One of the main stumbling blocks in developing rational design strategies for heterogeneous catalysis is that the complexity of the catalysts impairs efforts to characterize their active sites. We show how to identify the crucial atomic structure motif for the industrial Cu/ZnO/Al(2)O(3) methanol synthesis catalyst by using a combination of experimental evidence from bulk, surface-sensitive, and imaging methods collected on real high-performance catalytic systems in combination with density functional theory calculations. The active site consists of Cu steps decorated with Zn atoms, all stabilized by a series of well-defined bulk defects and surface species that need to be present jointly for the system to work.

Standing out from the vast majority of metal organic coordination polymers is the class of highly porous basic zinc carboxylates developed by Yaghi and co-workers.[1] Its prototype is MOF-5 (MOF = metal organic framework), in which {Zn 4 O} building blocks are linked together by terephthalate bridges to form a zeolite-like, cubic framework.[2] The extremely high specific surface area [2] of up to 4500 m 2 g À1 and a pore volume of 0.69 cm 3 cm À3 (for MOF-177), which has not been surpassed by any other crystalline substance, and thermal stability (up to 350 8C) opens up fascinating perspectives for the supramolecular host-guest chemistry.[3] Applications for these materials in miniaturized fuel cells and convenient gas-storage devices (for H 2 , CH 4 ), as gas sensors and for gas separation, as catalyst materials, and also for molecular electronics are emerging. [4] A report on the quantitative inclusion of C 60 and large polycyclic dye molecules (e.g. Astrazon Orange R) into the cavities of MOF-177 single crystals attracted our attention. [5] Could these MOF host lattices also be suitable to efficiently and selectively absorb typical metal organic chemical vapor deposition (CVD) precursors, provided these were volatile (gas absorption) or very soluble in nonpolar hydrocarbons and had matching size and shape to fit into the cavity? The release of the metal atoms of the precursors imbedded in the

Addition of small amounts of promoters to solid catalysts can cause pronounced improvement in the catalytic properties. For the complex catalysts employed in industrial processes, the fate and mode of operation of promoters is often not well understood, which hinders a more rational optimization of these important materials. Herein we show for the example of the industrial Cu/ZnO/Al2O3 catalyst for methanol synthesis how structure-performance relationships can deliver such insights and shed light on the role of the Al promoter in this system. We were able to discriminate a structural effect and an electronic promoting effect, identify the relevant Al species as a dopant in ZnO, and determine the optimal Al content of improved Cu/ZnO:Al catalysts. By analogy to Ga- and Cr-promoted samples, we conclude that there is a general effect of promoter-induced defects in ZnO on the metal-support interactions and propose the relevance of this promotion mechanism for other metal/oxide catalysts also.

The pronounced Lewis acidity explains the exceptional activity of the title compound as catalyst for olefin epoxidations with hydrogen peroxide. The system MTO/tBuOH/H2O2 transforms olefins selectively and efficiently into epoxides under very mild conditions (−30 to + 60°C, but normally at room temperature). In general, 0.1 to 1 mol% MTO is sufficient to achieve high turnovers. Variation of the alkyl group and addition of cocatalysts (e.g. amines) should influence activity and stereoselectivity.

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