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60 records · Page 4

Microwave-Assisted Reactive CO 2 Capture with the SrCO 3 -Graphite System

This study details the initial development of a microwave heat-driven reactive CO 2 capture (RCC) process using the SrO/SrCO 3 cycle and graphitic carbon to absorb ppm-levels of CO 2 from humidified room temperature air and selectively convert it into CO. By combining first-principles density functional theory (DFT) simulations with thermogravimetric analysis (TGA) and X-ray diffraction (XRD) verification, it is demonstrated that SrO spontaneously absorbs moisture to generate Sr(OH) 2 followed by Sr(OH) 2 *1H 2 O, which then can spontaneously react with atmospheric levels of CO 2 to form SrCO 3 . The resulting SrCO 3 can then react with solid carbon at elevated temperatures to selectively produce CO and regenerate SrO. Graphitic carbon is an excellent microwave absorber that can quickly generate temperatures approaching 1000 °C and then cool to room temperature within minutes, potentially allowing for integration with intermittent electricity. It is shown that using microwaves to selectively heat a mixture of graphitic carbon and SrCO 3 produced CO with 85 ± 3% selectivity and stable performance over ten cycles. The rapid heating for release and room temperature CO 2 uptake processes appeared to prevent performance loss from particle sintering typically observed with traditional thermal systems. In conclusion, these results demonstrate a new RCC approach that adds to the growing number of potential technologies available for converting CO 2 to useful chemicals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Facile Interfacial Reduction Suppresses Redox Chemical Expansion and Promotes the Polaronic to Ionic Transition in Mixed Conducting (Pr,Ce)O 2−δ Nanoparticles

Mixed ionic/electronic conductors (MIECs) are essential components of solid-state electrochemical devices, such as solid oxide fuel/electrolysis cells. For efficient performance, MIECs are typically nanostructured, to enhance the reaction kinetics. However, the effect of nanostructuring on MIEC chemo-mechanical coupling and transport properties, which also impact cell durability and efficiency, has not yet been well understood. Here, in this work, Pr 0.2 Ce 0.8 O 2−δ (PCO20) nanopowders were prepared by coprecipitation, then sintered in a modified dilatometer at three different temperatures (600, 725, and 850 °C) for microstructure evolution, resulting in three samples with different average particle sizes (23, 30, and 53 nm). The chemical strain and electronic/ionic conductivity were then measured simultaneously on stable nanostructures in four isotherms from 550 to 400 °C with steps in pO 2 (1 to 10 –4 atm O 2 ). A microcrystalline bar was prepared and measured for comparison. Particle size reduction led to a monotonically decreasing isothermal redox chemical strain, confirmed by in situ high-temperature, controlled-atmosphere XRD measurements. The corresponding conductivity measurements provided defect chemical insight into the particle size-dependent chemical expansion behavior. The significant weakening of the pO 2 dependence and decreased activation energy for electrical conduction with decreasing particle size indicated a decrease in the reduction enthalpy of PCO, shifting the transition from (Pr) polaronic to ionic behavior to higher pO 2 . STEM-EELS measurements confirmed the majority of Pr was reduced to 3+ in the nanoparticles, while Ce remained 4+. These results demonstrate suppression of deleterious chemical expansion and tailoring of the dominant charge carrier simply through controlling the particle size, providing insights for MIEC microstructural design.

ceria↗

Investigation of oxygen ion mobility through Zr x Ta 2 O 2x+5 (ZTOx) and Hf 6 Ta 2 O 17 (HTO) at elevated temperatures

Thermal Protection Systems (TPS) allow for technology to withstand high heat, which is especially critical for aerospace applications. As technology advances, better TPS are required to keep up with more extreme operating temperatures. Ultra-High Temperature Ceramics (UHTCs) are of interest because of their high melting points above 3000°C, but they suffer from oxidation when exposed to the atmosphere. A standard remedy to prevent oxidation is the use an oxide coating to shield from oxygen in the atmosphere while still allowing high operating temperatures and thermal cycling. However, standard oxide coatings such as yttria stabilized zirconia (YSZ) have limited operating temperatures before they allow oxygen to diffuse into the substrate material. A recently proposed alternative material has the formula A 6 B 2 O 17 (A: Zr or Hf) (B: Ta or Nb). In this study, determination of the oxygen protection ability of Hf 6 Ta 2 O 17 (HTO), Zr 6 Ta 2 O 17 (ZTO6), and various Zr x Ta 2 O 2x+5 (ZTOx) was determined using Electrochemical Impedance Spectroscopy (EIS). Optimal synthesis and sintering conditions were determined for ZTO6 and several of its ZTO variations. Activation energy for oxygen mobility was also determined. The importance of ball milling was found to be crucial to achieve high sintering density with these ceramics. The sintering study revealed that the ideal temperature of the ZTO variations increased with increased Zr/Ta ratio in the formulation. It was determined that both HTO and the ZTO variations conduct oxygen ions less than current ceramic coatings such as YSZ, with HTO conducting the least, with results confirming the validity of both HTO and ZTO materials as candidates for TPS coatings based on their low oxygen ion conductivity.

36 MATERIALS SCIENCE↗

Biphasic Janus Particles Explain Self-Healing in Pt–Pd Diesel Oxidation Catalysts

The addition of Pd to Pt-based diesel oxidation catalysts is known to enhance performance and restrict the anomalous growth of Pt nanoparticles when subjected to aging at high temperatures in oxidative environments. To gain a mechanistic understanding, we studied the transport of the mobile Pt and Pd species to the vapor phase, since vapor phase transport is the primary route for sintering in these catalysts. The results are surprising: there is a 30-fold drop in the effective vapor pressure of Pt in the Pt-Pd catalysts compared to monometallic Pt. At the same time, there is a significant enhancement in the vapor pressure of Pd, compared to PdO, which otherwise has a negligible vapor pressure at the aging temperature. Such behavior cannot be explained simply by alloying Pt and Pd in the metallic phase, or a core-shell morphology where a PdO shell covers a Pt core. Transmission electron microscopic examination of catalysts aged up to 50 h in air at 800 °C shows that the particles exhibit a biphasic “Janus”-like structure. The metal and oxide phases are conjoined, exposing a metal and an oxide face to the gas phase. The high mobility of the Pt and Pd allows them to be partitioned into the metal and oxide phases, in apparent thermodynamic equilibrium. The PdO helps to trap mobile PtO2 and as a result contains high concentrations of Pt oxide, consistent with its role in mitigating the transport of Pt to the vapor phase and preventing the growth of anomalously large particles. In turn, Pt allows Pd to remain metallic, allowing the catalyst to retain both metal and oxide functionality for catalysis. The regeneration of deactivated catalysts typically requires an external input, such as a change in the working environment from reducing to oxidizing or vice-versa. Here, we show that the mobile species, which are primary contributors to catalyst sintering are effectively returned to the active site, hence our use of the term “selfhealing”. The detailed insights into the inner workings of the Pt-Pd diesel oxidation catalysts can help provide clues to the design of robust and durable heterogeneous catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydrogen permeability and stability of palladium films in a high pressure reactor

Palladium (Pd) thin films were fabricated by colloidal spray deposition (CSD) on substrates of porous yttrium stabilized zirconium oxide (YSZ). The films were sintered at 1140–1160 °C for 2–3 h in argon and had thickness of 5–11 μm. The hydrogen (H 2 ) permeation flux for the Pd film was measured with simulated feed gases (90% H 2 /He, syn-gas/steam, or syn-gas/steam with H 2 S) flowing on the film side and sweep gas (Ar) flowing on the substrate side. Here, the hydrogen flux with the Pd film was obtained by adjusting the flow rate and pressure of the gas. Hydrogen flux values of 121–173 cm 3 min -1 cm -2 were measured at 388–596 °C (feed: 90% H 2 /He at 200 mL min -1 ; sweep: Ar at 1400 mL min -1 ; and ΔP = ~170 psi), and the permeability was calculated and compared with literature values. Because Pd is known to be sensitive to some gases, the stability of Pd films was evaluated by examining the microstructures of samples after their exposure to gas mixtures containing CO, CO 2 , H 2 O, and H 2 S. From the results of stability tests in H 2 S-containing atmospheres, the Pd/Pd 4 S phase boundary was determined, and this measured boundary was compared to the Pd/Pd 4 S boundary calculated from the thermodynamic data in the literature.

36 MATERIALS SCIENCE↗

Temperature-dependent diffuse reflectance measurements of ceramic powders in the near- and mid-infrared spectra

Radiative properties are critical to quantify radiative energy fluxes between surfaces and in participating media. However, there is limited experimental data on temperature-dependent radiative properties of materials. Herein, this work focuses on experimentally measuring temperature-dependent diffuse reflectance in the near- and mid-infrared spectra (1–20 μm) for ceramic particles with applications as heat-transfer and thermal-storage media in concentrated solar power (CSP) plants. Specifically, a commercially available sintered bauxite proppant, ACCUCAST ID80, and its primary chemical constituents—alumina (Al 2 O 3 ) and silica (SiO 2 )—are measured in powder form using a Fourier transform infrared spectrometer (FTIR) coupled with a specialized diffuse reflectance accessory and a heated stage. Room-temperature diffuse reflectance measurements show increased absorption in tests with greater mass fractions of the ceramic samples. There is a strong correlation in the measured reflectance spectra of ACCUCAST with alumina and silica in the spectral range 2000–500 cm –1 (5–20 μm). Whereas, for shorter wavelengths (< 5 μm), the absorptance for ACCUCAST is greater than the absorptance for alumina and silica, indicating contributions from other chemical species present in the composite material. For the first time, temperature-dependent diffuse reflectance measurements are reported for ACCUCAST up to 1000 °C. These results are compared against those of alumina and silica through the calculation of a thermal emittance. All three materials exhibit a calculated emittance of ~0.9 at room temperature. However, this value decreases to ~0.6 for ACCUCAST and drops to less than 0.4 for alumina and silica at 1000 °C. Thermal cycling in air at 1000 °C resulted in a visible color change from dark grey to light orange for ACCUCAST and a subsequent larger increase in reflectance for wavelengths less than 5 μm as compared to ACCUCAST thermally cycled at 1000 °C in vacuum. Alumina and silica spectra proved to be largely unaffected by thermal cycling under atmospheric conditions. Overall, this study establishes a powerful technique for the characterization of radiative properties of particulate materials as a function of temperature and presents a detailed case study of ACCUCAST, a candidate for next-generation particle-based CSP.

14 SOLAR ENERGY↗