Breaking Structural Instability and Orbital Symmetry Mismatch in p-Block Metal Monochalcogenides for CO₂ Electroreduction via Noninvasive van der Waals Doping

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Апрель 24, 2025

P-block metal monochalcogenides (MX) adopting black phosphorus (BP)-like structures are promising electrocatalysts due to their abundant exposed sites and tunable electronic structures. However, practical application is limited by structural instability arising from lone-pair electron-induced distortions, along with an inherent orbital symmetry mismatch the frontier orbitals of small molecules (e.g., CO2), reducing activation efficiency. Here, we report a noninvasive doping strategy overcome both in p-block for efficient CO2 electroreduction, through engineering periodic van der Waals (vdW) superlattice, known as misfit superlattice. These vdW superlattices sublayer ratios contain catalytically active p-electron-rich MX sublayers conductive transition dichalcogenide current collectors. Taking [BiS]1[TaS2]1 proof-of-concept, presence ionic interactions between crucial modulating stabilizing BiS transforming Bi into higher valence state Bi(2+δ). Concurrently, interlayer induces uneven electron redistribution Bi's p-orbitals, breaking its LUMO CO2, thereby barrier. In situ characterization theoretical calculations reveal that optimized exhibit moderate adsorption *OCHO, endowing superlattice exceptional selectivity (>90%) formate electroreduction. This work advances versatile platform synergistically layered materials tailoring alignment leveraging doping, achieving optimal catalytic performance electrochemical conversion molecules.

Язык: Английский

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Quantum-dot-like Bi/Bi2O2CO3 heterostructures via in situ MOF reconstruction toward efficient CO2-to-Formate conversion over a wide potential window

Applied Surface Science, Год журнала: 2025, Номер unknown, С. 163351 - 163351

Опубликована: Апрель 1, 2025

Язык: Английский

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Controllable Reconstruction of β-Bi₂O₃/Bi₂O₂CO₃ Composite for Highly Efficient and Durable Electrochemical CO₂ Conversion

Nano Letters, Год журнала: 2025, Номер unknown

Опубликована: Апрель 9, 2025

The uncontrollable electrochemical reduction reconstruction, leading to the destruction of well-defined structure and subsequent low durability, is main obstacle catalytic performance Bi-based composites toward CO2 reaction (eCO2RR). Herein, we address this issue through construction a novel β-Bi2O3/Bi2O2CO3 composite, which can resist reconstruction materials metallic Bi during eCO2RR process by modulating more alkaline microenvironment that facilitates formation new Bi-O bonds. synergistic interactions directional electron transfer between β-Bi2O3 Bi2O2CO3 components, together with stable composite structure, result in its superior activity selectivity for formate production high faradaic efficiencies (FEs) over 94% from -0.7 -1.1 V, remarkable durability maintenance 80% FE after continuous electrocatalysis 720 h. This work sheds light on designing advanced high-performance nanomaterials other practical applications.

Язык: Английский

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In situ embedded bismuth nanoparticles among highly porous carbon fibers for efficient carbon dioxide reduction

Rare Metals, Год журнала: 2024, Номер 43(9), С. 4312 - 4320

Опубликована: Май 25, 2024

Язык: Английский

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Microfluidic Continuous Synthesis of Size‐ and Facet‐Controlled Porous Bi₂O₃ Nanospheres for Efficient CO₂ to Formate Catalysis

Small, Год журнала: 2024, Номер 20(43)

Опубликована: Июль 1, 2024

Abstract Bismuth‐based catalysts are effective in converting carbon dioxide into formate via electrocatalysis. Precise control of the morphology, size, and facets bismuth‐based is crucial for achieving high selectivity activity. In this work, an efficient, large‐scale continuous production strategy developed a porous nanospheres Bi 2 O 3 ‐FDCA material. First‐principles simulations conducted advance indicate that (111)/(200) help reduce overpotential electrocatalytic reduction reaction (ECO RR). Subsequently, using microfluidic technology molecular to precisely adjust amount 2, 5‐furandicarboxylic acid, nanomaterials rich successfully synthesized. Additionally, morphology significantly increases adsorption capacity active sites dioxide. These synergistic effects allow stably operate 90 h flow cell at current density ≈250 mA cm − , with average Faradaic efficiency exceeding 90%. The approach theoretically guided synthesis finely structured, efficient materials ECO RR may provide valuable references chemical engineering intelligent nanocatalysts.

Язык: Английский

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