Highly Efficient CO2 Electrolysis on Cathodes with Exsolved Alkaline Earth Oxide Nanostructures.

The solid oxide CO2 electrolyzer has the potential to provide storage solutions for intermittent renewable energy sources as well as to reduce greenhouse gas emissions. One of the key challenges remains the poor adsorption and activity toward CO2 reduction on the electrolyzer cathode at typical operating conditions. Here, we show a novel approach in tailoring a perovskite titanate (La, Sr)TiO3+δ cathode surface, by the in situ growing of SrO nanoislands from the host material through the control of perovskite nonstoichiometry. These nanoislands provide very enhanced CO2 adsorption and activation, with stability up to 800 °C, which is shown to be in an intermediate form between carbonate ions and molecular CO2. The activation of adsorbed CO2 molecules results from the interaction of exsolved SrO nanoislands and the defected titanate surface as revealed by DFT calculations. These cathode surface modifications result in an exceptionally high direct CO2 electrolysis performance with current efficiencies near 100%.

[1]  Kui Xie,et al.  Efficient CO2 electrolysis with scandium doped titanate cathode , 2017 .

[2]  Kui Xie,et al.  Enhancing CO2 electrolysis through synergistic control of non-stoichiometry and doping to tune cathode surface structures , 2017, Nature Communications.

[3]  Xingbao Zhu,et al.  Efficient electrolysis of CO2 in symmetrical solid oxide electrolysis cell with highly active La0.3Sr0.7Fe0.7Ti0.3O3 electrode material , 2016 .

[4]  Rafiqul Gani,et al.  Toward the Development and Deployment of Large-Scale Carbon Dioxide Capture and Conversion Processes , 2016 .

[5]  M. Koper,et al.  In Situ Spectroscopic Study of CO2 Electroreduction at Copper Electrodes in Acetonitrile , 2016 .

[6]  S. Assabumrungrat,et al.  Metals (Mg, Sr and Al) modified CaO based sorbent for CO2 sorption/desorption stability in fixed bed reactor for high temperature application , 2016 .

[7]  Kui Xie,et al.  Redox‐Reversible Iron Orthovanadate Cathode for Solid Oxide Steam Electrolyzer , 2015, Advanced science.

[8]  Q. Ma,et al.  Modified strontium titanates: from defect chemistry to SOFC anodes , 2015 .

[9]  Heng Zhang,et al.  Effect of CO2 on the stability of strontium doped lanthanum manganite cathode , 2014 .

[10]  Mogens Bjerg Mogensen,et al.  High temperature electrolysis in alkaline cells, solid proton conducting cells, and solid oxide cells. , 2014, Chemical reviews.

[11]  Fereshteh Meshkani,et al.  Effect of alkaline earth promoters (MgO, CaO, and BaO) on the activity and coke formation of Ni catalysts supported on nanocrystalline Al2O3 in dry reforming of methane , 2014 .

[12]  Yong Zhang,et al.  A composite cathode based on scandium doped titanate with enhanced electrocatalytic activity towards direct carbon dioxide electrolysis. , 2014, Physical chemistry chemical physics : PCCP.

[13]  J. Stevenson,et al.  High-efficiency intermediate temperature solid oxide electrolyzer cells for the conversion of carbon dioxide to fuels , 2014 .

[14]  Dragos Neagu,et al.  In situ growth of nanoparticles through control of non-stoichiometry. , 2013, Nature chemistry.

[15]  E. Longo,et al.  Long-range and short-range structures of cube-like shape SrTiO3 powders: microwave-assisted hydrothermal synthesis and photocatalytic activity. , 2013, Physical chemistry chemical physics : PCCP.

[16]  D. Dong,et al.  Composite fuel electrode La(0.2)Sr(0.8)TiO(3-δ)-Ce(0.8)Sm(0.2)O(2-δ) for electrolysis of CO2 in an oxygen-ion conducting solid oxide electrolyser. , 2012, Physical chemistry chemical physics : PCCP.

[17]  Ping Liu,et al.  Direct octane fuel cells: A promising power for transportation , 2012 .

[18]  B. Viswanathan,et al.  Photocatalytic reduction of carbon dioxide by water on titania: Role of photophysical and structural properties , 2012 .

[19]  G. Tsekouras,et al.  The role of defect chemistry in strontium titanates utilised for high temperature steam electrolysis , 2011 .

[20]  Ping Liu,et al.  Promotion of water-mediated carbon removal by nanostructured barium oxide/nickel interfaces in solid oxide fuel cells , 2011, Nature communications.

[21]  T. Chen,et al.  Surface Phases of TiO2 Nanoparticles Studied by UV Raman Spectroscopy and FT-IR Spectroscopy , 2008 .

[22]  Christopher W. Jones,et al.  Designing adsorbents for CO2 capture from flue gas-hyperbranched aminosilicas capable of capturing CO2 reversibly. , 2008, Journal of the American Chemical Society.

[23]  Yee Soong,et al.  Thermal and Chemical Stability of Regenerable Solid Amine Sorbent for CO2 Capture , 2006 .

[24]  R. Moos,et al.  Defect Chemistry of Donor‐Doped and Undoped Strontium Titanate Ceramics between 1000° and 1400°C , 2005 .

[25]  W. Jauch,et al.  ANOMALOUS ZERO-POINT MOTION IN SRTIO3 : RESULTS FROM GAMMA -RAY DIFFRACTION , 1999 .

[26]  Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.

[27]  Kresse,et al.  Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. , 1996, Physical review. B, Condensed matter.

[28]  Hafner,et al.  Ab initio molecular dynamics for open-shell transition metals. , 1993, Physical review. B, Condensed matter.

[29]  Paxton,et al.  High-precision sampling for Brillouin-zone integration in metals. , 1989, Physical review. B, Condensed matter.

[30]  W. Kohn,et al.  Self-Consistent Equations Including Exchange and Correlation Effects , 1965 .

[31]  P. Hohenberg,et al.  Inhomogeneous Electron Gas , 1964 .

[32]  Chenghao Yang,et al.  Electrolysis of Carbon Dioxide in a Solid Oxide Electrolyzer with Silver-Gadolinium-Doped Ceria Cathode , 2015 .

[33]  D. Dong,et al.  Composite cathode La0.4Sr0.4TiO3−δ–Ce0.8Sm0.2O2−δ impregnated with Ni for high-temperature steam electrolysis , 2014 .

[34]  K. Suslick,et al.  Mechanical activation of CaO-based adsorbents for CO(2) capture. , 2013, ChemSusChem.

[35]  X. Yue,et al.  Alternative Cathode Material for CO2 Reduction by High Temperature Solid Oxide Electrolysis Cells , 2012 .