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Presentation prepared by NNSS Radiography and Advanced Imaging Development (RAID) Project Manager to provide an overview of the project to his collaborators at the Los Alamos National Laboratory (LANL) Proton Radiography (pRad) facility.
This project aims to develop highly compacted microchannel protonic ceramic membrane reactors (HCM-PCMRs) for efficient and cost-effective methane dehydrogenation to aromatics (MDA, e.g., benzene). The integration of single-atom catalysis, electrocatalysis, membrane catalysis, membrane separation, and advanced manufacturing is designed to fulfill this goal. This project's success will ultimately develop a new cost-effective, efficient, and highly compacted infrastructure technology to address the flare and venting issue during oil and gas operations and other gas-to-liquid technologies. The key objectives for the three budget periods (BPs) are as follows.
Proton conduction in acceptor-doped perovskites is fundamentally a vibronic process: mobile H + and D + do not move independently, but dynamically co-vibrate with the surrounding oxygen–metal framework. Direct experimental evidence for this behavior is presented using in situ 119 𝑆𝑛 nuclear resonance vibrational spectroscopy (NRVS) on hydrated, deuterated, and dry 𝐵𝑎𝑆𝑛 1−𝑥 𝑌 𝑥 𝑂 3−𝛿 . Hydration induces systematic redistributions in the Sn-projected phonon density of states (PDOS), including an upshift of the first spectral moment by about 0.4 meV, indicating a stiffening of the extended Sn–O network. H/D isotopic substitution leaves the Sn-projected PDOS largely unchanged, with only subtle isotope-dependent spectral reweighting, demonstrating that protonic degrees of freedom are not localized oscillators but are embedded in collective lattice modes. These results are rationalized using a classical coupled proton–phonon oscillator model that links the observed PDOS variations to changes in effective force constants and vibrational mass terms. The model captures how H + and D + participate in cooperative lattice dynamics rather than forming isolated OH/OD entities. Overall, NRVS probes proton–lattice coupling in ceramic proton conductors and quantitatively describes how protonic defects modulate host lattice dynamics to enable phonon-assisted long-range proton transport.
Proton exchange membrane fuel cells (PEMFCs) with 0.1 and 0.4 mg Pt cm -2 cathode catalyst loadings were separately contaminated with seven organic species: Acetonitrile, acetylene, bromomethane, iso-propanol, methyl methacrylate, naphthalene, and propene. The lower catalyst loading led to larger cell voltage losses at the steady state. Three closely related electrical equivalent circuits were used to fit impedance spectra obtained before, during, and after contamination, which revealed that the cell voltage loss was due to higher kinetic and mass transfer resistances. A significant correlation was not found between the steady-state cell voltage loss and the sum of the kinetic and mass transfer resistance changes. Major increases in research program costs and efforts would be required to find a predictive correlation, which suggests a focus on contamination prevention and recovery measures rather than contamination mechanisms.
The [FeFe]-hydrogenases are enzymes that catalyze the reversible activation of H 2 coupled to the reduction–oxidation of electron carriers. Members of the different taxonomic groups of [FeFe]-hydrogenases display a wide range of preference, or bias, for H 2 oxidation or H 2 production reactions, despite sharing a common catalytic cofactor, or H-cluster. Identifying the properties that control reactivity remains an active area of investigation, and models have emerged that include diversity in the catalytic site coordination environments and compositions of electron transfer chains. The kinetics of proton-coupled electron transfer at the H-cluster might be expected to be a point of control of reactivity. To test this hypothesis, systematic changes were made to the conserved cysteine residue that functions in proton exchange with the H-cluster in the three model enzymes: CaI, CpII, and CrHydA1. CaI and CpII both employ electron transfer accessory clusters but differ in bias, whereas CrHydA1 lacks accessory clusters having only the H-cluster. Changing from cysteine to either serine (more basic) or aspartate (more acidic) modifies the sidechain pKa and thus the barrier for the proton exchange step. The reaction rates for H 2 oxidation or H 2 evolution were surveyed and measured for model [FeFe]-hydrogenases, and the results show that the initial proton-transfer step in [FeFe]-hydrogenase is tightly coupled to the control of reactivity; a change from cysteine to more basic serine favored H 2 oxidation in all enzymes, whereas a change to more acidic aspartate caused a shift in preference toward H 2 evolution. Overall, the changes in reactivity profiles were profound, spanning 10 5 in ratio of the H 2 oxidation-to-H 2 evolution rates. The fact that the change in reactivity follows a common trend implies that the effect of changing the proton-transfer residue pKa may also be framed as an effect on the scaling relationship between the H-cluster di(thiolmethyl)amine (DTMA) ligand pKa and E m values of the H-cluster. Experimental observations that support this relationship, and how it relates to catalytic function in [FeFe]-hydrogenases, are discussed.
Hydration-induced strains in proton-conducting oxides compromise chemo-mechanical stability when these materials are applied in protonic ceramic electrochemical cells. Here, to develop design principles for zero-strain materials, we systematically studied the hydration coefficients of chemical expansion (CCEs) in perovskite (Sr, Ba)(Ce, Zr, Y)O 3–x solid solutions with in situ dilatometry and thermogravimetric analysis in the range of 430–630 °C. By including and decoupling a wide range of tolerance factors and lattice parameters, we were able to identify a minimum in hydration CCEs (0–0.02) at intermediate tolerance factor values (t ≈ 0.95). Conversely, despite expectations of lower CCEs in larger unit cells, no general trend in CCE versus lattice parameter was found, and opposite trends could be seen for Sr(Ce, Zr, Y)O 3–x versus Ba(Ce, Zr, Y)O 3–x separately. In situ neutron diffraction (ND) enabled atomistic insight. Upon decreasing t, chemical strain anisotropy increased, but this trend did not match the U-shaped dependence of macroscopic CCEs on t. Instead, perovskites with intermediate t, hosting intermediate octahedral tilt angles in the nominally dry state, underwent the largest change in the B–O–B angles during hydration. Accommodating hydration through decreasing B–O–B angles is beneficial because it does not result in large lattice parameter changes. We propose an intermediate tolerance factor as a simple structural descriptor to enable near-zero hydration strains in proton-conducting perovskites.
A multi-detector fast neutron radiography panel was built using the previous work on scalable neutron radiography using the IDEAS ROSSPAD readout module. A new aluminum housing was built to accommodate a large number of detectors tiled together. Additional changes to startup and processing code were made to operate the detector as one cohesive unit. Spatial resolution of the full panel using Cs-137 gammas was reported to be 0.42 line pairs per centimeter at 90% MTF and 2.09 line pairs per centimeter at 10% MTF. Here, three neutron radiographs generated using a Cf-252 fission neutron source were used to determine the spatial resolution of the panel for neutrons. The experiments had 90% MTF values of 0.24, 0.3, and 0.27 line pairs per centimeter and 10% MTF values of 1.30, 1.46, and 1.40 line pairs per centimeter. An example neutron radiograph was also used to prove that the radiography panel can perform true neutron radiography.
Radiographic imaging and tomography (RadIT) come in many flavors such as X-ray imaging and tomography (IT), proton IT, neutron IT, muon IT, neutrino IT, etc. We identify five RadIT themes: Physics, Sources, Detectors, Methods, and Data Science, which are integral parts of image interpretation and three-dimensional (3D) tomographic reconstruction. Traditionally, RadIT have been driven by medicine, non-destructive testing, material sciences, and security applications. The latest thrusts of growth come from automation, machine vision, additive manufacturing and virtual reality (‘metaverse’). The five RadIT themes parallel their counterparts in optical IT. Synergies among different forms of RadIT and with optical IT motivate further advances towards multi-modal IT and quantum IT.
Scintillator detectors are an integral component of radiation detection systems for a variety of applications such as medical imaging, accelerator diagnostics, and space science. Typically, a scintillator detector’s response is characterized using gamma sources to understand the detection response to different types of radiation, including charged particle detection. However, there exists a nonlinearity of the amount of light produced from an incident gamma ray of specific energy and the light produced from an incident charged particle of the same energy. This important effect, known as quenching, must be accounted for to interpret energies from charged particles incident on detectors. In this article, we present results of quenching parameterization for two types of cerium-doped inorganic scintillators, Y2SiO5:Ce (YSO:Ce) and Gd3Al2Ga3O12:Ce (GAGG:Ce). We measured the light output from incident proton energies from 1 to 25 MeV using a 3-MV tandem accelerator and two reactions: Au(p,p)Au and 3He(d,p)⁴He. Using gamma-ray sources to calibrate the detectors, we compared the measured electron-equivalent energy versus the incident energy expected. Using an adaptation of the Birks semi-empirical formula, we extracted the Birks parameter (kB) to understand quenching. For one of the GAGG:Ce samples, the kB parameter of 0.0072 [g cm-2 MeV-1] is comparable to a similar study where the value of kB was 0.0065 [g cm-2 MeV-1]. For YSO:Ce, no other kB values were found in the literature. Three different types of GAGG:Ce were used to collect measurements of kB as a function of dopant concentration.
Non-destructive measurements of longitudinal beam profile in non-relativistic hadron accelerators are usually performed with Bunch Shape Monitors that utilize secondary electron emission to reproduce the shape of a primary ion beam. The existing devices, however, have poor electron collection efficiency from the wire and are limited to one dimensional measurements of the phase coordinate. Here, we present the development of a bunch shape monitor with improved performance for proton beams to be used in the Spallation Neutron Source accelerator. This improvement was achieved by adding focusing optics between the wire and the entrance slit, which will also allow measurements over a much higher dynamic range. Here we present the design, simulation and experimental test results of the developed new electron beam guidance system for the existing SNS bunch shape monitor that allowed significant improvement in the collection efficiency.
Proton exchange kinetics plays an important role in governing the performance of intermediate-temperature protonic ceramic electrolysis cells (PCECs) for hydrogen production. Our understanding of the nature of the surface hydration reaction at the single-cell level, however, remains very limited, hampering further efficiency improvements. Here, in this study, we developed a custom operando diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) platform that operates under high temperature and steam conditions with applied bias. Quantitative investigations of surface H 2 O/D 2 O isotope exchange in a BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3−δ (BZCYYb1711) protonic electrolyte-based single cell were conducted under different applied voltages using this DRIFTS platform, to gain molecular-level insight into hydration kinetics. The findings show that the application of an external voltage significantly enhances the surface proton exchange rate, decreasing the apparent activation energy from 29.1 kJ mol −1 at open-circuit voltage (OCV) to 6.8 kJ mol −1 at 1.3 V. In addition, distinct voltage-induced spectral shifts in O–D vibrations point to dynamic changes in surface hydration. These findings demonstrate a sensitive spectroscopic platform for probing interfacial proton processes and reveal strong electrochemical control over surface proton kinetics, offering new opportunities for probing electrolyte hydration behavior in PCECs.
The Second Target Station (STS) at the Spallation Neutron Source (SNS) will address emerging scientific challenges by providing a source of intense cold neutrons to instruments optimized for this source. The STS target will use rotating tungsten blocks and will receive 1.3 GeV proton beam pulses from the SNS accelerator at a repetition rate of 15 Hz. The facility life is planned for 40 years, and each target assembly life is expected to be approximately 10 years. An accurate strain prediction is then critical for fatigue life assessment of STS target blocks because they will be subject to approximately 10 8 beam pulses per lifetime. As an R&D activity, the Los Alamos Neutron Science Center (LANSCE) Weapons Neutron Research (WNR) Target 2 (Blue Room) facility was used to test the strain response of prototypical target blocks to the thermal shock of a proton pulse. The blue room was well suited for a pulsed proton beam impact test of subscale STS target blocks; the 800 MeV proton energy is approximately 60 % of the 1.3 GeV proton energy expected from the SNS accelerator to the STS. The LANSCE Proton Storage Ring (PSR) and SNS are both short-pulse proton beam sources with nominal pulse widths of 250 ns and 661 ns, respectively, so the energy deposition in the target occurs in <1 μs pulse duration. Strain measurements on the outer surface of three target blocks (bare tungsten, tantalum-clad tungsten, niobium-clad tungsten) were recorded for comparison against neutronics and structural simulations. In conclusion, this experiment and the supporting simulations satisfied the following primary research goals for the STS target.
The U.S. Spallation Neutron Source (SNS) is a state-of-the-art neutron scattering facility delivering the world's most intense pulsed neutron beams to a wide array of instruments which are used to conduct investigations in many fields of science and engineering. Neutrons are produced from spallation of liquid Hg by bombardment of short (~1 μs), intense (~35 A) pulses of protons delivered at 60 Hz by a storage ring which is fed by a high-intensity, ~1 GeV H - LINAC. This facility has operated almost continuously since 2006, with ion source performance increasing over those years, and currently providing 50–60 mA of H - ions with a duty-factor of 6% for maintenance-free runs of several months with near 100% availability. Ion source research and development at ORNL has played a key role in enabling and supporting this success: this report provides an update on some of the ongoing ion source research and development efforts which have been undertaken since the previous Negative Ion Beams and Sources (NIBS) conference in 2020. These include significant improvements to H - beam current by extraction from a larger source outlet aperture and improvements to the electron dumping system which should eliminate the gradual loss of electrode voltage over the course of a run which has occasionally impacted SNS operations. Improvement and simplification of the plasma ignition system for the external antenna ion source, a long-standing problem, was also realized. Lastly, RF coupling efficiency was measured for both the SNS internal and external antenna ion sources.
In this work, we established porous metal-organic frameworks (MOFs) as designer conductors of electrons and ions relevant to fundamental research and technological applications. MOFs are porous, crystalline materials composed of organic linkers and inorganic nodes. While most MOFs are insulating with respect to ionic and electronic charge carriers, a number of exceptions have been reported in recent years. Electrically conductive MOFs are highly attractive for applications including electrical energy storage, chemiresistive sensing, and optoelectronics because of their high surface areas and tunable chemical properties. Ion-conducting MOFs are desirable for the synthetically tunable size, shape, and polarity of their pore environments, allowing for the tailored development of solid state electrolytes for metal-ion batteries. We developed systematic strategies for the design of MOFs that conduct ions and electrons. For each objective, we leveraged the versatile chemistry of these materials to obtain frameworks with targeted properties towards electronic or ionic charge carriers. We studied the factors that govern electrical transport in MOFs in order to gain fundamental knowledge of this emerging class of materials. We took several approaches to tackle this problem from multiple angles. Namely, we synthesized and characterized new frameworks, investigated post-synthetic modifications to enhance conductivity, and correlated theory and experiment to uncover new mechanistic findings. These results, which put forth new design principles for conductive MOFs, move the field toward one of the DOE Basic Energy Sciences Grand Challenges: to “design and perfect atom- and energy-efficient synthesis of revolutionary new forms of matter with tailored properties.” In addition to investigating the movement of electrons in MOFs, we also studied the movement of other charged species in MOFs, such as protons, lithium, and magnesium. Proton-conducting frameworks could be appealing materials for solid state electrolytes in fuel cells. In addition, they contain crystallographically defined proton-conducting channels, in contrast with state-of-the-art polymer membranes such as Nafion, which are amorphous. Controlling pore size and polarity in MOFs can thus shed light on proton and other ion transport mechanisms, ultimately enabling the design of more advanced electrolyte materials and potentially novel electrical energy storage materials.
The structure and mechanism of the water-oxidation chemistry that occurs in photosystem II have been subjects of great interest. The advent of X-ray free electron lasers allowed the determination of structures of the stable intermediate states and of steps in the transitions between these intermediate states, bringing a new perspective to this field. The room-temperature structures collected as the photosynthetic water oxidation reaction proceeds in real time have provided important novel insights into the structural changes and the mechanism of the water oxidation reaction. The time-resolved measurements have also given us a view of how this reaction—which involves multielectron, multiproton processes—is facilitated by the interaction of the ligands and the protein residues in the oxygen-evolving complex. These structures have also provided a picture of the dynamics occurring in the channels within photosystem II that are involved in the transport of the substrate water to the catalytic center and protons to the bulk.
Protein kinases transmit chemical signals by phosphorylating substrate proteins, thus regulating a multitude of cellular processes. cAMP-dependent protein kinase (PKA), a prototypical enzyme for the whole kinase family, has been the focus of research for several decades, however, the details of the chemical mechanism of phosphoryl group transfer have remained unknown. We used neutron crystallography to map key proton sites and hydrogen bonding interactions in the PKA catalytic subunit (PKAc) in a product complex containing adenosine diphosphate (ADP) and the phosphorylated high affinity protein kinase substrate (pPKS) peptide. To improve neutron diffraction, we deuterated PKAc allowing us to use very small crystals. In the product complex, the phosphoryl group of pPKS is protonated whereas the catalytic Asp166 is not. H/D exchange analysis of the main-chain amides and comparison with the NMR analysis of PKAc with inhibitor peptide complex revealed exchangeable amides that may distinguish the catalytic and inhibited states.
Laser-driven proton acceleration, as produced during the interaction of a high-intensity (I > 1 × 10 18 W/cm 2 ), short pulse (<1 ps) laser with a solid target, is a prosperous field of endeavor for manifold applications in different domains, including astrophysics, biomedicine and materials science. These emerging applications benefit from the unique features of the laser-accelerated particles such as short duration, intense flux and energy versatility, which allow obtaining unprecedented temperature and pressure conditions. In this paper, we show that laser-driven protons are perfectly suited for producing, in a single sub-ns laser pulse, metallic nanocrystals with tunable diameter ranging from tens to hundreds of nm and very high precision. Our method relies on the intense and very quick proton energy deposition, which induces in a bulk material an explosive boiling and produces nanocrystals that aggregate in a plasma plume composed by atoms detached from the proton-irradiated surface. The properties of the obtained particles depend on the deposited proton energy and on the duration of the thermodynamical process. Suitably controlling the irradiated dose allows fabricating nanocrystals of a specific size with low polydispersity that can easily be isolated in order to obtain a monodisperse nanocrystal solution. Molecular Dynamics simulations confirm our experimental results.
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