Nano-socketed nickel particles with enhanced coking resistance grown in situ by redox exsolution

Metal particles supported on oxide surfaces are used as catalysts for a wide variety of processes in the chemical and energy conversion industries. For catalytic applications, metal particles are generally formed on an oxide support by physical or chemical deposition, or less commonly by exsolution from it. Although fundamentally different, both methods might be assumed to produce morphologically and functionally similar particles. Here we show that unlike nickel particles deposited on perovskite oxides, exsolved analogues are socketed into the parent perovskite, leading to enhanced stability and a significant decrease in the propensity for hydrocarbon coking, indicative of a stronger metal–oxide interface. In addition, we reveal key surface effects and defect interactions critical for future design of exsolution-based perovskite materials for catalytic and other functionalities. This study provides a new dimension for tailoring particle–substrate interactions in the context of increasing interest for emergent interfacial phenomena.

[1]  William T. Wallace,et al.  The nucleation, growth, and stability of oxide-supported metal clusters , 2005 .

[2]  Hubert A. Gasteiger,et al.  Handbook of fuel cells : fundamentals technology and applications , 2003 .

[3]  J. Irvine,et al.  Enhancing electronic conductivity in strontium titanates through correlated A and B-site doping , 2011 .

[4]  T. Okamoto,et al.  Self-regeneration of a Pd-perovskite catalyst for automotive emissions control , 2002, Nature.

[5]  N. Browning,et al.  Ultralow Contact Resistance at an Epitaxial Metal/Oxide Heterojunction Through Interstitial Site Doping , 2013, Advanced materials.

[6]  J. House,et al.  Atomic Structure and Properties , 2016 .

[7]  Acknowledgements , 1992, Experimental Gerontology.

[8]  Bilge Yildiz,et al.  Cation size mismatch and charge interactions drive dopant segregation at the surfaces of manganite perovskites. , 2013, Journal of the American Chemical Society.

[9]  H. Hwang,et al.  BASIC NOTIONS , 2022 .

[10]  K. Szot,et al.  Surfaces of reduced and oxidized SrTiO 3 from atomic force microscopy , 1999 .

[11]  O. Joubert,et al.  New SOFC electrode materials: The Ni-substituted LSCM-based compounds (La0.75Sr0.25)(Cr0.5Mn0.5 − xNix)O3 − δ and (La0.75Sr0.25)(Cr0.5 − xNixMn0.5)O3 − δ , 2010 .

[12]  Jens Kehlet.  Mechanisms for catalytic carbon nanofiber growth studied by ab initio density functional theory calculations , 2016 .

[13]  C. Campbell,et al.  Ceria Maintains Smaller Metal Catalyst Particles by Strong Metal-Support Bonding , 2010, Science.

[14]  San Ping Jiang,et al.  Nanoscale and nano-structured electrodes of solid oxide fuel cells by infiltration: Advances and challenges , 2012 .

[15]  P. Fornasiero,et al.  Embedded phases: a way to active and stable catalysts. , 2010, ChemSusChem.

[16]  Wuzong Zhou,et al.  Disruption of extended defects in solid oxide fuel cell anodes for methane oxidation , 2006, Nature.

[17]  Yan Chen,et al.  Impact of Sr segregation on the electronic structure and oxygen reduction activity of SrTi1−xFexO3 surfaces , 2012 .

[18]  G. Tsekouras,et al.  Step-change in high temperature steam electrolysis performance of perovskite oxide cathodes with exsolution of B-site dopants , 2013 .

[19]  Yusuke Yamada,et al.  Nanocrystal bilayer for tandem catalysis. , 2011, Nature chemistry.

[20]  L. Marks,et al.  La0.8Sr0.2Cr1 − xRuxO3 − δ–Gd0.1Ce0.9O1.95 solid oxide fuel cell anodes: Ru precipitation and electrochemical performance , 2009 .

[21]  Akira Ohtomo,et al.  A high-mobility electron gas at the LaAlO3/SrTiO3 heterointerface , 2004, Nature.

[22]  E. Ivers-Tiffée,et al.  Formation and migration of cation defects in the perovskite oxide LaMnO3 , 1999 .

[23]  R. Waser,et al.  Switching the electrical resistance of individual dislocations in single-crystalline SrTiO3 , 2006, Nature materials.

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

[25]  D. Bonnell,et al.  Scanning probe microscopy of oxide surfaces: atomic structure and properties , 2008 .

[26]  J. Rostrup-Nielsen,et al.  Innovation and science in the process industry: Steam reforming and hydrogenolysis , 1999 .

[27]  Scott A. Barnett,et al.  SOFC Anode Performance Enhancement through Precipitation of Nanoscale Catalysts , 2007 .

[28]  G. Xiao,et al.  Coking- and Sintering-Resistant Palladium Catalysts Achieved Through Atomic Layer Deposition , 2012, Science.

[29]  C. Ewels,et al.  Carbon nanotube growth mechanism switches from tip- to base-growth with decreasing catalyst particle size , 2008 .

[30]  Kui Zhang,et al.  Reversible precipitation/dissolution of precious-metal clusters in perovskite-based catalyst materials: Bulk versus surface re-dispersion , 2012 .

[31]  Christopher B. Murray,et al.  Control of Metal Nanocrystal Size Reveals Metal-Support Interface Role for Ceria Catalysts , 2013, Science.

[32]  Norma E. Conner,et al.  Advances and Challenges , 2016, The American journal of hospice & palliative care.

[33]  Satoshi Hamakawa,et al.  Partial oxidation of methane over aNi/BaTiO3 catalyst prepared by solid phasecrystallization , 1997 .

[34]  J. Nørskov,et al.  Atomic-scale imaging of carbon nanofibre growth , 2004, Nature.