances in the design of advanced catalysts for PDH and the new understanding of the structure-performance relationship in supported metal catalysts. Furthermore, we discuss the gaps between fundamental research and practical industrial applications in the catalyst developments for the PDH process.

Isolated Pt Atoms Stabilized by GaO Clusters Confined in ZSM-5 for Nonoxidative Activation of Ethane.

Selective activation of light alkanes is an essential reaction in the petrochemical industry for producing commodity chemicals, such as light olefins and aromatics. Because of the much higher intrinsic activities of noble metals in comparison to non-noble metals, it is desirable to employ solid catalysts with low noble metal loadings to reduce the cost of catalysts. Herein, we report the introduction of a tiny amount of Pt (at levels of hundreds of ppm) as a promoter of the GaO clusters encapsulated in ZSM-5 zeolite, which leads to ∼20-fold improvement in the activity for ethane dehydrogenation reaction.

Boosting the Stability of Subnanometer Pt Catalysts by the Presence of Framework Indium(III) Sites in Zeolite.

Subnanometer metal clusters show advantages over conventional metal nanoparticles in numerous catalytic reactions owing to their high percentage of exposed surface sites, abundance of under-coordinated metal sites and unique electronic structures. However, the applications of subnanometer metal clusters in high-temperature catalytic reactions (>600 °C) are still hindered, because of their low stability under harsh reaction conditions. In this work, we have developed a zeolite-confined bimetallic PtIn catalyst with exceptionally high stability against sintering.

Reactant-Induced Structural Evolution of Pt Catalysts Confined in Zeolite.

Reactant-induced structural evolutions of heterogeneous metal catalysts are frequently observed in numerous catalytic systems, which can be associated with the formation or deactivation of active sites. In this work, we will show the structural transformation of subnanometer Pt clusters in pure-silica MFI zeolite structure in the presence of CO, O, and/or HO and the catalytic consequences of the Pt-zeolite materials derived from various treatment conditions. By applying the appropriate pretreatment under a reactant atmosphere, we can precisely modulate the size distribution of Pt species spanning from single Pt atoms to small Pt nanoparticles (1-5 nm) in the zeolite matrix, resulting in the desirably active and stable Pt species for CO oxidation.

Generation of Subnanometer Metal Clusters in Silicoaluminate Zeolites as Bifunctional Catalysts.

Zeolite-encapsulated subnanometer metal catalysts are an emerging class of solid catalysts with superior performances in comparison to metal catalysts supported on open-structure solid carriers. Currently, there is no general synthesis methodology for the encapsulation of subnanometer metal catalysts in different zeolite structures. In this work, we will show a general synthesis method for the encapsulation of subnanometer metal clusters (Pt, Pd, and Rh) within various silicoaluminate zeolites with different topologies (MFI, CHA, TON, MOR).

Integrated immediate postmortem and acute bereavement care: Competency-based entrustable professional activities for nursing.

Background: Integrated immediate postmortem and acute bereavement care alleviates emotional distress due to losing a loved one; however, the provision of effective nursing care remains insufficient. Therefore, preparing nursing students with such skills is essential in end-of-life care education, and entrustable professional activities (EPAs) offer potential to address this gap.

Objectives: To establish EPAs concerning immediate postmortem and acute bereavement care with a seven-category description for EPAs, milestones, and assessment tools.

Bimetallic Sites for Catalysis: From Binuclear Metal Sites to Bimetallic Nanoclusters and Nanoparticles.

Heterogeneous bimetallic catalysts have broad applications in industrial processes, but achieving a fundamental understanding on the nature of the active sites in bimetallic catalysts at the atomic and molecular level is very challenging due to the structural complexity of the bimetallic catalysts. Comparing the structural features and the catalytic performances of different bimetallic entities will favor the formation of a unified understanding of the structure-reactivity relationships in heterogeneous bimetallic catalysts and thereby facilitate the upgrading of the current bimetallic catalysts. In this review, we will discuss the geometric and electronic structures of three representative types of bimetallic catalysts (bimetallic binuclear sites, bimetallic nanoclusters, and nanoparticles) and then summarize the synthesis methodologies and characterization techniques for different bimetallic entities, with emphasis on the recent progress made in the past decade.

Dominance of Influencing Factors on Cooling Effect of Urban Parks in Different Climatic Regions.

The enhancement of the park cooling effect (PCE) is one method used to alleviate the urban heat island (UHI). The cooling effect is affected by park factors; however, the importance of these factors in the case of the PCE is still unclear. Optimizing or planning urban parks according to the importance of the influencing factors can effectively enhance the PCE.

Single-Atom Ce-Modified α-FeO for Selective Catalytic Reduction of NO with NH.

A single-atom Ce-modified α-FeO catalyst (FeCeO catalyst with 7% atomic percentage of Ce) was synthesized by a citric acid-assisted sol-gel method, which exhibited excellent performance for selective catalytic reduction of NO with NH (NH-SCR) over a wide operating temperature window. Remarkably, it maintained ∼93% NO conversion efficiency for 168 h in the presence of 200 ppm SO and 5 vol % HO at 250 °C. The structural characterizations suggested that the introduction of Ce leads to the generation of local Fe-O-Ce sites in the FeO matrix.

Tuning the Catalytic Performance of Cobalt Nanoparticles by Tungsten Doping for Efficient and Selective Hydrogenation of Quinolines under Mild Conditions.

Non-noble bimetallic CoW nanoparticles (NPs) partially embedded in a carbon matrix (CoW@C) have been prepared by a facile hydrothermal carbon-coating methodology followed by pyrolysis under an inert atmosphere. The bimetallic NPs, constituted by a multishell core-shell structure with a metallic Co core, a W-enriched shell involving CoW alloyed structures, and small WO patches partially covering the surface of these NPs, have been established as excellent catalysts for the selective hydrogenation of quinolines to their corresponding 1,2,3,4-tetrahydroquinolines under mild conditions of pressure and temperature. It has been found that this bimetallic catalyst displays superior catalytic performance toward the formation of the target products than the monometallic Co@C, which can be attributed to the presence of the CoW alloyed structures.

Direct assessment of confinement effect in zeolite-encapsulated subnanometric metal species.

Subnanometric metal species confined inside the microporous channels/cavities of zeolites have been demonstrated as stable and efficient catalysts. The confinement interaction between the metal species and zeolite framework has been proposed to play the key role for stabilization, though the confinement interaction is elusive to be identified and measured. By combining theoretical calculations, imaging simulation and experimental measurements based on the scanning transmission electron microscopy-integrated differential phase contrast imaging technique, we have studied the location and coordination environment of isolated iridium atoms and clusters confined in zeolite.

Type of mandibular asymmetry affects changes and outcomes of bimaxillary surgery for class III asymmetry.

Objectives: Various methods have been used to classify class III asymmetry. There is little information on the use of an asymmetry index to examine soft tissue changes and outcomes for patients with class III asymmetry. This study aimed to (1) evaluate soft tissue changes and outcomes for three types of mandibular asymmetry and (2) determine if measures are associated with type of asymmetry.

Correction: Direct synthesis of the organic and Ge free Al containing BOG zeolite (ITQ-47) and its application for transformation of biomass derived molecules.

[This corrects the article DOI: 10.1039/D0SC04044D.].

Direct synthesis of the organic and Ge free Al containing BOG zeolite (ITQ-47) and its application for transformation of biomass derived molecules.

Aluminosilicate boggsite (Si/Al-BOG) has been hydrothermally synthesized without adding organic structure-directing agents (OSDAs) in the synthesis gel using the borosilicogermanium ITQ-47 (Si/B-ITQ-47) zeolite as seeds. The introduction of the costly and environmentally less benign phosphazene organic structure-directing agent is not required to grow the zeolite. Physicochemical characterization experiments show that Si/Al-BOG has good crystallinity, high surface area, tetrahedral Al species, and acid sites.

Structural transformations of solid electrocatalysts and photocatalysts.

Heterogeneous catalysts often undergo structural transformations when they operate under thermal reaction conditions. These transformations are reflected in their evolving catalytic activity, and a fundamental understanding of the changing nature of active sites is vital for the rational design of solid materials for applications. Beyond thermal catalysis, both photocatalysis and electrocatalysis are topical because they can harness renewable energy to drive uphill reactions that afford commodity chemicals and fuels.

Tutorial: structural characterization of isolated metal atoms and subnanometric metal clusters in zeolites.

The encapsulation of subnanometric metal entities (isolated metal atoms and metal clusters with a few atoms) in porous materials such as zeolites can be an effective strategy for the stabilization of those metal species and therefore can be further used for a variety of catalytic reactions. However, owing to the complexity of zeolite structures and their low stability under the electron beam, it is challenging to obtain atomic-level structural information of the subnanometric metal species encapsulated in zeolite crystallites. In this protocol, we show the application of a scanning transmission electron microscopy (STEM) technique that records simultaneously the high-angle annular dark-field (HAADF) images and integrated differential phase-contrast (iDPC) images for structural characterization of subnanometric Pt and Sn species within MFI zeolite.

Regioselective Generation of Single-Site Iridium Atoms and Their Evolution into Stabilized Subnanometric Iridium Clusters in MWW Zeolite.

Preparation of supported metal catalysts with uniform particle size and coordination environment is a challenging and important topic in materials chemistry and catalysis. In this work, we report the regioselective generation of single-site Ir atoms and their evolution into stabilized subnanometric Ir clusters in MWW zeolite, which are located at the 10MR window connecting the two neighboring 12MR supercages. The size of the subnanometric Ir clusters can be controlled by the post-synthesis treatments and maintain below 1 nm even after being reduced at 650 °C, which cannot be readily achieved with samples prepared by conventional impregnation methods.

Low-Temperature Catalytic NO Reduction with CO by Subnanometric Pt Clusters.

The catalytic subnanometric metal clusters with a few atoms can be regarded as an intermediate state between single atoms and metal nanoparticles (>1 nm). Their molecule-like electronic structures and flexible geometric structures bring rich chemistry and also a different catalytic behavior, in comparison with the single-atom or nanoparticulate counterparts. In this work, by combination of operando IR spectroscopy techniques and electronic structure calculations, we will show a comparative study on Pt catalysts for CO + NO reaction at a very low temperature range (140-200 K).

Determination of the Evolution of Heterogeneous Single Metal Atoms and Nanoclusters under Reaction Conditions: Which Are the Working Catalytic Sites?

Identification of active sites in heterogeneous metal catalysts is critical for understanding the reaction mechanism at the molecular level and for designing more efficient catalysts. Because of their structural flexibility, subnanometric metal catalysts, including single atoms and clusters with a few atoms, can exhibit dynamic structural evolution when interacting with substrate molecules, making it difficult to determine the catalytically active sites. In this work, Pt catalysts containing selected types of Pt entities (from single atoms to clusters and nanoparticles) have been prepared, and their evolution has been followed, while they were reacting in a variety of heterogeneous catalytic reactions, including selective hydrogenation reactions, CO oxidation, dehydrogenation of propane, and photocatalytic H evolution reaction.

Hydrothermal Synthesis of Ruthenium Nanoparticles with a Metallic Core and a Ruthenium Carbide Shell for Low-Temperature Activation of CO to Methane.

Ruthenium nanoparticles with a core-shell structure formed by a core of metallic ruthenium and a shell of ruthenium carbide have been synthesized by a mild and easy hydrothermal treatment. The dual structure and composition of the nanoparticles have been determined by synchrotron X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure (NEXAFS) analysis, and transmission electron microscopy (TEM) imaging. According to depth profile synchrotron XPS and X-ray diffraction (XRD) analysis, metallic ruthenium species predominate in the inner layers of the material, ruthenium carbide species being located on the upper surface layers.

Regioselective generation and reactivity control of subnanometric platinum clusters in zeolites for high-temperature catalysis.

Subnanometric metal species (single atoms and clusters) have been demonstrated to be unique compared with their nanoparticulate counterparts. However, the poor stabilization of subnanometric metal species towards sintering at high temperature (>500 °C) under oxidative or reductive reaction conditions limits their catalytic application. Zeolites can serve as an ideal support to stabilize subnanometric metal catalysts, but it is challenging to localize subnanometric metal species on specific sites and modulate their reactivity.

The study of regional thermal environments in urban agglomerations using a new method based on metropolitan areas.

Urban agglomerations (UAs) are an outcome of regional urbanization reaching relatively advanced stages of development. The advancement of UAs in regional-spatial organization has been recognized worldwide. However, due to dense regional urbanization, UAs are threatened by various regional eco-environmental stresses.

Generation of gold nanoclusters encapsulated in an MCM-22 zeolite for the aerobic oxidation of cyclohexane.

In this work, we will report the generation of Au clusters in a purely siliceous MCM-22 zeolite. The catalytic properties of these Au clusters have been tested for the selective oxidation of cyclohexane to cyclohexanol and cyclohexanone (KA-oil). The Au clusters encapsulated in the MCM-22 zeolite are highly active and selective for the oxidation of cyclohexane to KA-oil, which is superior to Au nanoparticles on the same support.

Base-Controlled Heck, Suzuki, and Sonogashira Reactions Catalyzed by Ligand-Free Platinum or Palladium Single Atom and Sub-Nanometer Clusters.

The assumption that oxidative addition is the key step during the cross-coupling reaction of aryl halides has led to the development of a plethora of increasingly complex metal catalysts, thereby obviating in many cases the exact influence of the base, which is a simple, inexpensive, and necessary reagent for this paramount transformation. Here, a combined experimental and computational study shows that the oxidative addition is not the single kinetically relevant step in different cross-coupling reactions catalyzed by sub-nanometer Pt or Pd species, since the reactivity control is shifted toward subtle changes in the base. The exposed metal atoms in the cluster cooperate to enable an extremely easy oxidative addition of the aryl halide, even chlorides, and allow the base to bifurcate the coupling.