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At least 757 records · Page 42

Evaluation of Getter Metals in Na–Al–Si–O Aerogels and Xerogels for the Capture of Iodine Gas

In this paper, sodium aluminosilicate aerogels and xerogels were evaluated as scaffolds for a variety of different getters including: Ag + , Cs + , Cu 2+ , Fe 3+ , K + , Li + , Rb + , Sb 3+ , Sn 2+ , and Sn 4+ . The exchange capacities varied widely from a near complete exchange in the case of Ag + to much lower exchange levels for some of the Sn compounds [i.e., colloidal SnO 2 , Sn(II) acetate, Sn(IV) acetate]. Several of the additives showed great promise at allowing for high iodine loadings in the base materials including the following: AgNO 3 , colloidal SnO 2 , Sn(II) acetate, Sn(IV) acetate, Cu(NO 3 ) 2 , and CuSO 4 . From the standpoint of iodine uptake as a function of getter loading, the Sn4+ showed the most promise with a getter utilization (mass of iodine divided by mass of Sn, in atomic%) of 8.4, a chemical uptake of 60.7 mass% (oxygen excluded), and an mI $m_s^{-1}$ value of 0.881; these are some of the highest values reported to date for inorganic iodine sorbents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Polyacrylonitrile Composites of Ag–Al–Si–O Aerogels and Xerogels as Iodine and Iodide Sorbents

Mechanically robust engineered sorbents were constructed by embedding Ag-loaded aerogels or xerogels in a polyacrylonitrile (PAN) matrix at 30 or 50 mass% loadings of gel in PAN. Here, the process for making the base gels as well as the composite materials is described herein, a technology that is very flexible for making hybrid sorbents using various inorganic or organic active sorbents. The PAN-gel composite materials were evaluated for iodine uptake in the form of gaseous iodine [I 2(g) ] at room temperature and at 150°C as well as iodide (I – ) at room temperature from simulated liquid nuclear wastes. The composites show high I 2(g) uptake and high I – uptake (= 93 mass%) in simulated liquid secondary waste spiked with 5 mg L -1 I – . These results demonstrate the utility of such a composite form for iodine removal from contaminated gas and liquid streams.

36 MATERIALS SCIENCE↗

Climate, Hydrology, and Nutrients Control the Seasonality of Si Concentrations in Rivers

Abstract The seasonal behavior of fluvial dissolved silica (DSi) concentrations, termedDSi regime, mediates the timing of DSi delivery to downstream waters and thus governs river biogeochemical function and aquatic community condition. Previous work identified five distinct DSi regimes across rivers spanning the Northern Hemisphere, with many rivers exhibiting multiple DSi regimes over time. Several potential drivers of DSi regime behavior have been identified at small scales, including climate, land cover, and lithology, and yet the large‐scale spatiotemporal controls on DSi regimes have not been identified. We evaluate the role of environmental variables on the behavior of DSi regimes in nearly 200 rivers across the Northern Hemisphere using random forest models. Our models aim to elucidate the controls that give rise to (a) average DSi regime behavior, (b) interannual variability in DSi regime behavior (i.e., Annual DSi regime), and (c) controls on DSi regime shape (i.e., minimum and maximum DSi concentrations). Average DSi regime behavior across the period of record was classified accurately 59% of the time, whereas Annual DSi regime behavior was classified accurately 80% of the time. Climate and primary productivity variables were important in predicting Average DSi regime behavior, whereas climate and hydrologic variables were important in predicting Annual DSi regime behavior. Median nitrogen and phosphorus concentrations were important drivers of minimum and maximum DSi concentrations, indicating that these macronutrients may be important for seasonal DSi drawdown and rebound. Our findings demonstrate that fluctuations in climate, hydrology, and nutrient availability of rivers shape the temporal availability of fluvial DSi.

Environmental Sciences & Ecology↗

Promotion of adsorptive and catalytic properties of zeolitic Brønsted acid sites by proximal extra-framework Si(OH) x groups

Steric confinement in zeolites influences the catalytic conversion of alkanes. For zeolitic Brønsted acid sites, proximate extra-framework species introduce additional confinement to the pore constraints, enhancing the catalytic activity of alkane cracking. Although extra-framework alumina has been the most studied, here we report the element-specific impact of silica species. Further, by grafting extra-framework silica species close to Brønsted acid sites in H-ZSM-5 zeolite, the binding of bases like pyridine and amines is strengthened via van der Waals interactions with their aryl or alkyl chains. Brønsted acid sites close to extra-framework silica achieve a higher reaction rate of protolytic cracking of n-pentane via enthalpic (unlike entropic, as with extra-framework alumina) stabilization of the transition state by 24–51 kJ mol −1 . The lower activation energy points to an earlier transition state than in the presence of extra-framework alumina, with a better stabilization of the carbonium ions in the transition state compared to the parent zeolite.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗