Synthesis, Characterization and Application of intermetallic Pd-X (Ga, Zn) Nanoparticles derived from ternary Hydrotalcite-like precursors

A novel, feasible synthesis approach for supported intermetallic Pd2Ga and PdZn nanoparticles derived from Hydrotalcite-like compounds (HTlc) is introduced. Ternary HTlc with the nominal composition (Pd2+,M2+)0.70(M3+)0.30(OH)2(CO3)0.15 ∙ m H2O are synthesized by pH-controlled co-precipitation. Mg2+/Ga3+ and Zn2+/Al3+ are chosen as M2+/M3+ combinations to permit formation of the nanocrystalline Pd2Ga and PdZn intermetallic compounds on a porous MgO/MgGa2O4 and ZnO/ZnAl2O4 support, respectively. In addition, a PdMgAl HTlc is prepared as monometallic Pd reference compound on a MgO/MgAl2O4 support. Incorporation of Pd2+ into the HT structure requires octahedral coordination, while Pd2+ ions prefer square planar coordination in aqueous solution. At the same substitution degree of M2+ by Pd2+, complete insertion is achieved for PdZnAl HT. In case of PdMgGa and PdMgAl HT a minor fraction is present as segregated Pd2+ on the external surface of the platelet-like particles with a local environment similar to PdO, i.e. in a square planar coordination. A limit of incorporation into the HT lattice exists at < 1 mol% for the Pd2+ containing precursors. Upon thermal decomposition in reductive atmosphere, intermetallic and metallic nanoparticles ranging from below 2 nm to 6 nm in size and exhibiting monomodal particle size distributions are formed. Alloying of Pd with Ga and Zn changes the crystal structure as well as the electronic structure and leads to the increased formation of isolated adsorption sites at the surface. Furthermore, dynamic surface changes of intermetallic Pd2Ga nanoparticles were noticed at longer exposure time to CO and higher CO coverage. This is attributed to the decomposition into metallic Pd and Ga2O3. The nanostructured Pd2Ga catalyst shows excellent performance in the selective semi-hydrogenation of acetylene similar to a bulk Pd2Ga model catalyst. In comparison to the elemental Pd catalyst the selectivity to ethylene is drastically improved by formation of Pd2Ga. Interestingly, the nanostructered catalyst slowly activates in the feed gas. The activation is triggered faster by a treatment in oxidative atmosphere. These dynamics of the Pd2Ga nanoparticles can be explained by the interplay of surface decomposition into Pd0 and Ga2O3 in oxygen and reversal of the strong-metal support interaction state leading to an increased activity. Furthermore, increased activities and selectivities in methanol steam reforming and methanol synthesis from CO2 are observed for the Pd2Ga and PdZn nanoparticles in contrast to the unmodified Pd particles. These structurally modified Pd catalysts exhibit a considerably lower selectivity to CO and enhanced formation of methanol compared to the monometallic Pd catalyst.Abstract i Zusammenfassung iii Danksagung v List of Figures x List of Tables xiv List of Abbreviations xv Chapter 1: Introduction and Overview 1 1.1. Intermetallic compounds 1 1.2. Motivation 2 1.3. Synthesis strategy for binary Pd-X intermetallic nanoparticles 3 1.4. Pd-Ga system 6 1.5. The Pd-Ga intermetallic compound Pd2Ga 7 1.6. Pd-Zn phase system 9 1.7. Pd-Ga IMCs as selective acetylene hydrogenation catalysts 10 1.8. Pd based IMCs in methanol synthesis and methanol steam reforming 13 1.9. Aims of this work and thesis structure 15 1.10. References 17 Chapter 2: Intermetallic Compound Pd2Ga as a Selective Catalyst for the Semi-Hydrogenation of Acetylene: From Model to High performance Catalyst 21 2.1 Introduction 22 2.2 Experimental Section 24 2.2.1 Synthesis Procedures 24 2.2.2 Characterization Techniques 24 2.2.3 Catalytic Measurements 25 2.3 Results and Discussion 27 2.4 Conclusion 34 2.5 References 36 Chapter 3: Dynamic Surface Processes of nanostructured Pd2Ga catalysts derived from ternary Hydrotalcite-like Precursors 38 3.1 Introduction 39 3.2 Experimental 40 3.2.1 Synthesis conditions 40 3.2.2 Characterization 41 3.2.3 Catalytic performance in the selective hydrogenation of acetylene 43 3.3 Results and Discussion 44 3.3.1 Structural and textural properties of the precursor material 44 3.3.2 Reduction and intermetallic phase formation 49 3.3.3 Structural properties of Pd2Ga nanoparticles 54 3.3.4 IR characterization of supported Pd2Ga nanoparticles during exposure to CO 58 3.3.5 Catalytic performance 62 3.4 Conclusions 69 3.5 References 71 Supplementary Information 73 Chapter 4: Methanol Synthesis and Methanol Steam Reforming of Supported Pd2Ga and PdZn Intermetallic Nanoparticles 79 4.1. Introduction 80 4.2 Experimental 81 4.2.1 Synthesis conditions 81 4.2.2 Characterization 82 4.2.3 Catalytic performance 84 4.2.3.1 Methanol synthesis from CO2 84 4.2.3.2 Methanol steam reforming 85 4.3 Results and discussion 86 4.3.1 Properties of the HTlc precursors 86 4.3.2 Reducibility of the HTlc precursors and IMC formation 88 4.3.2.1 TPR and MS measurements 88 4.3.2.2 XANES measurements 91 4.3.3 Properties of the ex-HTlc samples after reduction 93 4.4 Catalytic properties of the IMCs 97 4.4.1 Methanol synthesis from CO2 97 4.4.2 Steam reforming of methanol 100 4.5 Conclusion 102 4.6 References 103 Supplementary Information 105 Chapter 5: Final summary and conclusion 108 Appendix xvii Curriculum vitae xvii Publications xvii Oral presentations xviii Patent application xviii Poster presentations xi

Structure-function relationship of Strong Metal-Support Interaction studied on supported Pd reference catalysts

Transition metal oxide supported, nano-scaled noble metal catalysts are known to show a variety of surface modifications when they are being reduced at increasing temperatures. Such processes involve for example (surface) alloying and the formation of partially reduced oxidic support overlayers that are both induced by the so-called strong metal-support interaction (SMSI). The present work investigated a series of oxide supported Palladium powder catalysts with a loading variation between 1-5 wt.-% on their structure-function relationship after reduction in different media and at different temperatures to create a reference system and explore the nature of SMSI. Hereby surface and bulk sensitive techniques like XPS, chemisorption, TEM, DRIFTS or XRD were applied to study the influence of electronic and structural modifications on the activity in catalytic oxidation of carbon monoxide which served as the main test reaction and was conducted at ambient pressure. The catalysts were synthesized reproducibly by a controlled co-precipitation approach and by impregnation. The investigated Pd/iron oxide system shows palladium surface decoration at comparably low reduction temperatures. The surface cover was found to be volatile in oxygen containing atmosphere and formed reversibly. Dependent on the Pd particle size it increases the CO oxidation activity. Alloy formation occurs at higher reduction temperatures. In case of the Pd/zinc oxide system reversible surface alloying takes place during reduction that is also beneficial for CO oxidation, but again deactivates fast. When being reduced at even higher temperatures the additional formation of an oxidic overlayer could be observed that does not further activate the system but leads to an overall reduction of active sites. Due to alloy formation, the zinc oxide system at higher conversions shows a different selectivity behavior in acetylene hydrogenation, compared to the iron oxide system. Also in case of the Pd/titania system, reversible surface decoration by partially reduced support happens during reduction. Different to the other investigated systems the surface-cover reversibly decreases CO oxidation activity however. The Pd/alumina system was studied as a less reducible reference. As expected, it does not show SMSI-induced modifications. In the end the work clearly shows that CO oxidation is a convenient method to study activity and stability of SMSI and decouple it from other involved processes. The effects of surface modification on the catalytic activity in this test reaction however strongly depend on the specific system and pre-conditioning and can either be of activating or deactivating nature. The basic principles involved in case of SMSI seem to apply both in UHV model systems and at powder systems at ambient pressure as found by the catalytic measurements.Übergangsmetalloxid geträgerte, nano-skalige Edelmetall-Katalysatoren sind bekannt dafür, eine Reihe von Oberflächen-Veränderungen zu erfahren, wenn sie bei erhöhter Temperatur reduziert werden. Diese Prozesse beinhalten beispielsweise (Oberflächen-) Legierungsbildung und die Ausblidung von teilweise reduzierten, oxidischen Träger- Schichten, in beiden Fällen hervorgerufen durch Starke Metall-Träger Wechselwirkung (Strong Metal-Support Interaction, SMSI). Die vorliegende Arbeit untersuchte eine Reihe von oxid-geträgerten Palladium Pulverkatalysatoren mit einer Variation der Beladung von 1- 5 Gewichts-% auf ihre Struktur-Eigenschafts Beziehungen nach Reduktion in verschiedenen Medien und bei veschiedenen Temperaturen, um ein Referenzsystem zu entwickeln und der Natur von SMSI auf den Grund zu gehen. Dabei kamen oberflächen- und volumensensitive Methoden wie XPS, Chemisorption, TEM, DRIFTS oder XRD zum Einsatz, um den Einfluss von elektronischen und strukturellen Veränderungen auf die Aktivität bei katalytischer Oxidation von Kohlenmonoxid zu untersuchen, welche als wichtigste Testreaktion bei Normaldruck durchgeführt wurde. Die Katalysatoren wurden auf reproduzierbare Weise durch kontrollierte Ko-Fällung und durch Imprägnierung hergestellt. Das untersuchte Pd/Eisenoxid System zeigt Bedeckung der Pd Oberfläche nach Reduktion bei vergleichsweise niedrigen Temperaturen. Diese Bedeckung war instabil in sauerstoffhaltiger Umgebung und bildete sich reversibel aus. Abhängig von der Pd Partikelgröße erhöht sie die Aktivität bei der CO-Oxidation. Legierungsbildung findet bei höheren Reduktionstemperaturen statt. Im Falle von Pd/Zinkoxid findet reversible Legierungsbildung an der Oberfläche statt, die ebenfalls die CO-Oxidation begünstigt, aber ebenfalls schnell deaktiviert. Nach Reduktion bei noch höheren Temperaturen konnte die zusätzliche Ausbildung einer oxidischen Überschicht beobachtet werden, die das System nicht weiter aktivierte, sondern insgesamt die Zahl der aktiven Plätze reduzierte. Wegen Legierungsbildung zeigt das Zinkoxid-System bei höheren Umsätzen in der Acetylenhydrierung ein anderes Selektivitätsverhalten als das Eisenoxid-System. Im Fall von Pd/Titanoxid kommt es während der Reduktion ebenfalls zu reversibler Oberflächen- Bedeckung durch teilweise reduzierten Träger. Anders als in den beiden anderen Fällen verringert diese Schicht hier jedoch die Aktivität in der CO-Oxidation. Pd/Aluminiumoxid wurde als schwer reduzierbares Referenz-System untersucht. Wie erwartet zeigt es keine durch SMSI hervorgerufenen Veränderungen. Schlussendlich konnte in dieser Arbeit gezeigt werden, dass CO-Oxidation eine einfache und geeignete Methode ist, SMSI zu untersuchen und ihren Einfluss auf Aktivität und Stabilität von dem anderer Prozesse zu trennen. Die Effekte von Oberflächenveränderungen auf die katalytische Aktivität dieser Test-Reaktion hängen jedoch stark vom entsprechenden System und der Vorbehandlung ab und können sowohl aktivierender als auch deaktivierender Natur sein. Die Grundlegenden Prinzipien, die bei SMSI eine Rolle spielen, scheinen sowohl im Fall von Modell-Systemen unter UHV-Bedingungen als auch bei Pulver-Systemen bei Normaldruck zu gelten, wie durch die katalytischen Messungen gezeigt wurde

APM 08279+5255: Keck Near- and Mid-IR High-Resolution Imaging

We present Keck high-resolution near-IR (2.2 microns; FWHM~0.15") and mid-IR (12.5 microns; FWHM~0.4") images of APM08279+5255, a z=3.91 IR-luminous BALQSO with a prodigious apparent bolometric luminosity of 5x10^{15} Lsun, the largest known in the universe. The K-band image shows that this system consists of three components, all of which are likely to be the gravitationally lensed images of the same background object, and the 12.5 micron image shows a morphology consistent with such an image configuration. Our lens model suggests that the magnification factor is ~100 from the restframe UV to mid-IR, where most of the luminosity is released. The intrinsic bolometric luminosity and IR luminosity of APM08279+5255 are estimated to be 5x10^{13} Lsun and 1x10^{13} Lsun, respectively. This indicates that APM 08279+5255 is intriniscally luminous, but it is not the most luminous object known. As for its dust contents, little can be determined with the currently available data due to the uncertainties associated with the dust emissivity and the possible effects of differential magnification. We also suggest that the lensing galaxy is likely to be a massive galaxy at z~3.Comment: 32 pages, 4 tables, 11 figures; Accepted for publication in Ap