Fe-S dually modulated adsorbate evolution and lattice oxygen compatible mechanism for water oxidation

IF 14.7 1区综合性期刊 Q1 MULTIDISCIPLINARY SCIENCES Nature Communications Pub Date : 2024-09-27 DOI:10.1038/s41467-024-52682-y

Xu Luo, Hongyu Zhao, Xin Tan, Sheng Lin, Kesong Yu, Xueqin Mu, Zhenhua Tao, Pengxia Ji, Shichun Mu

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Abstract

Simultaneously activating metal and lattice oxygen sites to construct a compatible multi-mechanism catalysis is expected for the oxygen evolution reaction (OER) by providing highly available active sites and mediate catalytic activity/stability, but significant challenges remain. Herein, Fe and S dually modulated NiFe oxyhydroxide (R-NiFeOOH@SO₄) is conceived by complete reconstruction of NiMoO₄·xH₂O@Fe,S during OER, and achieves compatible adsorbate evolution mechanism and lattice oxygen oxidation mechanism with simultaneously optimized metal/oxygen sites, as substantiated by in situ spectroscopy/mass spectrometry and chemical probe. Further theoretical analyses reveal that Fe promotes the OER kinetics under adsorbate evolution mechanism, while S excites the lattice oxygen activity under lattice oxygen oxidation mechanism, featuring upshifted O 2p band centers, enlarged d-d Coulomb interaction, weakened metal-oxygen bond and optimized intermediate adsorption free energy. Benefiting from the compatible multi-mechanism, R-NiFeOOH@SO₄ only requires overpotentials of 251 ± 5/291 ± 1 mV to drive current densities of 100/500 mA cm⁻² in alkaline media, with robust stability for over 300 h. This work provides insights in understanding the OER mechanism to better design high-performance OER catalysts.

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Fe-S二元调制吸附剂演化与晶格氧兼容的水氧化机制

同时激活金属和晶格氧位点以构建兼容的多机制催化，有望为氧进化反应（OER）提供高可用性的活性位点，并提高催化活性/稳定性，但这仍是一项重大挑战。在此，通过在 OER 过程中完全重构 NiMoO4-xH2O@Fe,S，构想出了铁和 S 双调制的氢氧化镍铁（R-NiFeOOH@SO4），并通过同时优化金属/氧位点实现了兼容的吸附剂进化机制和晶格氧氧化机制，这一点已通过原位光谱/质谱分析和化学探针得到证实。进一步的理论分析表明，铁在吸附剂演化机制下促进了 OER 动力学，而 S 在晶格氧氧化机制下激发了晶格氧活性，其特点是 O 2p 带中心上移、d-d 库仑相互作用扩大、金属-氧键减弱以及中间吸附自由能优化。得益于兼容的多机制，R-NiFeOOH@SO4 在碱性介质中只需要 251 ± 5/291 ± 1 mV 的过电位就能驱动 100/500 mA cm-2 的电流密度，并且稳定性超过 300 h。

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来源期刊

Nature Communications Biological Science Disciplines-

CiteScore

24.90

自引率

2.40%

发文量

6928

审稿时长

3.7 months

期刊介绍： Nature Communications, an open-access journal, publishes high-quality research spanning all areas of the natural sciences. Papers featured in the journal showcase significant advances relevant to specialists in each respective field. With a 2-year impact factor of 16.6 (2022) and a median time of 8 days from submission to the first editorial decision, Nature Communications is committed to rapid dissemination of research findings. As a multidisciplinary journal, it welcomes contributions from biological, health, physical, chemical, Earth, social, mathematical, applied, and engineering sciences, aiming to highlight important breakthroughs within each domain.