Impact of Gas-Solid Reaction Thermodynamics on the Performance of a Chemical Looping Ammonia Synthesis Process.

Novel ammonia catalysts seek to achieve high reaction rates under milder conditions, which translate into lower costs and energy requirements. Alkali and alkaline earth metal hydrides have been shown to possess such favorable kinetics when employed in a chemical looping process. The materials act as nitrogen carriers and form ammonia by alternating between pure nitrogen and hydrogen feeds in a two-stage chemical looping reaction. However, the thermodynamics of the novel reaction route in question are only partially available. Here, a chemical looping process was designed and simulated to evaluate the sensitivity of the energy and economic performance of the processes toward the appropriate gas-solid reaction thermodynamics. Thermodynamic parameters, such as reaction pressure and especially equilibrium ammonia yields, influenced the performance of the system. In comparison to a commercial ammonia synthesis unit with a 28% yield at 150 bar, the chemical looping process requires a yield greater than 38% to achieve similar energy consumptions and a yield greater than 26% to achieve similar costs at a given temperature and 150 bar. Entropies and enthalpies of formation of the following pairs were estimated and compared: LiH/Li2NH, MgH2/MgNH, CaH2/CaNH, SrH2/SrNH, and BaH2/BaNH. Only the LiH/Li2NH pair has satisfied the given criteria, and initial estimates suggest that a 62% yield is obtainable.

Emergence and Future of Exsolved Materials.

Supported nanoparticle systems have received increased attention over the last decades because of their potential for high activity levels when applied to chemical conversions, although, because of their nanoscale nature, they tend to exhibit problems with long-term durability. Over the last decade, the discovery of the so-called exsolution concept has addressed many of these challenges and opened many other opportunities to material design by providing a relatively simple, single-step, synthetic pathway to produce supported nanoparticles that combine high stability against agglomeration and poisoning with high activity across multiple areas of application. Here, the trends that define the development of the exsolution concept are reviewed in terms of design, functionality, tunability, and applicability. To support this, the number of studies dedicated to both fundamental and application-related studies, as well as the types of metallic nanoparticles and host or support lattices employed, are examined. Exciting future directions of research are also highlighted.

Trends and Prospects of Bimetallic Exsolution.

Supported bimetallic nanoparticles used for various chemical transformations appear to be more appealing than their monometallic counterparts, because of their unique properties mainly originating from the synergistic effects between the two different metals. Exsolution, a relatively new preparation method for supported nanoparticles, has earned increasing attention for bimetallic systems in the past decade, not only due to the high stability of the resulting nanoparticles but also for the potential to control key particle properties (size, composition, structure, morphology, etc.). In this review, we summarize the trends and advances on exsolution of bimetallic systems and provide prospects for future studies in this field.

Exsolution of Catalytically Active Iridium Nanoparticles from Strontium Titanate.

The search for new functional materials that combine high stability and efficiency with reasonable cost and ease of synthesis is critical for their use in renewable energy applications. Specifically in catalysis, nanoparticles, with their high surface-to-volume ratio, can overcome the cost implications associated with otherwise having to use large amounts of noble metals. However, commercialized materials, that is, catalytic nanoparticles deposited on oxide supports, often suffer from loss of activity because of coarsening and carbon deposition during operation. Exsolution has proven to be an interesting strategy to overcome such issues. Here, the controlled emergence, or exsolution, of faceted iridium nanoparticles from a doped SrTiO3 perovskite is reported and their growth preliminary probed by in situ electron microscopy. Upon reduction of SrIr0.005Ti0.995O3, the generated nanoparticles show embedding into the oxide support, therefore preventing agglomeration and subsequent catalyst degradation. The advantages of this approach are the extremely low noble metal amount employed (∼0.5% weight) and the catalytic activity reported during CO oxidation tests, where the performance of the exsolved SrIr0.005Ti0.995O3 is compared to the activity of a commercial catalyst with 1% loading (1% Ir/Al2O3). The high activity obtained with such low doping shows the possibility of scaling up this new catalyst, reducing the high cost associated with iridium-based materials.

Tracking the evolution of a single composite particle during redox cycling for application in H2 production.

Composite materials consisting of metal and metal oxide phases are being researched intensively for various energy conversion applications where they are often expected to operate under redox conditions at elevated temperature. Understanding of the dynamics of composite evolution during redox cycling is still very limited, yet critical to maximising performance and increasing durability. Here we track the microstructural evolution of a single composite particle over 200 redox cycles for hydrogen production by chemical looping, using multi-length scale X-ray computed tomography. We show that redox cycling triggers a centrifugal redispersion of the metal phase and a centripetal clustering of porosity, both seemingly driven by the asymmetric nature of oxygen exchange in composites. Initially, the particle develops a large amount of internal porosity which boosts activity, but on the long term this facilitates structural and compositional reorganisation and eventually degradation. These results provide valuable insight into redox-driven microstructural changes and also for the design of new composite materials with enhanced durability.

Measuring Membrane Permeation Rates through the Optical Visualization of a Single Pore.

Membranes are a critical technology for energy-efficient separation processes. The routine method of evaluating membrane performance is a permeation measurement. However, such measurements can be limited in terms of their utility: membrane microstructure is often poorly characterized; membranes or sealants leak; and conditions in the gas phase are poorly controlled and frequently far-removed from the conditions employed in the majority of real processes. Here, we demonstrate a new integrated approach to determine permeation rates, using two novel supported molten-salt membrane geometries. In both cases, the membranes comprise a solid support with laser-drilled pores, which are infiltrated with a highly CO2-selective molten carbonate salt. First, we fabricate an optically transparent single-crystal, single-pore model membrane by local laser drilling. By infiltrating the single pore with molten carbonate, monitoring the gas-liquid interface optically, and using image analysis on gas bubbles within the molten carbonate (because they change volume upon controlled changes in gas composition), we extract CO2 permeation rates with exceptional speed and precision. Additionally, in this arrangement, microstructural characterization is more straightforward and a sealant is not required, eliminating a major source of leakage. Furthermore, we demonstrate that the technique can be used to probe a previously unexplored driving force region, too low to access with conventional methods. Subsequently, we fabricate a leak-free tubular-supported molten-salt membrane with 1000 laser-drilled pores (infiltrated with molten carbonate) and employ a CO2-containing sweep gas to obtain permeation rates in a system that can be described with unprecedented precision. Together, the two approaches provide new ways to measure permeation rates with increased speed and at previously inaccesible conditions.

Endogenous Nanoparticles Strain Perovskite Host Lattice Providing Oxygen Capacity and Driving Oxygen Exchange and CH4 Conversion to Syngas.

Particles dispersed on the surface of oxide supports have enabled a wealth of applications in electrocatalysis, photocatalysis, and heterogeneous catalysis. Dispersing nanoparticles within the bulk of oxides is, however, synthetically much more challenging and therefore less explored, but could open new dimensions to control material properties analogous to substitutional doping of ions in crystal lattices. Here we demonstrate such a concept allowing extensive, controlled growth of metallic nanoparticles, at nanoscale proximity, within a perovskite oxide lattice as well as on its surface. By employing operando techniques, we show that in the emergent nanostructure, the endogenous nanoparticles and the perovskite lattice become reciprocally strained and seamlessly connected, enabling enhanced oxygen exchange. Additionally, even deeply embedded nanoparticles can reversibly exchange oxygen with a methane stream, driving its redox conversion to syngas with remarkable selectivity and long term cyclability while surface particles are present. These results not only exemplify the means to create extensive, self-strained nanoarchitectures with enhanced oxygen transport and storage capabilities, but also demonstrate that deeply submerged, redox-active nanoparticles could be entirely accessible to reaction environments, driving redox transformations and thus offering intriguing new alternatives to design materials underpinning several energy conversion technologies.

In Situ Observation of Nanoparticle Exsolution from Perovskite Oxides: From Atomic Scale Mechanistic Insight to Nanostructure Tailoring.

Understanding and controlling the formation of nanoparticles at the surface of functional oxide supports is critical for tuning activity and stability for catalytic and energy conversion applications. Here, we use a latest generation environmental transmission electron microscope to follow the exsolution of individual nanoparticles at the surface of perovskite oxides, with ultrahigh spatial and temporal resolution. Qualitative and quantitative analysis of the data reveals the atomic scale processes that underpin the formation of the socketed, strain-inducing interface that confers exsolved particles their exceptional stability and reactivity. This insight also enabled us to discover that the shape of exsolved particles can be controlled by changing the atmosphere in which exsolution is carried out, and additionally, this could also produce intriguing heterostructures consisting of metal-metal oxide coupled nanoparticles. Our results not only provide insight into the in situ formation of nanoparticles but also demonstrate the tailoring of nanostructures and nanointerfaces.

Towards efficient use of noble metals via exsolution exemplified for CO oxidation.

Many catalysts and in particular automotive exhaust catalysts usually consist of noble metal nanoparticles dispersed on metal oxide supports. While highly active, such catalysts are expensive and prone to deactivation by sintering and thus alternative methods for their production are being sought to ensure more efficient use of noble metals. Exsolution has been shown to be an approach to produce confined nanoparticles, which in turn are more stable against agglomeration, and, at the same time strained, displaying enhanced activity. While exsolution has been extensively investigated for relatively high metal loadings, it has yet to be explored for dilute loadings which is expected to be more challenging but more suitable for application of noble metals. Here we explore the substitution of Rh into an A-site deficient perovskite titante aiming to investigate the possibility of exsolving from dilute amounts of noble metal substituted perovskites. We show that this is possible and in spite of certain limitations, they still compete well against conventionally prepared samples with higher apparent surface loading when applied for CO oxidation.

Shape-persistent porous organic cage supported palladium nanoparticles as heterogeneous catalytic materials.

Porous Organic Cages (POCs) are an emerging class of self-assembling, porous materials with novel properties. They offer a key advantage over other porous materials in permitting facile solution processing and re-assembly. The combination of POCs with metal nanoparticles (NPs) unlocks applications in the area of catalysis. In this context, POCs can function as both the template of ultra-small NPs and a porous, but reprocessable, heterogeneous catalyst support. Here, we demonstrate the synthesis of ultra-small Pd NPs with an imine linked POC known as 'CC3', and show that hydrogen gas can be used to form metallic NPs at ∼200 °C without the reduction of the organic cage (and the accompanying, unwanted loss of crystallinity). The resulting materials are characterized using a range of techniques (including powder diffraction, scanning transmission electron microscopy and synchrotron X-ray absorption spectroscopy) and shown to be recrystallizable following dissolution in organic solvent. Their catalytic efficacy is demonstrated using the widely studied carbon monoxide oxidation reaction. This demonstration paves the way for using ultra-small NPs synthesized with POCs as solution-processable, self-assembling porous catalytic materials.

Overcoming chemical equilibrium limitations using a thermodynamically reversible chemical reactor.

All real processes, be they chemical, mechanical or electrical, are thermodynamically irreversible and therefore suffer from thermodynamic losses. Here, we report the design and operation of a chemical reactor capable of approaching thermodynamically reversible operation. The reactor was employed for hydrogen production via the water-gas shift reaction, an important route to 'green' hydrogen. The reactor avoids mixing reactant gases by transferring oxygen from the (oxidizing) water stream to the (reducing) carbon monoxide stream via a solid-state oxygen reservoir consisting of a perovskite phase (La0.6Sr0.4FeO3-δ). This reservoir is able to remain close to equilibrium with the reacting gas streams because of its variable degree of non-stoichiometry and thus develops a 'chemical memory' that we employ to approach reversibility. We demonstrate this memory using operando, spatially resolved, real-time, high-resolution X-ray powder diffraction on a working reactor. The design leads to a reactor unconstrained by overall chemical equilibrium limitations, which can produce essentially pure hydrogen and carbon dioxide as separate product streams.

Hainan mantle plume produced late Cenozoic basaltic rocks in Thailand, Southeast Asia.

Intraplate volcanism initiated shortly after the cessation of Cenozoic seafloor spreading in the South China Sea (SCS) region, but the full extent of its influence on the Indochina block has not been well constrained. Here we present major and trace element data and Sr-Nd-Pb-Hf isotope ratios of late Cenozoic basaltic lavas from the Khorat plateau and some volcanic centers in the Paleozoic Sukhothai arc terrane in Thailand. These volcanic rocks are mainly trachybasalts and basaltic trachyandesites. Trace element patterns and Sr-Nd-Pb-Hf isotopic compositions show that these alkaline volcanic lavas exhibit oceanic island basalt (OIB)-like characteristics with enrichments in both large-ion lithophile elements (LILE) and high field strength elements (HFSEs). Their mantle source is a mixture between a depleted Indian MORB-type mantle and an enriched mantle type 2 (EMII). We suggest that the post-spreading intraplate volcanism in the SCS region was induced by a Hainan mantle plume which spread westwards to the Paleozoic Sukhothai arc terrane.

Demonstration of chemistry at a point through restructuring and catalytic activation at anchored nanoparticles.

Metal nanoparticles prepared by exsolution at the surface of perovskite oxides have been recently shown to enable new dimensions in catalysis and energy conversion and storage technologies owing to their socketed, well-anchored structure. Here we show that contrary to general belief, exsolved particles do not necessarily re-dissolve back into the underlying perovskite upon oxidation. Instead, they may remain pinned to their initial locations, allowing one to subject them to further chemical transformations to alter their composition, structure and functionality dramatically, while preserving their initial spatial arrangement. We refer to this concept as chemistry at a point and illustrate it by tracking individual nanoparticles throughout various chemical transformations. We demonstrate its remarkable practical utility by preparing a nanostructured earth abundant metal catalyst which rivals platinum on a weight basis over hundreds of hours of operation. Our concept enables the design of compositionally diverse confined oxide particles with superior stability and catalytic reactivity.

Role of the Three-Phase Boundary of the Platinum-Support Interface in Catalysis: A Model Catalyst Kinetic Study.

A series of microstructured, supported platinum (Pt) catalyst films (supported on single-crystal yttria-stabilized zirconia) and an appropriate Pt catalyst reference system (supported on single-crystal alumina) were fabricated using pulsed laser deposition and ion-beam etching. The thin films exhibit area-specific lengths of the three-phase boundary (length of three-phase boundary between the Pt, support, and gas phase divided by the superficial area of the sample) that vary over 4 orders of magnitude from 4.5 × 102 to 4.9 × 106 m m-2, equivalent to structural length scales of 0.2 µm to approximately 9000 µm. The catalyst films have been characterized using X-ray diffraction, atomic force microscopy, high-resolution scanning electron microscopy, and catalytic activity tests employing the carbon monoxide oxidation reaction. When Pt is supported on yttria-stabilized zirconia, the reaction rate clearly depends upon the area-specific length of the three-phase boundary, l(tpb). A similar relationship is not observed when Pt is supported on alumina. We suggest that the presence of the three-phase boundary provides an extra channel of oxygen supply to the Pt through diffusion in or on the yttria-stabilized zirconia support coupled with surface diffusion across the Pt.

Borneo and Indochina are major evolutionary hotspots for Southeast Asian biodiversity.

Tropical Southeast (SE) Asia harbors extraordinary species richness and in its entirety comprises four of the Earth's 34 biodiversity hotspots. Here, we examine the assembly of the SE Asian biota through time and space. We conduct meta-analyses of geological, climatic, and biological (including 61 phylogenetic) data sets to test which areas have been the sources of long-term biological diversity in SE Asia, particularly in the pre-Miocene, Miocene, and Plio-Pleistocene, and whether the respective biota have been dominated by in situ diversification, immigration and/or emigration, or equilibrium dynamics. We identify Borneo and Indochina, in particular, as major "evolutionary hotspots" for a diverse range of fauna and flora. Although most of the region's biodiversity is a result of both the accumulation of immigrants and in situ diversification, within-area diversification and subsequent emigration have been the predominant signals characterizing Indochina and Borneo's biota since at least the early Miocene. In contrast, colonization events are comparatively rare from younger volcanically active emergent islands such as Java, which show increased levels of immigration events. Few dispersal events were observed across the major biogeographic barrier of Wallace's Line. Accelerated efforts to conserve Borneo's flora and fauna in particular, currently housing the highest levels of SE Asian plant and mammal species richness, are critically required.

Catalytic and non-catalytic wet air oxidation of sodium dodecylbenzene sulfonate: kinetics and biodegradability enhancement.

Wet air oxidation (WAO) and catalytic wet air oxidation (CWAO) were investigated as suitable precursors for the biological treatment of industrial wastewater containing sodium dodecylbenzene sulfonate (DBS). Two hours WAO semi-batch experiments were conducted at 15 bar of oxygen partial pressure (P(O2)) and at 180, 200 and 220 degrees C. It was found that the highest temperature provides appreciable total organic carbon (TOC) and chemical oxygen demand (COD) abatement of about 42 and 47%, correspondingly. Based on the main identified intermediates (acetic acid and sulfobenzoic acid) a reaction pathway for DBS and a kinetic model in WAO were proposed. In the case of CWAO experiments, seventy-two hours tests were done in a fixed bed reactor in continuous trickle flow regime, using a commercial activated carbon (AC) as catalyst. The temperature and P(O2) were 140-160 degrees C and 2-9 bar, respectively. The influence of the operating conditions on the DBS oxidation, the occurrence of oxidative coupling reactions over the AC, and the catalytic activity (in terms of substrate removal) were established. The results show that the AC without any supported active metal behaves bi-functional as adsorbent and catalyst, giving TOC conversions up to 52% at 160 degrees C and 2 bar of P(O2), which were comparable to those obtained in WAO experiments. Respirometric tests were completed before and after CWAO and to the main intermediates identified through the WAO and CWAO oxidation route. Then, the readily biodegradable COD (COD(RB)) of the CWAO and WAO effluents were found. Taking into account these results it was possible to compare whether or not the CWAO or WAO effluents were suitable for a conventional activated sludge plant inoculated with non adapted culture.

Kinetics of low frequency sonodegradation of linear alkylbenzene sulfonate solutions.

The decomposition of sodium dodecylbenzene sulfonate (SDBS) in water by means of ultrasound irradiation at 20kHz was investigated. Experiments were conducted at surfactant concentrations of 175, 260 and 350 mg l(-1), liquid volumes of 120, 170 and 220 ml, temperatures of 20, 30 and 45 degrees C and applied power of 40, 80 and 125 W. The extent of degradation was followed monitoring substrate and organic carbon concentrations, while hydrogen peroxide concentration was also measured; the latter is a product of water sonolysis due to hydroxyl radical recombination. 80% SDBS conversion was achieved after 120 min of sonication at 125 W and 30 degrees C; nonetheless, SDBS and its degradation intermediates proved difficult to oxidise as only about 20-25% of the initial carbon content was transformed to carbon dioxide. At the initial stages of the reaction, degradation rate appears to be only weakly dependent on the substrate concentration with the rate increasing from 3.1 to 4 mg l(-1)min(-1) with increasing concentration from 175 to 350 mg l(-1). Degradation appears to occur at the bubble-liquid interface through hydroxyl radical-mediated reactions whose role was established by performing experiments in the presence of radical scavengers, namely potassium bromide and sodium benzoate. Degradation rates increased with increasing power and decreasing temperature and volume.