Spiers Memorial Lecture: Interplay of theory and computation in chemistry—examples from on-water organic catalysis, enzyme catalysis, and single-molecule fluctuations

In this lecture, several examples are considered that illustrate the interplay of experiment, theory, and computations. The examples include on-water catalysis of organic reactions, enzymatic catalysis, single molecule fluctuations, and some much earlier work on electron transfer and atom or group transfer reactions. Computations have made a major impact on our understanding and in the comparisons with experiments. There are also major advantages of analytical theories that may capture in a single equation an entire field and relate experiments of one type to those of another. Such a theory has a generic quality. These topics are explored in the present lecture

Single-Atom Catalysis in Organic Synthesis

Single-atom catalysts hold the potential to significantly impact the chemical sector, pushing the boundaries of catalysis in new, uncharted directions. These materials, featuring isolated metal species ligated on solid supports, can exist in many coordination environments, all of which have shown important functions in specific transformations. Their emergence has also provided exciting opportunities for mimicking metalloenzymes and bridging the gap between homogeneous and heterogeneous catalysis. This review outlines the impressive progress made in recent years regarding the use of single-atom catalysts in organic synthesis. We also illustrate potential knowledge gaps in the search for more sustainable, earth-abundant single-atom catalysts for synthetic applications

Catalytic applications of small bite-angle diphosphorus ligands with single-atom linkers

Diphosphorus ligands connected by a single atom (R2PEPR2; E = CR2, CCR2and NR) give chelating ligands with very small bite-angles as well as enable access to other properties such as bridging modes and hemilability. ThisPerspectivereviews the properties of diphosphorus ligands featuring a single-atom linker and their applications in catalysis, including transformations of alkenes and transfer hydrogenation and hydrogen-borrowing reactions.</p

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Anchored Single-atom catalysts have emerged as a cutting-edge research field holding tremendous appeal for applications in the fields of chemicals, energy and the environment. However, single-atom-catalysts for crystal growth is a nascent field. Of the few studies available, all of them are based on state-of-the-art in situ microscopy investigations and computational studies, and they all look at the growth of monolayer graphene from a single-atom catalyst. Despite the limited number of studies, they do, collectively, represent a new sub-field of single-atom catalysis, namely single-atom catalytic growth of crystalline solids. In this review, we examine them on substrate-supported and as freestanding graphene fabrication, as well as rolled-up graphene, viz., single-walled carbon nanotubes (SWCNT), grown from a single atom. We also briefly discuss the catalytic etching of graphene and SWCNT’s and conclude by outlining the future directions we envision this nascent field to take

Substitutional Si impurities in monolayer hexagonal boron nitride

We report the first observation of substitutional silicon atoms in single-layer hexagonal boron nitride (h-BN) using aberration corrected scanning transmission electron microscopy (STEM). The medium angle annular dark field (MAADF) images reveal silicon atoms exclusively filling boron vacancies. This structure is stable enough under electron beam for repeated imaging. Density functional theory (DFT) is used to study the energetics, structure and properties of the experimentally observed structure. The formation energies of all possible charge states of the different silicon substitutions (Si$_\mathrm{B}$, Si$_\mathrm{N}$ and Si$_\mathrm{{BN}}$) are calculated. The results reveal Si$_\mathrm{B}^{+1}$ as the most stable substitutional configuration. In this case, silicon atom elevates by 0.66{\AA} out of the lattice with unoccupied defect levels in the electronic band gap above the Fermi level. The formation energy shows a slightly exothermic process. Our results unequivocally show that heteroatoms can be incorporated into the h-BN lattice opening way for applications ranging from single-atom catalysis to atomically precise magnetic structures

Metal-Support Interactions of Single-Atom Catalysts for Biomedical Applications

The development of single-atom catalysts (SACs) has become a rapidly growing research field. It is a critical challenge to understand the interactions between the single-atom metal active sites and the support materials. Recently, original research reports of SACs in biomedical applications have emerged in the literature, yet this topic has seldom been reviewed. Here, this review focuses on the latest advances in single-atom catalysis for biomedical applications and highlights the keys for the design of SACs, such as understanding the interactions between metals and supports and classifying various enzyme-like activities. This review helps bridge the knowledge of multiple disciplines and provides prospects regarding the development of SACs for biomedicine

Ligand–metal charge transfer induced via adjustment of textural properties controls the performance of single-atom catalysts during photocatalytic degradation

Because of their peculiar nitrogen-rich structure, carbon nitrides are convenient polydentate ligands for designing single atom-dispersed photocatalysts. However, the relation between catalysts’ textural properties and their photophysical–photocatalytic properties is rarely elaborated. Herein, we report the preparation and characterization of a series of single-atom heterogeneous catalysts featuring highly dispersed Ag and Cu species on mesoporous graphitic C3N4. We show that adjustment of materials textural properties and therefore metal single-atom coordination mode enables ligand-to-metal charge transfer (LMCT) or ligand-to-metal-to-ligand charge transfer (LMLCT), properties that were long speculated in single-atom catalysis but never observed. We employ the developed materials in the degradation of organic pollutants under irradiation with visible light. Kinetic investigations under flow conditions show that single atoms of Ag and Cu decrease the number of toxic organic fragmentation products while leading to a higher selectivity toward full degradation. The results correlate with the selected mode of charge transfer in the designed photocatalysts and provide a new understanding of how the local environment of a single-atom catalyst affects the surface structure and reactivity. The concepts can be exploited further to rationally design and optimize other single-atom materials

One Pot Cooperation of Single Atom Rh and Ru Solid Catalysts for a Selective Tandem Olefin Isomerization - Hydrosilylation Process

[EN] Realizing the full potential of oxide-supported single-atom metal catalysts (SACs) is key to successfully bridge the gap between the fields of homogeneous and heterogeneous catalysis. Here we show that the one-pot combination of Ru-1/CeO2 and Rh-1/CeO2 SACs enables a highly selective olefin isomerization-hydrosilylation tandem process, hitherto restricted to molecular catalysts in solution. Individually, monoatomic Ru and Rh sites show a remarkable reaction specificity for olefin double-bond migration and anti-Markovnikov alpha-olefin hydrosilylation, respectively. First-principles DFT calculations ascribe such selectivity to differences in the binding strength of the olefin substrate to the monoatomic metal centers. The single-pot cooperation of the two SACs allows the production of terminal organosilane compounds with high regio-selectivity (>95 %) even from industrially-relevant complex mixtures of terminal and internal olefins, alongside a straightforward catalyst recycling and reuse. These results demonstrate the significance of oxide-supported single-atom metal catalysts in tandem catalytic reactions, which are central for the intensification of chemical processes.X-ray absorption experiments were performed at the ALBA Synchrotron Light Source (Spain), experiments 2018082961 and 2019023278. L. Simonelli and C. Marini (CLAESSALBA beamline) are thanked for beamline setup. E. Andres, M. E. Martinez, M. Garcia, and I. Lopez (ITQ), are acknowledged for their assistance with XAS experiments. J. Buscher, J. Ternedien, B. Spliethoff, and C. Wirtz (MPI-KOFO) are acknowledged for the performance of XPS, XRD, BF-TEM and 2H NMR experiments, respectively. I. C. de Freitas (MPIKOFO) is thanked for assistance with Raman spectroscopy. J. M. Salas (ITQ) is gratefully acknowledged for his contribution to CO-FTIR experiments. J. J. Barnes and Shell (Amsterdam) are acknowledged for kindly providing an industrial olefin mixture as feed. Authors are thankful to F. Schuth for the provision of lab space and continued support. Part of the HRSTEM and EDX-STEM studies were conducted at the Laboratorio de Microscopias Avanzadas, Instituto de Nanociencia de Aragon, Universidad de Zaragoza, Spain. R.A. gratefully acknowledges the support from the Spanish Ministry of Economy and Competitiveness (MINECO) through project grant MAT2016-79776-P (AEI/FEDER, UE) and from the European Union H2020 programs "ESTEEM3" (823717). The authors acknowledge support by the state of Baden-Wurttemberg through bwHPC (bwUnicluster and JUSTUS, RV bw17D01), by the GRK 2450 and by the Helmholtz Association. 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