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NASA NTRS2011

Numerical Model Sensitivity to Heterogeneous Satellite Derived Vegetation Roughness

The sensitivity of a mesoscale weather prediction model to a 1 km satellite-based vegetation roughness initialization is investigated for a domain within the south central United States. Three different roughness databases are employed: i) a control or standard lookup table roughness that is a function only of land cover type, ii) a spatially heterogeneous roughness database, specific to the domain, that was previously derived using a physically based procedure and Moderate Resolution Imaging Spectroradiometer (MODIS) imagery, and iii) a MODIS climatologic roughness database that like (i) is a function only of land cover type, but possesses domain specific mean values from (ii). The model used is the Weather Research and Forecast Model (WRF) coupled to the Community Land Model within the Land Information System (LIS). For each simulation, a statistical comparison is made between modeled results and ground observations within a domain including Oklahoma, Eastern Arkansas, and Northwest Louisiana during a 4-day period within IHOP 2002. Sensitivity analysis compares the impact the three roughness initializations on time-series temperature, precipitation probability of detection (POD), average wind speed, boundary layer height, and turbulent kinetic energy (TKE). Overall, the results indicate that, for the current investigation, replacement of the standard look-up table values with the satellite-derived values statistically improves model performance for most observed variables. Such natural roughness heterogeneity enhances the surface wind speed, PBL height and TKE production up to 10 percent, with a lesser effect over grassland, and greater effect over mixed land cover domains.

Jasinski, Michael↗

NASA NTRS2012

Radiative Impacts of Cloud Heterogeneity and Overlap in an Atmospheric General Circulation Model

The radiative impacts of introducing horizontal heterogeneity of layer cloud condensate, and vertical overlap of condensate and cloud fraction are examined with the aid of a new radiation package operating in the GEOS-5 Atmospheric General Circulation Model. The impacts are examined in terms of diagnostic top-of-the-atmosphere shortwave (SW) and longwave (LW) cloud radiative effect (CRE) calculations for a range of assumptions and parameter specifications about the overlap. The investigation is conducted for two distinct cloud schemes, the one that comes with the standard GEOS-5 distribution, and another which has been recently used experimentally for its enhanced GEOS-5 distribution, and another which has been recently used experimentally for its enhanced cloud microphysical capabilities; both are coupled to a cloud generator allowing arbitrary cloud overlap specification. We find that cloud overlap radiative impacts are significantly stronger for the operational cloud scheme for which a change of cloud fraction overlap from maximum-random to generalized results to global changes of SW and LW CRE of approximately 4 Watts per square meter, and zonal changes of up to approximately 10 Watts per square meter. This is because of fewer occurrences compared to the other scheme of large layer cloud fractions and of multi-layer situations with large numbers of atmospheric being simultaneously cloudy, conditions that make overlap details more important. The impact on CRE of the details of condensate distribution overlap is much weaker. Once generalized overlap is adopted, both cloud schemes are only modestly sensitive to the exact values of the overlap parameters. We also find that if one of the CRE components is overestimated and the other underestimated, both cannot be driven towards observed values by adjustments to cloud condensate heterogeneity and overlap alone.

Oreopoulos, L.↗

NASA NTRS2013

Heterogeneous Formation of Polar Stratospheric Clouds- Part 1: Nucleation of Nitric Acid Trihydrate (NAT)

Satellite-based observations during the Arctic winter of 2009/2010 provide firm evidence that, in contrast to the current understanding, the nucleation of nitric acid trihydrate (NAT) in the polar stratosphere does not only occur on preexisting ice particles. In order to explain the NAT clouds observed over the Arctic in mid-December 2009, a heterogeneous nucleation mechanism is required, occurring via immersion freezing on the surface of solid particles, likely of meteoritic origin. For the first time, a detailed microphysical modelling of this NAT formation pathway has been carried out. Heterogeneous NAT formation was calculated along more than sixty thousand trajectories, ending at Cloud Aerosol Lidar with Orthogonal Polarization (CALIOP) observation points. Comparing the optical properties of the modelled NAT with these observations enabled a thorough validation of a newly developed NAT nucleation parameterisation, which has been built into the Zurich Optical and Microphysical box Model (ZOMM). The parameterisation is based on active site theory, is simple to implement in models and provides substantial advantages over previous approaches which involved a constant rate of NAT nucleation in a given volume of air. It is shown that the new method is capable of reproducing observed polar stratospheric clouds (PSCs) very well, despite the varied conditions experienced by air parcels travelling along the different trajectories. In a companion paper, ZOMM is applied to a later period of the winter, when ice PSCs are also present, and it is shown that the observed PSCs are also represented extremely well under these conditions.

Hoyle, C. R.↗

NASA NTRS2017

Heterogeneity of Water Concentrations in the Mantle Lithosphere Beneath Hawaii

The amount and distribution of water in the oceanic mantle lithosphere has implications on its strength and of the role of volatiles during plume/lithosphere interaction. The latter plays a role in the Earth's deep water cycle as water-rich plume lavas could re-enrich an oceanic lithosphere depleted in water at the ridge, and when this heterogeneous lithosphere gets recycled back into the deep mantle. The main host of water in mantle lithologies are nominally anhydrous minerals like olivine, pyroxene and garnet, where hydrogen (H) is incorporated in mineral defects by bonding to structural oxygen. Here, we report water concentrations by Fourier transform infrared spectrometry (FTIR) on olivine, clino- and orthopyroxenes (Cpx & Opx) from spinel peridotites from the Pali vent and garnet pyroxenite xenoliths from Aliamanu vent, both part of the rejuvenated volcanism at Oahu (Hawaii). Pyroxenes from the Aliamanu pyroxenites have high water concentrations, similar to the adjacent Salt Lake Crater (SLC) pyroxenites (Cpx ~400-500 ppm H2O, Opx ~200 ppm H2O). This confirms that pyroxenite cumulates form water-rich lithologies within the oceanic lithosphere. In contrast, the Pali peridotites have much lower water concentrations than the SLC ones (<25 ppm vs. 50-96 ppm H2O respectively) despite being relatively fertile with >10% modal Cpx and low spinel Cr# (0.09-0.10). The contrast between the two peridotite suites is also evident in their trace elements and radiogenic isotopes. The Pali Cpx are depleted in light REE, consistent with minimal metasomatism. Those of SLC have enriched light REE patterns and Nd and Hf isotopes consistent with metasomatism by alkaline melts. These observations are consistent with heterogeneous water distribution in the oceanic lithosphere that may be related to metasomatism, as well as relatively dry peridotites cross-cut by narrow (?) water-rich melt reaction zones.

Bizimis, M.↗

NASA NTRS2018

Heterogeneous Spacecraft Networks

The present invention provides a heterogeneous spacecraft network including a network management architecture to facilitate communication between a plurality of operations centers and a plurality of data user communities. The network management architecture includes a plurality of network nodes in communication with the plurality of operations centers. The present invention also provides a method of communication for a heterogeneous spacecraft network. The method includes: transmitting data from a first space segment to a first ground segment; transmitting the data from the first ground segment to a network management architecture; transmitting data from a second space segment to a second ground segment, the second space and ground segments having incompatible communication systems with the first space and ground segments; transmitting the data from the second ground station to the network management architecture; and, transmitting data from the network management architecture to a plurality of data user communities.

Nakamura, Yosuke↗

NASA NTRS2018

A Comparative Analysis of Micrometeorological Determinants of Evapotranspiration Rates Within a Heterogeneous Urban Environment

Variability in micrometeorological conditions and their influence on estimated reference evapotranspiration (RET) rates were evaluated across a heterogeneous urban environment. Micrometeorological data sets (incoming solar radiation, air temperature, relative humidity and wind speed) were collected over a one-year period at six weather stations in New York City, NY (USA). Weather stations are located at four new urban green space monitoring sites and two airports. Reference evapotranspiration (RET) rates were estimated from the micrometeorological data sets for a short reference surface at a daily time-step using the ASCE Standardized Reference Evapotranspiration Equation, a Penman-Monteith based combination equation. Nonparametric comparative statistical analyses (Kruskal-Wallis) revealed statistically significant differences (at significance level α = 0.05) in micrometeorological conditions and estimated RET rates between the six sites. On a cumulative annual basis, estimated RET varied by up to 40 percent between the sites. A new technique for adjusting weather data collected at one location (e.g. regional airports) for use at another location (e.g. interior engineered urban green spaces) was evaluated. The study highlights the importance, for accurate estimation of ET, of onsite micrometeorological data sets, but concludes that additional research is needed to more thoroughly characterize micrometeorological variability across heterogeneous urban environments, and also to evaluate the influence of non-meteorological determinants, e.g. vegetation type, soil/media type, media moisture conditions and anthropogenic heat fluxes, on urban ET.

Urban environment↗

NASA NTRSDate not supplied

Heterogeneity of Bulk Oxygen Isotopic Compositions in Anhydrous Interplanetary Dust Particles

Introduction: Anhydrous interplanetary dust particles are one of the least altered ancient solar systemmaterials. Their bulk chemical compositions match those of CI chondrites within a factor of 2-3, except for carbonwhich is enriched in both anhydrous and hydrated IDPs by ~4x CI [1]. Hydrous IDPs often show 16O-poor isotopiccompositions, likely due to the interaction with isotopically heavy H2O [2]. Anhydrous IDPs are interpreted tooriginate from comets from the outer solar system [3]. Oxygen isotopic data for these materials is scarce, but resultspoint to a wider range of compositions [4]. This heterogeneity might be a result of mixing between a 16O-rich and a16O-poor reservoir formed via self-shielding and photodissociation of CO [5]. Here, we report bulk oxygen isotopiccompositions of three anhydrous IDPs in context of their mineralogical composition and discuss possible origins ofisotopic heterogeneity. Experimental: Bulk chemical composition and mineralogy of 70 nm thin ultramicrotomed sections of threeanhydrous IDPs (L2099A7, L2099A8, and L2071AB1) were analyzed using a Thermo Scientific Titan Themis G360-300 TEM equipped with a four-quadrant energy-dispersive X-ray detector (Super-X G2) at University ofMünster. Bulk oxygen isotopic compositions were measured using a NanoSIMS 50 at the Max-Planck-Institut fürChemie in Mainz. A focused Cs+ ion beam (~1 pA, ~100 nm) was rastered over a field of view varying from 5 x 5 to6 x 6 μm2, depending on particle size for 15 layers. Negative secondary ions of 16O, 17O, 18O, 12C14N, and 28Si werecollected on electron multipliers. The 16OH contribution to the 17O peak was 1-2 ‰. As a standard, a matrix regionof meteorite CR2 Queen Alexandra Range (QUE) 99177 was used, whose oxygen isotopic composition wasmeasured by [6]. Results and Discussion: Particles A7 and A8 are both fine-grained, consisting mostly of small, 100 nm-sizedequilibrated aggregates (EA). Both particles exhibit discontinuous magnetite rims with thicknesses up to 50 nm inA7 and 100 nm in A8 on the outsides. In Particle AB1, the upper part of the particle consists of a few EAs, while thelower part contains lots of small GEMS grains with 100-200 nm diameter clustered together. Magnetite rims arenearly absent, the rare rims reaching maximum 20 nm thickness, indicating that AB1 is of more primitive naturethan the other two IDPs [1]. Furthermore, it contains several diffuse GEMS-like areas, identified by an amorphoussilicate groundmass with small nano-inclusions of Fe,Ni-metal and Fe-sulfides. All three particles are subsolar forall major element/Si ratios. Mean S/Si of particles A7 and A8 is 0.046 and 0.048, respectively, while it is an order ofmagnitude higher in AB1 (0.184). This reflects the higher degree of thermal alteration in A7 and A8, resulting in theloss of volatile S and oxidation of Fe-sulfides and FeNi-metal to magnetite as present in particle rims. A8 is rather16O-poor with δ17OSMOW = 7.8 ± 3.4 ‰ and δ18OSMOW = 9.5 ± 3.1 ‰ (1σ), followed by A7 with δ17OSMOW = − 0.8 ±4.6 ‰ and δ18OSMOW = −2.2 ± 3.4 ‰. In contrast to that, AB1 has the most 16O-rich bulk composition with δ17OSMOW= −24.2 ± 5.4 ‰ and δ18OSMOW = −25.3 ± 3.6 ‰. All investigated IDPs plot slightly above the CCAM line aspreviously reported for other anhydrous IDPs [4], maybe due to a contribution from circumstellar dust from AGBstars enriched in 17O [7]. The 16O-rich composition of AB1 is similar to the most 16O-rich anhydrous IDP U2015D21measured by [8] which is dominated by GEMS [9] and the GEMS-rich IDP GM4-2 reported by [10]. Nevertheless,it is unlikely that GEMS are the carrier for the 16O-rich composition of AB1 because most GEMS have O isotopiccompositions indistinguishable from terrestrial values, although errors on these analyses are large [11]. The isotopicheterogeneity is best explained by contribution of grains from different regions in the protoplanetary disk, samplingdifferent O isotope reservoirs, created by self-shielding and photodissociation of CO. This process resulted in 16O-rich CO gas and 16O-poor H2O that froze as ice-mantles onto dust grains [12]. Alternatively, the higher degree ofheating in A7 and A8 could have influenced isotopic fractionation, because higher δ17,18O values are reported fromthe regions of the atmosphere where small particles are heated and oxidized, as observed for the thermal alteration ofcosmic spherules [13]. Acknowledgements: We would like to thank NASA Astromaterials Acquisition & Curation Office for providing IDPsamples and DFG for funding this project (VO1816/5-1)

B Schulz↗

NASA NTRSDate not supplied

Investigating Amino Acid Heterogeneity in Milligram-Scale Samples of the Murchison CM2 Carbonaceous Chondrite

Analyses of different aliquots of the Tagish Lake meteorite have resulted in amino acid abundance variations of an order of magnitude or more, even when performed using the same techniques, by the same personnel, in the same laboratories (e.g., Simkus et al. 2019). Up to ~five-fold variations have been observed for specific amino acids in different samples of the same meteorite, such as α aminoisobutryic acid (AIB) in Murchison. These variations are often attributed differing sample composition or differing alteration history, neither of which is mutually exclusive. Distinguishing between these two explanations is challenging and time consuming, requiring detailed mineralogical analyses to be performed in conjunction with high precision organics analysis. The potential for innate sample-level heterogeneity presents a significant complication when parsing the effects of different processes or conditions during preparation of meteorite samples for analysis, as differences in organic yields or abundances could be due to differences in laboratory processing or differences among the samples themselves. In this work, we investigated the degree of innate organic heterogeneity present in a single ~250 mg chip of divided into 21 samples.

A. S. Burton↗

NASA NTRS2024

Heterogeneous Outgassing Regions Identified on Active Centaur 29P/Schwassmann–Wachmann 1

Centaurs are transitional objects between primitive trans-Neptunian objects and Jupiter-family comets. Their compositions and activities provide fundamental clues regarding the processes affecting the evolution of and interplay between these small bodies. Here we report observations of centaur 29P/Schwassmann–Wachmann 1 (29P) with the James Webb Space Telescope (JWST). We identified localized jets with heterogeneous compositions driving the outgassing activity. We employed the NIRSpec mapping spectrometer to study the fluorescence emissions of CO and obtain a definitive detection of CO 2 for this target. The exquisite sensitivity of the instrument also enabled carbon and oxygen isotopic signatures to be probed. Molecular maps reveal complex outgassing distributions, such as jets and anisotropic morphology, which indicate that 29P’s nucleus is dominated by active regions with heterogeneous compositions. These distributions could reflect that it has a bilobate structure with compositionally distinct components or that strong differential erosion takes place on the nucleus. As there are no missions currently planning to visit a centaur, these observations demonstrate JWST’s unique capabilities in characterizing these objects.

Sara Faggi↗

DOE OSTI2020

FLEET: Flexible Efficient Ensemble Training for Heterogeneous Deep Neural Networks

Parallel training of an ensemble of Deep Neural Networks (DNN) on a cluster of nodes is an effective approach to shorten the process of neural network architecture search and hyper-parameter tuning for a given learning task. Prior efforts have shown that data sharing, where the common preprocessing operation is shared across the DNN training pipelines, saves computational resources and improves pipeline efficiency. Data sharing strategy, however, performs poorly for a heterogeneous set of DNNs where each DNN has varying computational needs and thus different training rate and convergence speed. This paper proposes FLEET, a flexible ensemble DNN training framework for efficiently training a heterogeneous set of DNNs. We build FLEET via several technical innovations. We theoretically prove that an optimal resource allocation is NP-hard and propose a greedy algorithm to efficiently allocate resources for training each DNN with data sharing. We integrate data-parallel DNN training into ensemble training to mitigate the differences in training rates and introduce checkpointing into this context to address the issue of different convergence speeds. Experiments show that FLEET significantly improves the training efficiency of DNN ensembles without compromising the quality of the result.

Guan, Hui↗

DOE OSTI2021

Toward Performance Portable Programming for Heterogeneous System-on-Chips: Case Study with Qualcomm Snapdragon SoC

Future heterogeneous Domain-Specific System-on-Chips (DSSoC) will be extraordinarily complex in terms of processors, memory hierarchies, and interconnection networks.To manage this complexity, architects, system software designers, and application developers need programming technologies that are flexible, accurate, efficient, and productive. These technologies will need to be as independent of any one specific architecture as is practical, because the sheer dimensionality and scale of the complexity will not allow porting and optimizing applications foreach given DSSoC. To address these issues, we are developing Cosmic Castle, a performance portable programming toolchain for streaming applications on heterogeneous architectures. The primary focus of Cosmic Castle is on enabling efficient and performant code generation through the smart compiler and intelligent runtime system. This paper presents the preliminary evaluation of our ongoing work toward Cosmic Castle. Specifically, we detail our code porting efforts and evaluate various benchmarks on the Qualcomm Snapdragon SoC using tools developed through Cosmic Castle.

Cabrera, Anthony↗

DOE OSTI2023

MATBOX, an Open-Source Microstructure Analysis Toolbox for Meshing, Generation, Segmentation, and Characterization of 3D Heterogenous Volumes

Battery performance is strongly correlated with electrode microstructural properties. To account for its impact, lithium-ion battery (LIB) models either abstract the microstructural heterogeneity of composite electrodes using effective macroscopic properties (macro- or meso- scale models) or directly solve the system of equations on the microstructure geometry or mesh (microstructure-scale models). Therefore, to be adequate, both families of models require information from the microstructure geometry, which can be provided by the numerical tool presented in this work. MATBOX is a MATLAB open-source application [1] developed by NREL for performing various microstructure-related tasks including microstructure numerical generation, image filtering and microstructure segmentation, microstructure characterization and correlation, visualization, and microstructure meshing. MATBOX was originally developed for the analysis of LIB electrode microstructures; however, the algorithms provided by the toolbox are widely applicable to other heterogeneous materials. The toolbox provides a user-friendly experience thanks to a Graphical-User Interface, requires no coding by the user, and is well documented. This presentation will illustrate various MATBOX features for the characterization of a LIB electrode, including a fully automated Representative Volume Element (RVE) analysis, the numerical generation of complex 'virtual' microstructure, including dual-layer electrodes and carbon-binder additive phase, and the meshing of a complex NMC/graphite full cell microstructure suitable for 3D finite-element modeling. Other modules (segmentation, visualization, and correlation) will be briefly presented. Thanks to its modular, open-source approach, MATBOX can easily incorporate third-party algorithms to eventually build a standard in the field that will benefit the whole scientific community. Effective diffusion coefficient [2], additive phase numerical generation [3], and meshing [4] third-party algorithms have been already integrated in the toolbox with more to come.

DIRECT ENERGY CONVERSION,MATHEMATICS AND COMPUTING↗

DOE OSTI2020

Port Hope Area Initiative - Port Granby Project: Managing Highly Heterogeneous Low-Level Radioactive Waste - 20327

The Port Granby Project is a large remediation project currently approximately 95% complete. Initial waste characterization was provided through a borehole sampling program. As the waste was excavated, it was found to be highly heterogeneous, ranging from essentially 'clean' material to hundreds of Bq/g. This heterogeneity resulted in constantly changing site conditions. Methods to adapt to these conditions are described. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2024

sKokkos: Enabling Kokkos with Transparent Device Selection on Heterogeneous Systems using OpenACC

This paper presents a new feature to enable Kokkos with transparent device selection. For application developers, it is not easy toidentify which device is the most appropriate to use in a heterogeneous system, since this depends on the characteristics of both the application and the hardware. In Kokkos, a backend is associated with one specific programming model/hardware. Programmers decide which backend to use at compilation time. This new feature implemented on the OpenACC backend eliminates the burden of deciding which device to use, providing a highly productive programming solution for Kokkos applications. This work includes implementation details and a performance study conducted with a set of mini-benchmarks (i.e., AXPY and dot product), kernels (Lattice-Bolzmann method), and two mini-apps (LULESH and miniFE) on two heterogeneous systems with different hardware capabilities. This new Kokkos feature provides high accelerations of up to 35× thanks to automatic and transparent device selection.

Lee, Seyong↗

DOE OSTI2025

Performance Portability Evaluation of Fluid-Structure Interaction Simulations on Heterogeneous Platforms

The rapid proliferation of heterogeneous programming languages and multi-vendor hardware has underscored the critical need to evaluate the performance portability of scientific applications. In this work, we present the systematic porting and optimization of a massively parallel fluid-structure interaction code across multiple heterogeneous programming frameworks for deployment on leadership-class supercomputers from major vendors. Our analysis focuses on at-scale performance for simulations involving hundreds of millions of deformable cells, executed on a combination of CPUs and GPUs spanning thousands of nodes on exascale machines. We benchmark the performance of each implementation, highlighting the trade-offs inherent in adopting diverse programming models. Key insights regarding the portability of CUDA on multi-vendor platforms, the superior multi-core CPU performance from SYCL, and architectural considerations on performance optimization are distilled from our experience, offering guidance to other users of high performance computing based on our findings.

Martin, Aristotle [Duke University]↗

DOE OSTI2025

A Study on Co-existing Heterogeneous Wireless Networks for Data Transmission within a Nuclear Facility

Deployment of wireless technologies is a salient need for modernization, automation and improved operation of nuclear power plants (NPPs). As a single technology cannot support the ever-changing needs, it is required to have a heterogeneous wireless network architecture to address the different technical and economic challenges. However, the coexistence of these multiband heterogeneous wireless networks brings numerous challenges due to the factors including dissimilarity in their channel access mechanism, distance between nodes, transmit power level and many more. This paper develops real-world experiments and simulations of wireless coexistence for Wi-Fi, Fifth generation cellular (5G) and Zigbee in the unlicensed band to understand the challenges and opportunities. The experiments were conducted over the Platform for Open Wireless Data-driven Experimental Research (POWDER) testbed at the university of Utah. In addition, this paper is the first to propose a novel packet rate control technique at the network layer to create temporary opportunities for 5G or Zigbee signal transmissions focusing its application in a nuclear facility while using the shared band. The performance of the proposed coexistence solution is validated with experimental results and simulation.

5G↗

NASA NTRS2016

Applicability of the Effective-Medium Approximation to Heterogeneous Aerosol Particles.

The effective-medium approximation (EMA) is based on the assumption that a heterogeneous particle can have a homogeneous counterpart possessing similar scattering and absorption properties. We analyze the numerical accuracy of the EMA by comparing superposition T-matrix computations for spherical aerosol particles filled with numerous randomly distributed small inclusions and Lorenz-Mie computations based on the Maxwell-Garnett mixing rule. We verify numerically that the EMA can indeed be realized for inclusion size parameters smaller than a threshold value. The threshold size parameter depends on the refractive-index contrast between the host and inclusion materials and quite often does not exceed several tenths, especially in calculations of the scattering matrix and the absorption cross section. As the inclusion size parameter approaches the threshold value, the scattering-matrix errors of the EMA start to grow with increasing the host size parameter and or the number of inclusions. We confirm, in particular, the existence of the effective-medium regime in the important case of dust aerosols with hematite or air-bubble inclusions, but then the large refractive-index contrast necessitates inclusion size parameters of the order of a few tenths. Irrespective of the highly restricted conditions of applicability of the EMA, our results provide further evidence that the effective-medium regime must be a direct corollary of the macroscopic Maxwell equations under specific assumptions.

aerosols↗

DOE OSTI2021

Monolayer Support Control and Precise Colloidal Nanocrystals Demonstrate Metal-Support Interactions in Heterogeneous Catalysts

We report that electronic and geometric interactions between active and support phases are critical in determining the activity of heterogeneous catalysts, but metal-support interactions are challenging to study. Here, it is demonstrated how the combination of the monolayer-controlled formation using atomic layer deposition (ALD) and colloidal nanocrystal synthesis methods leads to catalysts with sub-nanometer precision of active and support phases, thus allowing for the study of the metal-support inter-actions in detail. The use of this approach in developing a fundamental understanding of support effects in Pd-catalyzed methane combustion is demonstrated. Uniform Pd nanocrystals are deposited onto Al2O 3 /SiO 2 spherical supports prepared with control over morphology and Al 2 O 3 layer thicknesses ranging from sub-monolayer to a ≈4 nm thick uniform coating. Dramatic changes in catalytic activity depending on the coverage and structure of Al 2 O 3 situated at the Pd/Al 2 O 3 interface are observed, with even a single monolayer of alumina contributing an order of magnitude increase in reaction rate. By building the Pd/Al 2 O 3 interface up layer-by-layer and using uniform Pd nanocrystals, this work demonstrates the importance of controlled and tunable materials in determining metal-support interactions and catalyst activity.

36 MATERIALS SCIENCE↗