Investigation of AFeO3 (A=Ba, Sr) Perovskites for the Oxidative Dehydrogenation of Light Alkanes under Chemical Looping Conditions.

Oxidative dehydrogenation (ODH) of light alkanes to produce C2-C3 olefins is a promising alternative to conventional steam cracking. Perovskite oxides are emerging as efficient catalysts for this process due to their unique properties such as high oxygen storage capacity (OSC), reversible redox behavior, and tunability. Here, we explore AFeO3 (A=Ba, Sr) bulk perovskites for the ODH of ethane and propane under chemical looping conditions (CL-ODH). The higher OSC and oxygen mobility of SrFeO3 perovskite contributed to its higher activity but lower olefin selectivity than its Ba counterpart. However, SrFeO3 perovskite is superior in terms of cyclic stability over multiple redox cycles. Transformations of the perovskite to reduced phases including brownmillerite A2Fe2O5 were identified by X-ray diffraction (XRD) as a cause of performance degradation, which was fully reversible upon air regeneration. A pre-desorption step was utilized to selectively tune the amount of lattice oxygen as a function of temperature and dwell time to enhance olefin selectivity while suppressing CO2 formation from the deep oxidation of propane. Overall, SrFeO3 exhibits promising potential for the CL-ODH of light alkanes, and optimization through surface and structural modifications may further engineer well-regulated lattice oxygen for maximizing olefin yield.

Influence of the Anionic Zinc-Adeninate Metal-Organic Framework Structure on the Luminescent Detection of Rare Earth Ions in Aqueous Streams.

Rare earth elements (REEs) are critical to numerous technologies; however, a combination of increasing demand, environmental concerns, and monopolistic marketplace conditions has spurred interest in boosting the domestic REE production from sources such as coal utilization byproducts. The economic viability of this approach requires rapid, inexpensive, and sensitive analytical techniques capable of characterizing the REE content during resource exploration and downstream REE processing (e.g., analyzing REE separation, concentration, and purification production steps). Luminescence-based sensors are attractive because many REEs may be sensitized to produce element-specific emission. Hence, a single material may simultaneously detect and distinguish multiple REEs. Metal-organic frameworks (MOFs) can sensitize multiple REEs, but their viability has been hindered by sensitivity and selectivity challenges. Understanding how the MOF structure impacts the REE sensing efficacy is critical to the rational design of new sensors. Here, we evaluate the sensing performance of seven different anionic zinc-adeninate MOFs with different organic linkers and/or structures for the visible-emitting REEs Tb, Dy, Sm, and Eu. The choice of a linker determines which REEs are sensitized and significantly influences their sensitivity and selectivity against competing species (here, Fe(II) and HCl). For a given linker, structural changes to the MOF can further fine-tune the performance. The MOFs produce some of the lowest detection limits (sub-10 ppb for Tb) reported for the aqueous sensitization-based REE detection. Importantly, the most selective MOFs demonstrated the ability to sensitize the REE signal at sub-ppm levels in a REE-spiked acid mine drainage matrix, highlighting their potential for use in real-world sensing applications.

Adsorption kinetics, thermodynamics, and isotherm studies for functionalized lanthanide-chelating resins.

Conventional ion exchange resins are widely utilized to remove metals from aqueous solutions, but their limited selectivity precludes dilute ion extraction. This research investigated the adsorption performance of ligand-functionalized resins towards rare earth elements (REE). Functionalized resin particles were synthesized by grafting different ligands (diethylenetriaminepentaacetic dianhydride (DTPADA), phosphonoacetic acid (PAA), or N,N-bis(phosphonomethyl)glycine (BPG)) onto pre-aminated polymeric adsorbents (diameter ∼ 0.6 mm). Lanthanide uptake trends were evaluated for the functionalized resins using batch adsorption experiments with a mixture of three REEs (Nd, Gd, and Ho at 0.1-1000 mg/L each). Resin physical-chemical properties were determined by measuring their surface area, ligand concentrations, and acidity constants. The aminated supports contained 4.0 mmol/g primary amines, and ligand densities for the functionalized resins were 0.33 mmol/g (PAA), 0.22 mmol/g (BPG), and 0.42 mmol/g (DTPADA). Kinetic studies revealed that the functionalized resins followed pseudo-second order binding kinetics with rates limited by intraparticle diffusion. Capacity estimates for total REE adsorption based on Langmuir qMax were 0.12 mg/g (amine; ≈ 0.77 µmol/g), 5.0 mg/g (PAA; ≈ 32.16 µmol/g), 3.0 mg/g (BPG; ≈ 19.30 µmol/g), and 2.9 mg/g (DTPADA; ≈ 18.65 µmol/g). Attaching ligands to the aminated resins greatly improved their REE binding strength and adsorption efficiency.

Zinc-Adeninate Metal-Organic Framework: A Versatile Photoluminescent Sensor for Rare Earth Elements in Aqueous Systems.

Rare earth elements (REEs) are strategically important for national security and advanced technologies. Consequently, significant effort has been devoted towards increasing REE domestic production, including the extraction of REEs from coal, coal combustion byproducts, and their associated waste streams such as acid mine drainage. Analytical techniques for rapid quantification of REE content in aqueous phases can facilitate REE recovery through rapid identification of high-value waste streams. In this work, we show that BioMOF-100 can be used as a fluorescent-based sensitizer for emissive REE ion detection in water, providing rapid (<10 min) analysis times and sensitive detection (parts-per-billion detection limits) for terbium, dysprosium, samarium, europium, ytterbium, and neodymium, even in the presence of acids or secondary metals.

Greenhouse Gas Molecule CO2 Detection Using a Capacitive Micromachined Ultrasound Transducer.

We manufactured and tested a capacitive micromachined ultrasound transducer (CMUT)-based sensor for CO2 detection at environmentally relevant concentrations using polyethylenimine as a CO2 binding material. The assembly of a sensing chip was 10 × 20 mm, and up to 5 gases can potentially be detected simultaneously using a masking technique and different sensing materials. The limit of detection was calculated to be 0.033 CO2 vol % while the limit of quantification was calculated to be 0.102%. The sensor exhibited a linear response between 0.06% and 0.30% CO2 while concentrations close to those in flue gas can also be measured using dilution with inert gas.

Perovskite Nanoparticle-Sensitized Ga2O3 Nanorod Arrays for CO Detection at High Temperature.

Noble metal nanoparticles are extensively used for sensitizing metal oxide chemical sensors through the catalytic spillover mechanism. However, due to earth-scarcity and high cost of noble metals, finding replacements presents a great economic benefit. Besides, high temperature and harsh environment sensor applications demand material stability under conditions approaching thermal and chemical stability limits of noble metals. In this study, we employed thermally stable perovskite-type La(0.8)Sr(0.2)FeO3 (LSFO) nanoparticle surface decoration on Ga2O3 nanorod array gas sensors and discovered an order of magnitude enhanced sensitivity to carbon monoxide at 500 °C. The LSFO nanoparticle catalysts was of comparable performance to that achieved by Pt nanoparticles, with a much lower weight loading than Pt. Detailed electron microscopy and X-ray photoelectron spectroscopy studies suggested the LSFO nanoparticle sensitization effect is attributed to a spillover-like effect associated with the gas-LSFO-Ga2O3 triple-interfaces that spread the negatively charged surface oxygen ions from LSFO nanoparticles surfaces over to ß-Ga2O3 nanorod surfaces with faster surface CO oxidation reactions.

Novel silica surface charge density mediated control of the optical properties of embedded optically active materials and its application for fiber optic pH sensing at elevated temperatures.

Silica and silica incorporated nanocomposite materials have been extensively studied for a wide range of applications. Here we demonstrate an intriguing optical effect of silica that, depending on the solution pH, amplifies or attenuates the optical absorption of a variety of embedded optically active materials with very distinct properties, such as plasmonic Au nanoparticles, non-plasmonic Pt nanoparticles, and the organic dye rhodamine B (not a pH indicator), coated on an optical fiber. Interestingly, the observed optical response to varying pH appears to follow the surface charge density of the silica matrix for all the three different optically active materials. To the best of our knowledge, this optical effect has not been previously reported and it appears universal in that it is likely that any optically active material can be incorporated into the silica matrix to respond to solution pH or surface charge density variations. A direct application of this effect is for optical pH sensing which has very attractive features that can enable minimally invasive, remote, real time and continuous distributed pH monitoring. Particularly, as demonstrated here, using highly stable metal nanoparticles embedded in an inorganic silica matrix can significantly improve the capability of pH sensing in extremely harsh environments which is of increasing importance for applications in unconventional oil and gas resource recovery, carbon sequestration, water quality monitoring, etc. Our approach opens a pathway towards possible future development of robust optical pH sensors for the most demanding environmental conditions. The newly discovered optical effect of silica also offers the potential for control of the optical properties of optically active materials for a range of other potential applications such as electrochromic devices.

A method for preparation and cleaning of uniformly sized arsenopyrite particles.

BACKGROUND: The oxidative dissolution of sulfide minerals, such as arsenopyrite (FeAsS), is of critical importance in many geochemical systems. A comprehensive understanding of their dissolution rates entails careful preparation of the mineral surface. Measurements of dissolution rates of arsenic from arsenopyrite are dependent on the size and degree of oxidation of its particles, among other factors. In this work, a method was developed for preparation and cleaning of arsenopyrite particles with size range of 150-250 µm. Four different cleaning methods were evaluated for effectiveness based on the removal of oxidized species of iron (Fe), arsenic (As) and sulfur (S) from the surface. The percentage oxidation of the surface was determined using X-ray photoelectron spectroscopy (XPS), and surface stoichiometry was measured using scanning electron microscopy - energy dispersive X-ray spectroscopy (SEM-EDS). RESULTS: Results indicate that sonicating the arsenopyrite particles and then cleaning them with 12N HCl followed by 50% ethanol, and drying in nitrogen was the most effective method. This method was successful in greatly reducing the oxide species of Fe while completely removing oxides of As and S from the arsenopyrite surface. CONCLUSIONS: Although sonication and acid cleaning have been widely used for mineral preparation, the method described in this study can significantly reduce grain size heterogeneity as well as surface oxidation, which enables greater control in surface and dissolution experiments.

Copolymer-templated nitrogen-enriched porous nanocarbons for CO2 capture.

Nitrogen-enriched porous carbon materials made via the carbonization of polyacrylonitrile containing block copolymer act as efficient and highly selective CO(2) sorbents. Nitrogen content and surface area, which are both influenced by pyrolysis temperature and atmosphere, are crucial for CO(2) adsorption performance.

Surface plasmon resonance label-free monitoring of antibody antigen interactions in real time.

Detection of biologically active compounds is one of the most important topics in molecular biology and biochemistry. One of the most promising detection methods is based on the application of surface plasmon resonance for label-free detection of biologically active compounds. This method allows one to monitor binding events in real time without labeling. The system can therefore be used to determine both affinity and rate constants for interactions between various types of molecules. Here, we describe the application of a surface plasmon resonance biosensor for label-free investigation of the interaction between an immobilized antigen bovine serum albumin (BSA) and antibody rabbit anti-cow albumin IgG1 (anti-BSA). The formation of a self-assembled monolayer (SAM) over a gold surface is introduced into this laboratory training protocol as an effective immobilization method, which is very promising in biosensing systems based on detection of affinity interactions. In the next step, covalent attachment via artificially formed amide bonds is applied for the immobilization of proteins on the formed SAM surface. These experiments provide suitable experience for postgraduate students to help them understand immobilization of biologically active materials via SAMs, fundamentals of surface plasmon resonance biosensor applications, and determination of non-covalent biomolecular interactions. The experiment is designed for master and/or Ph.D. students. In some particular cases, this protocol might be adoptable for bachelor students that already have completed an extended biochemistry program that included a background in immunology.

Photoresponse of p-type zinc-doped iron(III) oxide thin films.

Stable zinc-doped iron(III) oxide thin films that exhibit p-type behavior were synthesized by spray pyrolytic deposition (SPD) on conducting indium-doped tin oxide-coated glass substrate. The highest photocurrent density of 1.1 mA/cm2 was observed at an illumination intensity of 40 mW/cm2 at -0.8 V vs Pt for zinc-doped p-Fe2O3 samples prepared at an optimum substrate temperature of 663 K using an optimum spray time of 70 s. A quantum efficiency of 21.1% at 325 nm was found for SPD samples prepared using a dopant concentration of 0.0088 M zinc nitrate hexahydrate. X-ray diffraction results showed structures of alpha-Fe2O3 and ZnFe2O4. A direct band gap energy of 2.2 eV was found from monochromatic photocurrent density data and agrees closely with the band gap obtained from UV-vis absorption. The X-ray photoelectron spectroscopy results also confirm the presence of zinc dopant (4.0 atomic %) in thin films of zinc-doped p-Fe2O3.

Rapid determination of total sulfur in fuels using gas chromatography with atomic emission detection.

The purpose of this study is to determine whether gas chromatography (GC)-atomic emission detection (AED) can be used in a low-resolution mode for rapid, accurate determinations of total sulfur in fuels at trace levels to complement other popular methods of total sulfur analysis. A method for the rapid determination of total sulfur in fuels (called "fast GC-AED") is developed. The method is tested on gasoline, jet fuel, kerosene, and diesel fuel with sulfur concentrations ranging from 125 mg/L down to 2.5 mg/L. Fast GC-AED shows better performance than traditional GC-AED for total sulfur determinations, especially for complex mixtures containing many different sulfur-containing compounds at trace levels. This method also shows that GC-AED can be used for both rapid determinations of total sulfur and traditional determinations of speciated sulfur without requiring equipment changes. Fast GC-AED is competitive with other popular methods for sulfur analysis. The 5-min program that is developed for fast GC-AED is comparable with the time scale of other methods, such as wavelength dispersive X-ray fluorescence and UV-fluorescence (2 to 5 min). Fast GC-AED also compares favorably with UV-fluorescence for trace sulfur determinations, demonstrating accuracy down to 2.5-mg/L sulfur.