Andac Armutlulu

Cooperativity and Dynamics Increase the Performance of NiFe Dry Reforming Catalysts

The dry reforming of methane (DRM), i.e., the reaction of methane and CO2 to form a synthesis gas, converts two major greenhouse gases into a useful chemical feedstock. In this work, we probe the effect and role of Fe in bimetallic NiFe dry reforming catalysts. To this end, monometallic Ni, Fe, and bimetallic Ni-Fe catalysts supported on a MgxAlyOz matrix derived via a hydrotalcite-like precursor were synthesized. Importantly, the textural features of the catalysts, i.e., the specific surface area (172-178 m2/gcat), pore volume (0.51-0.66 cm3/gcat), and particle size (5.4-5.8 nm) were kept constant. Bimetallic, Ni4Fe1 with Ni/(Ni + Fe) = 0.8, showed the highest activity and stability, whereas rapid deactivation and a low catalytic activity were observed for monometallic Ni and Fe catalysts, respectively. XRD, Raman, TPO, and TEM analysis confirmed that the deactivation of monometallic Ni catalysts was in large due to the formation of graphitic carbon. The promoting effect of Fe in bimetallic Ni-Fe was elucidated by combining operando XRD and XAS analyses and energy-dispersive X-ray spectroscopy complemented with density functional theory calculations. Under dry reforming conditions, Fe is oxidized partially to FeO leading to a partial dealloying and formation of a Ni-richer NiFe alloy. Fe migrates leading to the formation of FeO preferentially at the surface. Experiments in an inert helium atmosphere confirm that FeO reacts via a redox mechanism with carbon deposits forming CO, whereby the reduced Fe restores the original Ni-Fe alloy. Owing to the high activity of the material and the absence of any XRD signature of FeO, it is very likely that FeO is formed as small domains of a few atom layer thickness covering a fraction of the surface of the Ni-rich particles, ensuring a close proximity of the carbon removal (FeO) and methane activation (Ni) sites.

The development of effective CaO-based CO2 sorbents via a sacrificial templating technique

A carbon-based sacrificial templating approach was employed to realize single-pot synthesis of cyclically stable CaO-based CO2 sorbents. The sacrificial carbonaceous template was formed through resorcinol-formaldehyde polymerization reaction. The resultant sorbents following the thermal decomposition of the carbonaceous template featured an inverse opal-like macrostructure composed of a highly porous nanostructured backbone. In addition to pure CaO, sorbents supported with Al2O3, MgO, Y2O3, and ZrO2 were synthesized. SEM and XRD were utilized to characterize the morphology and the chemical composition of the synthetic CO2 sorbents, respectively. The cyclic CO2 uptake performance of the synthetic sorbents was assessed by TGA and compared to limestone. All of the synthetic sorbents exhibited an improved CO2 uptake performance when compared to limestone. The performance enhancement became more pronounced in the case of supported sorbents. The sorbent with the best CO2 uptake performance was supported by a mixture of Al2O3 and Y2O3, and exhibited a CO2 uptake of 0.61 g CO2/g CaO after 10 cycles of calcination and carbonation under practically relevant operating temperatures, which exceeded the CO2 uptake of limestone by more than 350%.

A MEMS-enabled 3D zinc–air microbattery with improved discharge characteristics based on a multilayer metallic substructure

This paper reports the design, fabrication and testing of a three-dimensional zinc–air microbattery with improved areal energy density and areal capacity, particularly at high discharge rates. The device is based on a multilayer, micron-scale, low-resistance metallic skeleton with an improved surface area. This skeleton consists of alternating Cu and Ni layers supporting Zn as electrodeposited anode electrode, and provides a high surface area, low-resistance path for electron transfer. A proof-of-concept zinc–air microbattery based on this technology was developed, characterized and compared with its two-dimensional thin-film counterparts fabricated on the same footprint area with equal amount of the Zn anode electrode. Using this approach, we were able to improve a single-layer initial structure with a surface area of 1.3 mm2 to a scaffold structure with ten layers having a surface area of 15 mm2. Discharging through load resistances ranging from 100 to 3000 Ω, the areal energy density and areal capacity of the microbattery were measured as 2.5–3 mWh cm−2 and ~2.5 mAh cm−2, respectively.

A MEMS-enabled biodegradable battery for powering transient implantable devices

Active implantable medical devices (IMD) for the monitoring and treatment of transient disease states have garnered increasing interest in the medical research community. In order for these technologies to be fully viable, they require a similarly biodegradable energy source. This study presents a series of MEMS-enabled biodegradable batteries comprising Mg anodes and Fe cathodes in a 0.1 M MgCl2 electrolyte. The anode was fabricated by electroplating Mg from a non-aqueous solution and passivated with either polycaprolactone or poly(glycerol-sebacate). Mg anodes coated with the biodegradable polymers hindered parasitic corrosion of the biodegradable anode and significantly enhanced the performance of the battery. The batteries demonstrated a capacity and power delivery capability of up to 0.7 mAh and 26 μW, respectively, which are sufficient for powering MEMS-based IMD systems.

Development of Electroplated Magnesium Microstructures for Biodegradable Devices and Energy Sources

This paper presents fabrication approaches for magnesium (Mg) microstructures embedded in biodegradable polymers using through-mold Mg electrodeposition and metaltransfer-molding. Biodegradable implantable electronics have garnered increasing interest from the medical community for the monitoring and treatment of transient diseases. Magnesium is a biodegradable metal with desirable properties, and the ability to micropattern Mg thick films (i.e., about >1 μm) with direct microelectromechanical systems (MEMS) integration would support the development of more sophisticated and clinically relevant biodegradable devices and microsystems. Magnesium microstructures were electroplated through micropatterned water-soluble molds in a nonaqueous electrolyte and transfer molded into a biodegradable polymer. Electroplated Mg compared favorably with commercial Mg foil based on elemental composition, crystal orientation, electrical resistivity, and corrosion behavior. Magnesium electroplated to a thickness of up to 50 μm showed a grain size of ~10 μm, and minimum feature dimensions of 100 μm in width and spacing. Completely biodegradable Mg and poly-L-lactic acid constructs were demonstrated. The application of Mg thick films toward biodegradable energy sources was explored through the fabrication and testing of biodegradable Mg/Fe batteries. The batteries exhibited a capacity and power of up to 2.85 mAh and 39 μW, respectively. Results confirmed the advantages of electrodeposited Mg microstructures for biodegradable MEMS applications.

Multishelled CaO Microspheres Stabilized by Atomic Layer Deposition of Al2O3 for Enhanced CO2 Capture Performance

CO2 capture and storage is a promising concept to reduce anthropogenic CO2 emissions. The most established technology for capturing CO2 relies on amine scrubbing that is, however, associated with high costs. Technoeconomic studies show that using CaO as a high-temperature CO2 sorbent can significantly reduce the costs of CO2 capture. A serious disadvantage of CaO derived from earth-abundant precursors, e.g., limestone, is the rapid, sintering-induced decay of its cyclic CO2 uptake. Here, a template-assisted hydrothermal approach to develop CaO-based sorbents exhibiting a very high and cyclically stable CO2 uptake is exploited. The morphological characteristics of these sorbents, i.e., a porous shell comprised of CaO nanoparticles coated by a thin layer of Al2 O3 (<3 nm) containing a central void, ensure (i) minimal diffusion limitations, (ii) space to accompany the substantial volumetric changes during CO2 capture and release, and (iii) a minimal quantity of Al2 O3 for structural stabilization, thus maximizing the fraction of CO2 -capture-active CaO.

Microfabricated nickel-based electrodes for high-power battery applications

High-surface area, three-dimensional (3D) microstructures are designed and fabricated by the sequential electroplating of sacrificial and structural layers in a photoresist mold. A conformal coating of electrochemically deposited nickel hydroxide (Ni(OH)2) films on these MEMS-enabled multilayer structures enabled the formation of functional electrodes for electrochemical energy storage devices. The characterization of the electrodes is performed galvanostatically at various charge and discharge rates. Electrodes with a varying number of laminations are shown to yield areal capacities from 0.1 to 5.2 mAh cm–2. Power characteristics of the electrodes are determined by applying ultra-high charge rates of up to 120 C. At this high charge rate, the electrode is able to deliver 90% of its capacity.

CaO-Based CO2 Sorbents Effectively Stabilized by Metal Oxides

Calcium looping (i.e., CO2 capture by CaO) is a promising second-generation CO2 capture technology. CaO, derived from naturally occurring limestone, offers an inexpensive solution, but due to the harsh operating conditions of the process, limestone-derived sorbents undergo a rapid capacity decay induced by the sintering of CaCO3 . Here, we report a Pechini method to synthesize cyclically stable, CaO-based CO2 sorbents with a high CO2 uptake capacity. The sorbents synthesized feature compositional homogeneity in combination with a nanostructured and highly porous morphology. The presence of a single (Al2 O3 or Y2 O3 ) or bimetal oxide (Al2 O3 -Y2 O3 ) provides cyclic stability, except for MgO which undergoes a significant increase in its particle size with the cycle number. We also demonstrate a direct relationship between the CO2 uptake and the morphology of the synthesized sorbents. After 30 cycles of calcination and carbonation, the best performing sorbent, containing an equimolar mixture of Al2 O3 and Y2 O3 , exhibits a CO2 uptake capacity of 8.7 mmol CO2  g-1 sorbent, which is approximately 360 % higher than that of the reference limestone.

Optimization of the structural characteristics of CaO and its effective stabilization yield high-capacity CO 2 sorbents

Calcium looping, a CO2 capture technique, may offer a mid-term if not near-term solution to mitigate climate change, triggered by the yet increasing anthropogenic CO2 emissions. A key requirement for the economic operation of calcium looping is the availability of highly effective CaO-based CO2 sorbents. Here we report a facile synthesis route that yields hollow, MgO-stabilized, CaO microspheres featuring highly porous multishelled morphologies. As a thermal stabilizer, MgO minimized the sintering-induced decay of the sorbents’ CO2 capacity and ensured a stable CO2 uptake over multiple operation cycles. Detailed electron microscopy-based analyses confirm a compositional homogeneity which is identified, together with the characteristics of its porous structure, as an essential feature to yield a high-performance sorbent. After 30 cycles of repeated CO2 capture and sorbent regeneration, the best performing material requires as little as 11 wt.% MgO for structural stabilization and exceeds the CO2 uptake of the limestone-derived reference material by ~500%.The economic operation of a carbon dioxide capture technique of calcium looping necessitates highly effective CaO-based CO2 sorbents. Here, the authors report a facile one-pot synthesis approach to yield highly effective, MgO-stabilized, CaO-based CO2 sorbents featuring highly porous multishelled morphologies.

Atomic layer deposition of a film of Al2O3 on electrodeposited copper foams to yield highly effective oxygen carriers for chemical looping combustion-based CO2 capture

A rapid electrochemical deposition protocol is reported to synthesize highly porous Cu foams serving as model oxygen carriers for chemical looping, a promising technology to reduce anthropogenic CO2 emission. To overcome the sintering-induced decay in the oxygen carrying capacity of unsupported Cu foams, Al2O3 films of different thicknesses (0.1-25 nm) are deposited onto the Cu foams via atomic layer deposition (ALD). An ALD-grown Al2O3 overcoat of 20 nm thickness (∼4 wt % Al2O3) is shown to be sufficient to ensure excellent redox cyclic stability. Al2O3-coated Cu foams exhibit a capacity retention of 96% over 10 redox cycles, outperforming their coprecipitated counterpart (equal Al2O3 content). The structural evolution of the stabilized foams is probed in detail and compared to benchmark materials to elucidate the stabilizing role of the Al2O3 overcoat. Upon heat treatment, the initially conformal Al2O3 overcoat induces a fragmentation of large Cu(O) branches into small particles. After multiple redox cycles, the Al2O3 overcoat transforms into sub-micrometer-sized grains of aluminum-containing phases (δ-Al2O3, CuAl2O4, and CuAlO2) that are dispersed homogeneously within the CuO matrix. Finally, the diffusion of Cu through an Al2O3 layer upon heat treatment in an oxidizing atmosphere is probed in model thin films.