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Synergistic effects of mixing and strain in high entropy spinel oxides for oxygen evolution reactionAbstract 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.more » « less
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Despite tremendous advances in AI, it remains a significant challenge to develop interactive task guidance systems that can offer situated, personalized guidance and assist humans in various tasks. These systems need to have a sophisticated understanding of the user as well as the environment, and make timely accurate decisions on when and what to say. To address this issue, we created a new multimodal benchmark dataset, Watch, Talk and Guide (WTaG) based on natural interaction between a human user and a human instructor. We further proposed two tasks: User and Environment Understanding, and Instructor Decision Making. We leveraged several foundation models to study to what extent these models can be quickly adapted to perceptually enabled task guidance. Our quantitative, qualitative, and human evaluation results show that these models can demonstrate fair performances in some cases with no task-specific training, but a fast and reliable adaptation remains a significant challenge. Our benchmark and baselines will provide a stepping stone for future work on situated task guidance.more » « less
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Abstract Phonon polaritons, the hybrid quasiparticles resulting from the coupling of photons and lattice vibrations, have gained significant attention in the field of layered van der Waals heterostructures. Particular interest has been paid to hetero‐bicrystals composed of molybdenum oxide (MoO3) and hexagonal boron nitride (hBN), which feature polariton dispersion tailorable via avoided polariton mode crossings. In this work, the polariton eigenmodes in MoO3‐hBN hetero‐bicrystals self‐assembled on ultrasmooth gold are systematically studied using synchrotron infrared nanospectroscopy. It is experimentally demonstrated that the spectral gap in bicrystal dispersion and corresponding regimes of negative refraction can be tuned by material layer thickness, and these results are quantitatively matched with a simple analytic model. Polaritonic cavity modes and polariton propagation along “forbidden” directions are also investigated in microscale bicrystals, which arise from the finite in‐plane dimension of the synthesized MoO3micro‐ribbons. The findings shed light on the unique dispersion properties of polaritons in van der Waals heterostructures and pave the way for applications leveraging deeply sub‐wavelength mid‐infrared light‐matter interactions.more » « less
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Abstract Aqueous photoelectrochemical (PEC) cells have long been considered a promising technology to convert solar energy into hydrogen. However, the solar‐to‐H 2 (STH) efficiency and cost‐effectiveness of PEC water splitting are significantly limited by sluggish oxygen evolution reaction (OER) kinetics and the low economic value of the produced O 2 , hindering the practical commercialization of PEC cells. Recently, organic upgrading PEC reactions, especially for alternative OERs, have received tremendous attention, which improves not only the STH efficiency but also the economic effectiveness of the overall reaction. In this review, PEC reaction fundamentals and reactant‐product cost analysis of organic upgrading reactions are briefly reviewed, recent advances made in organic upgrading reactions, which are categorized by their reactant substrates, such as methanol, ethanol, glycol, glycerol, and complex hydrocarbons, are then summarized and discussed. Finally, the current status, further outlooks, and challenges toward industrial applications are discussed.more » « less
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Abstract Electrochemical two-electron water oxidation reaction (2e-WOR) has drawn significant attention as a promising process to achieve the continuous on-site production of hydrogen peroxide (H 2 O 2 ). However, compared to the cathodic H 2 O 2 generation, the anodic 2e-WOR is more challenging to establish catalysts due to the severe oxidizing environment. In this study, we combine density functional theory (DFT) calculations with experiments to discover a stable and efficient perovskite catalyst for the anodic 2e-WOR. Our theoretical screening efforts identify LaAlO 3 perovskite as a stable, active, and selective candidate for catalyzing 2e-WOR. Our experimental results verify that LaAlO 3 achieves an overpotential of 510 mV at 10 mA cm −2 in 4 M K 2 CO 3 /KHCO 3 , lower than those of many reported metal oxide catalysts. In addition, LaAlO 3 maintains a stable H 2 O 2 Faradaic efficiency with only a 3% decrease after 3 h at 2.7 V vs. RHE. This computation-experiment synergistic approach introduces another effective direction to discover promising catalysts for the harsh anodic 2e-WOR towards H 2 O 2 .more » « less
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