天津大学胡文平团队NC论文：N-CuO上的Pauling型吸附氧诱导电催化单线态氧的产生，用于有机污染物的降解
天津大学胡文平团队NC论文：N-CuO上的Pauling型吸附氧诱导电催化单线态氧的产生，用于有机污染物的降解
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第一作者： Liangbo Xie (天津大学)
通讯作者：胡文平 教授/展思辉 教授
通讯单位： 天津大学、南开大学
论文DOI： 10.1038/s41467-022-33149-4
由于环境友好的操作和现场生产力，通过O 2 生产电催化单线态氧 ( 1 O 2 ) 在环境净化方面具有极大的兴趣。然而，O 2 在催化剂表面的侧向构型会导致H 2 O的形成，严重限制了 1 O 2 生产的选择性和活性。近日，天津大学胡文平团队和南开大学展思辉团队联合在Nature子刊Nature Communications上发表题为“ Pauling-type adsorption of O2 induced electrocatalytic singlet oxygen production on N–CuO for organic pollutants degradation”的研究型论文。作者展示了一种稳健的N掺杂 CuO（N-CuO），在 N-Cu-O 3 位点具有Pauling-type（端接）吸附O 2 ，用于在直流电场下选择性生成 1 O 2 。他们提出O 2 的Pauling-type构型不仅降低了整体活化能垒，而且改变了形成 1 O 2 而不是H 2 O的反应途径，这是决定Cu-O键解离选择性的关键特征，而不是O-O键。所提出的N掺杂剂策略适用于一系列过渡金属氧化物，为现有的高性能电催化 1 O 2 生产提供了通用的电催化剂设计方案。
a Schematic of the molecular oxygen activation pathway of “side-on” and “end-on” adsorption configuration on the catalyst surface. b Fluorescence response of SOSG upon treatment with CuO and N–CuO within 240 min (λ ex = 504 nm and λ em = 525 nm). c Excitation and emission spectra of DMA in 10 wt% acetonitrile in H 2 O upon treatment with N–CuO system. The excitation was recorded from 280 to 420 nm with λ em = 425 nm. d HR-MS chromatogram of the typical DMA-O 2 from the oxidation of DMA in CuO and N–CuO EC system. e EPR spectra in CuO and N–CuO EC system using TEMP as trapping agents. f Degradation and first-order reaction kinetics of SMX removal in CuO and N–CuO EC system. g Comparison of electrocatalytic performances of metal oxides and the corresponding N-doped metal oxides in the 1 O 2 production process. Error bars represent the standard deviation from triplicate experiments.
a Schematic presentation of CuO structure (Top: CuO, Bottom: Nitrogen substitution site.). b HAADF-TEM image of N–CuO. Inset is the corresponding FFT pattern. The corresponding atomic model ( c ) and the corresponding elemental mapping images ( d ) of N–CuO. e Cu L -edge EELS spectra of CuO and N–CuO. Refined XRD profile ( f ) and Raman spectra ( g ) of the CuO and N–CuO. h TOF-SIMS of N–CuO.
a High-resolution N 1 s XPS spectrum of N–CuO. b Normalized Cu K -edge XANES spectra of N–CuO and its reference samples (Cu foil, Cu 2 O, and CuO). c, d Fourier transform-EXAFS spectra ( c ) and WT-EXAFS plots ( d ) from Cu K -edge XANES spectra. e EXAFS fitting analysis of N–CuO at R space. f Schematic optimized atomic coordination model of the N–CuO from EXAFS data.
1 O 2 production mechanism of N–CuO
a , b O 2 adsorption configurations and calculated differential charge densities on CuO (222) ( a ) and N–CuO (222) ( b ). Free energy diagrams of molecular oxygen activation process for N–CuO ( c ) and CuO ( d ). Key steps of 1 O 2 production for e N–CuO (222) and f CuO (222).
Liangbo Xie , et al. Pauling-type adsorption of O2 induced electrocatalytic singlet oxygen production on N-CuO for organic pollutants degradation , Nature Communications , 2022
论文DOI:
https://doi.org/10.1038/s41467-022-33149-4
备注: Permissions for the reuse of all Figures have been obtained from the original publisher. Copyright 2022, Springer Nature Inc.
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