Controlling the Phase Transformation of Alumina for Enhanced Stability and Catalytic Properties.

Current transition alumina catalysts require the presence of significant amounts of toxic, environmentally deleterious dopants for their stabilization. Herein, we report a simple and novel strategy to engineer transition aluminas to withstand aging temperatures up to 1200 °C without inducing the transformation to low-surface-area α-AlO and without requiring dopants. By judiciously optimizing the abundance of dominant facets and the interparticle distance, we can control the temperature of the phase transformation from θ-AlO to α-AlO and the specific surface sites on the latter.

Understanding of Active Sites and Interconversion of Pd and PdO during CH Oxidation.

Pd-based catalysts are widely used in the oxidation of CH and have a significant impact on global warming. However, understanding their active sites remains controversial, because interconversion between Pd and PdO occurs consecutively during the reaction. Understanding the intrinsic active sites under reaction conditions is critical for developing highly active and selective catalysts.

Engineering Catalysis within a Saturated In(III)-Based MOF Possessing Dynamic Ligand-Metal Bonding.

Metal-organic frameworks have developed into a formidable heterogeneous catalysis platform in recent years. It is well established that thermolysis of coordinated solvents from MOF nodes can render highly reactive, coordinatively unsaturated metal complexes which are stabilized via site isolation and serve as active sites in catalysis. Such approaches are limited to frameworks featuring solvated transition-metal complexes and must be stable toward the formation of "permanent" open metal sites.

Identification of the mechanism of NO reduction with ammonia (SCR) on zeolite catalysts.

Cu/zeolites efficiently catalyze selective reduction of environmentally harmful nitric oxide with ammonia. Despite over a decade of research, the exact NO reduction steps remain unknown. Herein, using a combined spectroscopic, catalytic and DFT approach, we show that nitrosyl ions (NO) in zeolitic micropores are the key intermediates for NO reduction.

Design of a Metal/Oxide/Carbon Interface for Highly Active and Selective Electrocatalysis.

Sustainable energy-conversion and chemical-production require catalysts with high activity, durability, and product-selectivity. Metal/oxide hybrid structure has been intensively investigated to achieve promising catalytic performance, especially in neutral or alkaline electrocatalysis where water dissociation is promoted near the oxide surface for (de)protonation of intermediates. Although catalytic promise of the hybrid structure is demonstrated, it is still challenging to precisely modulate metal/oxide interfacial interactions on the nanoscale.

Key Role of a-Top CO on Terrace Sites of Metallic Pd Clusters for CO Oxidation.

Pd-based catalysts are the most widely used for CO oxidation because of their outstanding catalytic activity and thermal stability. However, fundamental understanding of the detailed catalytic processes occurring on Pd-based catalysts under realistic conditions is still lacking. In this study, we investigated CO oxidation on metallic Pd clusters supported on Al O and SiO .

On the Nature of Extra-Framework Aluminum Species and Improved Catalytic Properties in Steamed Zeolites.

Steamed zeolites exhibit improved catalytic properties for hydrocarbon activation (alkane cracking and dehydrogenation). The nature of this practically important phenomenon has remained a mystery for the last six decades and was suggested to be related to the increased strength of zeolitic Bronsted acid sites after dealumination. We now utilize state-of-the-art infrared spectroscopy measurements and prove that during steaming, aluminum oxide clusters evolve (due to hydrolysis of Al out of framework positions with the following clustering) in the zeolitic micropores with properties very similar to (nano) facets of hydroxylated transition alumina surfaces.

Surface Density Dependent Catalytic Activity of Single Palladium Atoms Supported on Ceria*.

The analogy between single-atom catalysts (SACs) and molecular catalysts predicts that the specific catalytic activity of these systems is constant. We provide evidence that this prediction is not necessarily true. As a case in point, we show that the specific activity over ceria-supported single Pd atoms linearly increases with metal atom density, originating from the cumulative enhancement of CeO reducibility.

Precise Identification and Characterization of Catalytically Active Sites on the Surface of γ-Alumina*.

γ-alumina is one of the oldest and most important commercial catalytic materials with high surface area and stability. These attributes enabled its use as the first commercial large-scale heterogeneous catalyst for ethanol dehydration. Despite progress in materials characterization the nature of the specific sites on the surface of γ-alumina that are responsible for its unique catalytic properties has remained obscure and controversial.

High-Field One-Dimensional and Two-Dimensional Al Magic-Angle Spinning Nuclear Magnetic Resonance Study of θ-, δ-, and γ-AlO Dominated Aluminum Oxides: Toward Understanding the Al Sites in γ-AlO.

Herein, a detailed analysis was carried out using high-field (19.9 T) Al magic-angle spinning (MAS) nuclear magnetic resonance (NMR) on three specially prepared aluminum oxide samples where the γ-, δ-, and θ-AlO phases are dominantly expressed through careful control of the synthesis conditions. Specifically, two-dimensional (2D) multiquantum (MQ) MAS Al was used to obtain high spectral resolution, which provided a guide for analyzing quantitative 1D Al NMR spectra.

High-performance and stable photoelectrochemical water splitting cell with organic-photoactive-layer-based photoanode.

Considering their superior charge-transfer characteristics, easy tenability of energy levels, and low production cost, organic semiconductors are ideal for photoelectrochemical (PEC) hydrogen production. However, organic-semiconductor-based photoelectrodes have not been extensively explored for PEC water-splitting because of their low stability in water. Herein, we report high-performance and stable organic-semiconductors photoanodes consisting of p-type polymers and n-type non-fullerene materials, which is passivated using nickel foils, GaIn eutectic, and layered double hydroxides as model materials.

A General Strategy to Atomically Dispersed Precious Metal Catalysts for Unravelling Their Catalytic Trends for Oxygen Reduction Reaction.

Atomically dispersed precious metal catalysts have emerged as a frontier in catalysis. However, a robust, generic synthetic strategy toward atomically dispersed catalysts is still lacking, which has limited systematic studies revealing their general catalytic trends distinct from those of conventional nanoparticle (NP)-based catalysts. Herein, we report a general synthetic strategy toward atomically dispersed precious metal catalysts, which consists of "trapping" precious metal precursors on a heteroatom-doped carbonaceous layer coated on a carbon support and "immobilizing" them with a SiO layer during thermal activation.

Molecular Engineered Safer Organic Battery through the Incorporation of Flame Retarding Organophosphonate Moiety.

Here, we report the first electrochemical assessment of organophosphonate-based compound as a safe electrode material for lithium-ion batteries, which highlights the reversible redox activity and inherent flame retarding property. Dinickel 1,4-benzenediphosphonate delivers a high reversible capacity of 585 mA h g with stable cycle performance. It expands the scope of organic batteries, which have been mainly dominated by the organic carbonyl family to date.

Cross-linking Zr-based metal-organic polyhedra postsynthetic polymerization.

Metal organic polyhedra (MOPs) have potential as supramolecular building blocks, but utilizing MOPs for postsynthetic polymerization has not been explored. Although MOPs with flexible organic moieties have been recently reported to target enhanced processability, permanent porosity has not been demonstrated. Here, a novel synthetic strategy involving the cross-linking of MOPs a covalent bond is demonstrated by exploiting a condensation reaction between the MOP and flexible organic linkers.

Evolution of form in metal-organic frameworks.

Self-assembly has proven to be a widely successful synthetic strategy for functional materials, especially for metal-organic materials (MOMs), an emerging class of porous materials consisting of metal-organic frameworks (MOFs) and metal-organic polyhedra (MOPs). However, there are areas in MOM synthesis in which such self-assembly has not been fully utilized, such as controlling the interior of MOM crystals. Here we demonstrate sequential self-assembly strategy for synthesizing various forms of MOM crystals, including double-shell hollow MOMs, based on single-crystal to single-crystal transformation from MOP to MOF.

Efficient CO Oxidation by 50-Facet CuO Nanocrystals Coated with CuO Nanoparticles.

As carbon monoxide oxidation is widely used for various chemical processes (such as methanol synthesis and water-gas shift reactions HO + CO ⇄ CO + H) as well as in industry, it is essential to develop highly energy efficient, inexpensive, and eco-friendly catalysts for CO oxidation. Here we report green synthesis of ∼10 nm sized CuO nanoparticles (NPs) aggregated on ∼400 nm sized 50-facet CuO polyhedral nanocrystals. This CuO-NPs/50-facet CuO shows remarkable CO oxidation reactivity with very high specific CO oxidation activity (4.

Characterization of Fe²⁺ ions in Fe,H/SSZ-13 zeolites: FTIR spectroscopy of CO and NO probe molecules.

The IR spectra of adsorbed CO and NO probe molecules were used to characterize the coordination chemistry of Fe(2+) ions in solution ion exchanged Fe,H/SSZ-13 zeolites. The effects of Fe ion exchange levels, as well as the sample pre-treatment conditions, on the adsorption of these probe molecules were investigated. The ion exchange levels (in the range of the study) did not affect significantly the IR spectra of either probe molecule, and the IR features and their intensity ratios were very similar.

Low-temperature carbon monoxide oxidation catalysed by regenerable atomically dispersed palladium on alumina.

Catalysis by single isolated atoms of precious metals has attracted much recent interest, as it promises the ultimate in atom efficiency. Most previous reports are on reducible oxide supports. Here we show that isolated palladium atoms can be catalytically active on industrially relevant γ-alumina supports.

Dissecting the steps of CO₂ reduction: 2. The interaction of CO and CO₂ with Pd/γ-Al₂O₃: an in situ FTIR study.

Alumina supported Pd catalysts with metal loadings of 0.5, 2.5 and 10 wt% were investigated by in situ FTIR spectroscopy in order to understand the nature of adsorbed species formed during their exposure to CO2 and CO.

Dissecting the steps of CO₂ reduction: 1. The interaction of CO and CO₂ with γ-Al₂O₃: an in situ FTIR study.

The adsorption of CO2 and CO was investigated on a pure γ-Al2O3 support material that has been used in Pd and Ru catalysts for the reduction of CO2. The adsorption of CO2 resulted in the formation of carbonates, bicarbonates and linearly adsorbed CO2 species. The amount and the nature of the adsorbed species were dependent on the annealing temperature of the alumina support.

Molecular Active Sites in Heterogeneous Ir-La/C-Catalyzed Carbonylation of Methanol to Acetates.

We report that when Ir and La halides are deposited on carbon, exposure to CO spontaneously generates a discrete molecular heterobimetallic structure, containing an Ir-La covalent bond that acts as a highly active, selective, and stable heterogeneous catalyst for the carbonylation of methanol to produce acetic acid. This catalyst exhibits a very high productivity of ∼1.5 mol acetyl/mol Ir·s with >99% selectivity to acetyl (acetic acid and methyl acetate) without detectable loss in activity or selectivity for more than 1 month of continuous operation.

A common intermediate for N2 formation in enzymes and zeolites: side-on Cu-nitrosyl complexes.

Side on! Combined FTIR and NMR studies revealed the presence of a side-on nitrosyl species in the zeolite Cu-SSZ-13. This intermediate is very similar to those found in nitrite reductase enzyme systems. The identification of this intermediate led to the proposal of a reaction mechanism that is fully consistent with the results of both kinetic and spectroscopic studies.

Characterization of Cu-SSZ-13 NH3 SCR catalysts: an in situ FTIR study.

The adsorption of CO and NO over Cu-SSZ-13 zeolite catalysts, highly active in the selective catalytic reduction of NO(x) with NH(3), was investigated by FTIR spectroscopy, and the results obtained were compared to those collected from other Cu-ion exchanged zeolites (Y,FAU and ZSM-5). Under low CO pressures and at room temperature (295 K), CO forms monocarbonyls exclusively on the Cu(+) ions, while in the presence of gas phase CO dicarbonyls on Cu(+) and adsorbed CO on Cu(2+) centers form, as well. At low (cryogenic) sample temperatures, tricarbonyl formation on Cu(+) sites was also observed.

A large sample volume magic angle spinning nuclear magnetic resonance probe for in situ investigations with constant flow of reactants.

A large-sample-volume constant-flow magic angle sample spinning (CF-MAS) NMR probe is reported for in situ studies of the reaction dynamics, stable intermediates/transition states, and mechanisms of catalytic reactions. In our approach, the reactants are introduced into the catalyst bed using a fixed tube at one end of the MAS rotor while a second fixed tube, linked to a vacuum pump, is attached at the other end of the rotor. The pressure difference between both ends of the catalyst bed inside the sample cell space forces the reactants flowing through the catalyst bed, which improves the diffusion of the reactants and products.