Carbon Nanotube Growth on Nanozirconia under Strong Cathodic Polarization in Steam and Carbon Dioxide

Growth of carbon nanotubes (CNTs) catalyzed by zirconia nanoparticles was observed in the Ni–yttria doped zirconia (YSZ) composite cathode of a solid oxide electrolysis cell (SOEC) at approximately 875 °C during co‐electrolysis of CO2 and H2O to produce CO and H2. CNT was observed to grow under large cathodic polarizations specifically at the first 1 to 2 μm Ni–YSZ active cathode layer next to the YSZ electrolyte. High resolution transmission electron microscopy (HRTEM) shows that the CNTs are multi‐walled with diameters of approximately 20 nm and the catalyst particles have diameters in the range of 5 to 25 nm. The results of HRTEM and energy dispersive X‐ray spectroscopy (EDS) analysis confirm that the catalyst particles attached to the CNT are cubic zirconia. Most of the zirconia particles are located at one end of the CNTs, but particles embedded in the walls or inside the CNTs are also observed. Apart from the CNTs, graphitic layers covering zirconia nanoparticles are also widely observed. This work describes nano‐zirconia acting as a catalyst for the growth of CNT during electrochemical conversion of CO2 and H2O in a Ni‐YSZ cermet under strong cathodic polarization. An electrocatalytic mechanism is proposed for the CNT growth in SOECs. These findings provide further understanding not only on the mechanism of the catalytic growth of CNTs, but also on the local electrochemical properties of a highly polarized Ni–YSZ cathode at the micro and nano level.

[1]  S. Ebbesen,et al.  Degradation of Solid Oxide Cells during Co-Electrolysis of H2O and CO2: Carbon Deposition under High Current Densities , 2013 .

[2]  J. Robertson,et al.  Tantalum-oxide catalysed chemical vapour deposition of single- and multi-walled carbon nanotubes , 2013 .

[3]  R. Baughman,et al.  Carbon Nanotubes: Present and Future Commercial Applications , 2013, Science.

[4]  Suojiang Zhang,et al.  Catalytic Methanation of CO and CO2 in Coke Oven Gas over Ni–Co/ZrO2–CeO2 , 2013 .

[5]  F. Tietz,et al.  Degradation phenomena in a solid oxide electrolysis cell after 9000 h of operation , 2013 .

[6]  D. Su,et al.  Recent progress on the growth mechanism of carbon nanotubes: a review. , 2011, ChemSusChem.

[7]  R. Schlögl,et al.  Gelöster Kohlenstoff kontrolliert die erste Phase des Nanokohlenstoffwachstums , 2011 .

[8]  Qiang Zhang,et al.  Dissolved carbon controls the initial stages of nanocarbon growth. , 2011, Angewandte Chemie.

[9]  Chenghua Sun,et al.  Importance of oxygen in the metal-free catalytic growth of single-walled carbon nanotubes from SiO(x) by a vapor-solid-solid mechanism. , 2011, Journal of the American Chemical Society.

[10]  Jiaqi Huang,et al.  Embedded high density metal nanoparticles with extraordinary thermal stability derived from guest-host mediated layered double hydroxides. , 2010, Journal of the American Chemical Society.

[11]  A. Sakoda,et al.  Thin-walled carbon nanotubes grown using a zirconium catalyst , 2010 .

[12]  Jiaqi Huang,et al.  Carbon-nanotube-array double helices. , 2010, Angewandte Chemie.

[13]  Andrew T. Harris,et al.  An Updated Review of Synthesis Parameters and Growth Mechanisms for Carbon Nanotubes in Fluidized Beds , 2010 .

[14]  Christopher Graves,et al.  Production of Synthetic Fuels by Co-Electrolysis of Steam and Carbon Dioxide , 2009 .

[15]  J. Warner,et al.  Investigating the graphitization mechanism of SiO(2) nanoparticles in chemical vapor deposition. , 2009, ACS nano.

[16]  A. Rinzler,et al.  Nanoscale zirconia as a nonmetallic catalyst for graphitization of carbon and growth of single- and multiwall carbon nanotubes. , 2009, Journal of the American Chemical Society.

[17]  S. Barnett,et al.  Syngas Production By Coelectrolysis of CO2/H2O: The Basis for a Renewable Energy Cycle , 2009 .

[18]  Carl M. Stoots,et al.  Syngas Production via High-Temperature Coelectrolysis of Steam and Carbon Dioxide , 2009 .

[19]  Chang Liu,et al.  Metal-catalyst-free growth of single-walled carbon nanotubes. , 2009, Journal of the American Chemical Society.

[20]  Yong Qian,et al.  Metal-catalyst-free growth of single-walled carbon nanotubes on substrates. , 2009, Journal of the American Chemical Society.

[21]  Yiyu Feng,et al.  Horizontally aligned single-walled carbon nanotube on quartz from a large variety of metal catalysts. , 2008, Nano letters.

[22]  Satoru Suzuki,et al.  Mechanism of gold-catalyzed carbon material growth. , 2008, Nano letters.

[23]  Huaping Liu,et al.  Growth of Single-Walled Carbon Nanotubes from Ceramic Particles by Alcohol Chemical Vapor Deposition , 2008 .

[24]  T. Pichler,et al.  Oxide-driven carbon nanotube growth in supported catalyst CVD. , 2007, Journal of the American Chemical Society.

[25]  S. Jensen,et al.  Hydrogen and synthetic fuel production from renewable energy sources , 2007 .

[26]  C. Boothroyd,et al.  Dynamical observation of bamboo-like carbon nanotube growth. , 2007, Nano letters.

[27]  Zheng Zhang,et al.  Millimeter-Thick Single-Walled Carbon Nanotube Forests: Hidden Role of Catalyst Support , 2007, 0704.0915.

[28]  J. Robertson,et al.  In situ observations of catalyst dynamics during surface-bound carbon nanotube nucleation. , 2007, Nano letters.

[29]  Satoru Suzuki,et al.  Single-walled carbon nanotube growth from highly activated metal nanoparticles. , 2006, Nano letters.

[30]  W. Pompe,et al.  Novel catalysts, room temperature, and the importance of oxygen for the synthesis of single-walled carbon nanotubes. , 2005, Nano letters.

[31]  Anubhav Jain,et al.  Carbothermal reduction synthesis of nanocrystalline zirconium carbide and hafnium carbide powders using solution-derived precursors , 2004 .

[32]  Taeghwan Hyeon,et al.  Diameter-Controlled Synthesis of Discrete and Uniform-Sized Single-Walled Carbon Nanotubes Using Monodisperse Iron Oxide Nanoparticles Embedded in Zirconia Nanoparticle Arrays as Catalysts , 2004 .

[33]  S. Lau,et al.  The synthesis of carbon nanotubes and zirconium carbide composite films on a glass substrate , 2004 .

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

[35]  A. Nasibulin,et al.  The role of metal nanoparticles in the catalytic production of single-walled carbon nanotubes—a review , 2003 .

[36]  S. Pennycook,et al.  Nucleation of single-walled carbon nanotubes. , 2003, Physical review letters.

[37]  J. Janek,et al.  Microspectroscopy at a moving reduction front in zirconia solid electrolyte , 2002 .

[38]  J. Nørskov,et al.  Oxygen vacancies as active sites for water dissociation on rutile TiO(2)(110). , 2001, Physical review letters.

[39]  G. Thornton,et al.  Imaging Water Dissociation on TiO(2)(110). , 2001, Physical review letters.

[40]  K. D. de Jong,et al.  Carbon Nanofibers: Catalytic Synthesis and Applications , 2000 .

[41]  J. Yates,et al.  TI3+ DEFECT SITES ON TIO2(110) : PRODUCTION AND CHEMICAL DETECTION OF ACTIVE SITES , 1994 .

[42]  R. N. Blumenthal,et al.  Electronic Transport in 8 Mole Percent Y[sub 2]O[sub 3]-ZrO[sub 2] , 1989 .

[43]  R. N. Blumenthal,et al.  Thermodynamic Properties of Nonstoichiometric Yttria‐Stabilized Zirconia at Low Oxygen Pressures , 1989 .

[44]  A. Isenberg Energy conversion via solid oxide electrolyte electrochemical cells at high temperatures , 1981 .

[45]  J. Rostrup-Nielsen Mechanisms of carbon formation on nickel-containing catalysts , 1977 .

[46]  R. J. Waite,et al.  Formation of carbonaceous deposits from the platinum-iron catalyzed decomposition of acetylene , 1975 .

[47]  R. J. Waite,et al.  Nucleation and growth of carbon deposits from the nickel catalyzed decomposition of acetylene , 1972 .

[48]  T. Etsell,et al.  Overpotential Behavior of Stabilized Zirconia Solid Electrolyte Fuel Cells , 1971 .

[49]  S. Ebbesen,et al.  Carbon Deposition in Solid Oxide Cells during Co-Electrolysis of H2O and CO2 , 2014 .

[50]  Wei Zhang,et al.  Microstructural Degradation of Ni/YSZ Electrodes in Solid Oxide Electrolysis Cells under High Current , 2013 .

[51]  K. Lackner,et al.  Sustainable hydrocarbon fuels by recycling CO2 and H2O with renewable or nuclear energy , 2011 .

[52]  S. Singhal,et al.  Advanced anodes for high-temperature fuel cells , 2004, Nature materials.

[53]  W. Dönitz,et al.  High-temperature electrolysis of water vapor—status of development and perspectives for application , 1985 .