A robust volumetric apparatus and method for measuring high pressure hydrogen storage properties of nanostructured materials

A volumetric apparatus to measure hydrogen adsorption and desorption at room temperature and up to 100 atm has been constructed and studied for accuracy, reproducibility, and stability. The design principles are presented and considerable attention to detail is given to examine the effects of diurnal temperature changes in the manifold and helium adsorption by carbon-based adsorbents during free volume measurement. A heuristic for helium correction is derived from a model with a basis in literature and verified through calculation of adsorbent density. Several materials with well-known hydrogen capacities are studied to examine reproducibility. The microporous carbon AX-21 is studied to examine the effects of pressure step size and approach to equilibrium caused by gas mixing and the Joule-Thomson effect. Hydrogen spillover on a hybrid material, Pt on templated carbon, is examined for several loadings of metal. Kinetics of both physisorption and spillover are compared via the diffusion time constant (D/R(2)) estimated by fitting models for pore and surface diffusion to time-dependent adsorption profiles. No concentration dependence was found for pore diffusion; however, the surface diffusion time constant was shown to decrease with respect to increasing hydrogen concentration.     

Analysing inconsistent first-order knowledgebases

It is well-known that knowledgebases may contain inconsistencies. We provide a framework of measures, based on a first-order four-valued logic, to quantify the inconsistency of a knowledgebase. This allows for the comparison of the inconsistency of diverse knowledgebases that have been represented as sets of first-order logic formulae. We motivate the approach by considering some examples of knowledgebases for representing and reasoning with ontological knowledge and with temporal knowledge. Analysing ontological knowledge (including the statements about which concepts are subconcepts of other concepts, and which concepts are disjoint) can be problematical when there is a lack of knowledge about the instances that may populate the concepts, and analysing temporal knowledge (such as temporal integrity constraints) can be problematical when considering infinite linear time lines isomorphic to the natural numbers or the real numbers or more complex structures such as branching time lines. We address these difficulties by providing algebraic measures of inconsistency in first-order knowledgebases.     

NMR microscopy of single neurons at 500 MHZ

Previous NMR microimaging studies at 360 MHz have demonstrated a clear differentiation between the nucleus and cytoplasm in isolated single neurons. In particular, theT ₂ of the cell nucleus is 2.5 times larger than that of the cytoplasm. In order to determine the magnitude of possibleT ₂ ^* influences on these observations, images of single cells have been obtained at 500 MHz using spin-echo and line-narrowing sequences. Comparison of the images acquired by the two sequences, and of the spin-echo images at 360 and 500 MHz, imply that anyT ₂ ^* contributions are relatively small. Consequently, the measuredT ₂ differences in spin-echo imaging represent a true difference in theT ₂ relaxation in the two cellular compartments.     

Reaching the Fundamental Limitation in CO2 Reduction to CO with Single Atom Catalysts

The electrochemical CO₂ reduction reaction (CO₂RR) to value-added chemicals with renewable electricity is a promising method to decarbonize parts of the chemical industry. Recently, single metal atoms in nitrogen-doped carbon (MNC) have emerged as potential electrocatalysts for CO₂RR to CO with high activity and faradaic efficiency, although the reaction limitation for CO₂RR to CO is unclear. To understand the comparison of intrinsic activity of different MNCs, two catalysts are synthesized through a decoupled two-step synthesis approach of high temperature pyrolysis and low temperature metalation (Fe or Ni). The highly meso-porous structure results in the highest reported electrochemical active site utilization based on in situ nitrite stripping; up to 59±6% for NiNC. Ex situ X-ray absorption spectroscopy (XAS) confirms the penta-coordinated nature of the active sites. The catalysts are amongst the most active in the literature for CO₂ reduction to CO. The density functional theory calculations (DFT) show that their binding to the reaction intermediates approximates to that of Au surfaces. However, it is found that the turnover frequencies (TOFs) of the most active catalysts for CO evolution converge, suggesting a fundamental ceiling to the catalytic rates.     

Freestanding hierarchical porous carbon film derived from hybrid nanocellulose for high-power supercapacitors

Nanocellulose is a sustainable and eco-friendly nanomaterial derived from renewable biomass.In this study,we utilized the structural advantages of two types of nanocellulose and fabricated freestanding carbonized hybrid nanocellulose films as electrode materials for supercapacitors.The long cellulose nanofibrils (CNFs) formed a macroporous framework,and the short cellulose nanocrystals were assembled around the CNF framework and generated micro/mesopores.This two-level hierarchical porous structure was successfully preserved during carbonization because of a thin atomic layer deposited (ALD) Al2O3 conformal coating,which effectively prevented the aggregation of nanocellulose.These carbonized,partially graphitized nanocellulose fibers were interconnected,forming an integrated and highly conductive network with a large specific surface area of 1,244 m2·g-1.The two-level hierarchical porous structure facilitated fast ion transport in the film.When tested as an electrode material with a high mass loading of 4 mg·cm-2 for supercapacitors,the hierarchical porous carbon film derived from hybrid nanocellulose exhibited a specific capacitance of 170 F.g-1and extraordinary performance at high current densities.Even at a very high current of 50 A·g-1,it retained 65％ of its original specific capacitance,which makes it a promising electrode material for high-power applications.     

An Investigation of the Relationship Between the Gaussian Process Model Parameters and Surface Area in Three Dimensions

In this paper, we study the relationship between the fitted parameters in a Gaussian process (kriging) model and the complexity of the resulting response surface. This study is done for models with one response and two input variables. An analytical calculation of surface roughness is used as a measure of the complexity of the response surface fit by the Gaussian process model. Our findings indicate that the size of the fitted model parameters as measured across different fits and data sets do not give indication as to the complexity of the surface. We do, however, show that the magnitude of each of the parameters in a single fitted model gives indication about the amount of variability in the direction of that fitted parameter. Copyright © 2015 John Wiley & Sons, Ltd.     

Data-delay evaluation in integrated wireless networks based on local product-form solutions for voice occupancy

In this paper we consider the evaluation of data-packet delay in wireless integrated voice/data networks. In networks that support voice in the classical circuit-switched fashion, the voice occupancy process satisfies a product-form solution under reasonable modeling assumptions. Although this product-form solution provides an accurate characterization of equilibrium voicetraffic behavior, it does not directly provide a method to evaluate data-packet delay. However, examination of each link separately in a manner that incorporates interaction with the rest of the network permits us to take advantage of the wireless nature of the network and obtain a three-flow characterization of each link, which also satisfies a product-form solution and is hence termed a mini-product-form solution. By matching the values of these flows to the average values obtained from the product-form solution of the entire network, we obtain a three-dimensional Markov chain characterization of the voice occupancy state on the link, which permits a simpler evaluation of data-packet delay. A further reduction is possible by converting the three-dimensional chain to a single-dimensional one. Performance results demonstrate that these models provide satisfactory delay estimates that also appear to be upper bounds on delay.C.M. Barnhart was at the Naval Research Laboratory when this paper was written.