Stabilization of Ni-containing Keggin-type polyoxometalates with variable oxidation states as novel catalysts for electrochemical water oxidation.

The development of new recyclable and inexpensive electrochemically active species for water oxidation catalysis is the most crucial step for future utilization of renewables. Particularly, transition metal complexes containing internal multiple, cooperative metal centers to couple with redox catalysts in the inorganic Keggin-type polyoxometalate (POM) framework at high potential or under extreme pH conditions would be promising candidates. However, most reported Ni-containing POMs have been highly unstable towards hydrolytic decomposition, which precludes them from application as water oxidation catalysts (WOCs).

Confined Ru Sites in a 13X Zeolite for Ultrahigh H Production from NH Decomposition.

Catalytic NH synthesis and decomposition offer a new promising way to store and transport renewable energy in the form of NH from remote or offshore sites to industrial plants. To use NH as a hydrogen carrier, it is important to understand the catalytic functionality of NH decomposition reactions at an atomic level. Here, we report for the first time that Ru species confined in a 13X zeolite cavity display the highest specific catalytic activity of over 4000 h for the NH decomposition with a lower activation barrier, compared to most reported catalytic materials in the literature.

Metal-loaded zeolites in ammonia decomposition catalysis.

The viability of using ammonia as a hydrogen storage vector is contingent on the development of catalytic systems active for ammonia decomposition at low temperatures. Zeolite-supported metal catalysts, unlike systems based on supports like MgO or carbon nanotubes (CNTs), are crystalline and lend themselves to analytic techniques like synchrotron X-ray powder diffraction (SXRD) and Rietveld refinement, allowing precise characterisation of catalytic active sites, and therefore mechanistic elucidation. This study focuses on characterising and optimising novel zeolite-supported Ru catalysts for ammonia decomposition, with a focus on the effects of N-substitution on catalyst structure and activity.

Dispersed surface Ru ensembles on MgO(111) for catalytic ammonia decomposition.

Ammonia is regarded as an energy vector for hydrogen storage, transport and utilization, which links to usage of renewable energies. However, efficient catalysts for ammonia decomposition and their underlying mechanism yet remain obscure. Here we report that atomically-dispersed Ru atoms on MgO support on its polar (111) facets {denoted as MgO(111)} show the highest rate of ammonia decomposition, as far as we are aware, than all catalysts reported in literature due to the strong metal-support interaction and efficient surface coupling reaction.

Cooperative catalytically active sites for methanol activation by single metal ion-doped H-ZSM-5.

Catalytic conversion of methanol to aromatics and hydrocarbons is regarded as a key alternative technology to oil processing. Although the inclusion of foreign metal species in H-ZSM-5 containing Brønsted acid site (BAS) is commonly found to enhance product yields, the nature of catalytically active sites and the rationalization for catalytic performance still remain obscure. Herein, by acquiring comparable structural parameters by both X-ray and neutron powder diffractions over a number of metal-modified ZSM-5 zeolites, it is demonstrated for the first time that active pairs of metal site-BAS within molecular distance is created when single and isolated transition metal cation is ion-exchanged with the zeolites.

Structural insight into [Fe-S-Mo] motif in electrochemical reduction of N over Fe-supported molecular MoS.

The catalytic synthesis of NH from the thermodynamically challenging N reduction reaction under mild conditions is currently a significant problem for scientists. Accordingly, herein, we report the development of a nitrogenase-inspired inorganic-based chalcogenide system for the efficient electrochemical conversion of N to NH, which is comprised of the basic structure of [Fe-S-Mo]. This material showed high activity of 8.

High Loading of Transition Metal Single Atoms on Chalcogenide Catalysts.

Transition metal doped chalcogenides are one of the most important classes of catalysts that have been attracting increasing attention for petrochemical and energy related chemical transformations due to their unique physiochemical properties. For practical applications, achieving maximum atom utilization by homogeneous dispersion of metals on the surface of chalcogenides is essential. Herein, we report a detailed study of a deposition method using thiourea coordinated transition metal complexes.

Interstitial Boron Atoms in the Palladium Lattice of an Industrial Type of Nanocatalyst: Properties and Structural Modifications.

It is well-established that the inclusion of small atomic species such as boron (B) in powder metal catalysts can subtly modify catalytic properties, and the associated changes in the metal lattice imply that the B atoms are located in the interstitial sites. However, there is no compelling evidence for the occurrence of interstitial B atoms, and there is a concomitant lack of detailed structural information describing the nature of this occupancy and its effects on the metal host. In this work, we use an innovative combination of high-resolution B magic-angle-spinning (MAS) and Pd static solid-state NMR nuclear magnetic resonance (NMR), synchrotron X-ray diffraction (SXRD), in situ X-ray pair distribution function (XPDF), scanning transmission electron microscopy-annular dark field imaging (STEM-ADF), electron ptychography, and electron energy loss spectroscopy (EELS) to investigate the B atom positions, properties, and structural modifications to the palladium lattice of an industrial type interstitial boron doped palladium nanoparticle catalyst system (Pd-B/C NPs).

Nanoscale measurement of giant saturation magnetization in α″-FeN by electron energy-loss magnetic chiral dichroism.

Metastable α″-FeN thin films were reported to have a giant saturation magnetization of above 2200 emu/cm in 1972 and have been considered as candidates for next-generation rare-earth-free permanent magnetic materials. However, their magnetic properties have not been confirmed unequivocally. As a result of the limited spatial resolution of most magnetic characterization techniques, it is challenging to measure the saturation magnetization of the α″-FeN phase, as it is often mixed with the parent α'-FeN phase in thin films.

Effect of cation ratio and order on magnetic circular dichroism in the double perovskite SrFeReO.

Superexchange-based magnetic coupling of the two B-site cations in rock-salt-ordered double perovskite oxides is extremely sensitive to the cation ratio and degree of order. However, as a result of the limited spatial resolution of most magnetic characterization techniques, it is challenging to establish a direct relationship between magnetic properties and structure in these materials, including the effects of elemental segregation and cation disorder. Here, we use electron energy-loss magnetic chiral dichroism together with aberration-corrected electron microscopy and spectroscopy to record magnetic circular dichroism (MCD) spectra at the nm scale, in combination with structural and chemical information at the atomic scale from the very same region.