We report the preparation of porous hydrous zirconia by treatment of zirconium-based metal–organic framework (MOF) UiO-66 with a strong base. Microporosity of the original MOF was partially retained in the resultant porous hydrous zirconia. Ni^II centers were then adsorbed onto the OH-rich hydrous zirconia and in situ converted to highly dispersed Ni⁰ for CO₂ hydrogenation to CH₄. The activated catalyst after an induction period showed a turnover frequency of 345 h^–1 or a space–time yield of 5851 mmol·g_Ni^–1·h^–1 with a CH₄ selectivity of over 99%. The catalyst was tested for 100 h on stream, showing only a 4% decrease in activity, and was found to convert atmospheric CO₂ to CH₄ via CO₂ collection through Na₂CO₃/NaHCO₃ cycling. Thermal decomposition of NaHCO₃ released CO₂ for hydrogenation to CH₄, and the resultant Na₂CO₃ absorbed CO₂ from air to form NaHCO₃. This work highlights the opportunity in using MOFs as precursors to prepare highly porous metal oxide/hydroxide supports for solid–gas phase catalysis.

中文翻译：

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金属-有机骨架衍生的多孔含水氧化锆上的高分散镍催化剂用于CO ₂甲烷化

我们报道了通过处理具有强碱的锆基金属有机框架（MOF）UiO-66制备多孔含水氧化锆的方法。原始MOF的微孔部分保留在所得多孔含水氧化锆中。然后将Ni ^II中心吸附到富含OH的含水氧化锆上，并原位转化为高度分散的Ni ^0，以将CO ₂加氢成CH ₄。诱导期后的活化催化剂显示周转频率为345 h ^–1或时空产率为5851 mmol·g _Ni ^–1 ·h ^–1且具有CH ₄选择性超过99％。将催化剂用于在流100h中进行测试，仅示出在活性的4％的降低，并发现大气中的CO转换₂至CH ₄经由CO ₂收集通过的Na ₂ CO ₃ /碳酸氢钠₃循环。NaHCO _3的热分解释放出CO ₂以加氢成CH ₄，所得Na ₂ CO ₃从空气中吸收CO ₂形成NaHCO ₃。这项工作凸显了使用MOF作为前体来制备高度多孔的金属氧化物/氢氧化物载体以进行固-气相催化的机会。