Experimental measurements and numerical simulations of the transport and retention of nanocrystal CdSe/ZnS quantum dots in saturated porous media: Effects of electrolytes, organic ligand, and natural organic matter.

This study explores the transport and retention of CdSe/ZnS quantum dot (QD) nanoparticles in water-saturated sand columns as a function of electrolytes (Na+ and Ca2+), ionic strength, organic ligand citrate, and Suwannee River natural organic matter (SRNOM). Numerical simulations were carried out to understand the mechanisms that govern the transport and interactions of QDs in porous media and to assess how environmental parameters impact these mechanisms. An increase in the ionic strength of NaCl and CaCl2 increased QDs retention in porous media. The reduction of the electrostatic interactions screened by dissolved electrolyte ions and the increase of divalent bridging effect are the causes for this enhanced retention behavior. Citrate or SRNOM enhanced QDs transport in NaCl and CaCl2 systems by either increasing the repulsion energy barrier or inducing the steric interactions between QDs and the quartz sand collectors. A non-exponential decay characterized the retention profiles of QDs along the distance to the inlet. The modeling results indicated the four models containing the attachment, detachment, and straining terms - Model 1: M1-attachment, Model 2: M2-attachment and detachment, Model 3: M3-straining, and Model 4: M4-attachment, detachment, and straining - closely simulated the observed breakthrough curves (BTCs) but inadequately described the retention profiles.

Halogen Etch of Ti3AlC2 MAX Phase for MXene Fabrication.

The versatile property suite of two-dimensional MXenes is driving interest in various applications, including energy storage, electromagnetic shielding, and conductive coatings. Conventionally, MXenes are synthesized by a wet-chemical etching of the parent MAX-phase in HF-containing media. The acute toxicity of HF hinders scale-up, and competing surface hydrolysis challenges control of surface composition and grafting methods. Herein, we present an efficient, room-temperature etching method that utilizes halogens (Br2, I2, ICl, IBr) in anhydrous media to synthesize MXenes from Ti3AlC2. A radical-mediated process depends strongly on the molar ratio of the halogen to MAX phase, absolute concentration of the halogen, the solvent, and temperature. This etching method provides opportunities for controlled surface chemistries to modulate MXene properties.

20†µs-resolved high-throughput X-ray photon correlation spectroscopy on a 500k pixel detector enabled by data-management workflow.

The performance of the new 52 kHz frame rate Rigaku XSPA-500k detector was characterized on beamline 8-ID-I at the Advanced Photon Source at Argonne for X-ray photon correlation spectroscopy (XPCS) applications. Due to the large data flow produced by this detector (0.2 PB of data per 24 h of continuous operation), a workflow system was deployed that uses the Advanced Photon Source data-management (DM) system and high-performance software to rapidly reduce area-detector data to multi-tau and two-time correlation functions in near real time, providing human-in-the-loop feedback to experimenters. The utility and performance of the workflow system are demonstrated via its application to a variety of small-angle XPCS measurements acquired from different detectors in different XPCS measurement modalities. The XSPA-500k detector, the software and the DM workflow system allow for the efficient acquisition and reduction of up to ∼109 area-detector data frames per day, facilitating the application of XPCS to measuring samples with weak scattering and fast dynamics.

Experimental measurements and numerical simulations of the transport and retention of nanocrystal CdSe/ZnS quantum dots in saturated porous media: effects of pH, organic ligand, and natural organic matter.

The risks of environmental exposures of quantum dot (QD) nanoparticles are increasing, but these risks are difficult to assess because fundamental questions remain about factors affecting the mobility of QDs. The objective of this study is to help address this shortcoming by evaluating the physico-chemical mechanisms controlling the transport and retention of CdSe/ZnS QDs under various environmental conditions. The approach was to run a series of laboratory-scale column experiments where QDs were transported through saturated porous media with different pH values and concentrations of citrate and Suwannee River natural organic matter (SRNOM). Numerical simulations were then conducted and compared with the laboratory data in order to evaluate parameters controlling transport. QD suspensions were injected into the column in an upward direction and ICP-MS used to analyze Cd2+ concentrations (C) in column effluent and sand porous media samples. The increase in the background solution pH values enhanced the QD transport and decreased the QD retention. QD transport recovery percentages obtained from the column effluent samples were 2.6%, 83.2%, 101.7%, 96.5%, and 98.9%, at pH levels of 1.5, 3.5, 5, 7, and 9, respectively. The effects of citrate and SRNOM on the transport and retention of QDs were pH dependent as reflected in the influence of the electrostatic and steric interactions between QDs and sand surfaces. QDs were mobile under unfavorable deposition conditions at environmentally relevant pHs (i.e., 5, 7, and 9). Under favorable pH conditions for deposition (i.e., 1.5), QDs were completely retained within the porous media. The retention profiles of QDs showed a non-exponential decay with distance to the inlet, attributed to multiple deposition rates caused by the QD particles and surface heterogeneities of the quartz silica sand. Results of the diameter ratios of QDs to the median sand grains, in suspensions of DI water at pH 1.5, of citrate at pH 1.5, and of citrate at pH 3.5 indicate straining as the dominating mechanism for QD retention in porous media. The blocking effect and straining were significant under favorable deposition conditions and the detachment effect was non-negligible under unfavorable deposition conditions. Physico-chemical attachment and straining are the governing mechanisms that control the retention of QDs. Overall, experimental results indicate that aggregation, deposition, straining, blocking, and DLVO-type interactions affect the advective transport and retention of QDs in saturated porous media. The simulations were conducted using models that include terms describing attachment, detachment, and straining terms-model 1: M1-attachment, model 2: M2-attachment and detachment, model 3: M3-straining, and model 4: M4-attachment, detachment, and straining. The results from simulations with M2-attachment and detachment and M4-attachment, detachment, and straining matched best the observed breakthrough curves, but all four models inadequately described the retention profiles. Our findings demonstrate that QDs are mobile in porous media under a wide range of physico-chemical conditions representative of the natural environment. The mobility behavior of QDs in porous media indicated the potential risk of soil and groundwater contamination.

Colloidal Synthesis of Bulk-Bandgap Lead Selenide Nanocrystals.

Lead selenide quantum dots (QDs) are low-bandgap IV-VI semiconducting nanomaterials that have been studied for a variety of applications. Their preparation using colloidal methods can create small spherical to larger cubic nanocrystals, with an upper limit of ~17 nm reported to date. Here we describe methods for preparing cubic PbSe nanocrystals over a 20-40 nm size range using a twostep procedure. Specifically, ~10 nm PbSe QDs are generated using the rapid injection method, the products from which are overcoated with additional lead and selenium precursors. The use of two lead reagents were studied; lead oleate resulted in a maximum of 20 nm cubes, while more reactive lead hexyldecanoate resulted in much larger nanomaterials with bulk bandgaps. However, PbSe samples prepared with lead hexyldecanoate also contained agglomerates. Special care must be taken when characterizing larger strained nanomaterials with X-ray powder diffraction, for which the Scherrer equation is inadequate. A more rigorous approach using the Williamson-Hall method provides characterizations that are consistent with electron microscopy analysis.

Charge Carriers Modulate the Bonding of Semiconductor Nanoparticle Dopants As Revealed by Time-Resolved X-ray Spectroscopy.

Understanding the electronic structure of doped semiconductors is essential to realize advancements in electronics and in the rational design of nanoscale devices. Reported here are the results of time-resolved X-ray absorption studies on copper-doped cadmium sulfide nanoparticles that provide an explicit description of the electronic dynamics of the dopants. The interaction of a dopant ion and an excess charge carrier is unambiguously observed via monitoring the oxidation state. The experimental data combined with DFT calculations demonstrate that dopant bonding to the host matrix is modulated by its interaction with charge carriers. Furthermore, the transient photoluminescence and the kinetics of dopant oxidation reveal the presence of two types of surface-bound ions that create midgap states.

In vitro Detection of Hypoxia using a Ratiometric Quantum Dot-based Oxygen Sensor.

A quantum-dot based ratiometric fluorescent oxygen probe for the detection of hypoxia in live cells is reported. The system is comprised of a water-soluble near-infrared emissive quantum dot conjugated to perylene dye. The response to the oxygen concentration is investigated using enzymatic oxygen scavenging in water, while in vitro studies were performed with HeLa cells incubated under varying O2 levels. In both cases a significant enhancement in dye/QD emission intensity ratio was observed in the deoxygenated environment, demonstrating the possible use of this probe for cancer research.

Monolayer Silane-Coated, Water-Soluble Quantum Dots.

A one-step method to produce ≈12 nm hydrodynamic diameter water-soluble CdSe/ZnS quantum dots (QDs), as well as CdS/ZnS, ZnSe/ZnMnS/ZnS, AgInS2 /ZnS, and CuInS2 /ZnS QDs, by ligand exchange with a near-monolayer of organosilane caps is reported. The method cross-links the surface-bound silane ligands such that the samples are stable on the order of months under ambient conditions. Furthermore, the samples may retain a high quantum yield (60%) over this time. Several methods to functionalize aqueous QD dispersions with proteins and fluorescent dyes have been developed with reaction yields as high as 97%.