Xu Luo, Hongyu Zhao, Xin Tan, Sheng Lin, Kesong Yu, Xueqin Mu, Zhenhua Tao, Pengxia Ji, Shichun Mu
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引用次数: 0
摘要
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。
Fe-S dually modulated adsorbate evolution and lattice oxygen compatible mechanism for water oxidation
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.
期刊介绍：
The Journal of Combinatorial Chemistry has been relaunched as ACS Combinatorial Science under the leadership of new Editor-in-Chief M.G. Finn of The Scripps Research Institute. The journal features an expanded scope and will build upon the legacy of the Journal of Combinatorial Chemistry, a highly cited leader in the field.
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