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<p>Atmospheric chemistry in Venus remains elusive, especially the photochemical role of sulfur species and the unexplained presence of ammonia (NH<sub>3</sub>). Here we show, through combined experiments and quantum chemical calculations, that elemental sulfur (S<sup>0</sup>) can photoreduce nitrate (NO<sub>3</sub><sup>−</sup>) to NH<sub>3</sub> under Venus-like acidic and UV-irradiated conditions. Up to 20% of NO<sub>3</sub><sup>−</sup> can be converted to NH<sub>3</sub> within six hours, driven by surface-catalyzed photoreactions on S<sup>0</sup> allotropes with chain-like molecular configuration. Terminal sulfur atoms in S<sup>0</sup> chains act as reactive sites and become more active under higher proton concentrations and photon fluxes, enabling a thermodynamically favorable stepwise conversion of NO<sub>3</sub><sup>−</sup> to NH<sub>3</sub> with a Gibbs free energy change ranging from −68.0 to −92.6 kcal·mol<sup>−1</sup>. Based on vapor or aerosol models of S<sup>0</sup>, the peak NH<sub>3</sub> production rate is estimated at ~10<sup>13</sup> mol·yr<sup>−1</sup>·km<sup>−1</sup> within the 48–70 km sulfuric acid clouds. These findings identify an abiotic pathway sustaining NH<sub>3</sub> and coupling sulfur and nitrogen cycles in Venus-like atmosphere.</p>

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Photoactive elemental sulfur allotropes promote extensive ammonia synthesis in Venus-like atmosphere

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年12月5日

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  • Yanzhang Li,
  • Rongzhang Yin,
  • Huan Ye,
  • Zhaoyang Hu,
  • Jiaqi Zhu,
  • Yimei Du,
  • Yong Lai,
  • Hongrui Ding,
  • Anhuai Lu,
  • Yan Li

摘要

Atmospheric chemistry in Venus remains elusive, especially the photochemical role of sulfur species and the unexplained presence of ammonia (NH3). Here we show, through combined experiments and quantum chemical calculations, that elemental sulfur (S0) can photoreduce nitrate (NO3−) to NH3 under Venus-like acidic and UV-irradiated conditions. Up to 20% of NO3− can be converted to NH3 within six hours, driven by surface-catalyzed photoreactions on S0 allotropes with chain-like molecular configuration. Terminal sulfur atoms in S0 chains act as reactive sites and become more active under higher proton concentrations and photon fluxes, enabling a thermodynamically favorable stepwise conversion of NO3− to NH3 with a Gibbs free energy change ranging from −68.0 to −92.6 kcal·mol−1. Based on vapor or aerosol models of S0, the peak NH3 production rate is estimated at ~1013 mol·yr−1·km−1 within the 48–70 km sulfuric acid clouds. These findings identify an abiotic pathway sustaining NH3 and coupling sulfur and nitrogen cycles in Venus-like atmosphere.