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The idea of this book came up 2 years ago as an additional member of the RSC's ‘Catalysis’ series. When we were approached to edit it, it was not completely clear whether atomic-scale control of heterogeneous catalyst synthesis could indeed already be achieved with certainty. Is it a dream or reality? Recent developments in the preparation of catalysts, and especially multi-metallic nanoparticles, open up great perspectives to finely tune the catalytic properties of solids, either by their size and/or their composition that can now be adjusted and characterized with an atomic resolution.

We are proud to offer you this book with successful examples of catalysts controlled at the atomic scale. Rather than trying to find a unifying view on this subject matter, we have structured our book into self-contained chapters that each tackle atomic control using very different experimental methods. Each chapter represents one illustrative example of methodology that allows the synthesis of catalysts with a high degree of control. However, interestingly, there is a common ground: being more ‘physical’ or ‘chemical’ does not matter; each synthesis strategy presented is a ‘bottom-up’ approach, which aims at organizing matter with a high degree of complexity, rather than starting from bulk compounds and trying to downscale them.

The first three chapters use organometallic chemistry as the synthesis tool. The first chapter describes surface organometallic chemistry in order to build on solid supports single sites that mimic active species found in homogeneous catalysis. The second chapter immobilizes molecular metal complex catalysts within zeolites, to obtain uniform structures that facilitate understanding of factors governing catalytic activity. The third chapter presents the use of heteronuclear complexes or clusters as precursors of supported bimetallic nanoparticles with control of the composition within each individual nanoparticle. The fourth and fifth chapters disclose the use of atomically precise nanoclusters in catalytic applications to unravel the fundamental origins of structure–activity and structure–selectivity relationships. The next two chapters report more ‘physical’ methods with Chapter 6 covering monolayer electro-deposition techniques and Chapter 7 covering atomic layer deposition (ALD) in the vapor phase for the preparation of solid catalysts. Chapter 8 presents model catalysts (single crystals, films and fibers) that allow an understanding of reaction mechanisms at an advanced molecular level. Chapter 9 uses modern knowledge of nanoparticles (in terms of size, shape and compositional control) to prepare advanced electrocatalysts, presenting much improved activity and durability for electrochemical energy applications. Finally, Chapter 10 reports atom probe microscopies (APM) as ideal techniques to probe nano-structured catalysts at the atomic scale. We have deliberately chosen not to devote a whole chapter to a single characterization technique amenable to obtaining data at the atomic scale, even if these exist nowadays. One could think of HR-TEM and also in situ EXAFS or XRD techniques, for instance. However, throughout the examples treated in each chapter, the power (and limitations) of many such techniques appears clearly. The reader is referred to many other textbooks on modern characterization techniques to gather basic operating information.

Atomically precise methods for the synthesis of solid catalysts do exist. With its ten chapters emanating from different catalysis fields, this book proves it. Of course, it is not comprehensive and another collection of chapters could have made up the point. The preparation methods presented here seem to reach the ultimate level of control attainable, coming from bulk to microstructure, down to the nanoscale and eventually the atomic level. Is this the ultimate step of sophistication for synthesis methods that have been developed in heterogeneous catalysis over decades? Certainly not, as researchers always find new challenges to tackle. We are convinced that mastering the synthesis of nanostructured catalysts by means of atomically precise methods unravels a bright future for heterogeneous catalysis, its developments and applications.

Sophie Hermans and Thierry Visart de Bocarmé

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