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Formation kinetics of metal nanoparticles are generally describedviamass transport and thermodynamics‐based models, such as diffusion‐limited growth and classical nucleation theory (CNT). However, metal monomers are commonly assumed as precursors, leaving the identity of molecular intermediates and their contribution to nanoparticle formation unclear. Herein, liquid phase transmission electron microscopy (LPTEM) and reaction kinetic modeling are utilized to establish the nucleation and growth mechanisms and discover molecular intermediates during silver nanoparticle formation. Quantitative LPTEM measurements show that their nucleation rate decreases while growth rate is nearly invariant with electron dose rate. Reaction kinetic simulations show that Ag₄and Ag⁻follow a statistically similar dose rate dependence as the experimentally determined growth rate. We show that experimental growth rates are consistent with diffusion‐limited growthviathe attachment of these species to nanoparticles. The dose rate dependence of nucleation rate is inconsistent with CNT. A reaction‐limited nucleation mechanism is proposed and it is demonstrated that experimental nucleation kinetics are consistent with Ag₄²⁺aggregation rates at millisecond time scales. Reaction throughput analysis of the kinetic simulations uncovered formation and decay pathways mediating intermediate concentrations. We demonstrate the power of quantitative LPTEM combined with kinetic modeling for establishing nanoparticle formation mechanisms and principal intermediates. 

Water vapor condensation on hygroscopic aerosol particles plays an important role in cloud formation, climate change, secondary aerosol formation, and aerosol aging. Conventional understanding considers deliquescence of nanosized hygroscopic aerosol particles a nearly instantaneous solid to liquid phase transition. However, the nanoscale dynamics of water condensation and aerosol particle dissolution prior to and during deliquescence remain obscure due to a lack of high spatial and temporal resolution single particle measurements. Here we use real time in situ transmission electron microscopy (TEM) imaging of individual sodium chloride (NaCl) nanoparticles to demonstrate that water adsorption and aerosol particle dissolution prior to and during deliquescence is a multistep dynamic process. Water condensation and aerosol particle dissolution was investigated for lab generated NaCl aerosols and found to occur in three distinct stages as a function of increasing RH. First, a < 100 nm water layer adsorbed on the NaCl cubes and caused sharp corners to dissolve and truncate. The water layer grew to several hundred nanometers with increasing RH and was rapidly saturated with solute, as evidenced by halting of particle dissolution. Adjacent cube corners displayed second-scale curvature fluctuations with no net particle dissolution or water layer thickness change. We propose that droplet solute concentration fluctuations drove NaCl transport from regions of high local curvature to regions of low curvature. Finally, we observed coexistence of a liquid water droplet and aerosol particle immediately prior to deliquescence. Particles dissolved discretely along single crystallographic directions, separating by few second lag times with no dissolution. This work demonstrates that deliquescence of simple pure salt particles with sizes in the range of 100 nm to several microns is not an instantaneous phase transition and instead involves a range of complex dissolution and water condensation dynamics. 

Abstract One possible solution against the accumulation of petrochemical plastics in natural environments is to develop biodegradable plastic substitutes using natural components. However, discovering all-natural alternatives that meet specific properties, such as optical transparency, fire retardancy and mechanical resilience, which have made petrochemical plastics successful, remains challenging. Current approaches still rely on iterative optimization experiments. Here we show an integrated workflow that combines robotics and machine learning to accelerate the discovery of all-natural plastic substitutes with programmable optical, thermal and mechanical properties. First, an automated pipetting robot is commanded to prepare 286 nanocomposite films with various properties to train a support-vector machine classifier. Next, through 14 active learning loops with data augmentation, 135 all-natural nanocomposites are fabricated stagewise, establishing an artificial neural network prediction model. We demonstrate that the prediction model can conduct a two-way design task: (1) predicting the physicochemical properties of an all-natural nanocomposite from its composition and (2) automating the inverse design of biodegradable plastic substitutes that fulfils various user-specific requirements. By harnessing the model’s prediction capabilities, we prepare several all-natural substitutes, that could replace non-biodegradable counterparts as exhibiting analogous properties. Our methodology integrates robot-assisted experiments, machine intelligence and simulation tools to accelerate the discovery and design of eco-friendly plastic substitutes starting from building blocks taken from the generally-recognized-as-safe database. 

High entropy alloy (HEA) nanoparticles hold promise as active and durable (electro)catalysts. Understanding their formation mechanism will enable rational control over composition and atomic arrangement of multimetallic catalytic surface sites to maximize their activity. While prior reports have attributed HEA nanoparticle formation to nucleation and growth, there is a dearth of detailed mechanistic investigations. Here we utilize liquid phase transmission electron microscopy (LPTEM), systematic synthesis, and mass spectrometry (MS) to demonstrate that HEA nanoparticles form by aggregation of metal cluster intermediates. AuAgCuPtPd HEA nanoparticles are synthesized by aqueous co-reduction of metal salts with sodium borohydride in the presence of thiolated polymer ligands. Varying the metal : ligand ratio during synthesis showed that alloyed HEA nanoparticles formed only above a threshold ligand concentration. Interestingly, stable single metal atoms and sub-nanometer clusters are observed by TEM and MS in the final HEA nanoparticle solution, suggesting nucleation and growth is not the dominant mechanism. Increasing supersaturation ratio increased particle size, which together with observations of stable single metal atoms and clusters, supported an aggregative growth mechanism. Direct real-time observation with LPTEM imaging showed aggregation of HEA nanoparticles during synthesis. Quantitative analyses of the nanoparticle growth kinetics and particle size distribution from LPTEM movies were consistent with a theoretical model for aggregative growth. Taken together, these results are consistent with a reaction mechanism involving rapid reduction of metal ions into sub-nanometer clusters followed by cluster aggregation driven by borohydride ion induced thiol ligand desorption. This work demonstrates the importance of cluster species as potential synthetic handles for rational control over HEA nanoparticle atomic structure. 

Abstract Assembling 2D‐material (2DM) nanosheets into micro‐ and macro‐architectures with augmented functionalities requires effective strategies to overcome nanosheet restacking. Conventional assembly approaches involve external binders and/or functionalization, which inevitably sacrifice 2DM's nanoscale properties. Noble metal ions (NMI) are promising ionic crosslinkers, which can simultaneously assemble 2DM nanosheets and induce synergistic properties. Herein, a collection of NMI–2DM complexes are screened and categorized into two sub‐groups. Based on the zeta potentials, two assembly approaches are developed to obtain 1) NMI‐crosslinked 2DM hydrogels/aerogels for heterostructured catalysts and 2) NMI–2DM inks for templated synthesis. First, tetraammineplatinum(II) nitrate (TPtN) serves as an efficient ionic crosslinker to agglomerate various 2DM dispersions. By utilizing micro‐textured assembly platforms, various TPtN–2DM hydrogels are fabricated in a scalable fashion. Afterward, these hydrogels are lyophilized and thermally reduced to synthesize Pt‐decorated 2DM aerogels (Pt@2DM). The Pt@2DM heterostructures demonstrate high, substrate‐dependent catalytic activities and promote different reaction pathways in the hydrogenation of 3‐nitrostyrene. Second, PtCl₄can be incorporated into 2DM dispersions at high NMI molarities to prepare a series of PtCl₄–2DM inks with high colloidal stability. By adopting the PtCl₄–graphene oxide ink, various Pt micro‐structures with replicated topographies are synthesized with accurate control of grain sizes and porosities.