Micro-kinetic modeling of temporal analysis of products data using kinetics-informed neural networks
Kinetics-informed neural networks improve fit quality for multi-pulse and noisy temporal analysis of products datasets.
Nai, Dingqi↗
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Results for “temporal analysis of products”
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Global Validation of Columnar Water Vapor Derived from EOS MODIS-MAIAC Algorithm Against the Ground-Based AERONET Observations
The water vapor is a relevant greenhouse gas in the Earth's climate system, and satellite products become one of the most effective way to characterize and monitor the columnar water vapor (CWV) content at global scale. Recently, a new product (MCD19) was released as part of MODIS (Moderate Resolution Imaging Spectroradiometer) Collection 6 (C6). This operational product from the Multi-Angle Implementation for Atmospheric Correction (MAIAC) algorithm includes a high 1-kilometer resolution CWV retrievals. This study presents the first global validation of MAIAC C6 CWV obtained from MODIS MCD19A2 product. This evaluation was performed using Aerosol Robotic Network (AERONET) observations at 265 sites (2000-2017). Overall, the results show a good agreement between MAIAC/AERONET CWV retrievals, with correlation coefficient higher than 0.95 and RMS (Root Mean Square) error lower than 0.250 centimeters. The binned error analysis revealed an underestimation (approximately 10 percent) of Aqua CWV retrievals with negative bias for CWV higher than 3.0 centimeters. In contrast, Terra CWV retrievals show a slope of regression close to unity and a low mean bias of 0.075 centimeters. While the accuracy is relatively similar between 1.0 and 5.0 centimeters for both sensor products, Terra dataset is more reliable for applications in humid tropical areas (less than 5.0 centimeters). The expected error was defined as plus or minus 15 percent, with less than 68 percent of retrievals falling within this envelope. However, the accuracy is regionally dependent, and lower error should be expected in some regions, such as South America and Oceania. Since MODIS instruments have exceeded their design lifetime, time series analysis was also presented for both sensor products. The temporal analysis revealed a systematic offset of global average between Terra and Aqua CWV records. We also found an upward trend (approximately 0.2 centimeters per decade) in Terra CWV retrievals, while Aqua CWV retrievals remain stable over time. The sensor degradation influences the ability to detect climate signals, and this study indicates the need for revisiting calibration of the MODIS bands 17-19, mainly for Terra instrument, to assure the quality of the MODIS water vapor product. Finally, this study presents a comprehensive validation analysis of MAIAC CWV over land, raising the understanding of its overall quality.
MAIAC↗
Transient Catalytic Reaction Analysis Through Signal Defragmentation
The Temporal Analysis of Products (TAP) pulse response technique provides valuable insights into catalytic function and reaction kinetics. However, complex fragmentation patterns in the TAP mass spectrometry signals can complicate precise quantification, particularly when analyzing transient gas flux data typical of TAP experiments. This work demonstrates a standard defragmentation method that deconvolves transient TAP signals while maintaining the temporal resolution of the experiment. First, the integrals of calibration gas fluxes are used to determine the fingerprint fragmentation pattern and construct a fragmentation matrix. This matrix is then used to defragment experimental flux data at each recorded time point via a non-negative least squares regression. The effectiveness of this method is demonstrated using virtual data and control experiments with a TAP reactor system. The defragmentation is then applied to the more complex propane dehydrogenation reaction on a chromia/alumina catalyst, which can contain up to ten significant gas species in the reactor outlet. Initial propane pulsing reveals an induction period during which propane is fully oxidized to CO2, followed by partial reduction to CO. Afterwards, there is a transition in chemistries towards coking and propylene production. Our example illustrates a practical method for the accurate determination of the time-dependent reactant/product concentrations and rates for a thorough analysis of the propane dehydrogenation kinetics. This approach can be broadly applied to any transient mass spectrometry experiment for a better understanding of catalyst-reaction dynamics.
36 - MATERIALS SCIENCE↗
Current understanding of Oxidative Coupling of Methane (OCM) reaction over supported Mn-Na 2 WO 4 catalysts
This perspective reviews the current understanding of the Oxidative Coupling of Methane (OCM) reaction over the supported Mn-Na 2 WO 4 /SiO 2 catalyst, with a focus on recent insights gained from state-of-the-art in-situ and operando spectroscopic characterization and chemical probe experiments under controlled environments. The supported Mn-Na 2 WO 4 /SiO 2 catalyst exhibits dynamic structural changes during the OCM reaction, involving multiple reactive lattice and adsorbed oxygen species, each associated with different oxide phases. These oxygen species play distinct roles in various steps of the OCM mechanism. The catalytic active sites for activation of CH 4 are associated with isolated surface Na-WO x sites on the SiO 2 support and the role of surface MnO x sites on SiO 2 is to oxidatively dehydrogenate C 2 H 6 to C 2 H 4 . Furthermore, this paper provides a detailed discussion of these roles and also introduces new experimental data from Temporal Analysis of Products (TAP) studies to clarify the ongoing debate in the literature regarding the contributions of lattice versus adsorbed oxygen species in OCM reaction product formation. Additionally, recommendations are offered for optimizing the performance of supported Mn-Na 2 WO 4 /SiO 2 catalysts to enhance CH 4 activation and C 2 product selectivity.
03 - NATURAL GAS↗
Transient kinetic insights into selective propene oxidation over industrial bismuth molybdate catalysts
Selective oxidation of propene to acrolein over industrial multicomponent bismuth molybdate (BMO) catalysts significantly depends on reaction conditions that include operating parameters and catalyst state. Here, this work investigates selective propene oxidation in the intrinsic kinetic paradigm of Temporal Analysis of Products (TAP) reactor by systematically varying catalyst redox state, temperature, and oxygen-to-propene feed ratio. A 93 % propene conversion with an acrolein yield of 80 % is achieved at elevated temperatures (450 °C) on oxidized catalysts under oxygen-rich conditions (O 2 :C 3 H 6 = 10). However, these conditions diminish acrolein-to-CO 2 selectivity due to enhanced total oxidation to CO 2 . In contrast, a reduced catalyst state, moderate temperature (350 °C), and lower oxygen feed (O 2 :C 3 H 6 = 1) nearly doubles the acrolein to-CO 2 selectivity, albeit at a lower acrolein yield (33 %). Transient kinetic studies together with a kinetic model that simplify the major product formation pathways in lumped non-elementary forms reveal that the availability of surface oxygen species plays a pivotal role in governing reaction pathways. Additionally, density functional theory (DFT) calculations on pure BMO catalysts inform the role of surface redox states on propene and oxygen activation barriers. Lattice oxygen at acrolein-selective sites drives both acrolein and CO 2 formation, while adsorbed oxygen at activation sites favors unselective CO 2 generation. This work establishes a critical relationship between transient product selectivity and surface oxygen availability, which is strongly influenced by catalyst redox state, feed ratio, and reaction temperature. These insights underscore the importance of dynamic reactor operation strategies and offer a foundation for designing next-generation propene oxidation processes with tunable acrolein selectivity.
42 - ENGINEERING↗
Statistical distributions for transient transport
Here, this paper introduces the use of statistical distributions based on transport differential equations for clear distinction of transport modes within transient kinetic experiments. More specifically, novel techniques are developed for the transient data obtained through the Temporal Analysis of Products (TAP) reactor and are applicable to experiments where pulse response into a gas flow is used. The methodology allows distinguishing between two domains of diffusion transport in heterogeneous catalytic systems, i.e., Knudsen and non-Knudsen diffusion, using statistical fingerprints, and finding the transition domain. Two distribution parameters were obtained that directly result in coefficients that correspond to the concentration and the rate of transport. Using a linear relationship between the rate and concentration coefficients, Knudsen diffusion is revealed when the rate of transport is constant and non-Knudsen diffusion is confirmed when the rate of transport coefficient is a function of the concentration coefficient. As a result, accurate transport information can be extracted from experimental data even in the presence of comprising instrument drift or noise particularly when analyzing higher pressure pulse responses with complex transport. This enables more direct investigation of experiments influenced by gas-phase reactions.
TAP reactor↗
Mass Spectrometer Transient Analysis
This software implements a complete preprocessing pipeline for transient mass spectrometry (MS) data collected during TAP (Temporal Analysis of Products) experiments. It is designed to extract chemically meaningful fluxes from overlapping ion signals by applying a calibrated defragmentation matrix and solving the resulting linear system using non-negative least squares (NNLS) regression. The core script, preprocess_mass_spec.py, performs the following operations: Gain correction: Applies amplifier gain scalars derived from inert-packed calibration pulses to normalize signal intensities across AMUs and acquisition settings. Background subtraction: Removes experiment baselines using user-defined time windows, ensuring compatibility with slow-diffusing species and preventing negative values that would interfere with NNLS. Options to subtract before and after defragmentation. Defragmentation: Constructs a fragmentation matrix A from zeroth moments of calibration pulses (equal molar gas:inert mixtures) and solves Ax=b at each time point, where b is the raw MS signal and x is the estimated species flux. The matrix is normalized to inert signals and accounts for instrument-specific fragmentation behavior. Pulse-mode handling: Supports both averaged and individual pulse modes, enabling statistical treatment of fluxes and calculation of standard deviations. Integration and output: Computes zeroth moments (integrated fluxes) and exports time-resolved and integrated data in CSV format, suitable for downstream kinetic modeling. The software is validated using both virtual TAP simulations (VTAP) and experimental data from propane dehydrogenation (PDH) on CrOx/Al2O3 catalysts. It preserves temporal resolution by applying NNLS point-by-point across the pulse duration (typically 6,000+ time slices per pulse), leveraging the linear superposition principle to reconstruct full flux profiles. The defragmented outputs are compatible with kinetic extraction methods such as the G and Y procedures, which are used to derive rate–concentration relationships from TAP data. The details of these validations are discussed in detail in the supporting manuscript and supporting information. Example data and output files are also included. The methodology is robust to experimental noise and drift, with calibration protocols that account for pulse size effects, MS aging, and inert gas normalization. The software is modular, reproducible, and tailored for high-throughput TAP-MS workflows in catalysis research.
Kristy, Stephen [Idaho National Laboratory (INL), ↗
Machine Learning-Assisted Recovery of Delicate Kinetic Information from Transient Reactor Experiments
Identifying active sites and their roles in chemical reaction steps remains a vital challenge in heterogeneous catalysis. Transient experiments offer a unique way to probe active sites and distinguish subtle kinetic features. Although physics-based analysis methods may be well-developed, they can be highly susceptible to experimental noise, and smoothing methods may erase or even distort important features; a smooth curve is not always the best curve. We demonstrate a new workflow for the direct interpretation of intrinsic kinetic information from exit flux curves measured in transient reactor experiments. This workflow contains three artificial neural networks (ANNs), including a noise reducer, a concentration predictor, and a rate predictor to analyze experimental data, followed by the virtual TAP (VTAP) physics-based reactor model and density functional theory (DFT) calculations of adsorption energies on specific sites. We use this workflow to analyze the data from experiments titrating Pt/Al 2 O 3 and Pt/SiO 2 catalysts with carbon monoxide (CO) in the temporal analysis of products (TAP) reactor. Our workflow separates the time-evolving chemical reaction and mass transfer information contained in the TAP pulse response. The existence of strong- and weak-binding sites on the Pt/Al 2 O 3 catalyst is observed in the catalyst titration experiment in the transient reactor. The structures of the strong- and weak-binding sites are then identified by using DFT calculations. We find that the Pt/SiO 2 catalyst has only strong-binding sites, which aligns with the inactive support effect of SiO 2 . We demonstrate how machine learning methods provide unique insights with high-resolution data analysis that cannot be achieved by using state-of-the-art physics-based methods.
Adsorption↗
Direct study of changes in catalyst structure-kinetic properties during redox transitions using a new time-resolved technique
Direct study of changes in catalyst structure-kinetic properties during redox transitions using a new time-resolved technique The Temporal Analysis of Products (TAP) pulse response methodology1 is a transient technique offering the time scale needed to deconvolve many reaction steps from the complex network typical to industrial catalytic processes. The traditional TAP measurement observes the gas phase dynamic response but, hereto now, has been devoid of any direct measurement of change in the catalyst itself. The development of an operando technique that couples gas phase transient kinetics to dynamic metal centers and surface species is presented. Significance Unification of the TAP methodology with time-resolved spectroscopic measurement can offer unprecedented insight into the complex kinetic phenomena regulated by the solid catalyst.
03 - NATURAL GAS↗
Direct Study of Changes in Catalyst Structure-Kinetic Properties During Redox Transitions
The Temporal Analysis of Products (TAP) pulse response methodology is a transient technique that provides the time resolution needed to deconvolve reaction steps from the complex networks typical in industrial catalytic processes. Traditionally, TAP measurements observe gas phase dynamics at the reactor exit but lack direct measurements of changes in the catalyst itself. Recently, a new operando technique was developed that couples gas phase transients to dynamic changes in metal centers with the precise TAP methodology for nanomole titration. Using an industrial CrOx/Al2O3 catalyst used for propane dehydrogenation, we demonstrate the capabilities of this unique device to reveal key catalytic processes: 1) total propane oxidation not associated with chromia centers, 2) reduction of Cr6+ to Cr3+ correlated with selective product formation, and 3) subsequent carbon accumulation. By utilizing incremental pulsing in a diffusion-only transport regime, the spectrokinetic device allows us to resolve detailed changes in catalyst structure, composition, and kinetic function that are otherwise indistinguishable in conventional operando devices. The unification of the TAP methodology with time-resolved spectroscopic measurements offers new and unique insights into the complex kinetic phenomena regulated by solid catalyst surfaces.
03 - NATURAL GAS↗
Studies of the net surface radiative flux from satellite radiances during FIFE
Studies of the net surface radiative flux from satellite radiances during First ISLSCP Field Experiment (FIFE) are presented. Topics covered include: radiative transfer model validation; calibration of VISSR and AVHRR solar channels; development and refinement of algorithms to estimate downward solar and terrestrial irradiances at the surface, including photosynthetically available radiation (PAR) and surface albedo; verification of these algorithms using in situ measurements; production of maps of shortwave irradiance, surface albedo, and related products; analysis of the temporal variability of shortwave irradiance over the FIFE site; development of a spectroscopy technique to estimate atmospheric total water vapor amount; and study of optimum linear combinations of visible and near-infrared reflectances for estimating the fraction of PAR absorbed by plants.
Frouin, Robert↗
A Spatio-Temporal Approach for Global Validation and Analysis of MODIS Aerosol Products
With the launch of the MODIS sensor on the Terra spacecraft, new data sets of the global distribution and properties of aerosol are being retrieved, and need to be validated and analyzed. A system has been put in place to generate spatial statistics (mean, standard deviation, direction and rate of spatial variation, and spatial correlation coefficient) of the MODIS aerosol parameters over more than 100 validation sites spread around the globe. Corresponding statistics are also computed from temporal subsets of AERONET-derived aerosol data. The means and standard deviations of identical parameters from MOMS and AERONET are compared. Although, their means compare favorably, their standard deviations reveal some influence of surface effects on the MODIS aerosol retrievals over land, especially at low aerosol loading. The direction and rate of spatial variation from MODIS are used to study the spatial distribution of aerosols at various locations either individually or comparatively. This paper introduces the methodology for generating and analyzing the data sets used by the two MODIS aerosol validation papers in this issue.
Ichoku, Charles↗
Fermi-Based Kinetic Model for the Sabatier Reaction: Sabatier Principle and Beyond It
The CO 2 methanation reaction (aka the Sabatier reaction) is one of the important carbon utilization technologies to reduce atmospheric greenhouse gases. In this study, kinetic modeling of the Sabatier reaction proceeding via the CO route has been presented by considering weak and strong chemisorption concepts rooted in electronic theory. Based on the single-route mechanism of the Sabatier reaction, the dependence of the reaction rate on the position of the catalyst Fermi level with respect to the antibonding states of the reagent (CO 2 ) and the product (CH 4 ), is demonstrated with the classic Sabatier volcano-shape. Furthermore, the model was applied to explain experimental results of reaction rates for Ni- and Ru-based catalytic systems and to understand origin of enhancement of turnover frequencies established for dynamic catalysis.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
High entropy alloys as catalysts: A focused review
A brief literature review of recent experimental and computational efforts on the use of high entropy alloys (HEAs) as catalysts is presented, while also sharing some perspectives and future insights. To fully broach the vast compositional possibilities of HEA materials, integrating computational modeling with high-throughput experimental synthesis and validation is necessary to accelerate their design and development. Once identified, specific HEAs can be a class of materials for the next generation of catalysts when addressing global challenges related to energy independence, commodity chemical production, environmental remediation, abating emissions, and modernized domestic supply chain resilience.
42 - ENGINEERING↗
Lowering the barrier to access information-rich transient kinetic data for machine learning methods
Transient kinetic data contain a wealth of information about intrinsic features of a catalyst as well as the reaction mechanism. Currently, high volume transient data is underutilized, and data science methods could both increase the value of information that can be extracted from this data, integrate experimental with theoretical data sources, and accelerate the pace of catalyst technology advancement. Transient kinetic characterizations with simple probe molecules exhibiting reversible adsorption, irreversible adsorption and bulk-surface diffusion are presented as training components for similar experiments with more complex surface reactions. In conclusion, by increasing the availability and accessibility of transient kinetic data through details of its structure and acquisition, we aim to decrease the barrier for data scientists to apply machine learning methods to this valuable data source.
Catalysis↗
Temporal Galactose‐Manganese Feeding in Fed‐Batch and Perfusion Bioreactors Modulates UDP‐Galactose Pools for Enhanced mAb Glycosylation Homogeneity
ABSTRACT Monoclonal antibodies (mAbs) represent a majority of biotherapeutics in the market today. These glycoproteins undergo posttranslational modifications, such as N‐linked glycosylation, that influence the structural & functional characteristics of the antibody. Glycosylation is a heterogenous posttranslational modification that may influence therapeutic glycoprotein stability and clinical efficacy, which is why it is often considered a critical quality attribute (CQA) of the mAb product. While much is known about the glycosylation pathways of Chinese Hamster Ovary (CHO) cells and how cell culture chemical modifiers may influence the N‐glycosylation profile of the final product, this knowledge is often based on the final cumulative glycan profile at the end of the batch process. Building a temporal understanding of N‐glycosylation and how mAb glycoform composition responds to real‐time changes in the biomanufacturing process will help build integrated process models that may allow for glycosylation control to produce a more homogenous product. Here, we look at the effect of specific nutrient feed media additives (e.g., galactose, manganese) and feeding times on the N‐glycosylation pathway to modulate N‐glycosylation of a Herceptin biosimilar mAb (i.e., Trastuzumab). We deploy the N‐GLYcanyzer process analytical technology (PAT) to monitor glycoforms in near real‐time for bench‐scale bioprocesses operated in both fed‐batch and perfusion modes to build an understanding of how temporal changes in mAb N‐glycosylation are dependent on specific media additives. We find that Trastuzumab terminal galactosylation is sensitive to media feeding times and intracellular nucleotide sugar pools. Temporal analysis reveals an increased desirable production of single and double galactose‐occupied glycoforms over time under glucose‐starved fed‐batch cultures. Comparable galactosylation profiles were also observed between fed‐batch (nutrient‐limited) and perfusion (non‐nutrient‐limited) bioprocess conditions. In summary, our results demonstrate the utility of real‐time monitoring of mAb glycoforms and feeding critical cell culture nutrients under fed‐batch and perfusion bioprocessing conditions to produce higher‐quality biologics.
Biotechnology & Applied Microbiology↗
Making Better Use of Satellite Data: The Satellite Needs Working Group
The U.S. Group on Earth Observations (USGEO) initiated in 2016 the Satellite Needs Working Group (SNWG) to identify and communicate the Earth observation needs of U.S. federal agencies. The SNWG identifies such needs through a biennial survey followed by interviews and follow-up discussions by the satellite Earth data providers of the U.S. Government: the National Aeronautics and Space Administration (NASA), the National Oceanic and Atmospheric Administration (NOAA), and the U.S. Geological Survey (USGS). Solutions and services are identified that leverage current or upcoming satellite missions to meet the identified needs; implementation of services that are estimated to significantly increase the level of satisfaction of multiple U.S. agencies are funded by NASA. The SNWG process has resulted in the implementation of numerous services that have impacted operations of not only U.S. agencies but of academic and international institutions as well. Notable examples include the Harmonized Landsat Sentinel-2 project that leverages European Space Agency (ESA) and NASA satellite assets to generate a global, analysis-ready, surface reflectance product with a temporal resolution of two days; the Airborne Data Management Group that curates and provides access to relevant resources, information and data from existing and past NASA field campaigns; and the Dynamic Surface Water Extent product which consists of harmonized but independent water extents derived from both from optical and radar data. These and other products are hosted at the NASA Distributed Active Archive Centers (DAACs) for free and open access. The SNWG Management Office at NASA’s Interagency Implementation and Advanced Concepts Team (IMPACT) manages the implementation of selected solutions and, importantly, NASA’s response to the needs of federal agencies through a Stakeholder Engagement Program. The impact of implemented services and solutions is hampered without efforts to build capacity around the use of the services. The Stakeholder Engagement Program ensures relevant training and outreach to SNWG agencies in collaboration with each solution implementation team.
remote sensing↗
Land Surface Temperature Measurements from EOS MODIS Data
This report summarizes the accomplishments made by the MODIS LST (Land-Surface Temperature) group at University of California, Santa Barbara, under NASA Contract. Version 1 of the MODIS Land-Surface Temperature Algorithm Theoretical Basis Document (ATBD) was reviewed in June 1994, version 2 reviewed in November 1994, version 3.1 in August 1996, and version 3.3 updated in April 1999. Based on the ATBD, two LST algorithms were developed, one is the generalized split-window algorithm and another is the physics-based day/night LST algorithm. These two LST algorithms were implemented into the production generation executive code (PGE 16) for the daily standard MODIS LST products at level-2 (MODII-L2) and level-3 (MODIIA1 at 1 km resolution and MODIIB1 at 5km resolution). PGE codes for 8-day 1 km LST product (MODIIA2) and the daily, 8-day and monthly LST products at 0.05 degree latitude/longitude climate model grids (CMG) were also delivered. Four to six field campaigns were conducted each year since 2000 to validate the daily LST products generated by PGE16 and the calibration accuracies of the MODIS TIR bands used for the LST/emissivity retrieval from versions 2-4 of Terra MODIS data and versions 3-4 of Aqua MODIS data. Validation results from temperature-based and radiance-based methods indicate that the MODIS LST accuracy is better than 1 C in most clear-sky cases in the range from -10 to 58 C. One of the major lessons learn from multi- year temporal analysis of the consistent V4 daily Terra MODIS LST products in 2000-2003 over some selected target areas including lakes, snow/ice fields, and semi-arid sites is that there are variable numbers of cloud-contaminated LSTs in the MODIS LST products depending on surface elevation, land cover types, and atmospheric conditions. A cloud-screen scheme with constraints on spatial and temporal variations in LSTs was developed to remove cloud-contaminated LSTs. The 5km LST product was indirectly validated through comparisons to the 1 km LST product. Twenty three papers related to the LST research work were published in journals over the last decade.
Wan, Zheng-Ming↗