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界面催化调控:由氧空位和重金属离子引发的电子重排及羟基自由基

Interface catalytic regulation electron rearrangement and hydroxyl radicals triggered by oxygen vacancies and heavy metal ions.

作者信息

Xiao Xiang-Yu, Song Zong-Yin, Zhang Chong-Chong, Zhao Yong-Huan, Gao Zhi-Wei, Chen Shi-Hua, Li Pei-Hua, Sun Yu-Feng, Yang Meng, Huang Xing-Jiu

机构信息

Key Laboratory of Environmental Optics and Technology, Environmental Materials and Pollution Control Laboratory, Institute of Solid State Physics, HFIPS, Chinese Academy of Sciences Hefei 230031 P. R. China

Department of Materials Science and Engineering, University of Science and Technology of China Hefei 230026 P. R. China.

出版信息

Chem Sci. 2023 Feb 17;14(11):2960-2970. doi: 10.1039/d2sc06762e. eCollection 2023 Mar 15.

Abstract

Although the enhanced intrinsic activities of some nano-metal oxides are obtained by manufacturing oxygen vacancies (OVs), the effect of multiple roles of OVs is ambiguous. Herein, an interface catalytic regulation electron rearrangement and hydroxyl radicals (˙OH) was proposed with the designed ZrO hollow sphere rich in OVs (V-rich ZrO). Surprisingly, it was shown that the catalytic ability of V-rich ZrO was 9.9 times higher than that of ZrO with little OVs in electrochemical catalytic reduction of Pb(ii). It was found that the generation of Zr and Zr caused by OVs results in the rearrangement of abundant free electrons to facilitate the catalytic reaction rates. The longer bond length between V-rich ZrO and reactants, and the lower adsorption energy are beneficial for reactants to desorb, improving the conversion rates. Besides, the produced ˙OH were captured which were induced by OVs and trace divalent heavy metal ions in electron paramagnetic resonance (EPR) experiments, contributing to lowering the energy barriers. This study not only revealed the enhanced interface catalytic effect of electron rearrangement and generated ˙OH triggered by OVs, but also provided unique insights into interface catalytic regulation on nano-metal oxides simulated by OVs.

摘要

尽管一些纳米金属氧化物通过制造氧空位(OVs)获得了增强的本征活性,但OVs多重作用的影响尚不明确。在此,通过设计富含OVs的ZrO空心球(富V的ZrO)提出了一种界面催化调控——电子重排和羟基自由基(˙OH)。令人惊讶的是,结果表明,在电化学催化还原Pb(II)过程中,富V的ZrO的催化能力比几乎没有OVs的ZrO高9.9倍。研究发现,OVs导致的Zr和Zr的生成会引起大量自由电子的重排,从而促进催化反应速率。富V的ZrO与反应物之间更长的键长以及更低的吸附能有利于反应物解吸,提高转化率。此外,在电子顺磁共振(EPR)实验中捕获了由OVs和痕量二价重金属离子诱导产生的˙OH,这有助于降低能垒。本研究不仅揭示了由OVs触发的电子重排和生成的˙OH增强的界面催化效应,还为通过OVs模拟的纳米金属氧化物的界面催化调控提供了独特的见解。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b6a4/10016426/bac0d9ac6fcd/d2sc06762e-f1.jpg

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