Effect of Dynamic and Preferential Decoration of Pt Catalyst Surfaces by WOx on Hydrodeoxygenation Reactions.

Catalysts containing Pt nanoparticles and reducible transition-metal oxides (WOx, NbOx, TiOx) exhibit remarkable selectivity to aromatic products in hydrodeoxygenation (HDO) reactions for biomass valorization, contrasting the undesired aromatic hydrogenation typically observed for metal catalysts. However, the active site(s) responsible for the high selectivity remains elusive. Here, theoretical and experimental analyses are combined to explain the observed HDO reactivity by interrogating the organization of reduced WOx domains on Pt surfaces at sub-monolayer coverage. The SurfGraph algorithm is used to develop model structures that capture the configurational space (∼1000 configurations) for density functional theory (DFT) calculations of a W3O7 trimer on stepped Pt surfaces. Machine-learning models trained on the DFT calculations identify the preferential occupation of well-coordinated Pt sites (≥8 Pt coordination number) by WOx and structural features governing WOx-Pt stability. WOx/Pt/SiO2 catalysts are synthesized with varying W loadings to test the theoretical predictions and relate them to HDO reactivity. Spectroscopy- and microscopy-based catalyst characterizations identify the dynamic and preferential decoration of well-coordinated sites on Pt nanoparticles by reduced WOx species, consistent with theoretical predictions. The catalytic consequences of this preferential decoration on the HDO of a lignin model compound, dihydroeugenol, are clarified. The effect of WOx decoration on Pt nanoparticles for HDO involves WOx inhibition of aromatic ring hydrogenation by preferentially blocking well-coordinated Pt sites. The identification of preferential decoration on specific sites of late-transition-metal surfaces by reducible metal oxides provides a new perspective for understanding and controlling metal-support interactions in heterogeneous catalysis.

Bond Selective Photochemistry at Metal Nanoparticle Surfaces: CO Desorption from Pt and Pd.

The use of visible photon fluxes to influence catalytic reactions on metal nanoparticle surfaces has attracted attention based on observations of reaction mechanisms and selectivity not observed under equilibrium heating. These observations suggest that photon fluxes can selectively impact the rates of certain elementary steps, creating nonequilibrium energy distributions among various reaction pathways. However, quantitative studies validating these hypotheses on metal nanoparticle surfaces are lacking. We examine the influence of continuous wave visible photon fluxes on the CO desorption rates from 1 to 2 nm diameter Pt and Pd nanoparticle surfaces supported on γ-Al2O3. Temperature-programmed desorption measurements quantified via diffuse reflectance infrared Fourier transform spectroscopy demonstrate that visible photon fluxes significantly enhanced the rate of CO desorption from Pt nanoparticles in a wavelength-dependent manner. 440 nm photons most efficiently promoted CO desorption from Pt nanoparticle surfaces, aligning with the excitation energy for the interfacial electronic transition within the Pt-CO bond. Conversely, visible photon fluxes had no measurable influence on CO desorption rates from Pd nanoparticle surfaces after accounting for photon-induced heating. Density functional theory calculations demonstrate that the Pt-CO bond exhibits a narrower LUMO resonance, stronger coupling between the photoexcitation and forces induced on the metal-C bond, and vibrational energy dissipation that more effectively couples to desorption as compared to Pd-CO. These results demonstrate the specificity photons provide in facilitating chemical reactions on metal nanoparticle surfaces and substantiate the idea that photon fluxes can steer processes and outcomes of catalytic reactions in ways not achievable by equilibrium heating.

Perceived Need Versus Current Spending: Gaps in Providing Foundational Public Health Services in Communities.

OBJECTIVE: Our objective was to estimate the gap between the costs for local health jurisdictions (LHJs) to provide foundational public health services (FPHS) and actual spending on FPHS and to examine factors associated with that gap. DESIGN: We employed resource-based cost estimation methods for this observational study and conducted multivariate analyses with measures derived from secondary administrative data. We used primary data collected from LHJ leaders that depicted 2014 spending and perceived need. We also included secondary administrative data depicting annual 2000-2013 expenditures organized into categories containing key elements of FPHS areas. SETTING: We included primary data from a representative sample of 10 LHJs in Washington State and secondary data for all 35 LHJs in Washington. PARTICIPANTS: Participants were public health practice leaders from each sample LHJ. MAIN OUTCOME MEASURE: Our main outcome of interest was the gap identified between current spending and the perceived spending needed to provide FPHS in a jurisdiction. RESULTS: Actual FPHS spending was approximately 65% of spending needed to provide overall FPHS for our sample LHJs, but the size of the gap varied substantially by program. Some gaps also varied widely by LHJ, with spending gaps widest among rural and high poverty communities. Percent poverty and the metropolitan nature of a jurisdiction were factors significantly related to FPHS spending in our multivariate analyses. CONCLUSIONS: Actual spending lags far behind local officials' estimates of spending needed to provide FPHS and is likely influenced by local conditions. Major apparent gaps between spending and need, particularly in areas such as costly Business Competencies, underscore the need for cross-cutting capabilities to support public health system responsiveness and for attention to be paid to local conditions.

Estimating the Cost of Providing Foundational Public Health Services.

OBJECTIVE: To estimate the cost of resources required to implement a set of Foundational Public Health Services (FPHS) as recommended by the Institute of Medicine. STUDY DESIGN: A stochastic simulation model was used to generate probability distributions of input and output costs across 11 FPHS domains. We used an implementation attainment scale to estimate costs of fully implementing FPHS. DATA COLLECTION/EXTRACTION METHODS: We use data collected from a diverse cohort of 19 public health agencies located in three states that implemented the FPHS cost estimation methodology in their agencies during 2014-2015. PRINCIPAL FINDINGS: The average agency incurred costs of $48 per capita implementing FPHS at their current attainment levels with a coefficient of variation (CV) of 16 percent. Achieving full FPHS implementation would require $82 per capita (CV=19 percent), indicating an estimated resource gap of $34 per capita. CONCLUSIONS: Substantial variation in costs exists across communities in resources currently devoted to implementing FPHS, with even larger variation in resources needed for full attainment. Reducing geographic inequities in FPHS may require novel financing mechanisms and delivery models that allow health agencies to have robust roles within the health system and realize a minimum package of public health services for the nation.