Versatile Synthesis of Hollow Metal Sulfides via Reverse Cation Exchange Reactions for Photocatalytic CO2 Reduction.

Herein, we explore a general Cu2-x S nanocube template-assisted and reverse cation exchange-mediated growth strategy for fabricating hollow multinary metal sulfide. Unlike the traditional cation exchange method controlled by the metal sulfide constant, the introduction of tri-n-butylphosphine (TBP) can reverse cation exchange to give a series of hollow metal sulfides. A variety of hollow multinary metal sulfide cubic nanostructures has been demonstrated while preserving anisotropic shapes to the as-synthesized templates, including binary compounds (CdS, ZnS, Ag2 S, PbS, SnS), ternary compound (CuInS2 , Znx Cd1-x S), and quaternary compound (single-atom platinum anchored Znx Cd1-x S; Znx Cd1-x S-Pt1 ). Experimental and density functional theory (DFT) calculations show that the hollow metal sulfide semiconductors obtained could significantly improve the separation and migration of photogenerated electron-hole pairs. Owing to the efficient charge transfer, the Znx Cd1-x S-Pt1 exhibited outstanding photocatalytic performance of CO2 to CO, with the highest CO generation rate of 75.31 µmol h-1 .

Cation Exchange Protocols to Radiolabel Aqueous Stabilized ZnS, ZnSe, and CuFeS2 Nanocrystals with 64Cu for Dual Radio- and Photo-Thermal Therapy.

Here, cation exchange (CE) reactions are exploited to radiolabel ZnSe, ZnS, and CuFeS2 metal chalcogenide nanocrystals (NCs) with 64Cu. The CE protocol requires one simple step, to mix the water-soluble NCs with a 64Cu solution, in the presence of vitamin C used to reduce Cu(II) to Cu(I). Given the quantitative cation replacement on the NCs, a high radiochemical yield, up to 99%, is reached. Also, provided that there is no free 64Cu, no purification step is needed, making the protocol easily translatable to the clinic. A unique aspect of the approach is the achievement of an unprecedentedly high specific activity: by exploiting a volumetric CE, the strategy enables to concentrate a large dose of 64Cu (18.5 MBq) in a small NC dose (0.18 µg), reaching a specific activity of 103 TBq g-1. Finally, the characteristic dielectric resonance peak, still present for the radiolabeled 64Cu:CuFeS2 NCs after the partial-CE reaction, enables the generation of heat under clinical laser exposure (1 W cm-2). The synergic toxicity of photo-ablation and 64Cu ionization is here proven on glioblastoma and epidermoid carcinoma tumor cells, while no intrinsic cytotoxicity is seen from the NC dose employed for these dual experiments.

ß-Cyclodextrin capped ZnS nanoparticles for CER-assisted colorimetric and spectrophotometric detection of Pb2⁺, Cu2⁺, and Hg2⁺ in an aqueous solution.

Herein, simple, low-cost, and room-temperature synthesis of beta-cyclodextrin (ß-CD) stabilized zinc sulfide nanoparticle (ZnS NP) through the chemical precipitation method has been reported for cation exchange reaction (CER) based colorimetric sensing of Pb2+, Cu2+, and Hg2+. Formation of ß-CD stabilized ZnS NPs (ZnS@ß-CD) was verified by physicochemical characterization techniques such as XRD, XPS, FE-SEM, and TEM. ZnS@ß-CD NPs showed color change selectively for the metal ions Pb2⁺, Cu2⁺, and Hg2⁺ among the various metal ions including Sn2⁺, Cr³âº, Mn2⁺, Fe³âº, Co2⁺, Ni2⁺, and Cd2⁺. The solubility product of reactants and the transformed products are the reason for selective CER of ZnS@ß-CD NPs towards Pb2⁺, Cu2⁺, and Hg2⁺ ions. ZnS@ß-CD NPs dispersion revealed rapid color change from white to orange, black, and bright yellow on the addition of higher concentrations of Pb2⁺, Cu2⁺, and Hg2⁺ respectively. This color change is due to the formation of complete CER-transformed nanostructures such as PbS, CuS, and HgS in higher concentrations (10⁻1- 10⁻³ M) of corresponding metal ions. The partial CER altered products Zn1-x,PbxS, Zn1-xCuxS and Zn1-xHgxS were detected due to the appearance of pale color in the lower metal ions concentrations of 10⁻4 - 10⁻6 M. This CER assisted transformation was also monitored through spectrophotometric methods. Moreover, infrared spectroscopic analysis was used to testify the structure of CER transformed product. The synthesized ZnS@ß-CD NPs act as an efficient CER-based sensor for distinguishing and determining Pb2⁺, Cu2⁺, and Hg2⁺ at different level concentrations in the aqueous solution.

Boosting CO2 Electroreduction via the Synergistic Effect of Tuning Cationic Clusters and Visible-Light Irradiation.

Introducing an external light field can increase the intrinsic activity and energy efficiency for electrochemical CO2 reduction. Herein, a synergistic strategy that introduces photosensitive components and visible light into a stable system is reported to improve the performance for CO2 reduction. The catalytic kinetics studies indicate that the synergistic effect of implantation of cationic Ti and additional light driving is the primary responsibility for accelerating the first electron transfer to form a *COO- intermediate. This leads to a satisfactory CO2 -to-CO conversion for Zr/Ti-NB-Co in terms of high selectivity (Faradaic efficiency of 93.6% at -0.7 V), remarkable catalytic activity (production rate up to 546 mmol g-1 h-1 at -1.1 V), excellent long-term stability (without performance decay over 11 h), and large turnover frequency of 1028 h-1 at -1.1 V under visible light. These results imply that the photodriven Ti-based porphyrin catalyst not only can deliver more electrons, but also can act as a photoswitch to adjust the electron transfer pathway.

Geochemical processes controlling water salinization in an irrigated basin in Spain: identification of natural and anthropogenic influence.

Salinization of water bodies represents a significant risk in water systems. The salinization of waters in a small irrigated hydrological basin is studied herein through an integrated hydrogeochemical study including multivariate statistical analyses and geochemical modeling. The study zone has two well differentiated geologic materials: (i) Quaternary sediments of low salinity and high permeability and (ii) Tertiary sediments of high salinity and very low permeability. In this work, soil samples were collected and leaching experiments conducted on them in the laboratory. In addition, water samples were collected from precipitation, irrigation, groundwater, spring and surface waters. The waters show an increase in salinity from precipitation and irrigation water to ground- and, finally, surface water. The enrichment in salinity is related to the dissolution of soluble mineral present mainly in the Tertiary materials. Cation exchange, precipitation of calcite and, probably, incongruent dissolution of dolomite, have been inferred from the hydrochemical data set. Multivariate statistical analysis provided information about the structure of the data, differentiating the group of surface waters from the groundwaters and the salinization from the nitrate pollution processes. The available information was included in geochemical models in which hypothesis of consistency and thermodynamic feasibility were checked. The assessment of the collected information pointed to a natural control on salinization processes in the Lerma Basin with minimal influence of anthropogenic factors.

Preparation of Cd/Pb Chalcogenide Heterostructured Janus Particles via Controllable Cation Exchange.

We developed a strategy for producing quasi-spherical nanocrystals of anisotropic heterostructures of Cd/Pb chalcogenides. The nanostructures are fabricated via a controlled cation exchange reaction where the Cd(2+) cation is exchanged for the Pb(2+) cation. The cation exchange reaction is thermally activated and can be controlled by adjusting the reaction temperature or time. We characterized the particles using TEM, XPS, PL, and absorption spectroscopy. With complete exchange, high quality Pb-chalcogenide quantum dots are produced. In addition to Cd(2+), we also find suitable conditions for the exchange of Zn(2+) cations for Pb(2+) cations. The cation exchange is anisotropic starting at one edge of the nanocrystals and proceeds along the ⟨111⟩ direction producing a sharp interface at a (111) crystallographic plane. Instead of spherical core/shell structures, we produced and studied quasi-spherical CdS/PbS and CdSe/PbSe Janus-type heterostructures. Nontrivial PL behavior was observed from the CdS(e)/PbS(e) heterostructures as the Pb:Cd ratio is increased.