通过非常规杂交促进 CO2 电还原为 C2H4：Ce-Cu2O 中的高阶 Ce4+ 4f 和 O 2p 相互作用以稳定 Cu+,ACS Nano

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通过非常规杂交促进 CO2 电还原为 C2H4：Ce-Cu2O 中的高阶 Ce4+ 4f 和 O 2p 相互作用以稳定 Cu+
ACS Nano ( IF 15.8 ) Pub Date : 2023-07-06 , DOI: 10.1021/acsnano.3c03952
Yanfei Sun ₁ , Jiangzhou Xie ₂ , Zhenzhen Fu ₁ , Huiying Zhang ₁ , Yebo Yao ₁ , Yixiang Zhou ₁ , Xiaoxuan Wang ₁ , Shiyu Wang ₁ , Xueying Gao ₁ , Zheng Tang ₁ , Shuyuan Li ₁ , Xiaojun Wang ₁ , Kaiqi Nie ₃ , Zhiyu Yang ₁ , Yi-Ming Yan ₁

Affiliation

由可再生电力提供动力，将二氧化碳 (CO ₂ ) 有效转化为增值材料和原料，为减少温室气体排放和关闭人为碳循环提供了一种有前景的策略。_{最近，人们对用于CO 2}还原反应（CO _{2 RR）的Cu}₂ O基催化剂产生了浓厚的兴趣，因为它们具有增强C-C耦合的能力。然而， Cu _{2 O中Cu}⁺的电化学不稳定性导致其不可避免地还原为Cu ⁰，导致C ₂₊产物的选择性较差。在此，我们提出了一种非常规且可行的策略，通过在Ce-Cu ₂ O中构建Ce ⁴⁺ 4f–O 2p–Cu ⁺ 3d网络结构来稳定Cu ⁺ 。实验结果和理论计算证实了非常规轨道杂化在Ce-Cu 2 O中的应用。与传统的d-p杂化相比，基于高阶Ce ^{4+ 4f和2p的}E _f可以更有效地抑制晶格氧的浸出，从而稳定Ce-Cu _{2 O中的Cu}^{+ 。}与纯Cu ₂ O相比，Ce-Cu _{2 O催化剂在-1.3 V的CO}_{2 RR过程中将C}₂ H ₄ /CO的比率提高了1.69倍。此外，利用原位和异位光谱技术以时间分辨率跟踪 CO ₂ RR 条件下铜的氧化价，识别Ce-Cu ₂ O 催化剂中维持良好的 Cu ⁺物质。这项工作不仅为涉及高阶4f和2p轨道杂化的CO _{2 RR催化剂设计提供了一条途径，而且还提供了对催化剂金属氧化态依赖性选择性的深入见解。}

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Boosting CO2 Electroreduction to C2H4 via Unconventional Hybridization: High-Order Ce4+ 4f and O 2p Interaction in Ce-Cu2O for Stabilizing Cu+

Efficient conversion of carbon dioxide (CO₂) into value-added materials and feedstocks, powered by renewable electricity, presents a promising strategy to reduce greenhouse gas emissions and close the anthropogenic carbon loop. Recently, there has been intense interest in Cu₂O-based catalysts for the CO₂ reduction reaction (CO₂RR), owing to their capabilities in enhancing C–C coupling. However, the electrochemical instability of Cu⁺ in Cu₂O leads to its inevitable reduction to Cu⁰, resulting in poor selectivity for C₂₊ products. Herein, we propose an unconventional and feasible strategy for stabilizing Cu⁺ through the construction of a Ce⁴⁺ 4f–O 2p–Cu⁺ 3d network structure in Ce-Cu₂O. Experimental results and theoretical calculations confirm that the unconventional orbital hybridization near E_f based on the high-order Ce⁴⁺ 4f and 2p can more effectively inhibit the leaching of lattice oxygen, thereby stabilizing Cu⁺ in Ce-Cu₂O, compared with traditional d–p hybridization. Compared to pure Cu₂O, the Ce-Cu₂O catalyst increased the ratio of C₂H₄/CO by 1.69-fold during the CO₂RR at −1.3 V. Furthermore, in situ and ex situ spectroscopic techniques were utilized to track the oxidation valency of copper under CO₂RR conditions with time resolution, identifying the well-maintained Cu⁺ species in the Ce-Cu₂O catalyst. This work not only presents an avenue to CO₂RR catalyst design involving the high-order 4f and 2p orbital hybridization but also provides deep insights into the metal-oxidation-state-dependent selectivity of catalysts.

更新日期：2023-07-06

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