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1. Domino Michael/Michael reaction catalyzed by switchable modularly designed organocatalysts

   https://doi.org/10.1039/D1OB01991K  

   Parella, Ramarao; Jakkampudi, Satish; Bora, Pranjal; Sakkani, Nagaraju; Zhao, John C.-G. (December 2021, Organic & Biomolecular Chemistry)

   The domino Michael/Michael reaction between ( E )-7-aryl-7-oxohept-5-enals and trans -cinnamaldehydes was investigated by using modularly designed organocatalysts (MDOs). It was found that both the enamine and iminium catalytic modes of the MDOs are switchable and can be individually switched on and off by using appropriate combinations of the precatalyst modules and the reaction conditions. When both the enamine and iminium catalysis modes of the MDOs are switched on, the desired domino reaction products can be obtained in good yields and stereoselectivities under optimized conditions. 

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2. Remote controlled optical manipulation of bimetallic nanoparticle catalysts using peptides

   https://doi.org/10.1039/D1CY00189B  

   Lawrence, Randy L.; Olagunju, Mary O.; Liu, Yang; Mahalingam, Krishnamurthy; Slocik, Joseph M.; Naik, Rajesh R.; Frenkel, Anatoly I.; Knecht, Marc R. (April 2021, Catalysis Science & Technology)

   null (Ed.)

   Bimetallic nanoparticles remain a promising avenue to achieve highly reactive catalysts. In this contribution, we demonstrate the use of a photoswitchable peptide for the production of PdAu bimetallic nanoparticles at a variety of Pd : Au ratios. Using this peptide, the biomolecular overlayer structure can be switched between two different conformations ( cis vs. trans ) via light irradiation, thus accessing two different surface structures. The composition and arrangement of the materials was fully characterized, including atomic-level analyses, after which the reactivity of the bimetallic materials was explored using the reduction of 4-nitrophenol as a model system. Using these materials, it was demonstrated that the reactivity was maximized for the particles prepared at a Pd : Au ratio of 1 : 3 and with the peptide in the cis conformation. Such results present routes to a new generation of catalysts that could be remotely activated for on/off reactivity as a function of the ligand overlayer conformation. 

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3. Neural network embeddings based similarity search method for atomistic systems

   https://doi.org/10.1039/D2DD00055E  

   Yang, Yilin; Liu, Mingjie; Kitchin, John R (October 2022, Digital Discovery)

   With the popularity of machine learning growing in the field of catalysis there are increasing numbers of catalyst databases becoming available. These databases provide us with the opportunity to search for catalysts with desired properties, which could lead to the discovery of new catalysts. However, while there are search methods for molecules based on similarity metrics, for solid-state catalyst systems there is not yet a straightforward search method. In this work, we propose a neural network embeddings based similarity search method that is applicable for both molecules and solid-state catalyst systems. We illustrate how the search method works and show search examples for the QM9, Materials Project (MP) and Open Catalyst 2020 (OC20) databases. We show that the configurations found present similarity in terms of geometry, composition, energy and in the electronic density of states. These results imply the neural network embeddings have encoded effective information that could be used to retrieve molecules and materials with similar properties. 

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4. Advances in the synthesis, characterisation, and mechanistic understanding of active sites in Fe-zeolites for redox catalysts

   https://doi.org/10.1039/D0DT01857K  

   Bols, Max L.; Rhoda, Hannah M.; Snyder, Benjamin E.; Solomon, Edward I.; Pierloot, Kristine; Schoonheydt, Robert A.; Sels, Bert F. (November 2020, Dalton Transactions)

   null (Ed.)

   The recent research developments on the active sites in Fe-zeolites for redox catalysis are discussed. Building on the characterisation of the α-Fe/α-O active sites in the beta and chabazite zeolites, we demonstrate a bottom-up approach to successfully understand and develop Fe-zeolite catalysts. We use the room temperature benzene to phenol reaction as a relevant example. We then suggest how the spectroscopic identification of other monomeric and dimeric iron sites could be tackled. The challenges in the characterisation of active sites and intermediates in NO X selective catalytic reduction catalysts and further development of catalysts for mild partial methane oxidation are briefly discussed. 

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5. Site heterogeneity and broad surface-binding isotherms in modern catalysis: Building intuition beyond the Sabatier principle

   https://doi.org/10.1016/j.jcat.2024.115725  

   Mayer, James M (November 2024, Journal of Catalysis)

   Mayer, James M (Ed.)

   Learning the science of heterogeneous catalysis and electrocatalysis always starts with the simple case of a flat, uniform sur-face with an ideal adsorbate. It has of course been recognized for a century that real catalysts are more complicated. For the increasingly complex catalysts of the 21st century, this Perspective argues that surface heterogeneity and non-ideal binding isotherms are central features, and their implications need to be incorporated in current thinking. A variety of systems are described herein where catalyst complexity leads to broad, non-Langmuirian surface isotherms for the binding of hydrogen atoms – and this occurs even for ideal, flat Pt(111) surfaces. Modern catalysis employs nanoscale materials whose surfaces have substantial step, edge, corner, impurity, and other defect sites, and they increasingly have both metallic and non-metallic elements MnXm, including metal oxides, chalcogenides, pnictides, carbides, doped carbons, etc. The surfaces of such catalysts are often not crystal facets of the bulk phase underneath, and they typically have a variety of potential active sites. Catalytic surfaces in operando are often non-stoichiometric, amorphous, dynamic, and impure, and often vary from one part of the surface to another. Understanding of the issues that arise at such nanoscale, multi-element catalysts is just beginning to emerge. Yet these catalysts are widely discussed using Brønsted/Bell-Evans-Polanyi (BEP) relations, volcano plots, Tafel slopes, the Butler-Volmer equation, and other linear free energy relations (LFERs), which all depend on the implicit assump-tion that the active sites are all “similar” and that surface adsorption is close to ideal. These assumptions underly the ubiqui-tous intuition based on the Sabatier Principle, that the fastest catalysis will occur when key intermediates have free energies of adsorption that are not too strong nor too weak. Current catalysis research often aims to minimize the complexity of non-ideal isotherms through experimental and computational design (e.g., the use of single crystal surfaces), and these studies are the foundation of the field. In contrast, this Perspective argues that the heterogeneity of binding sites and binding energies is an inherent strength of these catalysts. This diversity makes many nanoscale catalysts inherently a high-throughput screen wrapped in a tiny package. Only by making the heterogeneity part of the foundation of catalysis models, sorting the types of active sites and dissecting non-ideal binding isotherms, will modern catalysis learn to harness the inherent diversity of real catalysts. Controlling rather than avoiding diversity is needed to optimize complex modern catalysts and catalytic condi-tions. 

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