Ultralow Coordination Copper Sites Compartmentalized within Ordered Pores for Highly Efficient Electrosynthesis of n-Propanol from CO2

IF 14.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Qun Li, Jiabin Wu, Caoyu Yang, Siyang Li, Chang Long, Zechao Zhuang, Qian Li, Zhiqing Guo, Xuewei Huang, Zhiyong Tang, Huaiguang Li, Dingsheng Wang, Yadong Li
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Abstract

Coordinatively unsaturated copper (Cu) has been demonstrated to be effective for electrifying CO2 reduction into C3 products by adjusting the coupling of C1–C2 intermediates. Nevertheless, the intuitive impacts of ultralow coordination Cu sites on C3 products are scarcely elucidated due to the lack of synthetic recipes for Cu with low coordination numbers and its vulnerability to aggregation under reductive potentials. Herein, computational predictions revealed that Cu sites with higher levels of coordinative unsaturation favored the adsorption of C1 and C2 intermediates. Building upon the correlations, we constructed an ultralow coordination Cu catalyst from the in situ reduction of copper oxide nanoparticles (CuO NPs) compartmentalized within an ordered porous matrix, achieving a remarkable Faradaic efficiency (FE) for n-propanol (n-PrOH) from CO2 electroreduction, reaching up to 27.4% in the H-cell at −0.8 VRHE and 11.8% at 300 mA cm–2 in the flow cell. The presence and maintenance of ultralow coordination Cu sites during the rigorous electrolysis process contributed to the outstanding performances, as verified by the combination of in situ spectroscopy techniques, disclosing that the formed ultralow coordination Cu sites featured strong adsorption for *C1 and *C2 intermediates that lead to n-PrOH.

Abstract Image

有序孔内的超低配位铜位区隔用于CO2高效电合成正丙醇
配位不饱和铜(Cu)通过调节C1-C2中间体的偶联,可以有效地催化CO2还原成C3产物。然而,由于缺乏低配位数铜的合成配方,以及低配位数铜在还原电位下容易聚集,所以超低配位铜对C3产物的直观影响很少得到阐明。本文的计算预测表明,具有较高配位不饱和水平的Cu位点有利于C1和C2中间体的吸附。在此基础上,我们构建了一种超低配位Cu催化剂,通过原位还原在有序多孔基质内划分的氧化铜纳米颗粒(CuO NPs),实现了CO2电还原中正丙醇(n-PrOH)的显着法拉第效率(FE),在−0.8 VRHE下h电池中达到27.4%,在300 mA cm-2下流动电池中达到11.8%。在严格的电解过程中,超低配位Cu位点的存在和维持是优异性能的原因之一,结合原位光谱技术验证了形成的超低配位Cu位点对*C1和*C2中间体具有很强的吸附作用,导致n-PrOH。
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
CiteScore
24.40
自引率
6.00%
发文量
2398
审稿时长
1.6 months
期刊介绍: The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.
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