Understanding the electronic and structural effects in ORR intermediate binding on anion-substituted zirconia surfaces.

For oxygen reduction reaction (ORR), the surface adsorption energies of O* and OH* intermediates are key descriptors for catalytic activity. In this work, we investigate anion-substituted zirconia catalyst surfaces and determine that adsorption energies of O* and OH* intermediates is governed by both structural and electronic effects. When the adsorption energies are not influenced by the structural effects of the catalyst surface, they exhibit a linear correlation with integrated crystal orbital Hamiltonian population (ICOHP) of the adsorbate-surface bond. The influence of structural effects, due to re-optimisation slab geometry after adsorption of intermediate species, leads to stronger adsorption of intermediates. Our calculations show that there is a change in the bond order to accommodate the incoming adsorbate species which leads to stronger adsorption when both structural and electronic effects influence the adsorption phenomena. The insights into the catalyst-adsorbate interactions can guide the design of future ORR catalysts.

Synergistic effects of mixing and strain in high entropy spinel oxides for oxygen evolution reaction.

Developing stable and efficient electrocatalysts is vital for boosting oxygen evolution reaction (OER) rates in sustainable hydrogen production. High-entropy oxides (HEOs) consist of five or more metal cations, providing opportunities to tune their catalytic properties toward high OER efficiency. This work combines theoretical and experimental studies to scrutinize the OER activity and stability for spinel-type HEOs. Density functional theory confirms that randomly mixed metal sites show thermodynamic stability, with intermediate adsorption energies displaying wider distributions due to mixing-induced equatorial strain in active metal-oxygen bonds. The rapid sol-flame method is employed to synthesize HEO, comprising five 3d-transition metal cations, which exhibits superior OER activity and durability under alkaline conditions, outperforming lower-entropy oxides, even with partial surface oxidations. The study highlights that the enhanced activity of HEO is primarily attributed to the mixing of multiple elements, leading to strain effects near the active site, as well as surface composition and coverage.

Autonomous intelligent agents for accelerated materials discovery.

We present an end-to-end computational system for autonomous materials discovery. The system aims for cost-effective optimization in large, high-dimensional search spaces of materials by adopting a sequential, agent-based approach to deciding which experiments to carry out. In choosing next experiments, agents can make use of past knowledge, surrogate models, logic, thermodynamic or other physical constructs, heuristic rules, and different exploration-exploitation strategies. We show a series of examples for (i) how the discovery campaigns for finding materials satisfying a relative stability objective can be simulated to design new agents, and (ii) how those agents can be deployed in real discovery campaigns to control experiments run externally, such as the cloud-based density functional theory simulations in this work. In a sample set of 16 campaigns covering a range of binary and ternary chemistries including metal oxides, phosphides, sulfides and alloys, this autonomous platform found 383 new stable or nearly stable materials with no intervention by the researchers.

High-throughput calculations of catalytic properties of bimetallic alloy surfaces.

A comprehensive database of chemical properties on a vast set of transition metal surfaces has the potential to accelerate the discovery of novel catalytic materials for energy and industrial applications. In this data descriptor, we present such an extensive study of chemisorption properties of important adsorbates - e.g., C, O, N, H, S, CHx, OH, NH, and SH - on 2,035 bimetallic alloy surfaces in 5 different stoichiometric ratios, i.e., 0%, 25%, 50%, 75%, and 100%. To our knowledge, it is the first systematic study to compile the adsorption properties of such a well-defined, large chemical space of catalytic interest. We propose that a collection of catalytic properties of this magnitude can assist with the development of machine learning enabled surrogate models in theoretical catalysis research to design robust catalysts with high activity for challenging chemical transformations. This database is made publicly available through the platform www.Catalysis-hub.org for easy retrieval of the data for further scientific analysis.

Catalysis-Hub.org, an open electronic structure database for surface reactions.

We present a new open repository for chemical reactions on catalytic surfaces, available at https://www.catalysis-hub.org . The featured database for surface reactions contains more than 100,000 chemisorption and reaction energies obtained from electronic structure calculations, and is continuously being updated with new datasets. In addition to providing quantum-mechanical results for a broad range of reactions and surfaces from different publications, the database features a systematic, large-scale study of chemical adsorption and hydrogenation on bimetallic alloy surfaces. The database contains reaction specific information, such as the surface composition and reaction energy for each reaction, as well as the surface geometries and calculational parameters, essential for data reproducibility. By providing direct access via the web-interface as well as a Python API, we seek to accelerate the discovery of catalytic materials for sustainable energy applications by enabling researchers to efficiently use the data as a basis for new calculations and model generation.

Local Plasmon Engineering in Doped Graphene.

Single-atom B or N substitutional doping in single-layer suspended graphene, realized by low-energy ion implantation, is shown to induce a dampening or enhancement of the characteristic interband π plasmon of graphene through a high-resolution electron energy loss spectroscopy study using scanning transmission electron microscopy. A relative 16% decrease or 20% increase in the π plasmon quality factor is attributed to the presence of a single substitutional B or N atom dopant, respectively. This modification is in both cases shown to be relatively localized, with data suggesting the plasmonic response tailoring can no longer be detected within experimental uncertainties beyond a distance of approximately 1 nm from the dopant. Ab initio calculations confirm the trends observed experimentally. Our results directly confirm the possibility of tailoring the plasmonic properties of graphene in the ultraviolet waveband at the atomic scale, a crucial step in the quest for utilizing graphene's properties toward the development of plasmonic and optoelectronic devices operating at ultraviolet frequencies.

Interlayer Excitons and Band Alignment in MoS2/hBN/WSe2 van der Waals Heterostructures.

van der Waals heterostructures (vdWH) are ideal systems for exploring light-matter interactions at the atomic scale. In particular, structures with a type-II band alignment can yield detailed insight into carrier-photon conversion processes, which are central to, for example, solar cells and light-emitting diodes. An important first step in describing such processes is to obtain the energies of the interlayer exciton states existing at the interface. Here we present a general first-principles method to compute the electronic quasi-particle (QP) band structure and excitonic binding energies of incommensurate vdWHs. The method combines our quantum electrostatic heterostructure (QEH) model for obtaining the dielectric function with the many-body GW approximation and a generalized 2D Mott-Wannier exciton model. We calculate the level alignment together with intra- and interlayer exciton binding energies of bilayer MoS2/WSe2 with and without intercalated hBN layers, finding excellent agreement with experimental photoluminescence spectra. A comparison to density functional theory calculations demonstrates the crucial role of self-energy and electron-hole interaction effects.