Influence of single-nanoparticle electrochromic dynamics on the durability and speed of smart windows.

Nanomaterials have tremendous potential to increase electrochromic smart window efficiency, speed, and durability. However, nanoparticles vary in size, shape, and surface defects, and it is unknown how nanoparticle heterogeneity contributes to particle-dependent electrochromic properties. Here, we use single-nanoparticle-level electro-optical imaging to measure structure-function relationships in electrochromic tungsten oxide nanorods. Single nanorods exhibit a particle-dependent waiting time for tinting (from 100 ms to 10 s) due to Li-ion insertion at optically inactive surface sites. Longer nanorods tint darker than shorter nanorods and exhibit a Li-ion gradient that increases from the nanorod ends to the middle. The particle-dependent ion-insertion kinetics contribute to variable tinting rates and magnitudes across large-area smart windows. Next, we quantified how particle-particle interactions impact tinting dynamics and reversibility as the nanorod building blocks are assembled into a thin film. Interestingly, single particles tint 4 times faster and cycle 20 times more reversibly than thin films made of the same particles. These findings allow us to propose a nanostructured electrode architecture that optimizes optical modulation rates and reversibility across large-area smart windows.

Optical sensing of aqueous nitrate anion by a platinum(II) triimine salt based solid state material.

Selective and quantitative measurement of aqueous nitrate (NO3-) anion is achieved using solid [Pt(Cl-4-tpy)Cl]ClO4 salt (Cl-4-tpy = 4-chloro-2,2':6'2''-terpyridine), and as the salt supported on controlled porous glass. This detection method relies on the color change of the Pt(II) complex from yellow to red and intense luminescence response upon ClO4- exchange with NO3- due to concomitant enhancement of Pt⋯Pt interactions. The spectroscopic response is highly selective for NO3- over a large range of halides and oxoanions.

Local Substrate Heterogeneity Influences Electrochemical Activity of TEM Grid-Supported Battery Particles.

Understanding how particle size and morphology influence ion insertion dynamics is critical for a wide range of electrochemical applications including energy storage and electrochromic smart windows. One strategy to reveal such structure-property relationships is to perform ex situ transmission electron microscopy (TEM) of nanoparticles that have been cycled on TEM grid electrodes. One drawback of this approach is that images of some particles are correlated with the electrochemical response of the entire TEM grid electrode. The lack of one-to-one electrochemical-to-structural information complicates interpretation of genuine structure/property relationships. Developing high-throughput ex situ single particle-level analytical techniques that effectively link electrochemical behavior with structural properties could accelerate the discovery of critical structure-property relationships. Here, using Li-ion insertion in WO3 nanorods as a model system, we demonstrate a correlated optically-detected electrochemistry and TEM technique that measures electrochemical behavior of via many particles simultaneously without having to make electrical contacts to single particles on the TEM grid. This correlated optical-TEM approach can link particle structure with electrochemical behavior at the single particle-level. Our measurements revealed significant electrochemical activity heterogeneity among particles. Single particle activity correlated with distinct local mechanical or electrical properties of the amorphous carbon film of the TEM grid, leading to active and inactive particles. The results are significant for correlated electrochemical/TEM imaging studies that aim to reveal structure-property relationships using single particle-level imaging and ensemble-level electrochemistry.

pH-Mediated Colorimetric and Luminescent Sensing of Aqueous Nitrate Anions by a Platinum(II) Luminophore@Mesoporous Silica Composite.

Increased levels of nitrate (NO3-) in the environment can be detrimental to human health. Herein, we report a robust, cost-effective, and scalable, hybrid material-based colorimetric/luminescent sensor technology for rapid, selective, sensitive, and interference-free in situ NO3- detection. These hybrid materials are based on a square-planar platinum(II) salt [Pt(tpy)Cl]PF6 (tpy = 2,2';6',2″-terpyridine) supported on mesoporous silica. The platinum salt undergoes a vivid change in color and luminescence upon exposure to aqueous NO3- anions at pH ≤ 0 caused by substitution of the PF6- anions by aqueous NO3-. This change in photophysics of the platinum salt is induced by a rearrangement of its crystal lattice that leads to an extended Pt···Pt···Pt interaction, along with a concomitant change in its electronic structure. Furthermore, incorporating the material into mesoporous silica enhances the surface area and increases the detection sensitivity. A NO3- detection limit of 0.05 mM (3.1 ppm) is achieved, which is sufficiently lower than the ambient water quality limit of 0.16 mM (10 ppm) set by the United States Environmental Protection Agency. The colorimetric/luminescence of the hybrid material is highly selective to aqueous NO3- anions in the presence of other interfering anions, suggesting that this material is a promising candidate for the rapid NO3- detection and quantification in practical samples without separation, concentration, or other pretreatment steps.