Oxide-supported noble metal catalysts have been extensively studied for decades for the water gas shift (WGS) reaction, a catalytic transformation central to a host of large volume processes that ...variously utilize or produce hydrogen. There remains considerable uncertainty as to how the specific features of the active metal-support interfacial bonding-perhaps most importantly the temporal dynamic changes occurring therein-serve to enable high activity and selectivity. Here we report the dynamic characteristics of a Pt/CeO
system at the atomic level for the WGS reaction and specifically reveal the synergistic effects of metal-support bonding at the perimeter region. We find that the perimeter Pt
- O vacancy-Ce
sites are formed in the active structure, transformed at working temperatures and their appearance regulates the adsorbate behaviors. We find that the dynamic nature of this site is a key mechanistic step for the WGS reaction.
Electron microscopy touches on nearly every aspect of modern life, underpinning materials development for quantum computing, energy and medicine. We discuss the open, highly integrated and ...data-driven microscopy architecture needed to realize transformative discoveries in the coming decade.
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GEOZS, IJS, IMTLJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBMB, UL, UM, UPUK, ZAGLJ
Metallic nanoparticles have been used to harvest energy from a light source and transfer it to adsorbed gas molecules, which results in a reduced chemical reaction temperature. However, most reported ...reactions, such as ethylene epoxidation, ammonia decomposition and H-D bond formation are exothermic, and only H-D bond formation has been achieved at room temperature. These reactions require low activation energies (<2 eV), which are readily attained using visible-frequency localized surface plasmons (from ~1.75 eV to ~3.1 eV). Here, we show that endothermic reactions that require higher activation energy (>3.1 eV) can be initiated at room temperature by using localized surface plasmons in the deep-UV range. As an example, by leveraging simultaneous excitation of multiple localized surface plasmon modes of Al nanoparticles by using high-energy electrons, we initiate the reduction of CO
to CO by carbon at room temperature. We employ an environmental transmission electron microscope to excite and characterize Al localized surface plasmon resonances, and simultaneously measure the spatial distribution of carbon gasification near the nanoparticles in a CO
environment. This approach opens a path towards exploring other industrially relevant chemical processes that are initiated by plasmonic fields at room temperature.
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GEOZS, IJS, IMTLJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBMB, UL, UM, UPUK, ZAGLJ
Redox‐induced interconversions of metal oxidation states typically result in multiple phase boundaries that separate chemically and structurally distinct oxides and suboxides. Directly probing such ...multi‐interfacial reactions is challenging because of the difficulty in simultaneously resolving the multiple reaction fronts at the atomic scale. Using the example of CuO reduction in H2 gas, a reaction pathway of CuO → monoclinic m‐Cu4O3 → Cu2O is demonstrated and identifies interfacial reaction fronts at the atomic scale, where the Cu2O/m‐Cu4O3 interface shows a diffuse‐type interfacial transformation; while the lateral flow of interfacial ledges appears to control the m‐Cu4O3/CuO transformation. Together with atomistic modeling, it is shown that such a multi‐interface transformation results from the surface‐reaction‐induced formation of oxygen vacancies that diffuse into deeper atomic layers, thereby resulting in the formation of the lower oxides of Cu2O and m‐Cu4O3, and activate the interfacial transformations. These results demonstrate the lively dynamics at the reaction fronts of the multiple interfaces and have substantial implications for controlling the microstructure and interphase boundaries by coupling the interplay between the surface reaction dynamics and the resulting mass transport and phase evolution in the subsurface and bulk.
In situ environmental transmission electron microscopy shows atomic processes of CuO‐surface‐reduction induced multi‐interface transformations, in which surface oxygen vacancies diffuse into deeper atomic layers and activate multi‐interface transformations. Cu2O/m‐Cu4O3 interface shows a diffuse‐type interfacial transformation controlled by lattice diffusion of oxygen vacancies whereas the m‐Cu4O3/CuO transformation exhibits ledge‐propogation interfacial transformation regulated by oxygen desorption from the interfacial ledges.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Synthesis of low‐dimensional carbon nanomaterials such as carbon nanotubes (CNTs) is a key driver for achieving advances in energy storage, computing, and multifunctional composites, among other ...applications. Here, we report high‐yield thermal chemical vapor deposition (CVD) synthesis of CNTs catalyzed by reagent‐grade common sodium‐containing compounds, including NaCl, NaHCO3, Na2CO3, and NaOH, found in table salt, baking soda, and detergents, respectively. Coupled with an oxidative dehydrogenation reaction to crack acetylene at reduced temperatures, Na‐based nanoparticles have been observed to catalyze CNT growth at temperatures below 400 °C. Ex situ and in situ transmission electron microscopy (TEM) reveal unique CNT morphologies and growth characteristics, including a vaporizing Na catalyst phenomenon that we leverage to create CNTs without residual catalyst particles for applications that require metal‐free CNTs. Na is shown to synthesize CNTs on numerous substrates, and as the first alkali group metal catalyst demonstrated for CNT growth, holds great promise for expanding the understanding of nanocarbon synthesis.
Carbon nanotubes (CNTs) can be grown from common ingredients containing Na. Table salt, baking soda, lye, and washing soda can be dried onto substrates and subjected to a low‐temperature chemical vapor deposition (CVD) process below 400 °C, resulting in grown CNTs. Residual Na catalyst can be removed through an inert heat treatment anneal, resulting in catalyst‐free CNTs.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Defects may display high reactivity because the specific arrangement of atoms differs from crystalline surfaces. We demonstrate that high-temperature steam pretreatment of palladium catalysts ...provides a 12-fold increase in the mass-specific reaction rate for carbon-hydrogen (C–H) activation in methane oxidation compared with conventional pretreatments. Through a combination of experimental and theoretical methods, we demonstrate that an increase in the grain boundary density through crystal twinning is achieved during the steam pretreatment and oxidation and is responsible for the increased reactivity. The grain boundaries are highly stable during reaction and show specific rates at least two orders of magnitude higher than other sites on the palladium on alumina (Pd/Al
O
) catalysts. Theoretical calculations show that strain introduced by the defective structure can enhance C–H bond activation. Introduction of grain boundaries through laser ablation led to further rate increases.
Recent reports of hot-electron-induced dissociation of small molecules, such as hydrogen, demonstrate the potential application of plasmonic nanostructures for harvesting light to initiate catalytic ...reactions. Theories have assumed that plasmonic catalysis is mediated by the energy transfer from nanoparticles to adsorbed molecules during the dephasing of localized surface plasmon (LSP) modes optically excited on plasmonic nanoparticles. However, LSP-induced chemical processes have not been resolved at a sub-nanoparticle scale to identify the active sites responsible for the energy transfer. Here, we exploit the LSP resonance excited by electron beam on gold nanoparticles to drive CO disproportionation at room temperature in an environmental scanning transmission electron microscope. Using in situ electron energy-loss spectroscopy with a combination of density functional theory and electromagnetic boundary element method calculations, we show at the subparticle level that the active sites on gold nanoparticles are where preferred gas adsorption sites and the locations of maximum LSP electric field amplitude (resonance antinodes) superimpose. Our findings provide insight into plasmonic catalysis and will be valuable in designing plasmonic antennas for low-temperature catalytic processes.
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EMUNI, FIS, FZAB, GEOZS, GIS, IJS, IMTLJ, KILJ, KISLJ, MFDPS, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, SBMB, SBNM, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
Incessant antigenic evolution enables the persistence and spread of influenza virus in the human population. As the principal target of the immune response, the hemagglutinin (HA) surface antigen on ...influenza viruses continuously acquires and replaces N-linked glycosylation sites to shield immunogenic protein epitopes using host-derived glycans. Anti-glycan antibodies, such as 2G12, target the HIV-1 envelope protein (Env), which is even more extensively glycosylated and contains under-processed oligomannose-type clusters on its dense glycan shield. Here, we illustrate that 2G12 can also neutralize human seasonal influenza A H3N2 viruses that have evolved to present similar oligomannose-type clusters on their HAs from around 20 years after the 1968 pandemic. Using structural biology and mass spectrometric approaches, we find that two N-glycosylation sites close to the receptor binding site (RBS) on influenza hemagglutinin represent the oligomannose cluster recognized by 2G12. One of these glycan sites is highly conserved in all human H3N2 strains and the other emerged during virus evolution. These two N-glycosylation sites have also become crucial for fitness of recent H3N2 strains. These findings shed light on the evolution of the glycan shield on influenza virus and suggest 2G12-like antibodies can potentially act as broad neutralizers to target human enveloped viruses.
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DOBA, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
Solar cells made of polycrystalline thin-films can outperform their single-crystalline counterparts despite the presence of grain boundaries (GBs). To unveil the influence of GBs, high spatial ...resolution characterization techniques are needed to measure local properties in their vicinity. However, results obtained using single technique may provide limited aspects about the GB effect. Here, we employ two techniques, near-field scanning photocurrent microscopy (NSPM) and scanning transmission electron microscope based cathodoluminescence spectroscopy (STEM-CL), to characterize CdTe solar cells at the nanoscale. The signal contrast from the grain interiors (GIs) to the GBs, for high-efficiency cells where CdTe is deposited at a high substrate temperature (500 °C) and treated by CdCl2, is found reverse from one technique to another. NSPM reveals increased photocurrents at the GBs, while STEM-CL shows reduced CL intensity and energy redshifts of the spectral peak at the GBs. The results are attributed to the increased nonradiative recombination and the band bending mediated by the surface defects and the shallow-level defects at GBs, respectively. We discuss the advantages of sample geometry for room-temperature STEM-CL and present numerical simulations as well as analytical models to extract the ratio of GB recombination velocity to minority carrier diffusivity that can be used for evaluating the GB effect in other polycrystalline solar cells.
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IJS, KILJ, NUK, PNG, UL, UM
Background Extracorporeal membrane oxygenation (ECMO) has been utilized for patients in critical condition, such as those with life-threatening respiratory failure or postcardiotomy cardiogenic ...shock. This study analyzed the outcomes of patients treated with ECMO and identified the relationship between prognosis and the Acute Kidney Injury Network (AKIN) scores obtained at pre-ECMO support (AKIN 0-hour ); and at post-ECMO support 24 hours (AKIN 24-hour ) and 48 hours (AKIN 48-hour ). Methods This study reviewed the medical records of 102 critically ill patients on ECMO support at a specialized intensive care unit at a tertiary care university hospital between March 2002 and January 2008. Demographic, clinical, and laboratory variables were retrospectively collected as survival predicators. Results The overall mortality rate was 57.8%. The most common condition requiring ECMO support was cardiogenic shock. Goodness-of-fit was good for AKIN 0-hour , AKIN 24-hour , and AKIN 48-hour criteria. The AKIN 0-hour , AKIN 24-hour , and AKIN 48-hour scoring systems also had excellent areas under the receiver operating characteristic curve (0.804 ± 0.046, 0.811 ± 0.045, and 0.858 ± 0.040, respectively). Furthermore, multiple logistic regression analysis indicated that AKIN 48-hour , age, and Glasgow Coma Scale score on the first day of intensive care unit admission were independent risk factors for hospital mortality. Finally, cumulative survival rates at 6-month follow-up after hospital discharge differed significantly ( p < 0.05) for AKIN 48-hour stage 0 versus AKIN 48-hour stages 1, 2, and 3; and AKIN 48-hour stage 1 and 2 versus AKIN 48-hour stage 3. Conclusions During ECMO support, the AKIN 48-hour scoring system proved to be a reproducible evaluation tool with excellent prognostic abilities for these patients.
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