Nanoparticle surfactants for kinetically arrested photoactive assemblies to track light-induced electron transfer
Nanoparticle surfactants for kinetically arrested photoactive assemblies to track light-induced electron transfer
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DOI：
10.1038/s41565-021-00949-6
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发表时间：
2021-09-02
影响因子：
38.3
通讯作者：
Sokolowski, Kamil
中科院分区：
文献类型：
--
作者：
Huang, Junyang;Foldes, Tamas;Sokolowski, Kamil
小型半导体纳米晶体通过界面自限制聚集控制较大等离子体纳米结构的组装，从而产生可渗透且胶体稳定的光活性杂化物，用于光催化和光诱导电子转移的跟踪。大自然通过自我限制的过程控制着复杂建筑的组装；然而，迄今为止，模仿这些过程的人工策略很少。在这里，我们展示了一个由两种类型的纳米晶体（NC）组成的系统，其中一种NC组件的自限制组装控制另一种组件的聚集。我们的策略是使用半导体InP/ZnS核壳NCs （3nm）作为有效的组装调节剂和功能纳米颗粒表面活性剂，在葫芦[n]uril触发的AuNCs （5- 60nm）聚集中，允许快速形成（在几秒钟内）胶体稳定的杂交聚集体。由此产生的组件有效地收集半导体子结构内的光，诱导非平衡电子转移过程，现在可以通过集成的表面增强拉曼光谱活性等离子体隔间同时监测。杂交体中电子介质（例如甲基紫素（MV2+））的空间限制可以直接观察光产生的自由基物种以及实时的分子识别，为难以捉摸的sigma-(MV+)(2)二聚体物种的形成提供实验证据。这种方法为长期实时跟踪界面电荷转移过程的类似杂化物的广泛应用铺平了道路，例如在不可逆条件下，光驱动自由基的产生和用operando光谱催化。
Small semiconductor nanocrystals control the assembly of larger plasmonic nanostructures through interfacial self-limiting aggregation, leading to permeable and colloidally stable photoactive hybrids for photocatalysis and tracking of light-induced electron transfer.Nature controls the assembly of complex architectures through self-limiting processes; however, few artificial strategies to mimic these processes have been reported to date. Here we demonstrate a system comprising two types of nanocrystal (NC), where the self-limiting assembly of one NC component controls the aggregation of the other. Our strategy uses semiconducting InP/ZnS core-shell NCs (3 nm) as effective assembly modulators and functional nanoparticle surfactants in cucurbit[n]uril-triggered aggregation of AuNCs (5-60 nm), allowing the rapid formation (within seconds) of colloidally stable hybrid aggregates. The resultant assemblies efficiently harvest light within the semiconductor substructures, inducing out-of-equilibrium electron transfer processes, which can now be simultaneously monitored through the incorporated surface-enhanced Raman spectroscopy-active plasmonic compartments. Spatial confinement of electron mediators (for example, methyl viologen (MV2+)) within the hybrids enables the direct observation of photogenerated radical species as well as molecular recognition in real time, providing experimental evidence for the formation of elusive sigma-(MV+)(2) dimeric species. This approach paves the way for widespread use of analogous hybrids for the long-term real-time tracking of interfacial charge transfer processes, such as the light-driven generation of radicals and catalysis with operando spectroscopies under irreversible conditions.