Visualizing Ligand-Mediated Bimetallic Nanocrystal Formation Pathways with in Situ Liquid-Phase Transmission Electron Microscopy Synthesis

ACS Nano ◽  
2021 ◽  
Vol 15 (2) ◽  
pp. 2578-2588
Author(s):  
Mei Wang ◽  
Asher C. Leff ◽  
Yue Li ◽  
Taylor J. Woehl
Keyword(s):  
Electron Microscopy ◽  
Transmission Electron Microscopy ◽  
Liquid Phase ◽  
Transmission Electron ◽  
Nanocrystal Formation ◽  
Phase Transmission

scholarly journals Visualizing Ligand-Mediated Bimetallic Nanocrystal Formation Pathways with In Situ Liquid Phase Transmission Electron Microscopy Synthesis

2020 ◽  
Author(s):  
Mei Wang ◽  
Asher Leff ◽  
Yue Li ◽  
Taylor Woehl
Keyword(s):  
Electron Microscopy ◽  
Transmission Electron Microscopy ◽  
Electron Beam ◽  
Ex Situ ◽  
Formation Mechanisms ◽  
Transmission Electron ◽  
Thiolate Complexes ◽  
Nanocrystal Formation ◽  
Phase Transmission

Colloidal synthesis of alloyed multimetallic nanocrystals with precise composition control remains a challenge and a critical missing link in theory-driven rational design of functional nanomaterials. Liquid phase transmission electron microscopy (LP-TEM) enables directly visualizing nanocrystal formation mechanisms that can inform discovery of design rules for colloidal multimetallic nanocrystal synthesis, but it remains unclear whether the salient chemistry of the flask synthesis is preserved in the extreme electron beam radiation environment during LPTEM. Here we demonstrate controlled in situ LP-TEM synthesis of alloyed AuCu nanoparticles while maintaining the molecular structure of electron beam sensitive metal thiolate precursor complexes. Ex situ flask synthesis experiments showed that nearly equimolar AuCu alloys formed from heteronuclear metal thiolate complexes, while gold-rich alloys formed in their absence. Systematic dose rate-controlled in situ LP-TEM synthesis experiments established a range of electron beam synthesis conditions that formed alloyed AuCu nanoparticles with similar alloy composition, random alloy structure, and particle size distribution shape as those from ex situ flask synthesis, indicating metal thiolate complexes were preserved under these conditions. Reaction kinetic simulations of radical-ligand reactions revealed that polymer capping ligands acted as effective hydroxyl radical scavengers during LP-TEM synthesis and prevented metal thiolate oxidation at low dose rates. In situ synthesis experiments and ex situ atomic scale imaging revealed that a key role of metal thiolate complexes was to prevent copper atom oxidation and facilitate formation of prenucleation cluster intermediates. This work demonstrates that complex ion precursor chemistry can be maintained during LP-TEM imaging, enabling probing nanocrystal formation mechanisms with LP-TEM under reaction conditions representative of ex situ flask synthesis.

scholarly journals Accessing local electron-beam induced temperature changes during in situ liquid-phase transmission electron microscopy

2021 ◽  
Author(s):  
Birk Fritsch ◽  
Andreas Hutzler ◽  
Mingjian Wu ◽  
Saba Khadivianazar ◽  
Lilian Vogl ◽  
...  
Keyword(s):  
Electron Microscopy ◽  
Transmission Electron Microscopy ◽  
Electron Beam ◽  
Liquid Phase ◽  
Gas Bubble ◽  
Local Electron ◽  
Temperature Changes ◽  
Transmission Electron ◽  
Phase Transmission

Electron-beam induced heating in the vicinity of a gas bubble in liquid-phase TEM is quantified in situ.

scholarly journals Visualizing Ligand-Mediated Bimetallic Nanocrystal Formation Pathways with In Situ Liquid Phase Transmission Electron Microscopy Synthesis

2020 ◽  
Author(s):  
Mei Wang ◽  
Asher Leff ◽  
Yue Li ◽  
Taylor Woehl
Keyword(s):  
Electron Microscopy ◽  
Transmission Electron Microscopy ◽  
Electron Beam ◽  
Ex Situ ◽  
Formation Mechanisms ◽  
Transmission Electron ◽  
Thiolate Complexes ◽  
Nanocrystal Formation ◽  
Phase Transmission

Colloidal synthesis of alloyed multimetallic nanocrystals with precise composition control remains a challenge and a critical missing link in theory-driven rational design of functional nanomaterials. Liquid phase transmission electron microscopy (LP-TEM) enables directly visualizing nanocrystal formation mechanisms that can inform discovery of design rules for colloidal multimetallic nanocrystal synthesis, but it remains unclear whether the salient chemistry of the flask synthesis is preserved in the extreme electron beam radiation environment during LPTEM. Here we demonstrate controlled in situ LP-TEM synthesis of alloyed AuCu nanoparticles while maintaining the molecular structure of electron beam sensitive metal thiolate precursor complexes. Ex situ flask synthesis experiments showed that nearly equimolar AuCu alloys formed from heteronuclear metal thiolate complexes, while gold-rich alloys formed in their absence. Systematic dose rate-controlled in situ LP-TEM synthesis experiments established a range of electron beam synthesis conditions that formed alloyed AuCu nanoparticles with similar alloy composition, random alloy structure, and particle size distribution shape as those from ex situ flask synthesis, indicating metal thiolate complexes were preserved under these conditions. Reaction kinetic simulations of radical-ligand reactions revealed that polymer capping ligands acted as effective hydroxyl radical scavengers during LP-TEM synthesis and prevented metal thiolate oxidation at low dose rates. In situ synthesis experiments and ex situ atomic scale imaging revealed that a key role of metal thiolate complexes was to prevent copper atom oxidation and facilitate formation of prenucleation cluster intermediates. This work demonstrates that complex ion precursor chemistry can be maintained during LP-TEM imaging, enabling probing nanocrystal formation mechanisms with LP-TEM under reaction conditions representative of ex situ flask synthesis.

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