Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


Title: Enhanced CO 2 electrolysis with a SrTiO 3 cathode through a dual doping strategy
The significant role of perovskite defect chemistry through A-site doping of strontium titanate with lanthanum for CO 2 electrolysis properties is demonstrated. Here we present a dual strategy of A-site deficiency and promoting adsorption/activation by making use of redox active dopants such as Mn/Cr linked to oxygen vacancies to facilitate CO 2 reduction at perovskite titanate cathode surfaces. Solid oxide electrolysers based on oxygen-excess La 0.2 Sr 0.8 Ti 0.9 Mn(Cr) 0.1 O 3+δ , A-site deficient (La 0.2 Sr 0.8 ) 0.9 Ti 0.9 Mn(Cr) 0.1 O 3−δ and undoped La 0.2 Sr 0.8 Ti 1.0 O 3+δ cathodes are evaluated. In situ infrared spectroscopy reveals that the adsorbed and activated CO 2 adopts an intermediate chemical state between a carbon dioxide molecule and a carbonate ion. The double strategy leads to optimal performance being observed after 100 h of high-temperature operation and 3 redox cycles, suggesting a promising cathode material for CO 2 electrolysis.  more » « less
Award ID(s):
1832809
PAR ID:
10101315
Author(s) / Creator(s):
; ; ; ; ; ;
Date Published:
Journal Name:
Journal of Materials Chemistry A
Volume:
7
Issue:
6
ISSN:
2050-7488
Page Range / eLocation ID:
2764 to 2772
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ; ; ; ; (, Journal of Materials Chemistry A)
    null (Ed.)
    Sr(Ti 0.3 Fe 0.7 )O 3−δ (STF) and the associated exsolution electrodes Sr 0.95 (Ti 0.3 Fe 0.63 Ru 0.07 )O 3−δ (STFR), or Sr 0.95 (Ti 0.3 Fe 0.63 Ni 0.07 )O 3−δ (STFN) are alternatives to Ni-based cermet fuel electrodes for solid oxide electrochemical cells (SOCs). They can provide improved tolerance to redox cycling and fuel impurities, and may allow direct operation with hydrocarbon fuels. However, such perovskite-oxide-based electrodes present processing challenges for co-sintering with thin electrolytes to make fuel electrode supported SOCs. Thus, they have been mostly limited to electrolyte-supported SOCs. Here, we report the first example of the application of perovskite oxide fuel electrodes in novel oxygen electrode supported SOCs (OESCs) with thin YSZ electrolytes, and demonstrate their excellent performance. The OESCs have La 0.8 Sr 0.2 MnO 3−δ –Zr 0.92 Y 0.16 O 2−δ (LSM–YSZ) oxygen electrode-supports that are enhanced via infiltration of SrTi 0.3 Fe 0.6 Co 0.1 O 3−δ , while the fuel electrodes are either Ni-YSZ, STF, STFN, or STFR. Fuel cell power density as high as 1.12 W cm −2 is obtained at 0.7 V and 800 °C in humidified hydrogen and air with the STFR electrode, 60% higher than the same cell made with a Ni-YSZ electrode. Electrolysis current density as high as −1.72 A cm −2 is obtained at 1.3 V and 800 °C in 50% H 2 O to 50% H 2 mode; the STFR cell yields a value 72% higher than the same cell made with a Ni-YSZ electrode, and competitive with the widely used conventional Ni-YSZ-supported cells. The high performance is due in part to the low resistance of the thin YSZ electrolyte, and also to the low fuel electrode polarization resistance, which decreases with fuel electrode in the order: Ni-YSZ > STF > STFN > STFR. The high performance of the latter two electrodes is due to exsolution of catalytic metal nanoparticles; the results are discussed in terms of the microstructure and properties of each electrode material, and surface oxygen exchange resistance values are obtained over a range of conditions for STF, STFN, and STFN. The STF fuel electrodes also provide good stability during redox cycling. 
    more » « less
  2. ; ; ; ; ; ; (, Journal of Materials Chemistry A)
    Sr(Ti 1−x Fe x )O 3−δ (STF) has recently been explored as an oxygen electrode for solid oxide electrochemical cells (SOCs). Model thin film electrode studies show oxygen surface exchange rates that generally improve with increasing Fe content when x < 0.5, and are comparable to the best Co-containing perovskite electrode materials. Recent results on porous electrodes with the specific composition Sr(Ti 0.3 Fe 0.7 )O 3−δ show excellent electrode performance and stability, but other compositions have not been tested. Here we report results for porous electrodes with a range of compositions from x = 0.5 to 0.9. The polarization resistance decreases with increasing Fe content up to x = 0.7, but increases for further increases in x . This results from the interaction of two effects – the oxygen solid state diffusion coefficient increases with increasing x , but the electrode surface area and surface oxygen exchange rate decrease due to increased sinterability and Sr surface segregation for the Fe-rich compositions. Symmetric cells showed no degradation during 1000 h life tests at 700 °C even at a current density of 1.5 A cm −2 , showing that all the STF electrode compositions worked stably in both fuel cell mode and electrolysis modes. The excellent stability may be explained by X-ray Photoelectron Spectroscopy (XPS) results showing that the amount of surface segregated Sr did not change during the long-term testing, and by relatively low polarization resistances that help avoid electrode delamination. 
    more » « less
  3. ; ; ; ; ; ; (, Journal of Materials Chemistry A)
    La 0.7 Sr 0.2 Ni 0.2 Fe 0.8 O 3 (LSNF), having thermochemical stability, superior ionic and electronic conductivity, and structural flexibility, was investigated as a cathode in SOECs. Exsolution of nanoparticles by reduction of LSNF at elevated temperatures can modulate the characteristics of adsorption, electron transfer, and oxidation states of catalytically active atoms, consequently improving the electrocatalytic activity. The exsolution of NiFe and La 2 NiO 4 nanoparticles to the surface of LSNF under reducing atmosphere (5% H 2 /N 2 ) was verified at various temperatures (500–800 °C) by IFFT from ETEM, TPR and in situ XRD. The exsolved nanoparticles obtained uniform size distribution (4.2–9.2 nm) and dispersion (1.31 to 0.61 × 10 4 particle per μm 2 ) depending on the reduction temperature (700–800 °C) and time (0–10 h). The reoxidation of the reduced LSNF (Red-LSNF) was verified by the XRD patterns, indicative of its redox ability, which allows for redistribution of the nanoparticles between the surface and the bulk. TPD-DRIFTS analysis demonstrated that Red-LSNF had superior H 2 O and CO 2 adsorption behavior as compared to unreduced LSNF, which we attributed to the abundance of oxygen vacancy sites and the exsolved NiFe and La 2 NiO 4 nanoparticles. After the reduction of LSNF, the decreases in the oxidation states of the catalytically active ions, Fe and Ni, were characterized on the surface by XPS as well as in the bulk by XANES. The electrochemical performance of the Red-LSNF cell was superior to that of the LSNF cell for electrolysis of H 2 O, CO 2 , and H 2 O/CO 2 . 
    more » « less
  4. ; ; ; ; ; ; (, Advanced Energy and Sustainability Research)
    Conventional methods for hydrogen production, such as steam methane reforming, face increasing scrutiny due to their reliance on fossil fuels, high CO2emissions, and significant capital costs. Sorption‐enhanced steam reforming using renewable feedstocks, where CO2is captured in situ, presents a more sustainable alternative. This study investigates the suitability of A‐ and B‐site doped strontium ferrite‐type Ruddlesden–Popper oxides (RPO) as robust CO2sorbents, with particular attention on their application in glycerol‐based hydrogen production. Packed bed reactor experiments, complemented by comprehensive characterizations, are systematically conducted to assess and compare the performance of RPO with a stoichiometry of (SrxCa1−x)2Fe0.9Ni0.1O4−δ(RPOs) with that of traditional perovskite oxides, that is, SrxCa1−xFe0.9Ni0.1O4−δ(POs), and to unravel the underlying phase transition pathways. Specifically, RPO with a nominal stoichiometry of Sr1.4Ca0.6Fe0.9Ni0.1O4−δforms an Sr3Fe2O7‐type active phase, exhibiting high H2purities (≈95 vol%) coupled with stable CO2sorption capacity. Notably, its CO2prebreakthrough time is more than six times longer than that of its perovskite counterpart in the sequential Ni‐bed configuration. Finally, the interplay between the reduction and carbonation reactions is examined, highlighting the synergistic benefits that enable the sorbent to fully realize its CO2uptake potential. 
    more » « less
  5. ; ; ; ; ; ; ; ; ; (, Journal of Materials Chemistry A)
    Electron doping in perovskites is an effective approach to design and tailor the structure and property of materials. In A 2 BB′O 6−δ -type double perovskites, B-site cation order can be tunable by A-site modification, potentially leading to significant effect on the oxygen nonstoichiometry of the compounds. La 3+ -doped Sr 2 FeMoO 6−δ (Sr 2−x La x FeMoO 6−δ , SLFM with 0 ≤ x ≤ 1) double perovskites have been designed and characterized systematically in this study as anode materials for solid oxide fuel cells. Rietveld refinement of powder X-ray diffraction reveals a crystalline symmetry transition of SLFM from tetragonal to orthorhombic with the increase of La content, driven by the extra electron onto the antibonding orbitals of e g and t 2g of Fe/Mo cations. An increase in Fe/Mo anti-site defect accompanies this phase transition. Solid oxide fuel cells incorporating the Sr 1.8 La 0.2 FeMoO 6−δ (SLFM2) anode demonstrate impressive power outputs and stable performance under direct CH 4 operation because of its altered electronic structure, desired oxygen vacancy concentration and enhanced reducibility. Density functional theory plus U correction calculations provide an insight into how La doping affects the Fe/Mo anti-site defects and consequently the oxygen transport dynamics. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Text Encoded Conversion
  • XML
  • Save / Share this Record
  • Send to Email