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23 records · Page 2

Metal-Organic Framework-based Luminescent Sensors for Rare Earth Elements

Rare earth elements (REEs) are crucial for many applications and are particularly important in wind power and electric vehicle technologies, spurring projected demand increases for REEs in coming decades. However, the REE supply is restricted by a monopolistic global marketplace, tedious and costly processing steps for REE production, and environmental hazards associated with mining and processing. Coal and coal-utilization byproducts have emerged as potential domestic sources for REEs, however REE production from these sources is currently hindered by slow and expensive characterization techniques. Here, we demonstrate that metal-organic framework (MOF)-based sensitizers can effectively serve as luminescent sensors capable of rapidly detecting and distinguishing part-per-billion concentration levels of emissive REEs, including terbium, europium, dysprosium, samarium, neodymium, and ytterbium. Importantly, we demonstrate that the MOF structure plays a significant role in tuning the selectivity of the MOF for REEs in acidic environments, an essential step towards deployment in various REE-rich process streams. As a proof-of-concept, we demonstrate sensitive and reversible detection of REEs using a portable fiber-optic spectrometer

Crawford, Scott↗

Low-cost, portable optical sensors for critical mineral prospecting and process monitoring

A combination of projected demand increases for economically critical minerals and a monopolistic global marketplace for these minerals has caused concern over supply chain vulnerabilities, which would impact energy, national defense, and advanced technology production. Domestic production of critical minerals is hindered by expensive and non-portable methods for analyzing metal concentration, which is vital both for resource prospecting and process monitoring. Here, a suite of luminescent materials along with portable instrumentation is presented for fluorescence-based detection of trace concentrations of critical minerals (cobalt, rare earth elements, and aluminum) as well as common gangue metals that are removed during processing (iron and aluminum). A metal-organic framework comprised of zinc, adenine, and trimesic acid immobilized on a fiber optic tip is capable of sensing part-per-billion concentrations of terbium, europium, dysprosium, and samarium through a sensitization approach, in which individual elements produce characteristic emission bands enabling multiple rare earths to be simultaneously detected and distinguished. A deep-UV light emitting diode is used as the excitation source, while a portable spectrometer is used to detect the emitted light. A similar optical set-up is coupled with two different carbon dot materials, which can detect low part-per-million concentrations of cobalt and iron in acidic environments. Metal-organic framework thin films comprised of copper and 2-aminoterephthalic acid are used in tandem with a portable optical set-up to further detect aluminum, with successful deployment in real fly ash leachates. Taken together, these technologies provide an inexpensive and sensitive path towards characterizing economically critical metals.

characterization and extraction of rare earth elem↗

Rare Earth Elements (REE) and Critical Minerals (CM) in Middle Pennsylvanian-Age Coals and Associated Sediments in the Central Appalachian Basin, Eastern U.S.A.

The Central Appalachian Basin (CAB) of Kentucky, Tennessee, West Virginia and Virginia has a long history of coal mining and oil and gas extraction that has empowered the regional and national economies, the development of infrastructure, and a highly trained energy resources work force. As our societal demands for advanced technologies have rapidly increased in recent years, coal-related materials are viewed as an important new unconventional domestic source of critical minerals (CM) that are required for telecommunications, aerospace and transportation industries, electronics, the transition to low-carbon emissions energy production, and many consumer products. Coal-related materials encompass coal, associated sediments, coal mining waste materials, produced waters, and ash residues from coal-fired power plants. An important objective of the Evolve Central Appalachia Project (Evolve CAPP), sponsored by the U.S. Department of Energy (DOE) National Energy Technology Laboratory (NETL) is to assess the quantity and distribution of CM resources in the CAB region. The rare earth elements (REE) are considered highest priority, although other important CM such as niobium, gallium, and zirconium are known to occur in the Middle Pennsylvanian-age coals and sediments. Working with coal industry partners who provided access to drill cores, coal-related sediments and waste materials, over 600 samples have been collected for laboratory analysis, and over 730 materials have been scanned using portable x-ray fluorescence (pXRF) equipment. The application of pXRF provides the means for real-time semiquantitative analysis of CM content at very close spacings (typically 2-3 inch intervals) along drill core and in-situ channel samples that span the roof, coal seam, and floor rock. The comparison of pXRF geochemical data with laboratory results, geologic data, and downhole spectral gamma logs can provide high resolution input to lithologic and depositional models for future CM resource evaluations. The preliminary findings show that pXRF is capable of accurately measuring low concentrations of many of the CM with a high level of confidence (Ba, Cr, Ga, K, Nb, Rb, Sr, Th, Y), whereas for others (La, Ce, Co, Mn, Nd, Ni, Sc, Ti, V) the detection limits are very high or spectral interferences increase the uncertainty. Notably, the mean abundances of Y (34 ppm), La (86 ppm), Ga (40 ppm), and V (146 ppm) in coal underclays in the CAB region are up to 7X enriched compared with the overlying coal. These values also exceed the reported concentrations in published reference materials for upper continental crustal rocks (Rudnick and Gao, 2003), North American Shale Composite (Gromet et al., 1984), and North American coal (Finkelman, 1993). The pXRF data are in part verified by laboratory results that indicate the mean Y abundance (36 ppm) is highly correlated (R2 = 0.807) with total REE (ΣREE). The correlation is even higher (R2 = 0.957) with heavy REE (ΣHREE). Applying these correlations to the pXRF data for the coal underclays, the mean estimated values for ΣREE+Y and ΣHREE+Y are 270 ppm and 58 ppm, respectively. Although these average values are not considered high, the range of Y measured by pXRF in the coal underclays extended as high as 114 ppm, which would suggest ΣREE+Y equal to 847 ppm. The mean abundances of Zr (192 ppm) and Th (21 ppm) in coal underclays are also enriched compared with the overlying coal and these results likely reflect the presence of resistant detrital heavy minerals such as monazite, xenotime, and zircon in the underclay matrix. Several of the profiled coal seams and associated wall rocks contained thin volcanic ash layers up to 4-5 inches in thickness. The extent to which these ash fall layers provided a source for CM under the paleoenvironmental conditions that resulted in coal deposits in the CAB remains to be fully studied. Continuing investigations in the Evolve CAPP study area will include laboratory determinations of mineralogic and clay compositions, and evaluations of CM geochemical mobility in the coal and coal underclays.

Lassetter, Billy↗

Effect of Minor Ce Additions on Corrosion Behavior of Experimental Pipeline Steel

Minor additions of rare earth elements (REEs) have been shown to improve various steel properties. In particular, Cerium (Ce), as a relatively abundant and inexpensive element, has received attention as a potentially beneficial minor alloying addition for a variety of steel applications, including pipelines materials. The objective of this work is to investigate the effect of Ce on corrosion performance of experimental high-strength pipeline steel. Electrochemical corrosion experiments were carried out on steel without and with 0.006, 0.018, and 0.03 wt.% of Ce in 3.5 wt.% NaCl saturated with CO2 at 20 oC. For comparison purposes, X100 carbon steel specimens machined from an experimental pipe with a yield strength of 731 MPa were tested under the same conditions. The electrochemical techniques employed included: potentiodynamic polarization (PDP), linear polarization resistance (LPR), and electrochemical impedance spectroscopy (EIS). In addition, post-corrosion surface characterization was performed using scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectroscopy (EDS), while crystalline phases were determined by X-ray diffraction (XRD). The corrosion of base metal without Ce was lower (0.15 mm/y) compared to carbon steel X100 (0.9 mm/yr). The electrochemical results showed that adding Ce accelerates corrosion rates compared to base metal without Ce. No pitting corrosion of tested steel was detected.

Belarbi, Zineb↗