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). Here, we have prepared new tri-Ni-containing POMs with variable oxidation states by charge tailored synthetic strategies for the first time and developed them as recyclable POMs for water oxidation catalysts. In addition, by implanting corresponding POM anions into the positively charged MIL-101(Cr) metal-organic framework (MOF), the entrapped Ni2+/Ni3+ species can show complete recyclability for water oxidation catalysis without encountering uncontrolled hydrolysis of the POM framework. As a result, a low onset potential of approximately 1.46 V vs. NHE for water oxidation with stable WOC performance is recorded. Based on this study, rational design and stabilization of other POM-electrocatalysts containing different multiple transition metal centres could be made possible.

Confined Ru Sites in a 13X Zeolite for Ultrahigh H2 Production from NH3 Decomposition.

Catalytic NH3 synthesis and decomposition offer a new promising way to store and transport renewable energy in the form of NH3 from remote or offshore sites to industrial plants. To use NH3 as a hydrogen carrier, it is important to understand the catalytic functionality of NH3 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-1 for the NH3 decomposition with a lower activation barrier, compared to most reported catalytic materials in the literature. Mechanistic and modeling studies clearly indicate that the N-H bond of NH3 is ruptured heterolytically by the frustrated Lewis pair of Ruδ+-Oδ- in the zeolite identified by synchrotron X-rays and neutron powder diffraction with Rietveld refinement as well as other characterization techniques including solid-state nuclear magnetic resonance spectroscopy, in situ diffuse reflectance infrared transform spectroscopy, and temperature-programmed analysis. This contrasts with the homolytic cleavage of N-H displayed by metal nanoparticles. Our work reveals the unprecedented unique behavior of cooperative frustrated Lewis pairs created by the metal species on the internal zeolite surface, resulting in a dynamic hydrogen shuttling from NH3 to regenerate framework Brønsted acid sites that eventually are converted to molecular hydrogen.

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. Characterisation focuses on an unsubstituted and N-substituted Ru-zeolite Y pair with NMR, FTIR, TEM, XRD, XAS, ICP, and BET, demonstrating the successful incorporation of N into the zeolite framework and an enhancement in metal dispersion upon N-substitution. A series of 18 monometallic and bimetallic catalysts is then synthesised on X and USY supports and screened for catalytic activity. Ru is identified as the most active metal for ammonia decomposition. Observed trends suggest catalyst dispersion can be increased with substantially lower metal loadings, and in particular via the formation of stably anchored oligonuclear metal clusters within the zeolite framework, as opposed to much larger nanoparticles (NPs) on its exterior, following N-substitution of the framework. DFT modelling proposes a prismatic Ru6N6 cluster fitted to XAS data. High-activity catalyst Ru-ß (N) 2.4% demonstrates comparable or better ammonia conversion by Ru wt% than recently reported catalysts in the literature at 450 °C and 30 000 WHSV.

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. We have carefully investigated the loading effect of Ru from atomic form to cluster/nanoparticle on MgO(111). Progressive increase of surface Ru concentration, correlated with increase in specific activity per metal site, clearly indicates synergistic metal sites in close proximity, akin to those bimetallic N2 complexes in solution are required for the stepwise dehydrogenation of ammonia to N2/H2, as also supported by DFT modelling. Whereas, beyond surface doping, the specific activity drops substantially upon the formation of Ru cluster/nanoparticle, which challenges the classical view of allegorically higher activity of coordinated Ru atoms in cluster form (B5 sites) than isolated sites.

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. This method allows the preparation of a library of a wide range of single atoms including both noble and non-noble transition metals (Fe, Co, Ni, Cu, Pt, Pd, Ru) with a metal loading as high as 10 wt % on various ultrathin 2D chalcogenides (MoS2, MoSe2, WS2 and WSe2). As demonstrated by the state-of-the-art characterization, the doped single transition metal atoms interact strongly with surface anions and anion vacancies in the exfoliated 2D materials, leading to high metal dispersion in the absence of agglomeration. Taking Fe on MoS2 as a benchmark, it has been found that Fe is atomically dispersed until 10 wt %, and beyond this loading, formation of coplanar Fe clusters is evident. Atomic Fe, with a high electron density at its conduction band, exhibits a superior intrinsic activity and stability in CO2 hydrogenation to CO per Fe compared to corresponding surface Fe clusters and other Fe catalysts reported for reverse water-gas-shift reactions.

Structural insight into [Fe-S2-Mo] motif in electrochemical reduction of N2 over Fe1-supported molecular MoS2.

The catalytic synthesis of NH3 from the thermodynamically challenging N2 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 N2 to NH3, which is comprised of the basic structure of [Fe-S2-Mo]. This material showed high activity of 8.7 mgNH3 mgFe -1 h-1 (24 µgNH3 cm-2 h-1) with an excellent faradaic efficiency of 27% for the conversion of N2 to NH3 in aqueous medium. It was demonstrated that the Fe1 single atom on [Fe-S2-Mo] under the optimal negative potential favors the reduction of N2 to NH3 over the competitive proton reduction to H2. Operando X-ray absorption and simulations combined with theoretical DFT calculations provided the first and important insights on the particular electron-mediating and catalytic roles of the [Fe-S2-Mo] motifs and Fe1, respectively, on this two-dimensional (2D) molecular layer slab.

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. According to our DFT model, this could lead to the initial heterolytic cleavage of small molecules such as water and methanol by the pair with subsequent reactions to form products at high selectivity as that observed experimentally. It may account for their active and selective catalytic routes of small molecule activations.

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 11B magic-angle-spinning (MAS) and 105Pd 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-intB/C NPs). In this study, we report that upon B incorporation into the Pd lattice, the overall face centered cubic (FCC) lattice is maintained; however, short-range disorder is introduced. The 105Pd static solid-state NMR illustrates how different types (and levels) of structural strain and disorder are introduced in the nanoparticle history. These structural distortions can lead to the appearance of small amounts of local hexagonal close packed (HCP) structured material in localized regions. The short-range lattice tailoring of the Pd framework to accommodate interstitial B dopants in the octahedral sites of the distorted FCC structure can be imaged by electron ptychography. This study describes new toolsets that enable the characterization of industrial metal nanocatalysts across length scales from macro- to microanalysis, which gives important guidance to the structure-activity relationship of the system.

Nanoscale measurement of giant saturation magnetization in α″-Fe16N2 by electron energy-loss magnetic chiral dichroism.

Metastable α″-Fe16N2 thin films were reported to have a giant saturation magnetization of above 2200 emu/cm3 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″-Fe16N2 phase, as it is often mixed with the parent α'-Fe8N phase in thin films. Here, we use electron energy-loss magnetic chiral dichroism (EMCD), aberration-corrected transmission electron microscopy, X-ray diffraction and macroscopic magnetic measurements to study α″-Fe16N2 (containing ordered N atoms) and α'-Fe8N (containing disordered N atoms). The ratio of saturation magnetization in α″-Fe16N2 to that in α'-Fe8N is determined to be 1.31 ± 0.10 from quantitative EMCD measurements and dynamical diffraction calculations, confirming the giant saturation magnetization of α″-Fe16N2. Crystallographic information is also obtained about the two phases, which are mixed on the nanoscale.

Effect of cation ratio and order on magnetic circular dichroism in the double perovskite Sr2Fe1+xRe1-xO6.

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. We study nanoscale phases in ordered Sr2[Fe][Re]O6, ordered Sr2[Fe][Fe1/5Re4/5]O6 and disordered Sr[Fe4/5Re1/5]O3 individually, in order to understand the role of cation ratio and order on local magnetic coupling. When compared with ordered Sr2[Fe][Re]O6, we find that antiferromagnetic Fe3+-O2--Fe3+superexchange interactions arising from an excess of Fe suppress the MCD signal from Fe cations in ordered Sr2[Fe][Fe1/5Re4/5]O6, while dominant Fe3+-O2--Fe3+antiferromagnetic coupling in disordered Sr[Fe4/5Re1/5]O3 leads to a decrease in MCD signal down to the noise level. Our work demonstrates a protocol that can be used to correlate crystallographic, electronic and magnetic information in materials such as Sr2Fe1+xRe1-xO6, in order to provide insight into structure-property relationships in double perovskite oxides at the atomic scale.