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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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All sourcesNASA NTRSDOE OSTI
NASA NTRS1973

Evaluation of Electrochemical Nitrogen/hydrogen Gas Separator

An electrochemical nitrogen-hydrogen separator subsystem was investigated for use following catalytic dissociation of ammonia or hydrazine in a storage system being considered for long-duration manned space flight. An experimental cell with concentric tubular Pd-25Ag alloy hydrogen diffusion electrodes and hermetically sealed aqueous caustic electrolyte was developed.It was found that this cell operated satisfactorily at 210 C to 245 C and produced dry nitrogen and dry hydrogen with either or both gases at pressures up to 6.8 atmospheres (100 psia) or higher for storage. The final cell developed was operated satisfactorily for 176 days (4200 hours) with no evidence of deterioration of current-voltage performance. The best experimental performance was obtained at 245 C at currents up to 4 amperes (180 ma/sq cm and 360 ma/sq cm anode and cathode current densities, respectively) with a maximum steady-state cell voltage of 0.125 volt for an anode feed of pure hydrogen.

Clifford, J. E.↗
DOE OSTI2019

A multi-scale experimental investigation of flow properties in coarse-grained hydrate reservoirs during production (Final Scientific/Technical Report)

In this project, “A multi-scale experimental investigation of flow properties in coarse-grained hydrate reservoirs during production” we explored the relative permeability and dissipation behavior of hydrate-bearing coarse-grained sediment at the core scale and we observed the formation and dissociation of these materials at the pore scale with micro-CT and Raman experiments. The 3-year project results inform reservoir simulation efforts, critical to determining the viability of the coarse-grained hydrate reservoir as an energy resource. We performed the first 3 phase relative permeability experiments in a hydrate-bearing medium using the steady state method (gas and water flow in the presence of hydrate). Results support a model where water is the most wetting phase, hydrate is the intermediate wetting phase, and gas is the least wetting phase. This model can be used to predict relative permeability of gas and water in the presence of hydrate. We showed that when hydrate dissociates, it does so at a pressure and temperature predicted for fresh water (no salinity) conditions. At the scale of a grid block, reservoir simulation models should assume that hydrate dissociates at the freshwater phase boundary. We observed that the chemistry and the pore habit of methane hydrates change dramatically over the timescales of experiments (hours to weeks). It takes weeks to months for hydrates to evolve from a non-stoichiometric to stoichiometric compound with 3:1 large cage vs small cage occupancy. We documented hydrates forming initially in small clayey silt surfaces but gradually concentrated in large pores in sand-sized sediment.

03 NATURAL GAS↗
NASA NTRS1994

Ion Chemistry in Atmospheric and Astrophysical Plasmas

There are many differences and also remarkable similarities between the ion chemistry and physics of planetary ionospheres and the ion chemistry and physics of astronomical environments beyond the solar system. In the early Universe, an expanded cooling gas of hydrogen and helium was embedded in the cosmic background radiation field and ionized by it. As the Universe cooled by adiabatic expansion, recombination occurred and molecular formation was driven by catalytic reactions involving the relict electrons and protons. Similar chemical processes are effective in the ionized zones of gaseous and planetary nebulae and in stellar winds where the ionization is due to radiation from the central stars, in the envelopes of supernovae where the ionization is initiated by the deposition of gamma-rays, in dissociative shocks where the ionization arises from electron impacts in a hot gas and in quasar broad-line region clouds where the quasar is responsible for the ionization. At high altitudes in the atmospheres of the Jovian planets, the main constituents are hydrogen and helium and the ion chemistry and physics is determined by the same processes, the source of the ionization being solar ultraviolet radiation and cosmic rays. After the collapse of the first distinct astronomical entities to emerge from the uniform flow, heavy elements were created by nuclear burning in the cores of the collapsed objects and distributed throughout the Universe by winds and explosions. The chemistry and physics became more complicated. Over 90 distinct molecular species have been identified in interstellar clouds where they are ionized globally by cosmic ray impacts and locally by radiation and shocks associated with star formation and evolution. Complex molecules have also been found in circumstellar shells of evolved stars. At intermediate and low altitudes in the Jovian atmospheres, the ion chemistry is complicated by the increasing abundance of heavy elements such as carbon, and an extensive array of complex molecules has been predicted. Reactions involving heavy elements dominate the structure of the ionspheres of the terrestrial planets and the satellites Titan and Triton.

Dalgarno, A.↗
DOE OSTI2025

2025 ASMS Investigation of the Collision-Induced Dissociation Mechanism of Protonated TODGA with IRIS

Title (20 words): Investigation of the Collision-Induced Dissociation Mechanism of Protonated TODGA with IRIS Introduction (120 words): One of the challenges facing wide-spread adoption of nuclear power is the development of efficient separation processes for used nuclear fuel. The molecules in separation processes are subjected to an extreme environment due to the high radiation fields from the used fuel and highly acidic media used for fuel dissolution, which results in significant molecular degradation, leading to reduced process efficiency. These degradation products must be identified and studied so mitigation strategies can be developed to maintain process efficiency. However, complex systems can have many degradation products, complicating identification. Untargeted analysis tools could be used to understand radiation chemistry in complex systems. However, this would necessitate improved understanding of the gas-phase fragmentation mechanisms of fuel cycle molecules like tetraoctyldiglycolamide (TODGA). Methods (120 words): The gas-phase fragmentation of protonated TODGA was investigated using collision-induced dissociation (CID), resonance ejection, and infrared ion spectroscopy (IRIS). CID and resonance ejection experiments were conducted using a Bruker Daltonics (Bremen, Gemany) SolariX XR fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. IRIS spectra of protonated TODGA and its two CID fragmentation products were measured using a modified Bruker amaZon Speed ETD 3D quadrupole ion trap mass spectrometer coupled to the Free Electron Lasers for Infrared eXperiments (FELIX) free electron laser. Measured spectra were compared with density functional theory (DFT) calculations using the Gaussian 16, Revision C.02 software package with the ?B97X-D functional and def2-TZVPP basis sets. Candidate structures were generated using the CREST 3.0 conformational sampling software tool. Preliminary Data (300 words): Collision-induced dissociation of protonated TODGA ([C36H73N2O3]+, m/z=581.562) results two fragment ions, one at m/z=340.285 assigned as [C20H38NO3]+ and the other at m/z=312.290, assigned as [C19H38NO2]+. Based on the assigned formula and the structure of protonated TODGA, the fragment at m/z=340.285 is likely formed from elimination of neutral dioctylamine. Comparison of the IRIS spectrum of m/z=340.285 with DFT predictions suggests it contains a ring structure, and is assigned as N-octyl-N-(6-oxo-1,4-dioxan-2-ylidene)octan-1-aminium. Based on this structure and the structure of protonated TODGA, we hypothesize this fragment formed from elimination of neutral dioctylamine followed by a ring closure mechanism. Comparison of the IRIS spectrum of the fragment at m/z=312.290 with DFT predictions also indicated the presence of a ring structure, assigned as N-(1,3-dioxolan-4-ylidene)-N-octyloctan-1-aminium. This product could be formed from elimination of carbon monoxide from the ring of m/z=340.285 as a sequential fragmentation or formed directly from protonated TODGA via elimination of neutral N,N-dioctylformamide followed by a ring closure. Resonance ejection experiments where m/z=340 was continuously ejected from the IRC cell showed no decrease in intensity of m/z=312.290 across several collision energies, suggesting that the later, direct formation mechanism, dominates. The location of the ionizing proton in protonated TODGA is important for modeling the fragmentation mechanisms. DFT calculations suggested that the position of bands involving the coupled vibrations of the amide C—N and C=O bonds in TODGA are the most sensitive to proton location. Evaluation of the IRIS spectrum of protonated TODGA suggests that the ionizing proton is located between the two amid oxygens. This protonation location was calculated to lie approximately 30 kJ/mol lower in energy than the next lowest energy location, with the proton located solely on one of the amide oxygens. Novel aspect (20 words): Infrared ion spectroscopy combined with resonance ejection experiments and density functional theory to probe the collision-induced dissociation mechanism of tetraoctyldiglycolamide.

37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL C↗
DOE OSTI2020

Proton affinities of pertechnetate (TcO 4 - ) and perrhenate (ReO 4 - )

The anions pertechnetate, TcO 4 - , and perrhenate, ReO 4 - , exhibit very similar chemical and physical properties. Revealing and understanding disparities between them enhances fundamental understanding of both. Electrospray ionization generated the gas-phase proton bound dimer (TcO 4 - )(H + )(ReO 4 - ). Collision induced dissociation of the dimer yielded predominantly HTcO 4 - and ReO 4 - , which according to Cooks’ kinetic method indicates that the proton affinity (PA) of TcO 4 - is greater than that of Re O 4 - . Density functional theory computations agree with the experimental observation, providing PA[TcO 4 - ] = 300.1 kcal mol -1 and PA[ReO 4 - ] = 297.2 kcal mol -1 . Attempts to rationalize these relative PAs based on elementary molecular parameters such as atomic charges indicate that the entirety of bond formation and concomitant bond disruption needs to be considered to understand the energies associated with such protonation processes. Although in both the gas and solution phases, TcO 4 - is a stronger base than ReO 4 - , it is noted that the significance of even such qualitative accordance is tempered by the very different natures of the underlying phenomena.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Influence of counterion substitution on the properties of imidazolium-based ionic liquid clusters

Due to their unique physiochemical properties that may be tailored for specific purposes, ionic liquids (ILs) have been investigated for various applications, including chemical separations, catalysis, energy storage, and space propulsion. The different cations and anions comprising ILs may be selected to optimize a range of desired properties, such as thermal stability, ionic conductivity, and volatility, leading to the designation of certain ILs as designer “green” solvents. The effect of counterions on the properties of ILs is of both fundamental scientific interest and technological importance. Herein, we report a systematic experimental and theoretical investigation of the size, charge, stability toward dissociation, and geometric/electronic structure of 1-ethyl-3-methyl imidazolium (EMIM)-based IL clusters containing two different atomic counterions (i.e., bromide [Br − ] and iodide [I − ]). This work extends our studies of EMIM + cations with atomic chloride (Cl − ) and molecular tetrafluoroborate (BF 4 − ) anions reported previously by Baxter et al. [Chem. Mater. 34, 2612 (2022)] and Zhang et al . [J. Phys. Chem. Lett. 11, 6844 (2020)], respectively. Distributions of anionic IL clusters were generated in the gas phase using electrospray ionization and characterized by high mass resolution mass spectrometry, energy-resolved collision-induced dissociation, and negative ion photoelectron spectroscopy experiments. The experimental results reveal anion-dependent trends in the size distribution, relative abundance, ionic charge state, stability toward dissociation, and electron binding energies of the IL clusters. Complementary global optimization theory provides molecular-level insights into the bonding and electronic structure of a selected subset of clusters, including their low energy structures and electrostatic potential maps, and how these fundamental characteristics are influenced by anion substitution. Collectively, our findings demonstrate how the fundamental properties of ILs, which determine their suitability for many applications, may be tuned by substituting counterions. These observations are critical in the sub-nanometer cluster size regime where phenomena do not scale predictably to the bulk phase, and each atom counts toward determining behavior.

cluster↗
DOE OSTI2026

Dynamics of argon metastables in Ar–CH 4 radio frequency capacitively-coupled plasma: real-time monitoring with neural network-augmented broadband optical emission spectroscopy

In moderate-pressure radio frequency (RF) capacitively coupled plasmas generated in argon–methane mixtures, the density of argon metastable atoms (Ar 1 s 5 ) exhibits a non-monotonic dependence on methane (CH 4 ) concentration. Laser-induced fluorescence (LIF) was used to measure and compare local Ar 1 s 5 densities in Ar and Ar–CH 4 plasmas at 2.6 Torr and RF powers of 17–117 W. The addition of 1% CH 4 increases the metastable density, and 2% CH 4 triggers a strong depletion by an order of magnitude, compared to 1% CH 4 case. This non-monotonic behavior demonstrates the sensitivity of metastable populations to small gas admixtures, which is critical for processes where metastables drive precursor dissociation. For real-time monitoring of metastable population, broadband optical emission spectroscopy (OES) is augmented with a feedforward neural network (NN) to predict Ar s1 5 densities from spectral features. When trained on LIF data, the NN replicates the absolute densities and the dynamic trends of Ar 1 s 5 density variation. The NN-augmented broadband OES approach can be used as a simple and cost-effective tool for tracking Ar metastables in Ar-rich plasmas, facilitating industrial-scale optimization.

Yatom, Shurik [Princeton Plasma Physics Laboratory↗
NASA NTRS1991

Thermal design of a Mars oxygen production plant

The optimal design of the thermal components of a system that uses carbon dioxide from the Martian atmosphere to produce oxygen for spacecraft propulsion and/or life support is discussed. The gases are pressurized, heated and passed through an electrochemical cell. Carbon dioxide is reduced to carbon monoxide and oxygen due to thermal dissociation and electrocatalysis. The oxygen thus formed is separated from the gas mixture by the electrochemical cell. The objective of the design is to optimize both the overall mass and the power consumption of the system. The analysis shows that at electrochemical cell efficiencies of about 50 percent and lower, the optimal system would require unspent carbon dioxide in the exhaust gases to be separated and recycled. Various methods of efficiently compressing the intake gases to system pressures of 0.1 MPa are investigated. The total power requirement for oxygen production rates of 1, 5, and 10 kg/day at various cell efficiencies are presented.

Sridhar, K. R.↗
NASA NTRS1993

Transition on a sharp cone at high enthalpy - New measurements in the shock tunnel T5 at GALCIT

An exploratory study of the laminar, transitional and turbulent boundary layer on a slender cone in hypervelocity flow was conducted in the high-enthalpy shock tunnel T5. A novel flow visualization technique using sodium seeding to increase the sensitivity of conventional interferometric techniques by resonant enhancement of the refractivity of the medium was developed to study its structure. The experiments were designed to cover a large range of specific reservoir enthalpy, ranging from the perfect-gas region to the range where significant oxygen and some nitrogen dissociation and recombination effects may be expected in the boundary layer. Surface heat flux measurements indicate that the transition Reynolds number is approximately the same as that observed in cold hypersonic flow in conventional continuous flow facilities, but significantly lower than that observed in 'quiet' tunnels. No significant effect of reservoir specific enthalpy on transition was observed. The heat flux distribution showed differences between the air and the nitrogen experiments in the laminar regime. These are consistent with the presence of recombination of oxygen at the wall. This view is supported by the fact that this effect is absent in the low-enthalpy region, where the heat flux distribution agrees with the similarity theory.

Germain, P.↗
NASA NTRS1989

Convection and chemistry effects in CVD: A 3-D analysis for silicon deposition

The computational fluid dynamics code FLUENT has been adopted to simulate the entire rectangular-channel-like (3-D) geometry of an experimental CVD reactor designed for Si deposition. The code incorporated the effects of both homogeneous (gas phase) and heterogeneous (surface) chemistry with finite reaction rates of important species existing in silane dissociation. The experiments were designed to elucidate the effects of gravitationally-induced buoyancy-driven convection flows on the quality of the grown Si films. This goal is accomplished by contrasting the results obtained from a carrier gas mixture of H2/Ar with the ones obtained from the same molar mixture ratio of H2/He, without any accompanying change in the chemistry. Computationally, these cases are simulated in the terrestrial gravitational field and in the absence of gravity. The numerical results compare favorably with experiments. Powerful computational tools provide invaluable insights into the complex physicochemical phenomena taking place in CVD reactors. Such information is essential for the improved design and optimization of future CVD reactors.

Gokoglu, S. A.↗
NASA NTRS1972

Dissociative excitation of molecular hydrogen by electron impact.

A pulsed electron beam was employed in the experiment to excite a diffuse gas of hydrogen molecules. The energy resolution of the electron gun permitted careful measurements of the thresholds for the production of slow and fast H(2s) atoms. The experiment was conducted in a vacuum system that facilitated a systematic study of the angular distribution of the fragments in the dissociative excitation process. The results permit the identification of the several excited states that are involved in the production of the H(2s) fragments.

Misakian, M.↗
DOE OSTI2025

Accurate and reliable thermochemistry by data analysis of complex thermochemical networks using Active Thermochemical Tables: the case of glycine thermochemistry

Active Thermochemical Tables (ATcT) were successfully used to resolve the existing inconsistencies related to the thermochemistry of glycine, based on statistically analyzing and solving a thermochemical network that includes >3350 chemical species interconnected by nearly 35 000 thermochemically-relevant determinations from experiment and high-level theory. Here, the current ATcT results for the 298.15 K enthalpies of formation are −394.70 ± 0.55 kJ mol −1 for gas phase glycine, −528.37 ± 0.20 kJ mol −1 for solid α-glycine, −528.05 ± 0.22 kJ mol −1 for β-glycine, −528.64 ± 0.23 kJ mol −1 for γ-glycine, −514.22 ± 0.20 kJ mol −1 for aqueous undissociated glycine, and −470.09 ± 0.20 kJ mol −1 for fully dissociated aqueous glycine at infinite dilution. In addition, a new set of thermophysical properties of gas phase glycine was obtained from a fully corrected nonrigid rotor anharmonic oscillator (NRRAO) partition function, which includes all conformers. Corresponding sets of thermophysical properties of α-, β-, and γ-glycine are also presented.

Active Thermochemical Tables↗
DOE OSTI2020

Promoting the cleavage of C-O bonds at the interface between a metal oxide cluster and a Co(0001) support

As a first step toward the rational design of Co-based catalysts with a higher activity and selectivity, we determine how one can activate a C-O bond at the interface between a metal oxide cluster and a Co(0001) support. The hypothesis here is that the metal ions in metal oxide clusters on a Co(0001) support enhance the adsorption of CO and weaken the C-O bond strength, which can then facilitate the dissociation of the CO reactant. To test this hypothesis, we developed three computational models of Ti4O8/Co(0001), Zr4O8/Co(0001), and Mn8O8/Co(0001). We quantify the CO adsorption behavior at the interface sites between an oxide cluster and the Co(0001) support as well as the corresponding IR spectra. We correlate the computed CO stretch frequencies with their CO adsorption energies, as well as the CO stretch frequency with the C-O bond length, and related these findings to the changes in the chemical bonding in the bound CO. The interface is the most favorable site for CO adsorption. Adsorption results in an increase of the C-O bond length and a decrease in its vibrational frequency. From a chemical bonding analysis, the bond order in CO at this site drops from 3 (in the gas phase) to 1. This decrease in bond order is a necessary precursor stage for CO dissociation. The experimental measurements of the corresponding FTIR spectra support this point. The favorability of CO adsorption at the interface sites is due to an electron transfer from the metal ion in the metal oxide cluster to the O atom in CO. We establish a linear relationship between C-O bond length and CO frequency and this relationship is found to be independent of the support, type of metal oxide cluster, or the adsorption site.

Fischer-Tropsch Synthesis, Heterogeneous Catalysis↗
DOE OSTI2021

Pulse Detonation Engine for Advanced Oxy-Combustion of Coal-Based Fuel for Direct Power Extraction Applications

Pressure gain combustion and magnetohydrodynamic (MHD) systems have the potential to provide a step increase in the efficiency of combined-cycle power plants. Specific advantages include a net pressure increase to the system instead of a pressure drop, the high temperature of the detonation waves can increase the efficiency of power extraction compared to other processes, significant thermal energy can be released in a compact region, and the high velocities of the flow increase extraction of electrical power. In summary, a pressure gain combustor coupled with a MHD has the potential to be transformative. Despite the potential advantages, relatively little research has been conducted considering coupled pressure gain combustion systems with MHD systems. With this background and motivation, the overall goal of this effort was to advance the knowledge, technology, and computational tools associated with coupled detonation and MHD systems. A joint experimental and computational approach was used while seeking to accomplish the goals of this work. Specifically, two pulse detonation engines were developed and used for the experiments to produce detonations. Detonation speeds were measured for a variety of flow and fuel conditions (e.g., methane, propane, with coal particles). Preliminary electrical conductivity measurements were collected. An extensive amount of research was performed to identify sensitivities of detonation behaviors to the presence of combustion products. Computationally, a twofold approach was used in this work. First, a solver was developed for solving the governing equations for a reactive flow with coupled detonation and ionization chemistry. The solver was applied to study the impacts of seed material ionization on detonation. Second, a conservation element-solution element (CE-SE) based numerical solver for detonation studies with a reduced reaction mechanism for oxy-methane combustion was developed and verified on standard test cases. Key findings and contributions from this work are as follows. A system was developed for injecting powderized coal, or other seeding material, into a pulse-detonation system. The influence of a combustion product (i.e., CO 2 ) on detonation behavior was identified. Knowledge gained from this work is applicable to devices such as rotating detonation engines, where combustion products mix with fresh reactants. A system for measuring the electrical conductivity of the exhaust from a pulse-detonation engine was developed. The open-source solver, Clawpack, was extended to solve the reactive Euler equations for simulating detonations. A coupled combustion and ionization chemistry was developed in a single chemical kinetic model for methane oxidation. This model can be used to solve coupled MHD and detonation simulations. It was found that parasitic interactions from ionization chemistry with the magnetic field can reduce the detonation velocity by up to 8%, with a potential impact on power extraction of 15%. It is recommended that interactions between the detonation front and MHD field be considered. Higher gas temperatures and velocities were achieved owing to oxy-fuel detonations. Use of radical dissociation reactions in the reduced reaction mechanism, was found to be critical in predicting detonation temperature and velocity accurately.

01 COAL, LIGNITE, AND PEAT↗
NASA NTRS1972

A program for calculating expansion-tube flow quantities for real-gas mixtures and comparison with experimental results

A computer program written in FORTRAN 4 language is presented which determines expansion-tube flow quantities for real test gases CO2 N2, O2, Ar, He, and H2, or mixtures of these gases, in thermochemical equilibrium. The effects of dissociation and first and second ionization are included. Flow quantities behind the incident shock into the quiescent test gas are determined from the pressure and temperature of the quiescent test gas in conjunction with: (1) incident-shock velocity, (2) static pressure immediately behind the incident shock, or (3) pressure and temperature of the driver gas (imperfect hydrogen or helium). The effect of the possible existence of a shock reflection at the secondary diaphragm of the expansion tube is included. Expansion-tube test-section flow conditions are obtained by performing an isentropic unsteady expansion from the conditions behind the incident shock or reflected shock to either the test-region velocity or the static pressure. Both a thermochemical-equilibrium expansion and a frozen expansion are included. Flow conditions immediately behind the bow shock of a model positioned at the test section are also determined. Results from the program are compared with preliminary experimental data obtained in the Langley 6-inch expansion tube.

Miller, C. G., III↗
NASA NTRS1987

Investigation of hypersonic rarefied flow on a spherical nose of the AOTV

The Navier-Stokes (NS) equations were integrated numerically for investigating the flow characteristics on the forepart of the spherical nose of a space vehicle such as the AOTV or AFE by a modified Accelerated Successive Replacement (ASR) scheme under hypersonic rarefied conditions. Technical feasibility of the mathematical approach was demonstrated by computing the flowfield on a spherical nose under conditions that the AFE encounters at times t = 15 and 20 seconds after its reentry into the atmosphere. Local similar solutions for the merged layer flow along the stagnation line of the sphere were developed. These are correct to the same degree of accuracy as the NS equations. These solutions provided stagnation line boundary conditions for the domain of integration on the spherical noise. Also, a parametric study of the stagnation line solution was made with a view to understand the flow characteristics in tunnels with different ambient fluids. Analytical expressions for surface slip temperature, jump conditions, and concentration level in the presence of the real gas effects at the top of the Knudsen layer were derived and used to calculate the stagnation line flowfield with nonequilibrium dissociation and ionization. A number of graphics were drawn to illustrate the basic physics of the flowfields. The present analysis can be extended to include real gas effects and to bodies of arbitrary shapes. It can further provide boundary conditions for integrating the NS equations in the near wake region.

Jain, Amolak C.↗
DOE OSTI2024

Unraveling the CO Oxidation Mechanism over Highly Dispersed Pt Single Atom on Anatase TiO 2 (101)

Catalysts with noble metals deposited as single atoms on metal oxide supports have recently been studied extensively due to their maximized metal utilization and potential for performing difficult chemical conversions owing to their unique electronic properties. Understanding of the reaction mechanisms on supported single-metal atoms is still limited but is highly important for designing more efficient catalysts. In this study, we report the complexity of the CO oxidation reaction mechanism on Pt single atoms supported on anatase TiO 2 (Pt SA /a-TiO 2 ) by coupling density functional theory (DFT) calculations and microkinetic analysis with kinetic measurements, in situ/operando infrared, and X-ray absorption spectroscopies. Starting from the adsorbed Pt SA occupying an O vacancy induced by reductive pretreatment, we show that CO oxidation follows a complex mechanism consisting of initiation steps to reorganize the active site and multibranch reactive cycles, with the Pt SA /a-TiO 2 catalyst not returning to its initial configuration. The initiation step consists of CO and O 2 adsorption healing the O vacancy, followed by CO oxidation using gas-phase CO to form Pt(CO). The reactive cycle alternates O 2 adsorption and dissociation to oxidize the catalyst to Pt(O)(O)(CO) and branching pathways of competing Langmuir–Hinshelwood (LH)- or Eley–Rideal (ER)-type CO oxidation steps to reduce it again to Pt(CO). In situ/operando infrared experiments, including cryogenic CO adsorption and isotopic CO exchange, confirm the combined involvement of strongly adsorbed CO and gas-phase CO in an Eley–Rideal step along the reaction cycle. Microkinetic modeling shows that Pt single atoms are present in a mixture of Pt(CO), Pt(CO)(O 2 ), Pt(O)(CO)(O 2 ), and Pt(CO)(CO 3 ) structures as the main intermediates during steady-state CO oxidation, all having the C–O vibrational stretch close to the experimentally observed value of 2115 cm –1 . Microkinetic modeling also shows that the fractional orders of CO and O 2 measured experimentally originate from multiple steps with a high degree of rate control and not from a simple competitive adsorption. The results demonstrate the complex reaction pathways that even CO oxidation on a simple single-atom system can follow, providing mechanistic insights for designing efficient Pt-based single-atom catalysts. Here, we further show that microkinetic modeling results are sensitive to changes in energies of intermediate and transition states within errors of density functional theory, which can ultimately lead to incorrect conclusions regarding the reaction pathways and most abundant reaction intermediates if not accounted for by experiments.

36 MATERIALS SCIENCE↗