Sub-nanometric particles (SNPs) of atomic cluster sizes have shown great promise in many fields such as full atom-to-atom utilization, but their precise production and stabilization at high mass loadings remain a great challenge. As a solution to overcome this challenge, a strategy allowing synthesis and preservation of SNPs at high mass loadings within multishell hollow metal-organic frameworks (MOFs) is demonstrated. First, alternating water-decomposable and water-stable MOFs are stacked in succession to build multilayer MOFs. Next, using controlled hydrogen bonding affinity, isolated water molecules are selectively sieved through the hydrophobic nanocages of water-stable MOFs and transferred one by one to water-decomposable MOFs. The transmission of water molecules via controlled hydrogen bonding affinity through the water-stable MOF layers is a key step to realize SNPs from various types of alternating water-decomposable and water-stable layers. This process transforms multilayer MOFs into SNP-embedded multishell hollow MOFs. Additionally, the multishell stabilizes SNPs by π-backbonding allowing high conductivity to be achieved via the hopping mechanism, and hollow interspaces minimize transport resistance. These features, as demonstrated using SNP-embedded multishell hollow MOFs with up to five shells, lead to high electrochemical performances including high volumetric capacities and low overpotentials in Li-O2 batteries.

中文翻译：

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多壳空心金属有机骨架中高负载亚纳米颗粒的自生和稳定化及其在Li-O2电池中的高性能利用。

原子团簇大小的亚纳米粒子（SNP）在许多领域中都显示出了巨大的希望，例如完全利用原子间的原子，但是在高质量负载下如何精确生产和稳定仍然是巨大的挑战。作为克服这一挑战的解决方案，展示了一种策略，该策略允许在多壳中空金属有机框架（MOF）中以高质量负载合成和保存SNP。首先，交替堆叠可分解水和稳定水的MOF，以构建多层MOF。接下来，使用可控的氢键亲和力，将分离出的水分子通过水稳定型MOF的疏水性纳米笼进行选择性筛分，然后逐一转移到可水分解的MOF中。通过受控的氢键亲和力将水分子传输通过水稳定的MOF层是从各种类型的交替的水可分解层和水稳定层实现SNP的关键步骤。此过程将多层MOF转换为嵌入SNP的多壳空心MOF。另外，多壳结构通过π反向键合稳定SNP，从而允许通过跳变机制实现高电导率，并且中空间隙将传输阻力降至最低。如使用具有多达五个壳的SNP嵌入式多壳空心MOF所展示的，这些特性导致了高电化学性能，包括高容量容量和Li-O2电池中的低超电势。此过程将多层MOF转换为嵌入SNP的多壳空心MOF。另外，多壳结构通过π反向键合稳定SNP，从而允许通过跳变机制实现高电导率，并且中空间隙将传输阻力降至最低。如使用具有多达五个壳的SNP嵌入式多壳空心MOF所展示的，这些特性导致了高电化学性能，包括高容量容量和Li-O2电池中的低超电势。此过程将多层MOF转换为嵌入SNP的多壳空心MOF。另外，多壳结构通过π反向键合稳定SNP，从而允许通过跳变机制实现高电导率，并且中空间隙将传输阻力降至最低。如使用具有多达五个壳的SNP嵌入式多壳空心MOF所展示的，这些特性导致了高电化学性能，包括高容量容量和Li-O2电池中的低超电势。