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Understanding selectivity trends is a crucial hurdle in the developing innovative catalysts for generating hydrogen peroxide through the two‐electron oxygen reduction reaction (2e‐ORR). The identification of selectivity patterns has been made more accessible through the introduction of a newly developed selectivity descriptor derived from thermodynamics, denoted as ΔΔG introduced in Chem Catal. 2023, 3(3), 100568. To validate the suitability of this parameter as a descriptor for 2e‐ORR selectivity, we utilize an extensive library of 155 binary alloys. We validate that ΔΔG reliably depicts the selectivity trends in binary alloys reported for their high activity in the 2e‐ORR. This analysis also enables the identification of nine selective 2e‐ORR catalysts underscoring the efficacy of ΔΔG as 2e‐ORR selectivity descriptor. This work highlights the significance of concurrently considering both selectivity and activity trends. This holistic approach is crucial for obtaining a comprehensive understanding in the identification of high‐performance catalyst materials for optimal efficiency in various applications. [ABSTRACT FROM AUTHOR]

Precise electrochemical synthesis of commodity chemicals and fuels from CO 2 building blocks provides a promising route to close the anthropogenic carbon cycle, in which renewable but intermittent electricity could be stored within the greenhouse gas molecules. Here, we report state-of-the-art CO 2 -to-HCOOH valorization performance over a multiscale optimized Cu-Bi cathodic architecture, delivering a formate Faradaic efficiency exceeding 95% within an aqueous electrolyzer, a C-basis HCOOH purity above 99.8% within a solid-state electrolyzer operated at 100 mA cm -2 for 200 h and an energy efficiency of 39.2%, as well as a tunable aqueous HCOOH concentration ranging from 2.7 to 92.1 wt%. Via a combined two-dimensional reaction phase diagram and finite element analysis, we highlight the role of local geometries of Cu and Bi in branching the adsorption strength for key intermediates like *COOH and *OCHO for CO 2 reduction, while the crystal orbital Hamiltonian population analysis rationalizes the vital contribution from moderate binding strength of η 2 (O,O)-OCHO on Cu-doped Bi surface in promoting HCOOH electrosynthesis. The findings of this study not only shed light on the tuning knobs for precise CO 2 valorization, but also provide a different research paradigm for advancing the activity and selectivity optimization in a broad range of electrosynthetic systems., Competing Interests: Competing interests statement:The authors declare no competing interest.

Understanding selectivity trends is a crucial hurdle in the developing innovative catalysts for generating hydrogen peroxide through the two-electron oxygen reduction reaction (2e-ORR). The identification of selectivity patterns has been made more accessible through the introduction of a newly developed selectivity descriptor derived from thermodynamics, denoted as ΔΔG introduced in Chem Catal. 2023, 3(3), 100568. To validate the suitability of this parameter as a descriptor for 2e-ORR selectivity, we utilize an extensive library of 155 binary alloys. We validate that ΔΔG reliably depicts the selectivity trends in binary alloys reported for their high activity in the 2e-ORR. This analysis also enables the identification of nine selective 2e-ORR catalysts underscoring the efficacy of ΔΔG as 2e-ORR selectivity descriptor. This work highlights the significance of concurrently considering both selectivity and activity trends. This holistic approach is crucial for obtaining a comprehensive understanding in the identification of high-performance catalyst materials for optimal efficiency in various applications., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)