Controlling the Shapes of Nanoparticles by Dopant-Induced Enhancement of Chemisorption and Catalytic Activity: Application to Fe-Based Ammonia Synthesis

We showed recently that the catalytic efficiency of ammonia synthesis on Fe-based nanoparticles (NP) for Haber–Bosch (HB) reduction of N₂ to ammonia depends very dramatically on the crystal surface exposed and on the doping. In turn, the stability of each surface depends on the stable intermediates present during the catalysis. Thus, under reaction conditions, the shape of the NP is expected to evolve to optimize surface energies. In this paper, we propose to manipulate the shape of the nanoparticles through doping combined with chemisorption and catalysis. To do this, we consider the relationships between the catalyst composition (adding dopant elements) and on how the distribution of the dopant atoms on the bulk and facet sites affects the shape of the particles and therefore the number of active sites on the catalyst surfaces. We use our hierarchical, high-throughput catalyst screening (HHTCS) approach but extend the scope of HHTCS to select dopants that can increase the catalytically active surface orientations, such as Fe-bcc(111), at the expense of catalytically inactive facets, such as Fe-bcc(100). Then, for the most promising dopants, we predict the resulting shape and activity of doped Fe-based nanoparticles under reaction conditions. We examined 34 possible dopants across the periodic table and found 16 dopants that can potentially increase the fraction of active Fe-bcc(111) vs inactive Fe-bcc(100) facets. Combining this reshaping criterion with our HHTCS estimate of the resulting catalytic performance, we show that Si and Ni are the most promising elements for improving the rates of catalysis by optimizing the shape to decrease reaction barriers. Then, using Si dopant as a working example, we build a steady-state dynamical Wulff construction of Si-doped Fe bcc nanoparticles. We use nanoparticles with a diameter of ∼10 nm, typical of industrial catalysts. We predict that doping Si into such Fe nanoparticles at the optimal atomic content of ∼0.3% leads to rate enhancements by a factor of 56 per nanoparticle under target HB conditions

Highly Efficient Ni-Doped Iron Catalyst for Ammonia Synthesis from QM-Based Hierarchical High Throughput Catalyst Screening

To discover more efficient industrial catalysts for ammonia synthesis via the Haber–Bosch (HB) process, we employed quantum mechanics (QM)-based hierarchical high-throughput catalyst screening (HHTCS) to test a wide group of elements (34) as candidates to dope the Fe(111) catalyst subsurface. The QM free-energy reaction network of HB over Fe(111) yields ten barriers as potentially rate-determining, of which we select four as prototypical, arrange them hierarchically, and define a corresponding set of screening criteria, which we then use to screen candidate catalysts. This leads to two promising candidates (Co and Ni), from which we selected the most promising (Ni) for a complete QM and kinetic study. The kinetic Monte Carlo (kMC) simulations predict a 16-fold increase in HB turn-over frequency (TOF) for the Ni-doped catalyst compared to the pure Fe(111) surface under realistic conditions. The 16-fold increase in HB TOF is a significant improvement and may trigger future experimental studies to validate our prediction. This TOF improvement could lead to similar reaction rates as with pure Fe but at a reaction temperature decreased by 100° from 773 to 673 K and a total reactant pressure decreased by 6 times from 201 to 34 atm. We interpret the reasons underlying this improvement using valence bond and kinetic analyses. We suggest this Ni-doped Fe(111) catalyst as a candidate to reduce the world energy consumption for the HB process while satisfying future needs for energy and environment

Establishment of background water quality conditions in the Great Zab River catchment:influence of geogenic and anthropogenic controls on developing a baseline for water assessment and resource management

The Great Zab River catchment is a major left-bank tributary of the River Tigris and drains a substantial part of the Kurdistan Region, an autonomous region of Northern Iraq. Within Kurdistan, the water resources of the Great Zab River catchment are under pressure from population increase and are utilized for potable, domestic and agricultural and industrial supply. As with many parts of the world, effective management of water resources within Kurdistan is hindered by a lack of water quality data and established background concentrations. This study therefore represents the first regional survey of river water chemistry for the Great Zab River catchment and presents data on the spatial and temporal trends in concentrations of As, Ba, Ca, Cd, Co, Cr, Cu, Fe, Hg, Li, Mn, Mo, Ni, Pb, Sr, Zn, NO3?, SO42?, F?, Cl? and PO43?, in addition to pH, electrical conductivity, dissolved oxygen and turbidity. As a tool for underpinning the management and monitoring of water quality, background concentrations were defined for the Great Zab catchment using three methods. The influences of geogenic and anthropogenic controls upon spatial and temporal trends in water chemistry are also evaluated. The influence of geogenic loading from underlying bedrock was identifiable within the observed spatial trends, with the most notable differences found between waters sampled from the relatively more volcanic-rich Zagros zone to the north and those sampled from the lower catchment underlain by younger clay-, sand- and siltstones. The greatest anthropogenic influence, identifiable through elements such as Cl? and NO3?, is present in the more highly populated lower catchment. The background concentrations identified in the Great Zab catchment would be those expected as a result of geogenic loading with some anthropogenic influence and represent a more conservative value when compared to those such as the World Health Organization Maximum Admissible Concentration. However, background concentrations represent a powerful tool for identifying potential anthropogenic impacts on water quality and informing management of such occurrencespublishersversionPeer reviewe

Restriction Spectrum Imaging Differentiates True Tumor Progression From Immune-Mediated Pseudoprogression: Case Report of a Patient With Glioblastoma.

Immunotherapy is increasingly used in the treatment of glioblastoma (GBM), with immune checkpoint therapy gaining in popularity given favorable outcomes achieved for other tumors. However, immune-mediated (IM)-pseudoprogression is common, remains poorly characterized, and renders conventional imaging of little utility when evaluating for treatment response. We present the case of a 64-year-old man with GBM who developed pathologically proven IM-pseudoprogression after initiation of a checkpoint inhibitor, and who subsequently developed true tumor progression at a distant location. Based on both qualitative and quantitative analysis, we demonstrate that an advanced diffusion-weighted imaging (DWI) technique called restriction spectrum imaging (RSI) can differentiate IM-pseudoprogression from true progression even when conventional imaging, including standard DWI/apparent diffusion coefficient (ADC), is not informative. These data complement existing literature supporting the ability of RSI to estimate tumor cellularity, which may help to resolve complex diagnostic challenges such as the identification of IM-pseudoprogression

Effects of caustic cleaning on pore size of nanofiltration membranes and their rejection of trace organic chemicals

The aim of this study was to assess the impact of caustic cleaning on the rejection of three different trace organic chemical (TrOC) groups (i.e. neutral hydrophilic, neutral hydrophobic and negatively charged) by two nanofiltration (NF) membranes ‒ namely NF270 and NF90. Chemical cleaning was simulated by exposing virgin membrane samples to commercial caustic cleaning formulations as well as sodium hydroxide solutions containing analytical grade additives such as sodium dodecyl sulfate or ethylenediaminetetraacetic acid. The membrane average pore size before and after exposure to a commercially available caustic cleaning formulation was determined based on the pore transport model. The results show that caustic chemical cleaning could cause an increase in the membrane pore size, leading to an increase in permeability and decrease in rejection of conductivity. The impact of caustic cleaning on the pore size and solute rejection was a function of the membrane active skin layer and the chemistry of the cleaning formulation. Caustic cleaning led to a small increase in pore size of the NF270 membrane and resulted in a notable increase in the permeability and salt passage. By contrast, the impact on the NF90 membrane was negligible. The influence of caustic cleaning on TrOC rejection was dependent on physical characteristics of each TrOC including their molecular size, charge, and hydrophobicity. The rejection of neutral and hydrophobic TrOC by the NF270 membrane decreased significantly after exposure to caustic cleaning formulation. However, because the rejection of negatively charged TrOC is governed mostly by electrostatic interaction, their rejection was not significantly affected by caustic cleaning

Dechlorinative Oligomerization of Multiply Chlorinated Methanes Catalyzed by Activated Carbon Supported Pt-Co

The hydrodechlorination of dichloromethane, trichloromethane, and their mixtures catalyzed by a Pt- Co/C catalyst has been investigated in an effort to elucidate the chemistry associated with the generation of hydrocarbon oligomerization products. In the reaction of dichloromethane with hydrogen, the catalyst did not exhibit deactivation and maintained the steady-state activity within 18 h on stream at 523 K; whereas, when trichloromethane was added or converted in the absence of dichloromethane, significant deactivation occurred within the first 5 h on stream. Hydrocarbon oligomerization products were observed with all three reaction mixtures; the selectivity followed the order dichloromethane + dihydrogen < trichloromethane + dihydrogen < dichloromethane + trichloromethane + dihydrogen. The generation of ethane and propane was virtually independent of the reaction mixture composition. However, selectivity toward ethylene and propylene was significantly greater with the trichloromethane + dihydrogen and dichloromethane + trichloromethane + dihydrogen mixtures compared to the dichloromethane + dihydrogen feed. It was concluded that the saturated hydrocarbon products are formed by means of the alkyl mechanism of hydrocarbon chain growth; whereas, the alkenyl mechanism is responsible for the formation of the unsaturated hydrocarbons.Изучено дегидрохлорирование дихлорметана, трихлорметана и их смесей в присутствии Pt-Co/C катализатора с целью выяснения механизма образования высших углеводородов. Установлено, что в реакции дихлорметана с водородом при 523 К катализатор не подвергается дезактивации и сохраняет постоянную активность в течение, по крайней мере, 18 ч, в то время как присутствие трихлорметана в реакционной смеси вызывает значительную дезактивацию катализатора в течение первых 5 ч работы. Углеводородные продукты наблюдались во всех реакционных смесях с селективностью дихлорметан + водород < трихлорметан + водород < дихлорметан + трихлорметан + водород. При этом селективность по этану и пропану не зависела от состава реакционной смеси. В то же время селективность по этилену и пропилену была существенно выше в случае дехлорирования трихлорметана и дехлорирования смеси дихлорметана и трихлорметана, чем в случае дехлорирования дихлорметана. На основании полученных результатов сделано заключение, что насыщенные углеводороды образуются в соответствии с так называемым алкильным механизмом роста цепи, в то время как непредельные углеводороды образуются по алкенильному механизму

Integrase-deficient lentiviral vectors mediate efficient gene transfer to human vascular smooth muscle cells with minimal genotoxic risk

We have previously shown that injury-induced neointima formation was rescued by adenoviral-Nogo-B gene delivery. Integrase-competent lentiviral vectors (ICLV) are efficient at gene delivery to vascular cells but present a risk of insertional mutagenesis. Conversely, integrase-deficient lentiviral vectors (IDLV) offer additional benefits through reduced mutagenesis risk, but this has not been evaluated in the context of vascular gene transfer. Here, we have investigated the performance and genetic safety of both counterparts in primary human vascular smooth muscle cells (VSMC) and compared gene transfer efficiency and assessed the genotoxic potential of ICLVs and IDLVs based on their integration frequency and insertional profile in the human genome. Expression of enhanced green fluorescent protein (eGFP) mediated by IDLVs (IDLV-eGFP) demonstrated efficient transgene expression in VSMCs. IDLV gene transfer of Nogo-B mediated efficient overexpression of Nogo-B in VSMCs, leading to phenotypic effects on VSMC migration and proliferation, similar to its ICLV version and unlike its eGFP control and uninfected VSMCs. Large-scale integration site analyses in VSMCs indicated that IDLV-mediated gene transfer gave rise to a very low frequency of genomic integration compared to ICLVs, revealing a close-to-random genomic distribution in VSMCs. This study demonstrates for the first time the potential of IDLVs for safe and efficient vascular gene transfer

High-resolution broadband spectroscopy using externally dispersed interferometry at the Hale telescope: Part 1, data analysis and results

High-resolution broadband spectroscopy at near-infrared wavelengths (950 to 2450 nm) has been performed using externally dispersed interferometry (EDI) at the Hale telescope at Mt. Palomar. Observations of stars were performed with the “TEDI” interferometer mounted within the central hole of the 200-in. primary mirror in series with the comounted TripleSpec near-infrared echelle spectrograph. These are the first multidelay EDI demonstrations on starlight, as earlier measurements used a single delay or laboratory sources. We demonstrate very high (10×) resolution boost, from original 2700 to 27,000 with current set of delays (up to 3 cm), well beyond the classical limits enforced by the slit width and detector pixel Nyquist limit. Significantly, the EDI used with multiple delays rather than a single delay as used previously yields an order of magnitude or more improvement in the stability against native spectrograph point spread function (PSF) drifts along the dispersion direction. We observe a dramatic (20×) reduction in sensitivity to PSF shift using our standard processing. A recently realized method of further reducing the PSF shift sensitivity to zero is described theoretically and demonstrated in a simple simulation which produces a 350× times reduction. We demonstrate superb rejection of fixed pattern noise due to bad detector pixels—EDI only responds to changes in pixel intensity synchronous to applied dithering. This part 1 describes data analysis, results, and instrument noise. A section on theoretical photon limited sensitivity is in a companion paper, part 2