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富含缺陷的 PdIr 双金属纳米带具有原子间电荷局域化,用于异丙醇辅助海水分解。

Defect-Rich PdIr Bimetallene Nanoribbons with Interatomic Charge Localization for Isopropanol-Assisted Seawater Splitting.

机构信息

State Key Laboratory Breeding Base of Green-Chemical Synthesis Technology, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou, 310014, P. R. China.

出版信息

Small. 2023 Jun;19(25):e2300388. doi: 10.1002/smll.202300388. Epub 2023 Mar 18.

Abstract

Metallene with outstanding physicochemical properties is an efficient two-dimensional electrocatalysts for sustainable hydrogen (H ) production applications. However, the controllable fabrication of extended atomically thin metallene nanoribbons remains a formidable challenge. Herein, this work proposes a controllable preparation strategy for atomically thin defect-rich PdIr bimetallene nanoribbons (PdIr BNRs) with a thickness of only 1.5 nm for the efficient and stable isopropanol-assisted seawater electrolytic H production. When using PdIr BNRs as catalyst to build an isopropanol-assisted seawater electrolysis system, a voltage of only 0.38 V is required at @10 mA cm to achieve energy-saving H production, while producing high value-added acetone at the anode. The aberration-corrected high-resolution transmission electron microscopy (HRTEM) clearly reveals that the PdIr BNRs possess abundant structural defects, which can additionally serve as highly catalytically active sites. Density functional theory (DFT) calculations combined with X-ray absorption spectroscopy studies reveal that the introduction of Ir atoms can induce the formation of a localized charge region and shift the d-band center of Pd down, thereby reducing the adsorption energy on the catalyst in favor of the rapid desorption of H . This work opens the way for the controllable design and construction of defect-rich atomically thin metallene nanoribbons for efficient electrocatalytic applications.

摘要

具有优异物理化学性质的金属烯是一种高效的二维电催化剂,可用于可持续的氢气(H2)生产应用。然而,可控制备扩展原子级薄金属烯纳米带仍然是一个艰巨的挑战。在此,本工作提出了一种可控制备原子级薄富含缺陷的 PdIr 双金属烯纳米带(PdIr BNRs)的策略,其厚度仅为 1.5nm,可用于高效稳定的异丙醇辅助海水电解制氢。当使用 PdIr BNRs 作为催化剂构建异丙醇辅助海水电解系统时,仅需 0.38V 的电压即可在 @10mA cm 时实现节能制氢,同时在阳极产生高附加值的丙酮。经过像差校正的高分辨率透射电子显微镜(HRTEM)清晰地揭示出 PdIr BNRs 具有丰富的结构缺陷,这些缺陷可以作为高度催化活性位点。密度泛函理论(DFT)计算结合 X 射线吸收光谱研究表明,引入 Ir 原子可以诱导局域电荷区域的形成,并使 Pd 的 d 带中心向下移动,从而降低催化剂上的吸附能,有利于 H 的快速脱附。这项工作为可控设计和构建高效电催化应用的富含缺陷原子级薄金属烯纳米带开辟了道路。

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