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<p>Hydrogen-mediated transformations at heterointerfaces are often limited by a fundamental kinetic mismatch: the need for strong interfacial polarization to stabilize active hydrogen (H*) often creates high Schottky barriers that impede the necessary electron supply. Here, using a defect-engineered MoS<sub>2</sub>/Fe(OH)<sub>2</sub> heterojunction for chloroform (CF) hydrodechlorination, we resolve this trade-off by engineering a defect-band hybridization mechanism. We observe that while increasing sulfur-vacancy density in MoS<sub>2</sub> upshifts its conduction-band minimum—nominally raising the barrier for electron injection—it paradoxically enhances interfacial electron transport. Electronic structure analysis reveals that interfacial electric-field coupling drives strong hybridization between vacancy-derived states and the MoS<sub>2</sub> conduction band. This forms quasi-continuous, defect-assisted tunneling channels that allow electrons to bypass the energetic barrier. The resulting electronic reconstruction stabilizes interfacial H* in a reactive yet mobile state, shifting the reaction regime from an Fe(II)-dominated single-electron transfer to a precise H*-mediated hydrogen atom transfer pathway. This mechanism suppresses hydrogen evolution and enables highly selective deep hydrodechlorination, providing a generalizable blueprint for manipulating electron–proton coupling at mismatched heterointerfaces.</p>

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Bypassing Schottky constraints via defect-mediated hydrogen transfer in hydrodechlorination

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年6月22日

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  • Shunjie Zhu,
  • Haoran Chen,
  • Zhongjie Cui,
  • Shiwei Wang,
  • Li-Zhi Huang

摘要

Hydrogen-mediated transformations at heterointerfaces are often limited by a fundamental kinetic mismatch: the need for strong interfacial polarization to stabilize active hydrogen (H*) often creates high Schottky barriers that impede the necessary electron supply. Here, using a defect-engineered MoS2/Fe(OH)2 heterojunction for chloroform (CF) hydrodechlorination, we resolve this trade-off by engineering a defect-band hybridization mechanism. We observe that while increasing sulfur-vacancy density in MoS2 upshifts its conduction-band minimum—nominally raising the barrier for electron injection—it paradoxically enhances interfacial electron transport. Electronic structure analysis reveals that interfacial electric-field coupling drives strong hybridization between vacancy-derived states and the MoS2 conduction band. This forms quasi-continuous, defect-assisted tunneling channels that allow electrons to bypass the energetic barrier. The resulting electronic reconstruction stabilizes interfacial H* in a reactive yet mobile state, shifting the reaction regime from an Fe(II)-dominated single-electron transfer to a precise H*-mediated hydrogen atom transfer pathway. This mechanism suppresses hydrogen evolution and enables highly selective deep hydrodechlorination, providing a generalizable blueprint for manipulating electron–proton coupling at mismatched heterointerfaces.