Highly Selective Photocatalytic CO2 Reduction to C2H6 via Nanocluster-Single Atom-Vacancy on Ceria: Synergistic Mechanism and Orbital Effects

IF 9.1 1区材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Nano Letters Pub Date : 2025-04-07 DOI:10.1021/acs.nanolett.5c00791

Yingnan Duan, Hexiang Zhao, Jixiang Ji, Zhurui Shen, Yi Wang, Yaping Du

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Abstract

The photocatalytic reduction of CO₂ to high-value C₂ products involves sluggish multiple proton–electron couplings, resulting in low efficiency and selectivity. This study demonstrates that palladium (Pd) single-atom (Pd_SA)- and Pd nanocluster (Pd_NCs)-loaded CeO₂ with abundant oxygen vacancies (O_v) synergistically enhance photocatalytic CO₂-to-ethane (C₂H₆) conversion effectively and selectively. The Pd_SA+NCs/CeO₂ photocatalyst achieves 80.4% electron selectivity for C₂H₆ production with an electron consumption rate of 206.3 μmol g_cat^–1 h^–1 in pure water, representing a 172.4-fold enhancement over pristine CeO₂. Pd_NCs interact with neighboring Pd_SA and O_v to form a Fermi level with the continuous characteristics of discrete energy levels, improving the charge distribution in local spatial electric fields. This enhancement favors electron migration from the π to σ orbital of COCO*, promoting C–C coupling. Our findings provide new insights to rationally design synergistic interactions between SA, NCs, and O_v to achieve high selectivity toward C₂ products.

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纳米簇-单原子-铈空位高选择性光催化CO2还原为C2H6：协同机制和轨道效应

光催化还原CO2制取高价值C2产物过程中，多个质子-电子耦合缓慢，导致效率和选择性较低。本研究表明，具有丰富氧空位（Ov）的钯（Pd）单原子（PdSA）和钯纳米团簇（pdnc）负载CeO2可有效和选择性地协同促进光催化co2 -to-乙烷（C2H6）的转化。PdSA+NCs/CeO2光催化剂在纯水条件下产生C2H6的电子选择性为80.4%，电子消耗率为206.3 μmol gcat-1 h-1，比原始CeO2提高了172.4倍。pdnc与邻近的PdSA和Ov相互作用形成具有离散能级连续特性的费米能级，改善了局部空间电场中的电荷分布。这种增强有利于电子从π轨道向σ轨道迁移，促进C-C耦合。我们的研究结果为合理设计SA、nc和Ov之间的协同作用以实现对C2产品的高选择性提供了新的见解。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Nano Letters 工程技术-材料科学：综合

CiteScore

16.80

自引率

2.80%

发文量

1182

审稿时长

1.4 months

期刊介绍： Nano Letters serves as a dynamic platform for promptly disseminating original results in fundamental, applied, and emerging research across all facets of nanoscience and nanotechnology. A pivotal criterion for inclusion within Nano Letters is the convergence of at least two different areas or disciplines, ensuring a rich interdisciplinary scope. The journal is dedicated to fostering exploration in diverse areas, including: - Experimental and theoretical findings on physical, chemical, and biological phenomena at the nanoscale - Synthesis, characterization, and processing of organic, inorganic, polymer, and hybrid nanomaterials through physical, chemical, and biological methodologies - Modeling and simulation of synthetic, assembly, and interaction processes - Realization of integrated nanostructures and nano-engineered devices exhibiting advanced performance - Applications of nanoscale materials in living and environmental systems Nano Letters is committed to advancing and showcasing groundbreaking research that intersects various domains, fostering innovation and collaboration in the ever-evolving field of nanoscience and nanotechnology.