Atom-by-Atom Resolution of Structure-Function Relations over Low-Nuclearity Metal Catalysts.
Evgeniya VorobyevaEdvin FakoZupeng ChenSean Michael CollinsDuncan N JohnstonePaul A MidgleyRoland HauertOlga V SafonovaGianvito ViléNuria LópezSharon MitchellJavier Perez-RamirezPublished in: Angewandte Chemie (International ed. in English) (2019)
Controlling the structure sensitivity of catalyzed reactions over metals is central to developing atom-efficient chemical processes. Approaching the minimum ensemble size, the properties enter a non-scalable regime in which each atom counts. Almost all trends in this ultra-small frontier derive from surface science approaches using model systems, because of both synthetic and analytical challenges. Exploiting the unique coordination chemistry of carbon nitride, we discriminate through experiments and simulations the interplay between the geometry, electronic structure, and reactivity of palladium atoms, dimers, and trimers. Catalytic tests evidence application-dependent requirements of the active ensemble. In the semi-hydrogenation of alkynes, the nuclearity primarily impacts activity, whereas the selectivity and stability are affected in Suzuki coupling. This powerful approach will provide practical insights into the design of heterogeneous catalysts comprising well-defined numbers of atoms.
Keyphrases
- molecular dynamics
- electron transfer
- highly efficient
- room temperature
- public health
- convolutional neural network
- high resolution
- reduced graphene oxide
- quantum dots
- risk assessment
- human health
- transition metal
- metal organic framework
- drinking water
- deep learning
- gold nanoparticles
- mass spectrometry
- heavy metals
- drug discovery
- crystal structure