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<p>Nickel oxide (NiO)-based catalysts are recognized for their excellent low-temperature activity in the oxidative dehydrogenation of propane (ODHP), but typically suffer from low propene selectivity. In this study, we anchored sulfate groups onto the NiO surface, resulting in a significant enhancement in propene selectivity, from 30% to 68%, at a propane conversion of nearly 10% at a relatively low temperature (340 °C), which exhibited an extraordinary performance compared to previously reported low-temperature ODHP catalyst. Structural characterizations revealed that the sulfate groups were uniformly anchored on the surface, facilitating the dispersion of adsorbed oxygen and regulating the intrinsic reactivity of lattice oxygen through electronic interactions. Kinetic experiments, integrated with <i>in situ</i> X-ray absorption near-edge structure (XANES) and oxygen isotopic exchange analysis, confirmed that the activation mechanism consequently shifts from a cooperative interplay between lattice oxygen and contiguous adsorbed oxygen to a process predominantly governed by sulfate-dispersed adsorbed oxygen. Crucially, <i>in situ</i> diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and temperature-programmed reaction spectra (TPRS) indicated that these changes drive the propane dehydrogenation pathway from the homo-carbon sequential dehydrogenation (leading to acetone and over-oxidation) to highly selective hetero-carbon sequential dehydrogenation. Ultimately, the complete reaction network was elucidated through <i>in situ</i> synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS). These findings reveal how surface modification regulates reactive oxygen species and consequently alters catalytic processes at the gas-solid interface, providing a mechanistic basis for the rational design of high-performance ODHP catalysts.</p>

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Regulation of surface reactive oxygen species through sulfate group anchoring for low-temperature oxidative dehydrogenation of propane

  • 期刊论文

  • 发表日期：

    2026年7月8日

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  • Wenjie Li,
  • Hong Wang,
  • Long Zhu,
  • Qingbo Zhu,
  • Zhandong Wang,
  • Heng Cao,
  • Jun Bao

摘要

Nickel oxide (NiO)-based catalysts are recognized for their excellent low-temperature activity in the oxidative dehydrogenation of propane (ODHP), but typically suffer from low propene selectivity. In this study, we anchored sulfate groups onto the NiO surface, resulting in a significant enhancement in propene selectivity, from 30% to 68%, at a propane conversion of nearly 10% at a relatively low temperature (340 °C), which exhibited an extraordinary performance compared to previously reported low-temperature ODHP catalyst. Structural characterizations revealed that the sulfate groups were uniformly anchored on the surface, facilitating the dispersion of adsorbed oxygen and regulating the intrinsic reactivity of lattice oxygen through electronic interactions. Kinetic experiments, integrated with in situ X-ray absorption near-edge structure (XANES) and oxygen isotopic exchange analysis, confirmed that the activation mechanism consequently shifts from a cooperative interplay between lattice oxygen and contiguous adsorbed oxygen to a process predominantly governed by sulfate-dispersed adsorbed oxygen. Crucially, in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and temperature-programmed reaction spectra (TPRS) indicated that these changes drive the propane dehydrogenation pathway from the homo-carbon sequential dehydrogenation (leading to acetone and over-oxidation) to highly selective hetero-carbon sequential dehydrogenation. Ultimately, the complete reaction network was elucidated through in situ synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS). These findings reveal how surface modification regulates reactive oxygen species and consequently alters catalytic processes at the gas-solid interface, providing a mechanistic basis for the rational design of high-performance ODHP catalysts.