Hydrodearomatization attracts extensive interest for removing polycyclic aromatic hydrocarbons in diesel but still suffers from sluggish efficiency due to the vulnerable sulfur resistance of noble metal catalysts and inferior hydrogenation performance of traditional transition-metal catalysts. Herein, we propose a low-temperature in situ carbonization of the template strategy for constructing N-doped carbon interior-modified MCM-41 (NC@MCM)-confined ultra-dispersed Ni nanocluster catalysts (Ni/NC@MCM). The optimal hydrogenation catalyst Ni/NC₃₀₀@MCM with ultrafine Ni nanoclusters (2.4 nm) exhibits 100% naphthalene conversion and 100% decalin selectivity at 100 °C and atmospheric pressure. Additionally, trans-decalin stereoselectivity up to 95% is achieved compared with other catalysts. The N-doped carbon inside mesochannels not only plays a critical role in stabilizing and dispersing Ni species but also promotes H₂ adsorption/activation and enriches naphthalene molecules. Theoretical results reveal that the pyridinic-N and pyrrolic-N species can boost the adsorption of naphthalene. The dual confinement of active sites and reactants in this microenvironment makes the outstanding trans-decalin stereoselectivity a reality. Moreover, Ni/NC₃₀₀@MCM shows distinguished activities in selective hydrogenation of dibenzothiophene and quinoline, and the applicability of the template carbonization method on HMS and MCM-48 is confirmed. This work opens a unique avenue in promising metal nanocluster catalysts for stereoselective hydrogenation.

中文翻译：

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N 掺杂碳内部改性介孔二氧化硅限制镍纳米团簇用于立体选择性氢化

加氢脱芳构化脱除柴油中的多环芳烃引起了广泛关注，但由于贵金属催化剂的抗硫性差和传统过渡金属催化剂的加氢性能差，其效率仍然低下。在此，我们提出了一种模板策略的低温原位碳化，用于构建 N 掺杂碳内部改性 MCM-41 (NC@MCM)-限域超分散 Ni 纳米团簇催化剂 (Ni/NC@MCM)。最佳加氢催化剂Ni/NC ₃₀₀@具有超细 Ni 纳米团簇 (2.4 nm) 的 MCM 在 100 °C 和大气压下表现出 100% 的萘转化率和 100% 的萘烷选择性。此外，与其他催化剂相比，反式萘烷的立体选择性高达 95%。介观通道内的氮掺杂碳不仅在稳定和分散镍物种方面起着关键作用，而且促进 H ₂吸附/活化并富集萘分子。理论结果表明，吡啶-N 和吡咯-N 物种可以促进萘的吸附。这种微环境中活性位点和反应物的双重限制使得出色的反式萘烷立体选择性成为现实。此外，Ni/NC ₃₀₀@MCM 在二苯并噻吩和喹啉的选择性加氢中表现出卓越的活性，并证实了模板碳化方法在 HMS 和 MCM-48 上的适用性。这项工作为用于立体选择性氢化的有前途的金属纳米团簇催化剂开辟了一条独特的途径。