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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 NTRS1992

White-Light, Dispersed-Fringe Interferometric Keratometer

Proposed keratometer based on scheme involving spectral dispersal of white-light interference fringes. Instrument operates in "snapshot" mode: no scanning necessary, not necessary to immobilize patient's eye. Insensitive to vibration, involves no phase shifting, and has variable sensitivity. Intended primarily for use in medical assessments of human corneas, also used to measure shapes of animal corneas, lenses, and other aspherical or spherical reflective or partly reflective surfaces.

Hochberg, Eric B.↗
DOE OSTI2017

Optimisation of the prism coupling of optical whispering-gallery-mode microcavities

The methods for increasing the coupling efficiency of a prism with spheroidal microcavities, aimed at exciting whispering-gallery modes, have been analytically investigated. Optimal angles of incidence and incident beam parameters are obtained for a spheroidal cavity. The cavity eigenfrequency shift caused by the presence of a prism and the introduced loss by it is calculated. (resonators)

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2018

Transient modes of zeolite surface growth from 3D gel-like islands to 2D single layers

Zeolite crystallization occurs by multifaceted processes involving molecule attachment and nonclassical pathways governed by the addition of amorphous precursors. Here, we use scanning probe microscopy to monitor zeolite LTA crystallization in situ with a spatiotemporal resolution that captures dynamic processes in real time. We report a distinctive pathway involving the formation of gel-like islands from supersaturated solutions comprised of (alumino)silicate molecules. Three-dimensional assembly and evolution of these islands constitutes a unique mode of growth that differs from classical theories. Time-resolved imaging also reveals that growth can occur by (nearly) oriented attachment. At later stages of crystallization, a progressive transition to lower supersaturation shifts growth to a layered mechanism involving two-dimensional nucleation and spreading of layers. Here, we show that LTA crystallization occurs by multiple pathways, thereby reconciling putative hypotheses of growth mechanisms while also highlighting new modes of nonclassical crystallization that may prove relevant to other zeolites and related materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRSDate not supplied

Towards Simultaneous Multi-Parameter Measurements Using Burst-Mode Frequency-Scanning Planar Laser-Induced Fluorescence

While planar laser-induced fluorescence (PLIF) can provide valuable flow visualization, there are many challenges in extracting quantitative measurements from the fluorescence intensity. To overcome the multi-parameter dependence of the signal intensity, frequency scanning planar laser-induced fluorescence (FS-PLIF) provides the potential for 2D temperature, pressure, and velocity measurements by spectrally resolving the excitation spectrum of one or more fluorescence transitions to extract the Doppler shift, Doppler- and collisional-broadening of absorption lines, and the relative signal intensities of multiple transitions. This work aims to characterize a burst-mode FS-PLIF system consisting of a Spectral Energies, LLC burst-mode laser coupled with a Spectral Energies, LLC optical parametric oscillator using nitric oxide (NO) static pressure cell measurements. The effect of the OPO cavity on intensity fluctuations during frequency-scanning is investigated. A NO PLIF model is implemented to investigate the feasibility of property measurements using single- and two-NO-line scans.

burst-mode laser↗
DOE OSTI2015

Impact of inward turbulence spreading on energy loss of edge-localized modes

Nonlinear two-fluid and gyrofluid simulations show that an edge localized modes(ELM) crash has two phases: fast initial crash of ion temperature perturbation on the Alfvén time scale and slow turbulence spreading. The turbulencetransport phase is a slow encroachment of electron temperature perturbation due to the ELM event into pedestal region. Because of the inward turbulence spreading effect, the energy loss of an ELM decreases when density pedestal height increases. The Landau resonance yields the different cross phase-shift of ions and electrons. A 3 + 1 gyro-Landau-fluid model is implemented in BOUT++ framework. As a result, the gyrofluid simulations show that the kinetic effects have stabilizing effects on the ideal ballooning mode and the energy loss increases with the pedestal height.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2016

Theoretical study of NMR, infrared and Raman spectra on triple-decker phthalocyanines

Electronic structures and magnetic properties of multi-decker phthalocyanines were studied by theoretical calculation. Electronic structures, excited processes at multi-states, isotropic chemical shifts of {sup 13}C, {sup 14}N and {sup 1}H-nuclear magnetic resonance (NMR), principle V-tensor in electronic field gradient (EFG) tensor and asymmetry parameters (η), vibration mode in infrared (IR) and Raman spectra of triple-decker phthalocyanines were calculated by density functional theory (DFT) and time-dependent DFT using B3LYP as basis function. Electron density distribution was delocalized on the phthalocyanine rings with electron static potential. Considerable separation of chemical shifts in {sup 13}C, {sup 14}N and {sup 1}H-NMR was originated from nuclear spin interaction between nitrogen and carbon atoms, nuclear quadrupole interaction based on EFG and η of central metal under crystal field. Calculated optical absorption at multi-excited process was derived from overlapping π-orbital on the phthalocyanine rings. The vibration modes in IR and Raman spectra were based on in-plane deformation and stretching vibrations of metal-ligand coordination bond on the deformed structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Decadal Shift of NAO-Linked Interannual Sea Level Variability along the U.S. Northeast Coast

Recent studies have linked interannual sea level variability and extreme events along the U.S. northeast coast (NEC) to the North Atlantic Oscillation (NAO), a natural internal climate mode that prevails in the North Atlantic Ocean. The correlation between the NAO index and coastal sea level north of Cape Hatteras was weak from the 1960s to the mid-1980s, but it has markedly increased since around 1987. The causes for the decadal shift remain unknown. Yet understanding the abrupt change is vital for decadal sea level prediction and is essential for risk management. Here we use a robust method, the Bayesian dynamic linear model (DLM), to explore the nonstationary NAO impact on NEC sea level. The results show that a spatial pattern change of NAO-related winds near the NEC is a major cause of the NAO–sea level relationship shift. A new index using regional sea level pressure is developed that is a significantly better predictor of NEC sea level than is the NAO and is strongly linked to the intensity of westerly winds near the NEC. Finally, these results point to the vital importance of monitoring regional changes of wind and sea level pressure patterns, rather than the NAO index alone, to achieve more accurate predictions of sea level change along the NEC.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2014

High Pressure Sensing and Dynamics Using High Speed Fiber Bragg Grating Interrogation Systems

Fiber Bragg gratings (FBGs) are developing into useful sensing tools for measuring high pressure dynamics in extreme environments under shock loading conditions. Approaches using traditional diode array coupled FBG interrogation systems are often limited to readout speeds in the sub-MHz range. For shock wave physics, required detection speeds approaching 100 MHz are desired. We explore the use of two types of FBG sensing systems that are aimed at applying this technology as embedded high pressure probes for transient shock events. Both approaches measure time resolved spectral shifts in the return light from short (few mm long) uniform FBGs at 1550 nm. In the first approach, we use a fiber coupled spectrometer to demultiplex spectral channels into an array (up to 12) of single element InGaAs photoreceivers. By monitoring the detectors during a shock impact event with high speed recording, we are able to track the pressure induced spectral shifting in FBG down to a time resolution of 20 ns. In the second approach, developed at the Special Technologies Lab, a coherent mode-locked fiber laser is used to illuminate the FBG sensor. After the sensor, wavelength-to-time mapping is accomplished with a chromatic dispersive element, and entire spectra are sampled using a single detector at the modelocked laser repetition rate of 50 MHz. By sampling with a 12 GHz InGaAs detector, direct wavelength mapping in time is recorded, and the pressure induced FBG spectral shift is sampled at 50 MHz. Here, the sensing systems are used to monitor the spectral shifts of FBGs that are immersed into liquid water and shock compressed using explosives. In this configuration, the gratings survive to pressures approaching 50 kbar. We describe both approaches and present the measured spectral shifts from the shock experiments.

fiber Bragg grating sensors, shockwave diagnostics↗
DOE OSTI2014

Progress in understanding the enhanced pedestal H-mode in NSTX

The paper describes the enhanced pedestal (EP) H-mode observed in the National Spherical Torus Experiment (NSTX). The defining characteristics of EP H-mode are given, namely i)transition after the L- to H-mode transition, ii) region of very steep ion temperature gradient, and iii) associated region of strong rotational shear. A newly observed long-pulse EP H-mode example shows quiescent behavior for as long as the heating and current drive sources are maintained. Cases are shown where the region of steep ion temperature gradient is located at the very edge, and cases where it is shifted up to 10 cm inward from the plasma edge; these cases are united by a common dependence of the ion temperature gradient on the toroidal rotation frequency shear. EP H-mode examples have been observed across a wide range of q95 and pedestal collisionality. No strong changes in the fluctuation amplitudes have been observed following the eP H-mode transition, and transport analysis indicates that the ion t hermal transport is comparable to or less than anticipated from a simple neoclassical transport model. Cases are shown where EP H-modes were reliably generated, through these low-q95 examples were difficult to sustain. A case where an externally triggered ELM precipitates the transition to EP H-mode is also shown, though an initial experiment designed to trigger EP-H-modes in this fashion was successful.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2014

Progress In Understanding The Enhanced Petestal H-mode In NSTX

This paper describes the enhanced pedestal (EP) H-mode observed in the National Spherical Torus Experiment (NSTX). The defining characteristics of EP H-mode are given, namely i) transition after the L- to H-mode transition, ii) region of very steep ion temperature gradient, and iii) associated region of strong rotational shear. A newly observed long-pulse EP H-mode example shows quiescent behavior for as long as the heating and current drive sources are maintained. Cases are shown where the region of steep ion temperature gradient is located at the very edge, and cases where it is shifted up to 10 cm inward from the plasma edge; these cases are united by a common dependence of the ion temperature gradient on the toroidal rotation frequency shear. EP H-mode examples have been observed across a wide range of q 95 and pedestal collisionality. No strong changes in the fluctuation amplitudes have been observed following the eP H-mode transition, and transport analysis indicates that the ion thermal transport is comparable to or less than anticipated from a simple neoclassical transport model. Cases are shown where EP H-modes were reliably generated, through these low-q 95 examples were difficult to sustain. A case where an externally triggered ELM precipitates the transition to EP H-mode is also shown, though an initial experiment designed to trigger EP-H-modes in this fashion was successful.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
NASA NTRS2010

A Comparison Between Orion Automated and Space Shuttle Rendezvous Techniques

The Orion spacecraft will replace the space shuttle and will be the first human spacecraft since the Apollo program to leave low earth orbit. This vehicle will serve as the cornerstone of a complete space transportation system with a myriad of mission requirements necessitating rendezvous to multiple vehicles in earth orbit, around the moon and eventually beyond . These goals will require a complex and robust vehicle that is, significantly different from both the space shuttle and the command module of the Apollo program. Historically, orbit operations have been accomplished with heavy reliance on ground support and manual crew reconfiguration and monitoring. One major difference with Orion is that automation will be incorporated as a key element of the man-vehicle system. The automated system will consist of software devoted to transitioning between events based on a master timeline. This effectively adds a layer of high level sequencing that moves control of the vehicle from one phase to the next. This type of automated control is not entirely new to spacecraft since the shuttle uses a version of this during ascent and entry operations. During shuttle orbit operations however many of the software modes and hardware switches must be manually configured through the use of printed procedures and instructions voiced from the ground. The goal of the automation scheme on Orion is to extend high level automation to all flight phases. The move towards automation represents a large shift from current space shuttle operations, and so these new systems will be adopted gradually via various safeguards. These include features such as authority-to-proceed, manual down modes, and functional inhibits. This paper describes the contrast between the manual and ground approach of the space shuttle and the proposed automation of the Orion vehicle. I will introduce typical orbit operations that are common to all rendezvous missions and go on to describe the current Orion automation architecture and contrast it with shuttle rendezvous techniques and circumstances. The shuttle rendezvous profile is timed to take approximately 3 days from orbit insertion to docking at the International Space Station (ISS). This process can be divided into 3 phases: far-field, mid-field and proximity operations. The far-field stage is characterized as the most quiescent phase. The spacecraft is usually too far to navigate using relative sensors and uses the Inertial Measurement Units (IMU s) to numerically solve for its position. The maneuvers are infrequent, roughly twice per day, and are larger than other burns in the profile. The shuttle uses this opportunity to take extensive ground based radar updates and keep high fidelity orbit states on the ground. This state is then periodically uplinked to the shuttle computers. The targeting solutions for burn maneuvers are also computed on the ground and uplinked. During the burn the crew is responsible for setting the shuttle attitude and configuring the propulsion system for ignition. Again this entire process is manually driven by both crew and ground activity. The only automatic processes that occur are associated with the real-time execution of the burn. The Orion automated functionality will seek to relieve the workload of both the crew and ground during this phase

Ruiz, Jose O,↗
NASA NTRS2022

Spatial Characterization of PACE OCI ETU Using Time-Delay Mode

The OCI (Ocean Color Instrument) is the main sensor on the upcoming PACE (Plankton Aerosol Cloud ocean Ecosystem) mission. OCI has two hyperspectral CCD sensors covering 340nm to 885nm and 9 SWIR (Short Wave IR) bands from 940nm to 2260nm. SWIR bands have nominal 1km ground pixel size and CCD bands have native 1/8 km ground pixel size in diagnostic mode that will be aggregated into 1km pixels to improve SNR and meet the data rate constraints. OCI has a rotating telescope that is synchronized to the readout of the CCD and SWIR detectors. Full pre-launch system level testing for the OCI ETU (Engineering Test Unit) was completed in June 2021.With time-delayed scan mode, a sub-pixel level time-delay step is applied to the detector readout. This sub-pixel level time-delay step causes a sub-pixel level shift in the start of the data collection. After collecting time-delay step scans with different step sizes, a scan profile with sub-pixel resolution can be constructed. 1/8 and 1/4 of CCD pixel resolutions were achieved using this mode. In this paper, the OCI time-delayed scan mode will be described as well as how it was used to calculate OCI’s high spatial resolution PSF (Point Spread Function), IFOV (instantaneous Field of View), MTF (Modulation Transfer Function), and BBR (Band to Band Registration).

PACE↗
DOE OSTI2023

Quantification of Energy Savings and Demand Reduction for a Heat Pump Integrated with Thermal Energy Storage (Final Report)

To mitigate the variation in demand on the electric grid, thermal energy storage (TES) is an alternative to electric batteries or installing new peaking power plants. Stakeholders and policy makers across the United States have expressed interests in promoting TES, as demonstrated by the US Department of Energy’s Grid-Interactive Efficient Buildings program and the efforts of various state legislatures. However, the cost value provided by TES are unclear. If reliable cost benefits were determined, stakeholders would have a clearer picture of the financial returns that can be gained from their investment in TES. The study in this report is conducted by ORNL with collaboration with Emerson the Helix Innovation Center. In the first part of this report, EnergyPlus was used to perform whole-building simulations for two residential buildings in Indianapolis and Atlanta. The HVAC system in both buildings were equipped with phase change material TES. The TES tank was charged in off-peak hours and discharged in peak hours to perform load shifting. First, the economic value implied by existing time-of-use (TOU) rates offered by utility companies was analyzed via whole-building simulation. Second, existing demand reduction (DR) incentives sourced from 3 different electrical grid administrators (i.e., California, Texas, and New England region) were surveyed to determine their implied value. The study suggests that the traditional value analysis that focuses on ROI for the building owner significantly undervalues TES technology making economic viability difficult. A more comprehensive value analysis that includes peak demand management and deferred capital for peaking power plants shows that TES should be economically viable but here the value is greater for the utility and requires large market penetration and aggregation to fully realize the benefits. Therefore, to facilitate commercialization, new business models are needed that include a broader range of stakeholders and distribute the value of TES proportionally. In the 2 nd part of this project, the benefits of a novel phase change material (PCM) integrated heat pump configuration were evaluated via detailed component based simulation. A one-dimensional PCM heat exchanger model which discretizes the PCM tank and refrigerant tubes into small control volumes is developed. Each control volume can have different PCM temperatures, PCM properties, and heat transfer coefficients. The PCM tank is charged by a wrapped tank condenser and discharged by an internal refrigerant coil. The PCM heat exchanger model is integrated into DOE/ORNL Heat Pump Design Model for heat pump system simulation. To demonstrate the performance of the PCM integrated heat pump, a case study in Chicago was performed. A Time-of-Use utility structure-based control strategy is implemented to schedule the PCM tank charging and discharging mode switching. Compared with a conventional electric heat pump, the PCM integrated heat pump shows superior performance on load shifting and utility cost reduction. As a result, the proposed system demonstrates 24.6% utility saving for cooling application and 25.8% utility saving for heating application.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2026

Exploring Local Vibrational Structure in Protein-Bound Chlorophyll a: Isotope-Enrichment Experiments and Electrostatic Analysis

Local chlorophyll (Chl) vibrations play an essential role in biological photosynthesis by facilitating rapid energy transfer between pigments. In research studies, they also provide a useful spectroscopic probe of the local protein environment that surrounds each pigment. However, measuring the complete vibrational absorption spectrum of a protein-bound Chl molecule is much more difficult than, for example, Chl in neat solvent due to overlap with protein vibrations that typically drown out Chl vibrational features. Resonance Raman and fluorescence spectroscopies provide a way around this problem for Franck–Condon active vibrations, but these often rely on cryogenic measurement conditions and fail to capture vibrational signatures from, e.g., ester-group vibrations that lack coupling to a convenient electronic transition. In the present contribution, we use 13 C-enrichment of the protein backbone to shift protein background signals to lower frequency, providing a largely clean spectral window in which to study local Chl a C═O stretch modes. A room-temperature absorption spectrum for Chl a in the water-soluble chlorophyll protein (WSCP) of Lepidium virginicum is thus extracted as a difference between protein-plus-pigment and protein-only vibrational spectra. Excellent agreement in the molecular fingerprint region with the vibrational spectrum of Chl a in organic solvents confirms that the resulting spectrum represents the response of the protein-bound Chl a molecule. Furthermore, the ester group resonance is observed to shift in response to the S53P mutation that eliminates a 17 3 ester group hydrogen bond from the protein environment. Finally, we analyze these experimental results using MD-based electrostatic analysis, finding that electric-field mapping at the C atom of the ester group provides a satisfactory explanation for the observed frequency shifts between organic solvent and protein environment. MD analysis further suggests that a red-shifted ester peak observed experimentally for the S53P mutant results from solvation of the 17 3 Chl ester group due increase water penetration into the Chl-binding pocket relative to wild-type WSCP. Here, we anticipate that these results will prove useful both for benchmarking future simulation work and as a reference for interpreting Chl vibrational spectra as a probe of pigment–protein interactions.

14 SOLAR ENERGY↗
DOE OSTI2023

Multi-parameter distributed fiber optic sensing using double-Brillouin peak fiber in Brillouin optical time domain analysis

In this paper, we demonstrate a multi-parameter fiber sensing system based on stimulated Brillouin scattering in a double-Brillouin peak specialty fiber with enhanced Brillouin gain response. The amplitude level of the second Brillouin gain peak, which originated from the higher-order acoustic modes, has been improved with an approximately similar amplitude level to the first Brillouin gain peak from the fundamental acoustic mode. Compared to other multi-Brillouin peak fibers presented in the literature, the proposed fiber significantly reduces the measured Brillouin frequency shift error, thus improving strain and temperature accuracies. By utilizing the sensitivity values of the strain and temperature associated with each Brillouin gain spectrum (BGS) peak, a successful discriminative measurement of strain and temperature is performed with an accuracy of ±13 μɛ, and ±0.5 °C, respectively. The proposed double-Brillouin peak fiber appears to be a possible alternative to other multi-BGS peak fibers, for instance, large effective area fiber and dispersion compensating fibers, which are inherently accompanied by large measurement errors due to the weak Brillouin gain values originating from the higher-order acoustic modes. The demonstrated results show different strain and temperature coefficients of 47 kHz/µɛ, 1.15 MHz/°C for peak 1 and 51 kHz/µɛ, 1.37 MHz/°C for peak 2. Moreover, the enhanced BGS peak gains having nearly the same amplitude levels enable the discriminative measurement of strain and temperature. Such fibers in Brillouin interrogation eliminate the need for complex monitoring setups and reduce measurement errors. We recommend that for long-distance natural gas pipeline monitoring, where discriminative strain and temperature measurement is crucial, the proposed double-Brillouin peak fiber can be highly beneficial.

47 OTHER INSTRUMENTATION↗
DOE OSTI2019

Growth, Characterization and High-Field Magneto-Conductivity of Co{sub 0.1}Bi{sub 2}Se{sub 3} Topological Insulator

We report the crystal growth as well as transport properties of Co added Bi{sub 2}Se{sub 3} (Co{sub 0.1}Bi{sub 2}Se{sub 3}) single crystals. The values of the lattice parameters for pure and Co added sample were nearly the same. The Raman spectroscopy displayed slightly higher Raman shift of corresponding A{sub 1g}{sup 1}, Eg{sup 2}, and A{sub 1g}{sup 2} vibrational modes for Co{sub 0.1}Bi{sub 2}Se{sub 3}, and the resistivity curves with and without applied magnetic field show a metallic behavior. Both the crystals were subjected to magneto-resistance (MR) measurements under applied fields of 14 T. The value of MR is found to decrease from about 380% (5 K, 14 T) for Bi{sub 2}Se{sub 3} to 200% for Co{sub 0.1}Bi{sub 2}Se{sub 3}. To elaborate the transport properties of pure and Co added Bi{sub 2}Se{sub 3} crystals, the magneto-conductivity is fitted to the HLN (Hikami-Larkin-Nagaoka) equation, and it is found that the charge conduction is mainly dominated by surface-driven WAL (weak anti-localization) with negligible bulk WL (weak localization) contribution in both crystals alike. The MH curves of Co{sub 0.1}Bi{sub 2}Se{sub 3} crystal at different temperatures displayed a combination of both ferromagnetic and diamagnetic behavior. On the other hand, the electron paramagnetic resonance (EPR) revealed that pure Bi{sub 2}Se{sub 3} is diamagnetic, whereas Co orders ferromagnetically with resonating field around 3422 Oe at room temperature. The calculated value of Lande “g” factor is around 2.04 ± 0.05. Summarily, the short letter discusses the interesting magneto-conductivity and complex magnetism of Co in Co{sub 0.1}Bi{sub 2}Se{sub 3}.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2018

Crystal structure of the chloroplast RNA editing factor MORF2

Highlights: • Crystal structure of MORF2 is determined at 2.4 Å. • MORF2 forms dimer through hydrophobic interaction. • Dimerization interface of MORF2 overlaps with its PPR interacting site. • A dimer-to-monomer transition is implicated for MORF2's role in RNA editing. RNA editing is a post-transcription process that alters the genetic information on RNA molecules. In plastids and mitochondria of flowering plants, the multiple organellar RNA editing factors (MORFs) interact with the PLS-type pentatricopeptide repeat (PPR) proteins and participate in RNA editing of cytidine-to-uridine conversion. The PPR proteins recognize cytidine targets around the editing sites, and the MORF proteins modulate the RNA-binding activity of the PPR proteins. Here, we report the structure of the Arabidopsis thaliana chloroplast MORF2 at 2.4 Å resolution. The structure, adopting typical MORF-box fold as observed in mitochondrial MORF1 and chloroplast MORF9, reveals an MORF1-like dimerization mode. The difference between the two dimerization modes can be attributed to F157 (corresponding F162 in MORF1 and W160 in MORF9), which causes a 60° shift upon dimerization. This observation, together with the PPR–MORF2 model, suggests a dimer-to-monomer transition during RNA editosome formation.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2022

Competitive Adsorption of NH 3 and H 2 O in Metal–Organic Framework Materials: MOF-74

Elucidating the interaction between coadsorbed H 2 O and NH 3 in metal–organic frameworks (MOFs) is of paramount importance to uncover mechanistic details of their competitive coadsorption behavior as well as to guide the design of new materials for enhanced NH 3 adsorption in humid environments. Nevertheless, molecular competition between NH 3 and H 2 O within the confined nanopores of MOFs was rarely explored and is poorly understood due to challenges in characterization. Here, we combine in situ infrared spectroscopy with ab initio calculations to unveil the competition of NH 3 and H 2 O for occupying active adsorption sites in the representative MOF-74 material by analyzing the kinetics and energetics of the molecular exchange process. We find that at a high NH 3 /H 2 O ratio, the incoming NH 3 is capable of displacing metal-bound H 2 O and moving it to secondary adsorption sites due to the stronger binding of NH 3 compared with H 2 O. Interestingly, the reverse process of H 2 O displacing metal-bound NH 3 is also possible upon increasing water concentration. Our calculations show that H 2 O exchanging the preabsorbed NH 3 at the metal site is driven not only by a reduced kinetic barrier but also by a favorable energetical state resulting from the formation of water clusters at metal sites and intermolecular H-bonding between the metal-coordinated H 2 O and displaced NH 3 . Our finding emphasizes that the description of molecular occupation in MOFs at equilibrium cannot simply be established by comparing molecules’ binding energies at their strongest binding sites derived by single-component measurements; rather, intermolecular interactions can greatly affect molecular distribution at equilibrium. Furthermore, we show that vibrational modes of adsorbed NH 3 are markedly perturbed upon contact with water molecules, accompanied by a large frequency shift (>30 cm –1 ) and considerable intensity decrease, which arises from the freezing of NH 3 vibrations by coadsorbed H 2 O. As a result, the mechanistic insight obtained through our study sheds light on molecular coadsorption processes in MOFs and helps to assess NH 3 removal efficiency of MOFs containing open-metal sites under realistic conditions, particularly in the presence of humidity.

36 MATERIALS SCIENCE↗