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At least 109 records · Page 6

Laboratory Apparatus Generates Dual-Species Cold Atomic Beam

A laser cooling apparatus that generates a cold beam of rubidium and cesium atoms at low pressure has been constructed as one of several intermediate products of a continuing program of research on laser cooling and atomic physics. Laser-cooled atomic beams, which can have temperatures as low as a microkelvin, have been used in diverse applications that include measurements of fundamental constants, atomic clocks that realize the international standard unit of time, atom-wave interferometers, and experiments on Bose-Einstein condensation. The present apparatus is a prototype of one being evaluated for use in a proposed microgravitational experiment called the Quantum Interferometric Test of Equivalence (QuITE). In this experiment, interferometric measurements of cesium and rubidium atoms in free fall would be part of a test of Einstein s equivalence principle. The present apparatus and its anticipated successors may also be useful in other experiments, in both microgravity and normal Earth gravity, in which there are requirements for dual-species atomic beams, low temperatures, and low pressures. The apparatus includes a pyramidal magneto-optical trap in which the illumination is provided by multiple lasers tuned to frequencies characteristic of the two atomic species. The inlet to the apparatus is located in a vacuum chamber that contains rubidium and cesium atoms at a low pressure; the beam leaving through the outlet of the apparatus is used to transfer the atoms to a higher-vacuum (lower-pressure) chamber in which measurements are performed. The pyramidal magneto-optical trap is designed so that the laser cooling forces in one direction are unbalanced, resulting in a continuous cold beam of atoms that leak out of the trap (see figure). The radiant intensity (number of atoms per unit time per unit solid angle) of the apparatus is the greatest of any other source of the same type reported to date. In addition, this is the first such apparatus capable of producing a slow, collimated beam that contains two atomic species at the same time.

Thompson, Robert↗

Atomic Magnetometry Using a Metasurface Polarizing Beamsplitter in Silicon-on-Sapphire

Here, we demonstrate atomic magnetometry using a metasurface polarizing beamsplitter fabricated on a silicon-on-sapphire (SOS) platform. The metasurface splits a beam that is near-resonant with the rubidium atoms (795 nm) into orthogonal linear polarizations, enabling the measurement of magnetically sensitive circular birefringence in rubidium vapor through balanced polarimetry. We incorporated the metasurface into an atomic magnetometer based on nonlinear magneto-optical rotation and measured subnanotesla sensitivity, which is limited by low-frequency technical noise and transmission loss through the metasurface. To our knowledge, this work represents the first demonstration of SOS nanophotonics for atom-based sensing and paves the way for highly integrated, miniaturized atomic sensors with enhanced sensitivity and portability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Vapor-Cell-Based Atomic Electrometry for Detection Frequencies below 1 kHz

Rydberg-assisted atomic electrometry using alkali-metal atoms contained inside a vacuum environment for detecting external electric fields at frequencies below a few kilohertz has been quite challenging due to the low-frequency electric-field-screening effect that is caused by the alkali-metal atoms adsorbed on the inner surface of the container. In this work, we report a very slow electric-field-screening phenomenon with a timescale up to the order of seconds on a rubidium-vapor cell that is made of monocrystalline sapphire. Furthermore, using this sapphire rubidium-vapor cell with an optically induced, internal bias electric field, we demonstrate vapor-cell-based, low-frequency atomic electrometry that responds to the electric field strength linearly. Limited by the given experimental conditions, this demonstrated atomic electrometer uses an active volume of 11 mm 3 and delivers a spectral noise floor of around 0.34 mV/m √Hz and a 3-dB low cutoff frequency of around 770 Hz inside the vapor cell. This work investigates a regime of vapor-cell-basedatomic electrometry that was seldom studied before, which may enable more applications that use atomicelectric-field-sensing technology.

74 ATOMIC AND MOLECULAR PHYSICS↗

Cation Data for the East River Watershed, Colorado (2014-2025)

This data package contains mean values for cation concentration for water samples taken from the East River Watershed in Colorado. Inductively coupled plasma mass spectrometry (ICP-MS) has been used to measure the concentrations of elements of interest simultaneously for the East River Watershed, Colorado groundwater and surface water samples to inform insights on the biogeochemistry processes within the watershed. The East River is part of the Watershed Function Scientific Focus Area (WFSFA) located in the Upper Colorado River Basin, United States. For samples collected prior to 06-16-2021, the instrumentation, Elan DRC II, PerkinElmer SCIEX, automatically switches among the three models necessary to analyze all 37 elements. These 37 elements include: (1) Lithium (Li), Beryllium (Be), Boron (B), Sodium (Na), Magnesium (Mg), Aluminium (Al), Silicon (Si), Phosphorus (P), Titanium (Ti), Cobalt (Co), Nickel (Ni), Copper (Cu), Zinc (Zn), Germanium (Ge), Arsenic (As), Rubidium (Rb), Strontium (Sr), Zirconium (Zr), Molybdenum (Mo), Silver (Ag), Cadmium (Cd), Tin (Sn), Antimony (Sb), Caesium (Cs), Barium (Ba), Europium (Eu), Lead (Pb), Thorium (Th), Uranium (U) using standard model, argon Ar as reaction gas, (2) Potassium (K), Calcium (Ca), Vanadium (V), Chromium (Cr), Manganese (Mn), Iron (Fe) using dynamic reaction cell (DRC) model, ammonia NH3 as reaction gas, and (3) Phosphorus (P) and Selenium (Se) using DRC model, oxygen O2 as reaction gas. Note for the samples with higher concentrations of chloride (Cl-), asenic (As) concentrations were analysed with DRC model (oxygen O2 as reaction gas) to avoid the interference of chloride. For samples collected on and after 06-16-2021, an advanced Agilent 8900 triple quadrupole inductively coupled plasma mass spectrometry system (Agilent 8900 QQQ ICP-MS, Agilent Technologies) has been used to measure the concentrations of interested 36 elements simultaneously for environmental samples, including (1) Lithium (Li), Beryllium (Be) and Boron (B) using standard no gas mode, (2) Sodium (Na), Magnesium (Mg), Aluminium (Al) Phosphorus (P), Potassium (K), Chromium (Cr), Manganese (Mn), Iron (Fe), Cobalt (Co), Nickel (Ni), Copper (Cu), Zinc (Zn), Germanium (Ge), Arsenic (As), Rubidium (Rb), Strontium (Sr), Zirconium (Zr), Molybdenum (Mo), Silver (Ag), Cadmium (Cd), Tin (Sn), Antimony (Sb), Cesium (Cs), Barium (Ba), Europium (Eu), Lead (Pb), Thorium (Th) and Uranium (U) using standard helium (He) collision mode, (3) Titanium (Ti) and Vanadium (V) using high Energy (HEHe) helium (He) collision mode, and (4) Silicon (Si), Calcium (Ca) and Selenium (Se) using standard H2 reaction mode. All samples were prepared/diluted with 2% (v/v) ultrapure nitric acid in Milli-Q water (18.2 mega ohm-cm), and analyzed under a rigorous quality assurance and quality control (QA/QC) process. This data package contains (1) a zip file (cation_data_2014_2025.zip) containing a total of 5,849 files: 5.848 data files of cation data from across the Lawrence Berkeley National Laboratory (LBNL) Watershed Function Scientific Focus Area (SFA) which is reported in .csv files per location and a locations.csv (1 file) with latitude and longitude for each location; (2) a file-level metadata (v6_20260901_flmd.csv) file that lists each file contained in the dataset with associated metadata; (3) a data dictionary (v6_20260901_dd.csv) file that contains terms/column_headers used throughout the files along with a definition, units, and data type; (4) PDF and docx files for the detemination of Method Detection Limits (MDLs) for ICP-MS PerkinElmer DRC II instrumentation (Detemination_of_Method_Detection_Limits__MDLs__for_ICP_MS__PerkinElmer_Elan_DRC_II__LBL_Bldg74_Lab214D) for samples before November 2021; (5) PDF and docx files for the determination of MDLs for ICP-MS Agilent 8900 QQQ instrumentation (ICP_MS_Analysis_detection_limits_and_QA_QC_WenmingDong_updated_2026-08-06) for samples November 2021 and onward. Missing values within the anion data files are noted as either "-9999" or "0.0" for not detectable (N.D.) data. There are a total of 113 locations containing cation data. Update on 2021-04-11: Added Detemination of Method Detection Limits (MDLs) for ICP-MS document, which can be accessed as a PDF or with Microsoft Word. Update on 2022-06-10: versioned updates to this dataset was made along with these changes: (1) updated cation data for all locations up to 2021-12-31, (2) removal of units from column headers in datafiles, (3) added row underneath headers to contain units of variables, (4) removed suffix and prefix on two variables (“aqberylliumion_asberyllium” and “aqlithiumion_aslithium”), (5) added -9999 for empty numerical cells, and (6) the addition of the file-level metadata (flmd.csv) and data dictionary (dd.csv) were added to comply with the File-Level Metadata Reporting Format. Update on 2022-09-09: Updates were made to reporting format specific files (file-level metadata and data dictionary) to correct swapped file names, add additional details on metadata descriptions on both files, add a header_row column to enable parsing, and add version number and date to file names (v2_20220909_flmd.csv and v2_20220909_dd.csv). Update on 2023-08-08: Updates were made to both the data files and reporting format specific files. New available anion data was added, up until 2023-01-05. The file level metadata and data dictionary files were updated to reflect the additional data added. Update on 2024-03-11: Updates were made to both the data files and reporting format specific files. New available anion data was added, up until 2023-10-16. Further, revisions to the data files were made to remove incorrect data points (from 1970 and 2001). The reporting format specific files were updated to reflect the additional data added. Updated versions of the PDF and docx files for determination of MDLs for ICP-MS data were added to this dataset for samples starting in November 2021. Update on 2025-05-15: Updates were made to both the data files and reporting format specific files. New available cation data was added, up until the end of WY2024 (September 30, 2024). International Generic Sample Numbers (IGSNs), when registered, were added to the data files. The reporting format specific files were updated to reflect the additional data added. Update on 2026-09-01: Updates were made to both the data files and reporting format specific files. New available cation data was added, up until the end of WY2025 (September 30, 2025). Updated versions, as of 2026-08-06, of the PDF and docx files for determination of MDLs for ICP-MS data were added to this dataset for samples starting in November 2021.

54 ENVIRONMENTAL SCIENCES↗

Development Of Non-Invasive Beam Diagnostics By Quantum Optics-Based Detection

We report our effort and latest progress developing diagnostics using quantum optics-based detection method for determining the spatial properties and current of electron beams. As electrons pass through a dilute vapor of rubidium atoms, their magnetic field perturb the atomic spin’s quantum state and causes polarization rotation of a laser resonant with an optical transition of the atoms. By measuring the polarization rotation angle across the laser beam, we recreate a 2D projection of the magnetic field and use it to determine the e-beam position, size and total current. We tested this method for an e-beam with currents ranging from 30 to 110 µA. Our study shows this approach is insensitive to electron kinetic energy, and is initially verified experimentally between 10 to 20 keV. A different approach was also performed with highly excited rubidium atoms in Rydberg states through a coherent two photon process. We use this detection scheme to measure the electric field generated by a

Zhang, S. [Thomas Jefferson National Accelerator F↗

Spaceborne clock system: Some alternatives for a proposed NASA experiment

A spaceborne clock experiment is proposed with the objectives of improving international time and frequency comparisons, studying precise one-way Doppler tracking and one-way ranging techniques, performing relativistic studies, and developing new atomic frequency standards technology. Various alternatives are considered for accomplishing these goals, including the use of existing satellite and earth-based time dissemination systems as well as the development of a new frequency standard for this specific application. One conclusion is that several attractive alternatives already exist for meeting the goal of improved time and frequency dissemination. However, to achieve all the other 4 goals at the NASA-stated levels of accuracy, a spaceborne atomic frequency standard may be required. An analysis of achievements to date with quartz oscillators, rubidium standards, cesium beam standards, hydrogen masers, and several other possibilities leads to the conclusion that cesium and rubidium standards offer the best choices for the experiment as proposed by NASA. The greatest obstacle to a spaceborne atomic standard appears to be its electrical power requirements.

Beehler, R. E.↗

The origin of the moon and solar system.

The Rb-87/Sr-87 ages of many of the lunar rocks suggest that the fundamental differentiation took place 4.5 b.y. ago and that remelting occurred without exchange of the rubidium and strontium with the surroundings. The Apollo A rocks are an exception to this. They appear to have acquired rubidium without all of the Sr-87 produced during the first aeon. Also in the remelting about half of the radiogenic leads were lost to the surroundings by a vaporization process. We interpret these results to mean that remelting occured in a system that was nearly closed to the surroundings and that the high early concentrations of radioactive elements in highly insulating surroundings made this possible.

Urey, H. C.↗

Clocks for airborne systems

The potential performance of compact oscillators, needed for the development of accurate clocks for future airborne systems (such as Identification Friend or Foe schemes), is addressed. In particular, extensive testing of rubidium oscillators manufactured by Efratom is discussed. The results indicate that an accuracy of better than 10 microseconds should be achievable in tactical aircraft provided that appropriate measures are adopted to counter the many environmental factors. In a favorable environment a stability of better than 5 x 10 to the -13th power for one day is achievable with present commercial units, but improvements are required to suit operation in an aircraft. With further development of rubidium controlled clocks the ultimate limitation on time accuracy in aircraft will probably be associated with time dissemination, maintenance difficulties and doctrinal hurdles.

Houlding, N.↗

Investigations of laser pumped gas cell atomic frequency standard

The performance characteristics of a rubidium gas cell atomic frequency standard might be improved by replacing the standard rubidium discharge lamp with a single mode laser diode. Aspects of the laser pumped gas cell atomic clock studied include effects due to laser intensity, laser detuning, and the choice of the particular atomic absorption line. Results indicate that the performance of the gas cell clock may be improved by judicious choice of the operating parameters of the laser diode. The laser diode also proved to be a valuable tool in investigating the operation of the conventional gas cell clock. Results concerning linewidths, the light shift effect and the effect of isotopic spin exchange in the conventional gas cell clock are reported.

Volk, C. H.↗

Scattering of positrons and electrons by alkali atoms

Absolute total scattering cross sections (Q sub T's) were measured for positrons and electrons colliding with sodium, potassium, and rubidium in the 1 to 102 eV range, using the same apparatus and experimental approach (a beam transmission technique) for both projectiles. The present results for positron-sodium and -rubidium collisions represent the first Q sub T measurements reported for these collision systems. Features which distinguish the present comparisons between positron- and electron-alkali atom Q sub T's from those for other atoms and molecules (room-temperature gases) which have been used as targets for positrons and electrons are the proximity of the corresponding positron- and electron-alkali atom Q sub T's over the entire energy range of overlap, with an indication of a merging or near-merging of the corresponding positron and electron Q sub T's near (and above) the relatively low energy of about 40 eV, and a general tendency for the positron-alkali atom Q sub T's to be higher than the corresponding electron values as the projectile energy is decreased below about 40 eV.

Stein, T. S.↗

The classical microwave frequency standards

Some key problems are presented encountered in the classical microwave frequency standards which are still not solved today. The point of view expressed benefits from the experience gained both in the industry and in the research lab, on the following classical microwave frequency standards: active and passive H, conventional and laser pumped Cs beam tube, small conventional and laser pumped Rubidium. The accent is put on the Rubidium standard.

Busca, Giovanni↗

Analytical Investigation of Cycle Characteristics for Advanced Turboelectric Space Power Systems

An investigation was made of the relative influence of turbine inlet temperature, radiator temperature, and turbine efficiency on radiator area for Rankine cycles with rubidium, potassium, and sodium as working fluids. It was determined that, whereas turbine inlet temperature and turbine efficiency have gross effects on radiator size for a given inlet temperature a considerable latitude in the selection of radiator temperature may be accepted with only minor effects on required radiator size. Also investigated was the influence on turbine efficiency and design of the factors that distinguish alkali-metal vapor turbines from conventional gas turbines. The turbine configuration was determined to be a function of the involved working fluids and rotor blade speed. For a given blade speed, the number of stages required for high turbine efficiency was found to vary directly with turbine specific work output, and therefore to vary in the ratio 5 to 2.5 to 1 for sodium, potassium, and rubidium, respectively. Lower blade speeds than employed in conventional gas turbines may be required to satisfy critical stress considerations resulting from the elevated temperatures involved and the criterion of long-duration reliability. This will increase the number of turbine stages necessary to obtain high turbine efficiency and consequently increase turbine weight. The question of moisture formation was discussed and a calculation was made to indicate the nature of the aerodynamic losses due to moisture content. Various means of reducing moisture content were considered, including mechanical removal, increased radiator temperature, inefficient expansion, superheat, and reheat. Sample calculations were made in most cases to indicate their comparative effectiveness and resultant penalty in required radiator area.

Moffitt, Thomas P.↗

Molten salt compositions with enhanced heat transfer and reduced corrosion properties

A heat transfer (exchange) composition comprising a halide salt matrix having dispersed therein nanoparticles comprising elemental carbon in the absence of water and surfactants, wherein said halide is fluoride or chloride, wherein the halide salt may be an alkali halide salt (e.g., lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, sodium chloride, potassium chloride, rubidium chloride, and eutectic mixtures thereof) or an alkaline earth halide salt (e.g., fluoride or chloride salt of beryllium, magnesium, calcium, strontium, or barium), and wherein the nanoparticles comprising elemental carbon may be solid or hollow, and wherein the composition may further include nanoparticles comprising a fissile material (e.g., U, Th, or Pu) dispersed within the composition. Molten salt reactors (MSRs) containing these heat transfer compositions in coolant loops in thermal exchange with a reactor core, as well operation of such MSRs, are also described.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Exploring the Neutron Substructure with Advanced Polarized Helium-3 Targets (Or: How I Learned to Stop Worrying and Love Spectroscopy)

As we seek to understand the smallest, physical aspects of our universe, we cannot simply rely on our senses to probe the world around us as we did in the past. The smallest physical elements of our universe behave in strange, probabilistic ways and are completely invisible to the naked eye/ear/etc. So, we design clever experiments (such as scattering experiments) to probe these minute realms. Then, just as with the larger, observable world, we devise models and equations to describe what we think is happening. Due to the nature of the physical universe at the quantum scale and with the aid of symmetries such as Lorentz invariance, we can write down equations that describe the scattering, but the expressions contain functions, which we call ?form factors? and ?structure functions?, that we cannot compute from first principles. We can, however, formulate models that make predictions for these functions. By comparing our predictions with the observed data, we can gain insight into the validity of our models and thus a better physical understanding of what is happening at these minuscule scales. Studying the constituents inside of the nucleus of an atom adds another layer of difficulty if we can?t remove those components from the nucleus. This is the case with the neutron. When not bound in the nucleus with protons and other neutrons, the neutron will decay into a proton after about 15 minutes. So, we?re forced to study the neutron while it is still bound in the nucleus of an atom such as helium-3 (3He). For the last 1,000 years (rounding up), our group has developed high quality, polarized 3He targets made of an aluminosilicate glass. These targets are made in order to perform experiments at Jefferson Lab (JLab), experiments which let us determine the form factors and structure functions of the neutron by scattering polarized electrons from polarized neutrons (or rather polarized 3He). The specific experiments reported on in this thesis push the bounds of our understanding of the internal structure of the neutron. Good science is often about pushing experimental techniques to a new level. Toward that goal we study our polarized 3He targets both to advance the technology and to choose the best ones for our experiments. We do this using a process called nuclear magnetic resonance (NMR) to gauge the maximum polarization of a target and how fast the polarization decays with time. While these tests primarily provide us information that make analysis of our experimental scattering data possible, they also let us determine whether or not a target-cell is useful or even, dare I say, of spectacular quality. Our latest targets utilize a novel convection design allowing 3He to be polarized and quickly moved in front of the electron-beam, making it possible to use larger targets with higher electron-beam currents than ever before. This means more electrons scatter and we get more data. And by studying our targets in detail prior to using them in our experiments, we have found techniques to take effects which could have been detrimental to target quality and turn them to our advantage! It?s a real case of making lemonade out of lemons. We also use laser spectroscopy to study the absorption lines of alkali-metals in the target (potassium and rubidium, specifically). We add these alkali-metals to our target to facilitate polarizing the 3He. We can use the measurement of these pressure broadened absorption lines to determine the 3He density inside of the target with great precision. Historically, we understood the width of these lines would be dependent on the temperature of the target. Specifically, if I raise the temperature, the width should get bigger. I found that was not the case, which was very confusing at first, though very exciting now that I realize the data are self-consistent and suggestive of unexpected behavior. This thesis details the development of high quality, glass, polarized 3He targets for the 2020 An 1 /dn 2 and 2023 Gn E experiments, which utilized the first 3He convection targets and broke records in target quality. This thesis also covers the initial development of metal windows for the next-generation of 3He target-cells. Finally, this thesis documents the temperature dependence of the width of potassium (K) and rubidium (Rb) absorption lines as measured with laser spectroscopy.

Jantzi, Christopher↗

Enhancing the performance of the perovskite solar cells by modifying the SnO 2 electron transport layer

The tin oxide (SnO 2 ) electron transport layer (ETL) plays a vital role in the photo-conversion efficiency (PCE) and stability of organic-inorganic perovskite solar cells (PSCs). However, SnO 2 ETL-induced defects such as hydroxyl groups, oxygen vacancies, exposed Sn atoms, and dangling bonds hinder device performance. In this study, rubidium chloride (RbCl) has been used to modify the SnO 2 ETL. Perovskite film formed on the RbCl-modified SnO 2 ETL exhibits improved crystallinity with enlarged grain size and reduced grain boundaries and enhanced optical absorption. Further, the Hall-effect measurements indicate the improved carrier mobility, and the dark J-V curve shows the increment of electrical conductivity for the RbCl-modified SnO 2 ETL. X-ray photoelectron spectroscopy (XPS) results demonstrate the surface defects passivation of the perovskite layer by modifying the SnO 2 ETL. A champion PCE of 19.35% has been achieved for the RbCl-modified SnO 2 ETL-based devices with improved stability, while the control devices with unmodified SnO 2 ETL show a PCE of 17.18%.

14 SOLAR ENERGY↗

Atom femtosecond optical trap based on spectrally filtered laser radiation

We have examined the use of alkali metal (rubidium) vapour for spectral filtering of broadband pulsed laser light that is used to produce a femtosecond pulsed optical dipole trap. It has been shown that, even at large detuning of the centre emission frequency from the frequency of atomic transitions, spectral components present in the wings of the laser emission line are capable of heating localised atoms, thus reducing their lifetime in the atomic trap. Using atomic vapour for filtering the laser emission spectrum, we have suppressed its spectral components resulting in heating. This has made it possible to increase the lifetime of atoms in the pulsed optical dipole trap to a value comparable to their lifetime in an optical trap formed by narrow-band cw laser light. (paper)

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Low Temperature Water-Gas Shift: Enhancing Stability through Optimizing Rb Loading on Pt/ZrO 2

Recent studies have shown that appropriate levels of alkali promotion can significantly improve the rate of low-temperature water gas shift (LT-WGS) on a range of catalysts. At sufficient loadings, the alkali metal can weaken the formate C–H bond and promote formate dehydrogenation, which is the proposed rate determining step in the formate associative mechanism. In a continuation of these studies, the effect of Rb promotion on Pt/ZrO 2 is examined herein. Pt/ZrO 2 catalysts were prepared with several different Rb loadings and characterized using temperature programmed reduction mass spectrometry (TPR-MS), temperature programmed desorption (TPD), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), an X-ray absorption near edge spectroscopy (XANES) difference procedure, extended X-ray absorption fine structure spectroscopy (EXAFS) fitting, TPR-EXAFS/XANES, and reactor testing. At loadings of 2.79% Rb or higher, a significant shift was seen in the formate ν(CH) band. The results showed that a Rb loading of 4.65%, significantly improves the rate of formate decomposition in the presence of steam via weakening the formate C–H bond. However, excessive rubidium loading led to the increase in stability of a second intermediate, carbonate and inhibited hydrogen transfer reactions on Pt through surface blocking and accelerated agglomeration during catalyst activation. Optimal catalytic performance was achieved with loadings in the range of 0.55–0.93% Rb, where the catalyst maintained high activity and exhibited higher stability in comparison with the unpromoted catalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Promoting the Selectivity of Pt/m-ZrO 2 Ethanol Steam Reforming Catalysts with K and Rb Dopants

The ethanol steam reforming reaction (ESR) was investigated on unpromoted and potassium- and rubidium-promoted monoclinic zirconia-supported platinum (Pt/m-ZrO 2 ) catalysts. Evidence from in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) characterization indicates that ethanol dissociates to ethoxy species, which undergo oxidative dehydrogenation to acetate followed by acetate decomposition. The acetate decomposition pathway depends on catalyst composition. The decarboxylation pathway tends to produce higher overall hydrogen selectivity and is the most favored route at high alkali loading (2.55 wt.% K and higher or 4.25 wt.% Rb and higher). On the other hand, decarbonylation is a significant route for the undoped catalyst or when a low alkali loading (e.g., 0.85% K or 0.93% Rb) is used, thus lowering the overall H 2 selectivity of the process. Results of in situ DRIFTS and the temperature-programmed reaction of ESR show that alkali doping promotes forward acetate decomposition while exposed metallic sites tend to facilitate decarbonylation. In previous work, 1.8 wt.% Na was found to hinder decarbonylation completely. Due to the fact that 1.8 wt.% Na is atomically equivalent to 3.1 wt.% K and 6.7 wt.% Rb, the results show that less K (2.55% K) or Rb (4.25% Rb) is needed to suppress decarbonylation; that is, more basic cations are more efficient promoters for improving the overall hydrogen selectivity of the ESR process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗