Search

Platinum single-atom catalysts hold promise as a new frontier in heterogeneous electrocatalysis. However, the exact chemical nature of active Pt sites is highly elusive, arousing many hypotheses to compensate for the significant discrepancies between experiments and theories. Here, we identify the stabilization of low-coordinated Pt II species on carbon-based Pt single-atom catalysts, which have rarely been found as reaction intermediates of homogeneous Pt II catalysts but have often been proposed as catalytic sites for Pt single-atom catalysts from theory. Advanced online spectroscopic studies reveal multiple identities of Pt II moieties on the single-atom catalysts beyond ideally four-coordinated Pt II -N 4 . Notably, decreasing Pt content to 0.15 wt.% enables the differentiation of low-coordinated Pt II species from the four-coordinated ones, demonstrating their critical role in the chlorine evolution reaction. This study may afford general guidelines for achieving a high electrocatalytic performance of carbon-based single-atom catalysts based on other d 8 metal ions., (© 2023. The Author(s).)

Catalytic-materials design requires predictive modeling of the interaction between catalyst and reactants. This is challenging due to the complexity and diversity of structure-property relationships across the chemical space. Here, we report a strategy for a rational design of catalytic materials using the artificial intelligence approach (AI) subgroup discovery. We identify catalyst genes (features) that correlate with mechanisms that trigger, facilitate, or hinder the activation of carbon dioxide (CO 2 ) towards a chemical conversion. The AI model is trained on first-principles data for a broad family of oxides. We demonstrate that surfaces of experimentally identified good catalysts consistently exhibit combinations of genes resulting in a strong elongation of a C-O bond. The same combinations of genes also minimize the OCO-angle, the previously proposed indicator of activation, albeit under the constraint that the Sabatier principle is satisfied. Based on these findings, we propose a set of new promising catalyst materials for CO 2  conversion., (© 2022. The Author(s).)

Post-graphene organic Dirac (PGOD) materials are ordered two-dimensional networks of triply bonded sp 2 carbon nodes spaced by π-conjugated linkers. PGOD materials are natural chemical extensions of graphene that promise to have an enhanced range of properties and applications. Experimentally realised molecules based on two PGOD nodes exhibit a bi-stable closed-shell/multi-radical character that can be understood through competing Lewis resonance forms. Here, following the same rationale, we predict that similar states should be accessible in PGOD materials, which we confirm using accurate density functional theory calculations. Although for graphene the semimetallic state is always dominant, for PGOD materials this state becomes marginally meta-stable relative to open-shell multi-radical and/or closed-shell states that are stabilised through symmetry breaking, in line with analogous molecular systems. These latter states are semiconducting, increasing the potential use of PGOD materials as highly tuneable platforms for future organic nano-electronics and spintronics.