Elucidating the Role of Dissolved Organic Matter and Sunlight in Mediating the Formation of Ag-Au Bimetallic Alloy Nanoparticles in the Aquatic Environment.

Elucidating the interactions between metal ions and dissolved organic matter and deciphering mechanisms for their mineralization in the aquatic environment are central to understanding the speciation, transport, and toxicity of nanoparticles (NPs). Herein, we examine the interactions between Ag+ and Au3+ ions in mixed solutions (χAg = 0.2, 0.5, and 0.8) in the presence of humic acids (HAs) under simulated sunlight; these conditions result in the formation of bimetallic Ag-Au NPs. A key distinction is that the obtained alloy NPs are compositionally and morphologically rather different from NPs obtained from thermally activated dark processes. Photoillumination triggers a distinctive plasmon-mediated process for HA-assisted reductive mineralization of ions to bimetallic alloy NPs which is not observed in its dark thermal reduction counterpart. The initial nucleation of bimetallic NPs is dominated by differences in the cohesive energies of Ag and Au crystal lattices, whereas the growth mechanisms are governed by the strongly preferred incorporation of Ag ions, which stems from their greater photoreactivity. The bimetallic NPs crystallize in shapes governed by the countervailing influence of minimizing free energy through the adoption of Wulff constructions and the energetic penalties associated with twin faults. As such, assessments of the stability and the potential toxic effects of bimetallic NPs arising from their possible existence in aquatic environments will depend sensitively on the origins of their formation.

Atomic Hourglass and Thermometer Based on Diffusion of a Mobile Dopant in VO2.

Transformations between different atomic configurations of a material oftentimes bring about dramatic changes in functional properties as a result of the simultaneous alteration of both atomistic and electronic structure. Transformation barriers between polytypes can be tuned through compositional modification, generally in an immutable manner. Continuous, stimulus-driven modulation of phase stabilities remains a significant challenge. Utilizing the metal-insulator transition of VO2, we exemplify that mobile dopants weakly coupled to the crystal lattice provide a means of imbuing a reversible and dynamical modulation of the phase transformation. Remarkably, we observe a time- and temperature-dependent evolution of the relative phase stabilities of the M1 and R phases of VO2 in an "hourglass" fashion through the relaxation of interstitial boron species, corresponding to a 50 °C modulation of the transition temperature achieved within the same compound. The material functions as both a chronometer and a thermometer and is "reset" by the phase transition. Materials possessing memory of thermal history hold promise for applications such as neuromorphic computing, atomic clocks, thermometry, and sensing.

Stabilization of Ag-Au Bimetallic Nanocrystals in Aquatic Environments Mediated by Dissolved Organic Matter: A Mechanistic Perspective.

Gold and silver nanoparticles can be stabilized endogenously within aquatic environments from dissolved ionic species as a result of mineralization induced by dissolved organic matter. However, the ability of fulvic and humic acids to stabilize bimetallic nanoparticles is entirely unexplored. Elucidating the formation of such particles is imperative given their potential ecological toxicity. Herein, we demonstrate the nucleation, growth, and stabilization of bimetallic Ag-Au nanocrystals from the interactions of Ag+ and Au3+ with Suwannee River fulvic and humic acids. The mechanisms underpinning the stabilization of Ag-Au alloy NPs at different pH (6.0-9.0) values are studied by UV-vis spectrophotometry, X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HRTEM), and selected area electron diffraction (SAED). Complexation of free Ag+ and Au3+ ions with the Lewis basic groups (carbonyls, carboxyls, and thiols) of FA and HA, followed by electron-transfer from redox-active moieties present in dissolved organic matter initiates the nucleation of the NPs. Alloy formation and interdiffusion of Au and Ag atoms are further facilitated by a galvanic replacement reaction between AuCl4- and Ag. Charge-transfer from Au to Ag stabilizes the formed bimetallic NPs. A more pronounced agglomeration of the Ag-Au NPs is observed when HA is used compared to FA as the reducing agent. The bimetallic NPs are stable for greater than four months, which suggests the possible persistence and dispersion of these materials in aquatic environments. The mechanistic ideas have broad generalizability to reductive mineralization processes mediated by dissolved organic matter.

Atomic Layer Deposition of Hafnium(IV) Oxide on Graphene Oxide: Probing Interfacial Chemistry and Nucleation by using X-ray Absorption and Photoelectron Spectroscopies.

Interfacing graphene with metal oxides is of considerable technological importance for modulating carrier density through electrostatic gating as well as for the design of earth-abundant electrocatalysts. Herein, we probe the early stages of the atomic layer deposition (ALD) of HfO2 on graphene oxide using a combination of C and O K-edge near-edge X-ray absorption fine structure spectroscopies and X-ray photoelectron spectroscopy. Dosing with water is observed to promote defunctionalization of graphene oxide as a result of the reaction between water and hydroxyl/epoxide species, which yields carbonyl groups that further react with migratory epoxide species to release CO2 . The carboxylates formed by the reaction of carbonyl and epoxide species facilitate binding of Hf precursors to graphene oxide surfaces. The ALD process is accompanied by recovery of the π-conjugated framework of graphene. The delineation of binding modes provides a means to rationally assemble 2D heterostructures.

Effectiveness of zinc oxide-assisted photocatalysis for concerned constituents in reclaimed wastewater: 1,4-Dioxane, trihalomethanes, antibiotics, antibiotic resistant bacteria (ARB), and antibiotic resistance genes (ARGs).

Microbial and emerging chemical contaminants are unwanted constituents in reclaimed wastewater, due to the health concerns of using the water for agricultural irrigation, aquifer recharges, and potable water. Removal of these contaminants is required but it is currently challenging, given that there is no simple treatment technology to effectively remove the mixture of these contaminants. This study examined the effectiveness of ZnO-assisted photocatalytic degradation of several constituents, including 1,4-dioxane, trihalomethanes (THMs), triclosan (TCS), triclocarban (TCC), antibiotic resistant bacteria (ARB) and antibiotic resistant genes (ARGs), under low intensity of UV exposure. E. coli with an ARGs-carrying circular plasmid (pUC19) was used as a model antibiotic resistant bacterium. Our results show that commercial zinc oxide (C-ZnO) assisted photodegradation of 1,4-dioxane, and dehalogenation of THMs, TCS, and TCC, while tetrapodal zinc oxide (T-ZnO) enhanced the dehalogenation of TCS and TCC. Additionally, T-ZnO assisted the photocatalytic inactivation of the E. coli within 6 h and caused structural changes in the plasmid DNA (pUC19) with additional UV exposure, resulting in non-functional AGR-containing plasmids. These results also suggest that higher UV dose is required not only to inactivate ARB but also to damage ARGs in the ARB in order to decrease risks in promoting ARB population in the environment. Overall, our results implicated that, under low UV intensity, ZnO-assisted photocatalysis is a promising alternative to simultaneously remove biological and emerging chemical contaminants in treated wastewater for safe reuse.

Photodegradation of fluorotelomer carboxylic 5:3 acid and perfluorooctanoic acid using zinc oxide.

Occurrence of per- and poly-fluoroalkyl substances (PFASs) in the environment and biota has raised a great concern to public health because these compounds are persistent, bioaccumulative, and toxic. Biodegradation of polyfluoroalkyl substances, particularly long-chain fluorotelomer-based products, can lead to production of various short-chain PFASs, with 5:3 fluorotelomer carboxylic acid (referred as 5:3 FTCA hereafter) as a dominant polyfluoroalkyl metabolite. Perfluoroalkyl acids, particularly perfluorooctanoic acid (PFOA), are toxic and current removal methods are not cost-effective. This study reports the photodegradation of 5:3 FTCA and PFOA using ZnO as a photocatalyst under neutral pH and room temperature conditions. Under long UV wavelength (365 nm), both tetrapod and commercial ZnO can photodegrade 5:3 FTCA. Five removal products-perfluorohexanoic acid, perfluoropentanoic acid, perfluorobutyric acid, 5:2 fluorotelomer carboxylic acid (5:2 FTCA), and inorganic fluoride-were identified, with PFBA and F- as dominant end products. SEM and XPS high-resolution scans on the surface of the utilized ZnO showed less units of CF2 than that in 5:3 FTCA, supporting occurrence of photodegradation of 5:3 FTCA by ZnO. Defluorination of PFOA was not observed with ZnO only, but at pH 5 and in the co-presence of Fe-citrate. PFOA defluorination increased from 0.93% after 3 days of UV light exposure to 3.9% after additional 135 h under direct sunlight exposure. To the authors' best knowledge, this is the first report studying ZnO-catalyzed photodegradation of 5:3 FTCA, and examining the Fe co-addition for PFOA defluorination.

Two-dimensional graphene as a matrix for MALDI imaging mass spectrometry.

Here, a matrix using two-dimensional (2D) graphene is demonstrated for the first time in the context of MALDI IMS using a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. Although graphene flakes have been used previously in MALDI, it is described here how a single 2D layer of graphene is applied directly on top of rat brain sections and soybean leaves. Several classes of molecules are desorbed and ionized off of the surface of the tissues examined using 2D graphene, with minimal background interference from the matrix. Moreover, no solvents are employed in application of 2D graphene, eliminating the potential for analyte diffusion in liquid droplets during matrix application. Because 2D graphene is an elemental form of carbon, an additional advantage is its high compatibility with the long duration needed for many IMS experiments. Graphical Abstract ᅟ.