On the STM imaging contrast of graphite: towards a “true’' atomic resolution

Different phenomena observed in the high-resolution images of graphite by scanning tunneling microscopy (STM) or atomic force microscopy (AFM) such as the asymmetry in the charge density of neighboring carbon atoms in a hexagon, the high corrugation amplitudes and the apparent absence of point defects has led to a controversial discussion since the first published STM images of graphite. Different theoretical concepts and hypotheses have been developed to explain these phenomena. Despite these efforts a generally accepted interpretation is still lacking. In this paper we discuss a possible imaging mechanism based on mechanical considerations. Forces acting between tip and sample are taken into account to explain the image contrast. We present for the first time a direct atomic resolution of the graphite hexagonal structure by transmission electron microscopy (HRTEM), revealing the expected hexagonal array of atoms and the existence of several types of defects. We discuss the possibility that the STM image of graphite is a result of convolution of the electronic properties and the atomic hardness of graphite

Synthesis and catalytic performance of CeOCl in Deacon reaction

Surface chlorinated CeO2 is an efficient material for HCl oxidation, which raises the question whether an oxychloride phase could be also active in the same reaction. CeOCl was synthesized by solid state reaction of cerium oxide with anhydrous cerium chloride and tested in HCl oxidation using various feed compositions at 703 K. X-ray diffraction of post-reaction samples revealed that CeOCl is unstable, in both oxygen-rich and -lean conditions. Applying oxygen over-stoichiometric feeds led to complete transformation of CeOCl into CeO2. Considerable HCl conversions were obtained only after this transformation, which confirms the essential role of bulk cerium oxide in this catalytic system

In Situ Diffuse Reflectance IR Spectroscopic Investigation of n-Butane Isomerization on Promoted Sulfated Zirconia Catalysts

Introduction Sulfated zirconia (SZ) is an attractive catalyst for low temperature butane isomerization [1]. Its activity can be improved by 1–2 orders of magnitude through addition of promoters such as iron or manganese in cationic form [2,3]. The state of these promoters has been characterized, and depending on the method of preparation, a major fraction is found to form a solid solution with zirconia [4]. It has been proposed that promoters facilitate reaction initiation via oxidative dehydrogenation to butenes, which may be converted into the reaction carriers, viz. carbenium ions. Only indirect evidence such as better activity after activation in oxidizing than in inert atmosphere has been presented [5]. Reaction profiles recorded under moderate reaction conditions (e.g. 323 K, 1 kPa n-butane) show an induction period and zero conversion in the extrapolation to zero time on stream. Either the catalyst becomes active only in the feed, or intermediates accumulate on the surface. We have focused on manganese as a promoter and have used in situ diffuse reflectance IR spectroscopy (DRIFTS) to reveal the effects of activation or regeneration in inert gas or O2, and to monitor the events during the induction period. References 1. Hino, M., Arata, K., J. Am. Chem. Soc. 101, 6439 (1979). 2. Hsu, C.-Y., Heimbuch, C.R., Armes, C.T., Gates, B.C., Chem. Commun. 1645 (1992). 3. Lange, F.C., Cheung, T.-K., Gates, B.C., Catal. Lett. 41, 95 (1996). 4. Jentoft, F.C., Hahn, A., Kröhnert, J., Lorenz, G., Jentoft, R.E., Ressler, T., Wild, U., Schlögl, R., J. Catal. 224, 124 (2004). 5. Wan, K.T., Khouw, C.B., Davis, M.E., J. Catal. 158, 311 (1996)

Sulfated Zirconia Thin Films

Sulfated zirconia (SZ) has been found to be catalytically active for the isomerization of n-butane at room temperature [1]. This discovery has led to numerous investigations into the catalyst; however, no consistent theories have been devised to satisfactorily explain its structure, acidity and reactivity [2]. In order to improve surface characterization, a model system consisting of a nanocrystalline SZ thin film supported on a silicon wafer has previously been developed [3, 4]. The films are prepared using an aqueous route via a self-assembled monolayer (SAM), in which the film thickness is accurately controlled by deposition time. SZ thin films have been synthesized as described in [3, 4]. Successful formation of a SZ thin film has been verified by using XPS, SEM and HRTEM techniques. References [1] M. Hino, K. Arata., J. Am. Chem. Soc., 1979, 101, 6439-6441. [2] X. Song and A. Sayari, Catal. Rev. - Sci. Eng., 1996, 38, 329-412. [3] F.C. Jentoft, A. Fischer, G. Weinberg, U. Wild, R. Schlögl, Stud. Surf. Sci. Cat., 2000, 130, 209-214. [4] A. Fischer, Doctoral Thesis, Fritz Haber Institute, 2001

Ammonia as a possible element in an energy infrastructure: catalysts for ammonia decomposition

The possible role of ammonia in a future energy infrastructure is discussed. The review is focused on the catalytic decomposition of ammonia as a key step. Other aspects, such as the catalytic removal of ammonia from gasification product gas or direct ammonia fuel cells, are highlighted as well. The more general question of the integration of ammonia in an infrastructure is also covered