Liquid-cell electron microscopy (LC-EM) provides a unique approach for in-situ imaging morphology change of nanocrystals in liquids under electron beam irradiation. However, nanoscale real-time imaging of chemical/physical reaction processes in liquids under optical stimulus is still challenging. Here, we report direct observation of photomorphic reaction dynamics of gold nanoparticles (AuNPs) in water by liquid-cell four-dimensional electron microscopy (4D-EM) with high spatiotemporal resolution. The photoinduced agglomeration, coalescence, and fusion dynamics of AuNPs at different temperatures are studied. At low laser fluences, the AuNPs show a continuous aggregation in several seconds, and the aggregate size decreases with increasing fluence. At higher fluences close to melting threshold of AuNP, the aggregates further coalesced into nanoplates. While at fluences far above the melting threshold, the aggregates fully fuse into bigger NPs, which completes within tens of nanoseconds. This liquid-cell 4D-EM would also permit study of other numerical physical/chemical reaction processes in their native environments.
TOC GraphicPage 2 of 28
ACS Paragon Plus EnvironmentThe Journal of Physical Chemistry Letters 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 3
Main TextOwing to the unique optical and electronic properties that are not available in either molecules or bulk counterparts, noble metallic nanoparticles (NPs), for example gold NPs (AuNPs), have attracted great interests and found vast applications in a wide range of fields such as solar cells, [1][2] photocatalysis, 3-4 biosensors [5][6] and drug delivery. [7][8] In general, metallic NPs exhibit a surface-enhanced plasmon band as a result of intraband transitions through the photoexcitation of free conduction electrons on their surface. The surface plasmonic properties (e.g., peak position, width and intensity) of the NPs are determined by their size and shape. 9 It has been widely demonstrated that the morphology and size of the metal colloidal NPs can be significantly modified by light or laser irradiation. Because of subsequent aggregation, coalescence and fusion of NPs, other nanostructures including nanorods, nanobipyramids, nanoprisms and nanodisks can form, where the structures of the products strongly depend on the light wavelength, light intensity and capping ligands. [10][11][12][13][14][15] The control of the morphology and size of the metallic NPs by light not only provides a unique avenue of synthesis but also allows one to modulate their surface plasmon properties in a highly dynamic fashion. 15 In previous studies, however, the prevailing methods for detecting the morphological change of NPs under light irradiation, e.g., time-resolved or static optical scattering and absorption spectroscopies only provided indirect information of the NPs morphology ...