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Adsorbed atomic O facilitates nonselective reaction pathways that greatly reduce the selectivity of ethylene epoxidation. 

Over the last 80 years, chlorine (Cl) has been the primary promoter of the ethylene epoxidation reaction valued at ~40 billion USD per year, providing a ~25% selectivity increase over unpromoted silver (Ag) (~55%). Promoters such as cesium, rhenium, and molybdenum each add a few percent of selectivity enhancements to achieve 90% overall, but their codependence on Cl makes optimizing and understanding their function complex. We took a theory-guided, single-atom alloy approach to identify nickel (Ni) as a dopant in Ag that can facilitate selective oxidation by activating molecular oxygen (O₂) without binding oxygen (O) too strongly. Surface science experiments confirmed the facile adsorption/desorption of O₂on NiAg, as well as demonstrating that Ni serves to stabilize unselective nucleophilic oxygen. Supported Ag catalyst studies revealed that the addition of Ni in a 1:200 Ni to Ag atomic ratio provides a ~25% selectivity increase without the need for Cl co-flow and acts cooperatively with Cl, resulting in a further 10% initial increase in selectivity. 

Abstract Improving control over active‐site reactivity is a grand challenge in catalysis. Single‐atom alloys (SAAs) consisting of a reactive component doped as single atoms into a more inert host metal feature localized and well‐defined active sites, but fine tuning their properties is challenging. Here, a framework is developed for tuning single‐atom site reactivity by alloying in an additional inert metal, which this work terms an alloy‐host SAA. Specifically, this work creates about 5% Pd single‐atom sites in a Pd₃₃Ag₆₇(111) single crystal surface, and then identifies Sn based on computational screening as a suitable third metal to introduce. Subsequent experimental studies show that introducing Sn indeed modifies the electronic structure and chemical reactivity (measured by CO desorption energies) of the Pd sites. The modifications to both the electronic structure and the CO adsorption energies are in close agreement with the calculations. These results indicate that the use of an alloy host environment to modify the reactivity of single‐atom sites can allow fine‐tuning of catalytic performance and boost resistance against strong‐binding adsorbates such as CO. 

Despite the broad catalytic relevance of metal–support interfaces, controlling their chemical nature, the interfacial contact perimeter (exposed to reactants), and consequently, their contributions to overall catalytic reactivity, remains challenging, as the nanoparticle and support characteristics are interdependent when catalysts are prepared by impregnation. Here, we decoupled both characteristics by using a raspberry-colloid-templating strategy that yields partially embedded PdAu nanoparticles within well-defined SiO₂or TiO₂supports, thereby increasing the metal–support interfacial contact compared to nonembedded catalysts that we prepared by attaching the same nanoparticles onto support surfaces. Between nonembedded PdAu/SiO₂and PdAu/TiO₂, we identified a support effect resulting in a 1.4-fold higher activity of PdAu/TiO₂than PdAu/SiO₂for benzaldehyde hydrogenation. Notably, partial nanoparticle embedding in the TiO₂raspberry-colloid-templated support increased the metal–support interfacial perimeter and consequently, the number of Au/TiO₂interfacial sites by 5.4-fold, which further enhanced the activity of PdAu/TiO₂by an additional 4.1-fold. Theoretical calculations and in situ surface-sensitive desorption analyses reveal facile benzaldehyde binding at the Au/TiO₂interface and at Pd ensembles on the nanoparticle surface, explaining the connection between the number of Au/TiO₂interfacial sites (via the metal–support interfacial perimeter) and catalytic activity. Our results demonstrate partial nanoparticle embedding as a synthetic strategy to produce thermocatalytically stable catalysts and increase the number of catalytically active Au/TiO₂interfacial sites to augment catalytic contributions arising from metal–support interfaces. 

If a critical acetylene surface coverage threshold above one monolayer is attained, acetylene conversion to benzene occurs with 100% selectivity on Ag(111). The presence of multiple monolayers has the unforeseen effect of increasing benzene production while maintaining selectivity. 

We leveraged Bayesian optimization (BO) to search for potential high-performing catalysts. Our BO workflow can be initialized with as few as 2 to 8 data points, and often identifies the optimal single-atom alloy surface in just a few iterations. 

Abstract A catalytic surface should be stable under reaction conditions to be effective. However, it takes significant effort to screen many surfaces for their stability, as this requires intensive quantum chemical calculations. To more efficiently estimate stability, we provide a general and data-efficient machine learning (ML) approach to accurately and efficiently predict the surface energies of metal alloy surfaces. Our ML approach introduces an element-centered fingerprint (ECFP) which was used as a vector representation for fitting models for predicting surface formation energies. The ECFP is significantly more accurate than several existing feature sets when applied to dilute alloy surfaces and is competitive with existing feature sets when applied to bulk alloy surfaces or gas-phase molecules. Models using the ECFP as input can be quite general, as we created models with good accuracy over a broad set of bimetallic surfaces including most d-block metals, even with relatively small datasets. For example, using the ECFP, we developed a kernel ridge regression ML model which is able to predict the surface energies of alloys of diverse metal combinations with a mean absolute error of 0.017 eV atom⁻¹. Combining this model with an existing model for predicting adsorption energies, we estimated segregation trends of 596 single-atom alloys (SAAs)with and without CO adsorbed on these surfaces. As a simple test of the approach, we identify specific cases where CO does not induce segregation in these SAAs. 

Abstract Lithium‐ion and sodium‐ion batteries (LIBs and SIBs) are crucial in our shift toward sustainable technologies. In this work, the potential of layered boride materials (MoAlB and Mo₂AlB₂) as novel, high‐performance electrode materials for LIBs and SIBs, is explored. It is discovered that Mo₂AlB₂shows a higher specific capacity than MoAlB when used as an electrode material for LIBs, with a specific capacity of 593 mAh g⁻¹achieved after 500 cycles at 200 mA g⁻¹. It is also found that surface redox reactions are responsible for Li storage in Mo₂AlB₂, instead of intercalation or conversion. Moreover, the sodium hydroxide treatment of MoAlB leads to a porous morphology and higher specific capacities exceeding that of pristine MoAlB. When tested in SIBs, Mo₂AlB₂exhibits a specific capacity of 150 mAh g⁻¹at 20 mA g⁻¹. These findings suggest that layered borides have potential as electrode materials for both LIBs and SIBs, and highlight the importance of surface redox reactions in Li storage mechanisms.