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At least 1,603 records · Page 89

Hybrid data-driven and model-informed online tool wear detection in milling machines

Precision machining tool wear is responsible for low product throughput and quality. Monitoring the tool wear online is vital to prevent degradation in machining quality. However, direct real-time tool wear measurement is not practical. This paper presents residual-based anomaly detection models, combining a hybrid model comprised of a physics-based model and a data-driven model (a decision tree or a neural network) to predict signals of interest (e.g., power or forces) under nominal conditions, followed by Page’s cumulative sum test for detecting tool wear on-line using the computer numerical control machine measurements. The most informative features are ranked using dynamic programming and its approximation variants from real-time measurements and machine settings, such as the width of cut, depth of cut, feed rate and spindle speed, that serve as inputs to the predictive models. The baseline nominal model is incrementally updated with experimental data via a gradient boosted adaptation model to generate the residuals that account for discrepancies between the actual machine data under normal conditions and the baseline nominal model predictions. The hybrid model is validated against 20 Mazak milling machine experimental tests and one Haas run-to-failure experiment. The proposed anomaly detector is applied to synthetic data from simulations of the physics-based model at different operating conditions, measurement noise levels, and tool wear levels, and the methods were able to achieve an overall 92% accuracy in data with 1% noise. The anomaly detection methods based on hybrid model reduced the false alarms of either the data-driven or physical-based models alone, and are found to be capable of good online detection of tool wear.

Online anomaly detection↗

Longitudinal analysis of risk factors for dementia based on Mild Cognitive Impairment Screen results and questionnaire responses from healthy Japanese individuals registered in an online database

Abstract Introduction Despite an urgent need for developing remedial measures against dementia, no disease‐modifying drugs have been developed. Efficient protocols for participant recruitment need to be established for conducting clinical trials. To meet this need, a large‐scale online registry system, the Integrated Registry of Orange Plan (IROOP ® ), was created for healthy individuals. Although the risk factors for dementia have been discussed in our previous studies for a short interval of 6 months, some factors remain controversial. The present study aimed to explore factors affecting longitudinal changes in cognitive function for a longer interval of 18 months using the IROOP ® data. Methods This study assessed the longitudinal changes in the collated data for predicting the risk of dementia and included 473 individuals (175 men and 298 women; mean age 59.6 ± 10.1 years) registered in the IROOP ® between July 5, 2016 and January 15, 2018 who completed the initial questionnaire and brief assessment of cognitive function (Mild Cognitive Impairment Screen) at baseline and the regular questionnaire and the Mild Cognitive Impairment Screen at least once after baseline. Statistical analyses were performed using IBM SPSS, version 23.0, for Windows for demographic data and the MIXED procedure in SAS, version 9.4, for the linear mixed‐effect model. In each analysis, the statistical significance level was set at P < .05. Results Mood, sleep, quality of life, and medical histories including cognition were found to influence longitudinal changes in cognitive function. Discussion Given the multifactorial etiology of dementia, preventive measures targeting multiple domains are required for maintaining cognitive function, instead of focusing on one lifestyle factor.

Ogawa, Masayo↗

A study of the degree of fluorination in regioregular poly(3-hexylthiophene)

Here, we systematically varied the degree of fluorination along the backbone of a series of highly regioregular 3-hexylthiophene-based polymers, P3HT-50F, P3HT-33F and P3HT-25F, in which 50%, 33% and 25% of the thiophene units within the polymer chain contain fluorine atoms in the available 4-position. These materials were homopolymerized using the Kumada catalyst transfer polycondensation method from a set of mono-fluorinated bi-, ter- and quarterthiophenes, to ensure high polymer regioregularity and evenly-spaced fluorine atoms along the conjugated thiophene backbone. The monomers were obtained from a synthetic route consisting of iterative Migita-Stille couplings of fluorinated and non-fluorinated 3- hexylthiophenes. The effect of the fluorine atoms on both polymer structure and properties is presented, with supporting quantum mechanical calculations that rationalize the intrinsic conformation preferences of the three P3HT derivatives. P3HT-50F (M¯ n = 34 kg/mol, 98.5% rr), P3HT-33F (M¯ n = 46 kg/mol, 98% rr) and P3HT-25F (M¯ n = 53 kg/mol, 95% rr) displayed HOMO levels of -5.34, -5.26 and -5.24 eV, bandgaps of 1.98, 1.98 and 1.97 eV, and average field-effect transistor hole mobilities of 4.5 × 10 -3 , 2.7 × 10 -2 , and 1.2 × 10 -2 cm 2 V -1 s -1 , respectively.

36 MATERIALS SCIENCE↗

Monitoring Change Through Hierarchical Segmentation of Remotely Sensed Image Data

NASA's Goddard Space Flight Center has developed a fast and effective method for generating image segmentation hierarchies. These segmentation hierarchies organize image data in a manner that makes their information content more accessible for analysis. Image segmentation enables analysis through the examination of image regions rather than individual image pixels. In addition, the segmentation hierarchy provides additional analysis clues through the tracing of the behavior of image region characteristics at several levels of segmentation detail. The potential for extracting the information content from imagery data based on segmentation hierarchies has not been fully explored for the benefit of the Earth and space science communities. This paper explores the potential of exploiting these segmentation hierarchies for the analysis of multi-date data sets, and for the particular application of change monitoring.

Tilton, James C.↗

Automated Generation and Assessment of Autonomous Systems Test Cases

This slide presentation reviews some of the issues concerning verification and validation testing of autonomous spacecraft routinely culminates in the exploration of anomalous or faulted mission-like scenarios using the work involved during the Dawn mission's tests as examples. Prioritizing which scenarios to develop usually comes down to focusing on the most vulnerable areas and ensuring the best return on investment of test time. Rules-of-thumb strategies often come into play, such as injecting applicable anomalies prior to, during, and after system state changes; or, creating cases that ensure good safety-net algorithm coverage. Although experience and judgment in test selection can lead to high levels of confidence about the majority of a system's autonomy, it's likely that important test cases are overlooked. One method to fill in potential test coverage gaps is to automatically generate and execute test cases using algorithms that ensure desirable properties about the coverage. For example, generate cases for all possible fault monitors, and across all state change boundaries. Of course, the scope of coverage is determined by the test environment capabilities, where a faster-than-real-time, high-fidelity, software-only simulation would allow the broadest coverage. Even real-time systems that can be replicated and run in parallel, and that have reliable set-up and operations features provide an excellent resource for automated testing. Making detailed predictions for the outcome of such tests can be difficult, and when algorithmic means are employed to produce hundreds or even thousands of cases, generating predicts individually is impractical, and generating predicts with tools requires executable models of the design and environment that themselves require a complete test program. Therefore, evaluating the results of large number of mission scenario tests poses special challenges. A good approach to address this problem is to automatically score the results based on a range of metrics. Although the specific means of scoring depends highly on the application, the use of formal scoring - metrics has high value in identifying and prioritizing anomalies, and in presenting an overall picture of the state of the test program. In this paper we present a case study based on automatic generation and assessment of faulted test runs for the Dawn mission, and discuss its role in optimizing the allocation of resources for completing the test program.

Testing challenges↗

Reconstituted Three-Dimensional Interactive Imaging

A method combines two-dimensional images, enhancing the images as well as rendering a 3D, enhanced, interactive computer image or visual model. Any advanced compiler can be used in conjunction with any graphics library package for this method, which is intended to take digitized images and virtually stack them so that they can be interactively viewed as a set of slices. This innovation can take multiple image sources (film or digital) and create a "transparent" image with higher densities in the image being less transparent. The images are then stacked such that an apparent 3D object is created in virtual space for interactive review of the set of images. This innovation can be used with any application where 3D images are taken as slices of a larger object. These could include machines, materials for inspection, geological objects, or human scanning. Illuminous values were stacked into planes with different transparency levels of tissues. These transparency levels can use multiple energy levels, such as density of CT scans or radioactive density. A desktop computer with enough video memory to produce the image is capable of this work. The memory changes with the size and resolution of the desired images to be stacked and viewed.

Hamilton, Joseph↗

Far Term Noise Reduction Roadmap for the Mid-Fuselage Nacelle Subsonic Transport

A noise reduction technology roadmap study is presented to determine the feasibility for the Mid-Fuselage Nacelle (MFN) aircraft concept to achieve the noise goal set by NASA for the Far Term time frame, beyond 2035. The study starts with updating the noise prediction of the existing MFN configuration that had been modeled for the time frame between 2025 and 2035. The updated prediction for the Mid Term time frame is 34.3 dB cumulative effective perceived noise level (EPNL) below the Stage 4 regulation. A suite of technologies that are deemed feasible to mature for practical implementation in the Far Term and whose potentials for noise reduction have been illustrated is selected for analysis. For each technology, component noise reduction is modeled either by available experimental data or by physics-based modeling with aircraft system level methods. The noise reduction is then applied to the corresponding noise component predicted by advanced aircraft system noise prediction tools, and the total aircraft noise is predicted as the incoherent summation of the components. It is shown that the Far Term MFN aircraft has the potential to achieve a cumulative noise level of 40.2 EPNL dB below Stage 4. The key technologies to achieve this low aircraft noise level are assessed by the impact of each technology on the aircraft system noise. This roadmap shows the potential of this revolutionary, yet still tube-and-wing, MFN concept to reach the NASA Far Term noise goal.

Guo, Yueping↗

Magnetic Field Intermittency in the Solar Wind: Parker Solar Probe and SolO Observations Ranging from the Alfvén Region up to 1AU

Parker Solar Probe (PSP) and SolO data are utilized to investigate magnetic field intermittency in the solar wind (SW). Small-scale intermittency (20−100 di) is observed to radially strengthen when methods relying on higher-order moments are considered (SFq; SDK), but no clear trend is observed at larger scales. However, lower-order moment-based methods (e.g., partial variance of increments; PVI) are deemed more appropriate for examining the evolution of the bulk of coherent structures (CSs), PVI ≥ 3. Using PVI, we observe a scale-dependent evolution in the fraction of the data set occupied by CSs, fPVI≥3. Specifically, regardless of the SW speed, a subtle increase is found in fPVI≥3 for ℓ = 20 di, in contrast to a more pronounced radial increase in CSs observed at larger scales. Intermittency is investigated in relation to plasma parameters. Though, slower SW speed intervals exhibit higher fPVI≥6 and higher kurtosis maxima, no statistical differences are observed for fPVI≥3. Highly Alfvénic intervals display lower levels of intermittency. The anisotropy with respect to the angle between the magnetic field and SW flow, ΘVB is investigated. Intermittency is weaker at ΘVB ≈ 0° and is strengthened at larger angles. Considering the evolution at a constant alignment angle, a weakening of intermittency is observed with increasing advection time of the SW. Our results indicate that the strengthening of intermittency in the inner heliosphere is driven by the increase in comparatively highly intermittent perpendicular intervals sampled by the probes with increasing distance, an effect related directly to the evolution of the Parker spiral.

Nikos Sioulas↗

Discovery of Activities via Statistical Clustering of Fixation Patterns

Human behavior often consists of a series of distinct activities, each characterized by a unique signature of visual behavior. This is true even in a restricted domain, such as piloting an aircraft, where patterns of visual signatures might represent activities like communicating, navigating, and monitoring. We propose a novel analysis method for gaze-tracking data, to perform blind discovery of these activities based on their behavioral signatures. The method is in some respects similar to recurrence analysis, but here we compare not individual fixations, but groups of fixations aggregated over a fixed time interval. The duration of this interval is a parameter that we will refer to as τ. We assume that the environment has been divided into a set of N different areas-of-interest (AOIs). For a given interval of time of duration τ, we compute the proportion of time spent fixating each AOI, resulting in an N-dimensional vector. These proportions can be converted to counts by multiplying by τ divided by the average fixation duration (another parameter that we fix at 280 milliseconds). We compare different intervals by computing the chi-square statistic. The p-value associated with the statistic is the likelihood of observing the data under the hypothesis that the data in the two intervals were generated by a single process with a single set of probabilities governing the fixation of each AOI. We have investigated the method using a set of 10 synthetic "activities," that sample 4 AOIs. Four of these activities visit 3 of the 4 AOIs, with equal probability; as there are four different ways to leave-one- out, there are four such activities. Similarly, there are six different activities that leave-two-out. Sequences of simulated behavior were generated by running each activity for 40 seconds, in sequence, for a total of 6.7 minutes. The figure to the right shows the matrix of chi-square statistics, using a value of 2.8 seconds for τ, corresponding to 10 fixations. Low values (dark) indicate poor evidence for activity differences, while high values (bright) indicate strong evidence. The dark squares along the main diagonal each correspond to the forty second intervals in which the activity was held constant; the 4x4 block at the lower left corresponds to the four leave-one-out activities, while the 6x6 block in the upper right corresponds to the leave-two-out activities. (The anti-diagonal pattern of white squares indicates those activity pairs that share no AOIs.) The chi-square values can be binarized by choosing a particular significance level; we are interested in grouping bins that represent the same activity, effectively accepting the null hypothesis. Therefore, we may adopt a relatively lax criterion; for example, choosing a p-value of 0.2 means that two behaviors that have only a 1-in-5 chance of being produced by a single activity might nevertheless be clustered together. We have explored several methods to perform clustering on the data and solving for the activity probabilities. Greedy methods begin by selecting the time bin that is similar to the most (or least) other bins, and then forming a cluster from it and all other non-discriminable bins. These methods show mediocre performance, as they do not take into account temporal contiguity. Preliminary results indicate that methods that "grow" clusters in time from seed points perform better.

activity analysis↗

Electronic Structure Theory Calculations Using Modern Architectures: KNL vs Haswell

The time to solution and parallel efficiency of several commonly used electronic structure methods (Hartree–Fock, density functional theory, second order perturbation theory, resolution of the identity second order perturbation theory, coupled cluster) are evaluated on both the Intel Xeon Haswell and the Intel Xeon Phi Knights Landing (KNL) architectures. The Haswell completes the benchmark calculations with a faster time to solution than the KNL for all molecules and methods tested. While the Haswell exhibits an average speedup of at least 3.5 relative to the KNL for all nonthreaded computations, the KNL has a better parallel efficiency than the Haswell with increasing core counts. The architectures are further tested using a more computationally costly coupled cluster method on a transition state reaction. The Haswell appears to be the best choice to minimize the time to solution, though for very large systems and high levels of theory that require memory intensive processes the superior memory hierarchy and larger on node memory of the KNL can make it a better choice. These results are used to showcase aspects of novel architectures that will increase efficiency for quantum chemistry applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Use of a GPS-Derived Troposphere Model to Improve InSAR Deformation Estimates in the San Gabriel Valley, California

We evaluate the potential of troposphere models derived from ground meteorological data (pressure, temperature, and relative humidity) and Global Positioning System (GPS) data to improve InSAR measurements and models derived from them. We test this approach on an ERS-2/Envisat data set collected during a transient surface deformation episode that occurred from January to July 2005 in the San Gabriel Valley, southern California, USA. We find that the interferometric phase change observed over the corresponding period cannot be solely attributed to hydrological uplift associated with rising groundwater levels but also includes a significant contribution from differential tropospheric delay due to differing quantities of water vapor in the troposphere on the two SAR observation dates. We show that, if the tropospheric phase contribution is mistakenly interpreted as the range change associated with changes in groundwater storage, both the surface displacement and the groundwater storage coefficient may be overestimated by up to 30%. Finally, this method could be applied in real time where meteorological measurements are available near one or more GPS permanent site(s).

54 ENVIRONMENTAL SCIENCES↗

SU-F-T-685: Evaluation of Tumor Hypoxic Fraction Using Serial Volumetric Imaging During Radiation Therapy

Purpose: To develop a tumor response model which could be uses to compute tumor hypoxic fraction using serial volumetric tumor imaging. This algorithm may be used for treatment response assessment and also for guidance of more expensive PET imaging of hypoxia. Methods: Previously developed two-level cell population tumor response model was modified to include a third cell level describing hypoxic and necrotic cells. This third level was considered constant value during radiotherapy treatment; therefore, inclusion additional parameter did not compromise stability of model fitting to imaging data. Fitting the model to serial volumetric imaging data was performed using a least squares objective function and simulated annealing algorithm. The problem of reconstruction of radiobiological parameters from serial imaging data was considered as inverse ill-posed problem described by the Fredholm integral equation of the first kind. Variational regularization was used to stabilize solutions. Results: To evaluate performance of the algorithm, we used a set of serial CT imaging data on tumor-volume for 14 head and neck cancer patients. The hypoxic fractions were reconstructed for each patient and the distribution of hypoxic fractions was compared to the distribution of initial hypoxic fractions previously measured using histograph. The measured and reconstructed from imaging data distributions of hypoxic fractions are in good agreement. The reconstructed distribution of cell surviving fraction was also in better agreement with in vitro data than previously obtained using the two-level cell population model. Conclusion: Our results indicate that it is possible to evaluate the initial hypoxic tumor fraction using serial volumetric imaging and a tumor response model. This algorithm can be used for treatment response assessment and guidance of more expensive PET imaging.

60 APPLIED LIFE SCIENCES↗

Spectrometric Estimation of Total Nitrogen Concentration in Douglas-Fir Foliage

Spectral measurements of fresh and dehydrated Douglas-fir foliage, from trees cultivated under three fertilization treatments, were acquired with a laboratory spectrophotometer. The slope (first-derivative) of the fresh- and dry-leaf absorbance spectra at locations near known protein absorption features was strongly correlated with total nitrogen (TN) concentration of the foliage samples. Particularly strong correlation was observed between the first-derivative spectra in the 2150-2170 nm region and TN, reaching a local maximum in the fresh-leaf spectra of -0.84 at 2 160 nm. Stepwise regression was used to generate calibration equations relating first derivative spectra from fresh, dry/intact, and dry/ground samples to TN concentration. Standard errors of calibration were 1.52 mg g-1 (fresh), 1.33 (dry/intact), and 1.20 (dry/ground), with goodness-of-fit 0.94 and greater. Cross-validation was performed with the fresh-leaf dataset to examine the predictive capability of the regression method; standard errors of prediction ranged from 1.47 - 2.37 mg g(exp -1) across seven different validation sets, prediction goodness of fit ranged from .85-.94, and wavelength selection was fairly insensitive to the membership of the calibration set. All regressions in this study tended to select wavelengths in the 2100-2350 nm region, with the primary selection in the 2142-2172 nm region. The study provides positive evidence concerning the feasibility of assessing TN status of fresh-leaf samples by spectrometric means. We assert that the ability to extract biochemical information from fresh-leaf spectra is a necessary but insufficient condition regarding the use of remote sensing for canopy-level biochemical estimation.

Johnson, Lee F.↗

More Data Needed for Failure Rate Estimation, Validation, and Uncertainty Reduction

Current Environmental Control and Life Support System (ECLSS) development and test activities are not generating data fast enough to provide statistically-supportable precise Orbital Replacement Unit (ORU) failure rate estimates for future missions. Accurate and precise failure rate estimates are critical for missions beyond Low Earth Orbit (LEO) because current risk mitigation approaches – namely regular resupply and rapid abort capabilities – will not be available. Safe operations will depend on mission planners’ ability to accurately forecast spares demand and efficiently provide the necessary resources. However, even after more than a decade of operations on board the International Space Station (ISS), a significant amount of uncertainty remains in failure rate estimates. Uncertain or inaccurate failure rates result in increased risk and spares mass for future missions. A Bayesian failure rate estimation approach, such as the one currently implemented by the ISS Program, can help reduce uncertainty by incorporating engineering judgement into failure rate estimates. However, experience on the ISS and with other complex systems shows that these prior failure rate estimates are often inaccurate. In addition, prior failure rate estimates are typically point values; some level of uncertainty must be added to convert these into probability distributions for Bayesian updating, and there are several potential methods for doing so. Due to the low rate of data collection, these subjective (and often inaccurate) prior estimates currently have a strong influence on the end result. This paper examines the challenges associated with failure rate estimation, validation, and uncertainty reduction in the context of ECLSS development for beyond-LEO missions. A variety of techniques for generating and updating Bayesian priors are discussed and evaluated using both real-world and simulated data. Potential solutions for improving failure rate estimation, including testing additional units, are analyzed and discussed, and a set of recommendations are provided for next-generation system development activities.

Supportability↗

Multilevel graph embedding

The goal of the present paper is the design of embeddings of a general sparse graph into a set of points in $\mathbb{R}^d$ for appropriate d ≥ 2. The embeddings that we are looking at here aim to keep vertices that are grouped in communities together and keep the rest apart. To achieve this property, we utilize coarsening that respects possible community structures of the given graph. We employ a hierarchical multilevel coarsening approach that identifies communities (strongly connected groups of vertices) at every level. The multilevel strategy allows any given (presumably expensive) graph embedding algorithm to be made into a more scalable (and faster) algorithm. We demonstrate the presented approach on a number of given embedding algorithms and large-scale graphs and achieve speed-up over the methods in a recent paper.

97 MATHEMATICS AND COMPUTING↗

Temperature induces significant changes in both glycolytic reserve and mitochondrial spare respiratory capacity in colorectal cancer cell lines

Thermotherapy, as a method of treating cancer, has recently attracted considerable attention from basic and clinical investigators. A number of studies and clinical trials have shown that thermotherapy can be successfully used as a therapeutic approach for various cancers. However, the effects of temperature on cancer bioenergetics have not been studied in detail with a real time, microplate based, label-free detection approach. This study investigates how changes in temperature affect the bioenergetics characteristics (mitochondrial function and glycolysis) of three colorectal cancer (CRC) cell lines utilizing the Seahorse XF96 technology. Experiments were performed at 32 °C, 37 °C and 42 °C using assay medium conditions and equipment settings adjusted to produce equal oxygen and pH levels ubiquitously at the beginning of all experiments. The results suggest that temperature significantly changes multiple components of glycolytic and mitochondrial function of all cell lines tested. Under hypothermia conditions (32 °C), the extracellular acidification rates (ECAR) of CRC cells were significantly lower compared to the same basal ECAR levels measured at 37 °C. Mitochondrial stress test for SW480 cells at 37 °C vs 42 °C demonstrated increased proton leak while all other OCR components remained unchanged (similar results were detected also for the patient-derived xenograft cells Pt.93). Interestingly, the FCCP dose response at 37 °C vs 42 °C show significant shifts in profiles, suggesting that single dose FCCP experiments might not be sufficient to characterize the mitochondrial metabolic potential when comparing groups, conditions or treatments. These findings provide valuable insights for the metabolic and bioenergetic changes of CRC cells under hypo- and hyperthermia conditions that could potentially lead to development of better targeted and personalized strategies for patients undergoing combined thermotherapy with chemotherapy.

60 APPLIED LIFE SCIENCES↗

Confocal Raman Microscopy for the Determination of Protein and Quaternary Ammonium Ion Loadings in Biocatalytic Membranes for Electrochemical Energy Conversion and Storage

Here, the need to immobilize active enzyme, while ensuring high rates of substrate turnover and electronic charge transfer with an electrode, is a centrally important challenge in the field of bioelectrocatalysis. In this work, we demonstrate the use of confocal Raman microscopy as a tool for quantitation and molecular-scale structural characterization of ionomers and proteins within biocatalytic membranes to aid in the development of energy efficient biofuel cells. A set of recently available short side chain Aquivion ionomers spanning a range of equivalent weight (EW) suitable for enzyme immobilization was investigated. Aquivion ionomers (790 EW, 830 EW and 980 EW) received in the proton-exchanged (SO 3 H) form were treated with tetra-n-butylammonium bromide (TBAB) to neutralize the ionomer and expand the size of ionic domains for enzyme incorporation. Through the use of confocal Raman microscopy, membrane TBA+ ion content was predicted in calibration studies to within a few percent of the conventional titrimetric method across the full range of TBA + : SO 3 - ratios of practical interest (0.1 to 1.7). Protein incorporation into membranes was quantified at the levels expected in biofuel cell electrodes. Furthermore, features associated with the catalytically active, enzyme-coordinated copper center were evident between 400 cm -1 - 500 cm -1 in spectra of laccase catalytic membranes, demonstrating the potential to interrogate mechanistic chemistry at the enzyme active site of biocathodes under fuel cell reaction conditions. When benchmarked against the 1100 EW Nafion ionomer in glucose/air enzymatic fuel cells (EFCs), EFCs with laccase air-breathing cathodes prepared from TBA + modified Aquivion ionomers were able to reach maximum power densities (P max ) up to 1.5 times higher than EFCs constructed with cathodes prepared from TBA + modified Nafion. The improved performance of EFCs containing the short side chain Aquivion ionomers relative to Nafion is traced to effects of ionomer ion-exchange capacity (IEC, where IEC = EW -1 ), where the greater density of SO 3 - moieties in the Aquivion materials produces an environment more favourable to mass transport and higher TBA + concentrations.

36 MATERIALS SCIENCE↗

Hydrogen Activation by Silica Supported Metal Ion Catalysts: Catalytic Properties of Metals and Performance of DFT Functionals

Single-site heterogeneous catalysts (SSHC) have received increasing attention due to their well-defined active sites and potentially high specific activity. Detailed computational studies were carried out on a set of potential SSHC’s, i.e., silica-supported metal ions, to investigate the reactivity of these catalysts with H2 as well as to evaluate the performance of density functional theory (DFT) methods in conjunction with triple-ζ quality basis sets (i.e., cc-pVTZ) on reaction energetics. The ions considered include 4d and 5d metals as well as several post-transition metal ions. A representative cluster model of silica is used to calculate reaction free energies of the metal hydride formation that results from the heterolytic cleavage of H2 on the M–O bond. The hydride formation free energy is previously shown to be strongly correlated with the catalytic activity of such catalysts for alkene hydrogenation. ONIOM calculations (CCSD(T)//MP2) are used to assess the accuracy and reliability of the MP2 results and it is found that MP2 is a suitable level of theory for gauging the performance of DFT functionals. The performance of various DFT functionals is assessed relative to MP2 results and it is found that the wB97xd and PBE0 functionals have the lowest standard deviation (STD) value while the MN12SX and PBE functionals have the lowest mean absolute deviation (MAD) values. The B3LYP functional is shown to have similar MAD and STD values as the top performing functionals. Potential active SSHC’s for exergonic hydrogen activation predicted in this study include mostly late and post transition metal ions, i.e., Au3+, Pd2+, Pt4+, Pd4+, Ir4+, Hg2+, Rh3+, Pb4+, Tl3+, In3+, Ir3+, Os4+, Cd2+, Ru2+, and Ga3+. This study provides important guidance to future computational studies of such catalyst systems.

Plascencia, Cesar↗