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Jaime Gómez Díaz

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FIRST-PRINCIPLES MECHANISTIC STUDIES OF AMMONIA-RELATED INDUSTRIAL PROCESSES Jaime Gómez Díaz ISBN: 978-84-694-1247-3 Dipòsit Legal: T-317-2011 ADVERTIMENT. La consulta d’aquesta tesi queda condicionada a l’acceptació de les següents condicions d'ús: La difusió d’aquesta tesi per mitjà del servei TDX (www.tesisenxarxa.net) ha estat autoritzada pels titulars dels drets de propietat intel·lectual únicament per a usos privats emmarcats en activitats d’investigació i docència. No s’autoritza la seva reproducció amb finalitats de lucre ni la seva difusió i posada a disposició des d’un lloc aliè al servei TDX. No s’autoritza la presentació del seu contingut en una finestra o marc aliè a TDX (framing). Aquesta reserva de drets afecta tant al resum de presentació de la tesi com als seus continguts. En la utilització o cita de parts de la tesi és obligat indicar el nom de la persona autora. ADVERTENCIA. La consulta de esta tesis queda condicionada a la aceptación de las siguientes condiciones de uso: La difusión de esta tesis por medio del servicio TDR (www.tesisenred.net) ha sido autorizada por los titulares de los derechos de propiedad intelectual únicamente para usos privados enmarcados en actividades de investigación y docencia. No se autoriza su reproducción con finalidades de lucro ni su difusión y puesta a disposición desde un sitio ajeno al servicio TDR. No se autoriza la presentación de su contenido en una ventana o marco ajeno a TDR (framing). Esta reserva de derechos afecta tanto al resumen de presentación de la tesis como a sus contenidos. En la utilización o cita de partes de la tesis es obligado indicar el nombre de la persona autora. WARNING. On having consulted this thesis you’re accepting the following use conditions: Spreading this thesis by the TDX (www.tesisenxarxa.net) service has been authorized by the titular of the intellectual property rights only for private uses placed in investigation and teaching activities. Reproduction with lucrative aims is not authorized neither its spreading and availability from a site foreign to the TDX service. Introducing its content in a window or frame foreign to the TDX service is not authorized (framing). This rights affect to the presentation summary of the thesis as well as to its contents. In the using or citation of parts of the thesis it’s obliged to indicate the name of the author. UNIVERSITAT ROVIRA I VIRGILI FIRST-PRINCIPLES MECHANISTIC STUDIES OF AMMONIA-RELATED INDUSTRIAL PROCESSES Jaime Gómez Díaz ISBN:978-84-694-1247-3/T-317-2011 UNIVERSITAT ROVIRA I VIRGILI FIRST-PRINCIPLES MECHANISTIC STUDIES OF AMMONIA-RELATED INDUSTRIAL PROCESSES Jaime Gómez Díaz ISBN:978-84-694-1247-3/T-317-2011 UNIVERSITAT ROVIRA I VIRGILI FIRST-PRINCIPLES MECHANISTIC STUDIES OF AMMONIA-RELATED INDUSTRIAL PROCESSES Jaime Gómez Díaz ISBN:978-84-694-1247-3/T-317-2011 First-principles mechanistic studies of ammonia-related industrial processes Jaime G´omezD´ıaz Doctoral Thesis supervised by: Dra. N´uria L´opez Alonso Departament de Qu´ımica F´ısica i Inorg`anica Tarragona 2010 UNIVERSITAT ROVIRA I VIRGILI FIRST-PRINCIPLES MECHANISTIC STUDIES OF AMMONIA-RELATED INDUSTRIAL PROCESSES Jaime Gómez Díaz ISBN:978-84-694-1247-3/T-317-2011 UNIVERSITAT ROVIRA I VIRGILI FIRST-PRINCIPLES MECHANISTIC STUDIES OF AMMONIA-RELATED INDUSTRIAL PROCESSES Jaime Gómez Díaz ISBN:978-84-694-1247-3/T-317-2011 Institute of Chemical Research of Catalonia Avgda. Pa¨ısos Catalans 16 43007 Tarragona (Spain) I STATE that the present work entitled “First-principles mechanistic studies of ammonia-related processes” presented by Jaime G´omez D´ıaz to opt to the title of European Doctor, has been carried out under my su- pervision at the Institute of Chemical Research of Catalonia (ICIQ) and that it fulfils all the necessary requirements. Tarragona, November 2010 Dr. N´uria L´opez UNIVERSITAT ROVIRA I VIRGILI FIRST-PRINCIPLES MECHANISTIC STUDIES OF AMMONIA-RELATED INDUSTRIAL PROCESSES Jaime Gómez Díaz ISBN:978-84-694-1247-3/T-317-2011 UNIVERSITAT ROVIRA I VIRGILI FIRST-PRINCIPLES MECHANISTIC STUDIES OF AMMONIA-RELATED INDUSTRIAL PROCESSES Jaime Gómez Díaz ISBN:978-84-694-1247-3/T-317-2011 Acknowledgments Esta tesis no hubiera sido posible sin su directora, N´uria L´opez, y sin la beca que me concedi´opara trabajar en un centro con recursos tan ex- traordinarios como los del ICIQ. Haluan kiitt¨a¨at¨all¨aerityisell¨atavalla FT Karoliina Honkalaa h¨anen vieraanvaraisuudestaan, mutta ennen kaikkea h¨anen yst¨av¨allisest¨aomistautumisestaan ohjaamiselleni. Una altra per- sona que em va ajudar for¸ca a acabar aquesta tesi va ser la N´uria Vendrell i la seva, sempre impecable, feina. Me gustar´ıa tambi´en agradecer a todas las instituciones que han financiado/apoyado mi trabajo de investigaci´on: ante todo el ICIQ, pero tambi´en otras como BSC, CSC, HPC-Europa2 program, etc. Ahora bien, si he llegado a esta etapa del camino en casi aceptables condiciones de salud mental y con pelo por encima de las cejas, es tambi´en culpa de mucha otra gente. No me gustar´ıa imaginarme como hubieran sido estos m´as de 4 a˜nos sin ella en el despacho... ¡Hecho, M´onica! Mucho, much´ısimo han contribuido tambi´en a esta tesis el resto de “los te´oricos”. Gracias, Ata, Gerard, Pere, Torstein, Maria, Eva, Crisa, Mart´ın, Joan y tod@s los dem´as (as´ıno me dejar´ea nadie y no llenar´e8 p´aginas...), con un saludo especial para Carles y Feliu. He de agradecer a mi cocina el regalarme una hora diaria (y alguna extra los fines de semana) de buen humor, conversaciones y sobre todo desconexi´on: ¡muchas gracias, chic@s! Thanks also to Ville, Sergio, Jenni, Riita-Liisa, Vesa, Kaisa, Olga and Lauri; for making me feel as in my own (cold) home at Jyv¨askyl¨aand Helsinki. Gracias tambi´en al resto de gente del ICIQ, de la URV, de Tarragona-city y de la UAM (¡con vosotros empez´otodo esto!) que no formaba parte de ninguno de los subconjuntos anteriores, pero, especial- UNIVERSITAT ROVIRA I VIRGILI FIRST-PRINCIPLES MECHANISTIC STUDIES OF AMMONIA-RELATED INDUSTRIAL PROCESSES Jaime Gómez Díaz ISBN:978-84-694-1247-3/T-317-2011 viii mente, a mis incre´ıbles compa˜neros de los cursos de doctorado y del mas- ter: ¡c´omo nos lo pasamos! Muchas gracias tambi´en a toda la gente que rodea “mi otra vida”. Especialmente a Mar´ıa, Ricardo, Chus y tod@s (nunca olvidados, os lo prometo) los dem´as: Luis, Willy, Kaka, Nuria, Sergio, el Kalvo, Marcos, Robles, Zahara, Berta, Bel´en, Dani, Yolanda, Ana, Alla, Nacho, Desi, la gente del GRM... y muchos, muchos otros. Tengo mucho que agradecer a mi familia: mis padres (¡todav´ıa me acuerdo de lo de la gasolinera!), mi hermana, Nena y Diana; y por ´ultimo, a Laura. Espero que el dejarla en ´ultimo lugar represente de alguna manera todas las cosas que le tengo que agradecer y que no creo que se pudieran expresar en papel (ni en formato electr´onico). UNIVERSITAT ROVIRA I VIRGILI FIRST-PRINCIPLES MECHANISTIC STUDIES OF AMMONIA-RELATED INDUSTRIAL PROCESSES Jaime Gómez Díaz ISBN:978-84-694-1247-3/T-317-2011 Nada habr´ıa podido suceder si alguien no lo hubiera imaginado primero, Reinhold Messner UNIVERSITAT ROVIRA I VIRGILI FIRST-PRINCIPLES MECHANISTIC STUDIES OF AMMONIA-RELATED INDUSTRIAL PROCESSES Jaime Gómez Díaz ISBN:978-84-694-1247-3/T-317-2011 UNIVERSITAT ROVIRA I VIRGILI FIRST-PRINCIPLES MECHANISTIC STUDIES OF AMMONIA-RELATED INDUSTRIAL PROCESSES Jaime Gómez Díaz ISBN:978-84-694-1247-3/T-317-2011 Contents I Introduction 1 1 Introduction 3 1.1 Catalysis ............................ 3 1.1.1 Heterogeneous catalysis . 4 1.2 Ostwald process: HNO3 production.............. 5 1.2.1 HNO3:propertiesanduses . 5 1.2.2 Production ....................... 6 1.3 Degussa and Andrussow processes: HCN production . 9 1.3.1 HCN:propertiesanduses . 9 1.3.2 Production ....................... 10 1.4 MacArthur-Forrest process: gold ore extraction . 13 1.4.1 Gold: properties and uses . 13 1.4.2 Extraction........................ 14 1.5 Thesisoutline.......................... 16 2 Theoretical background 17 2.1 Introduction........................... 17 2.2 Density Functional Theory . 18 2.3 Formalism............................ 18 2.4 Approximations......................... 21 2.5 Implementation......................... 22 2.5.1 Pseudopotentials . 22 2.5.2 Plane waves as basis sets . 24 2.5.3 Realspacemethods . 24 2.5.4 k-points ......................... 26 2.5.5 Electronic minimization . 27 xi UNIVERSITAT ROVIRA I VIRGILI FIRST-PRINCIPLES MECHANISTIC STUDIES OF AMMONIA-RELATED INDUSTRIAL PROCESSES Jaime Gómez Díaz ISBN:978-84-694-1247-3/T-317-2011 xii CONTENTS 2.6 Ionicrelaxation......................... 27 2.6.1 Supercells........................ 29 2.7 Baderanalysis ......................... 30 2.8 Electron Localization Function . 30 2.9 Transition state searching . 32 2.9.1 RegularNEBmethod . 33 2.9.2 Climbing Image NEB method . 34 2.10 Ab-Initio thermodynamics. .. .. .. .. .. 35 2.11 Linearrelationships. 36 2.11.1 Brønsted-Evans-Polanyi relations . 37 2.11.2 Adsorption energy with binding energy of an atom relations......................... 37 II Results 39 3 HNO3 synthesis: Results 41 3.1 Computational details . 41 3.2 A particular case: Au(111) . 42 3.2.1 Previousworks ..................... 43 3.2.2 Ammonia dehydrogenation on Au(111) . 44 3.2.3 NO and N2 formation on Au(111) . 48 3.2.4 Kineticmodeling . 50 3.2.5 Kinetic model for the Au(111) surface. 53 3.3 A more general case: Transition Metals . 56 3.3.1 Previousworks ..................... 56 3.3.2 NO and N2 formation on transition metals . 58 3.3.3 Reactivity on Me(111) flat surfaces . 59 3.3.4 Reactivity on Me(211) stepped surfaces .
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