ABSTRACT
Plasmonic Cu@semiconductor heteronanocrystals (HNCs) have many favorable properties, but the synthesis of solid structures is often hindered by the nanoscale Kirkendall effect. Herein, we present the use of an atomically thin Au3Cu palisade interlayer to reduce lattice mismatch and mediate the Kirkendall effect, enabling the successive topological synthesis of Cu@Au3Cu@Ag, Cu@Au3Cu@Ag2S, and further transformed solid Cu@Au3Cu@CdS core-shell HNCs via cation exchange. The atomically thin and intact Au3Cu palisade interlayer effectively modulates the diffusion kinetics of Cu atoms as demonstrated by experimental and theoretical investigations and simultaneously alleviates the lattice mismatch between Cu and Ag as well as Cu and CdS. The Cu@Au3Cu@CdS HNCs feature exceptional crystallinity and atomically organized heterointerfaces between the plasmonic metal and the semiconductor. This results in the efficient plasmon-induced injection of hot electrons from Cu@Au3Cu into the CdS shell, enabling the Cu@Au3Cu@CdS HNCs to achieve high activity and selectivity for the photocatalytic reduction of CO2 to CO.
ABSTRACT
III-V quantum dots (QDs), in particular InP QDs, have emerged as high-performance and environmentally friendly candidates to replace cadmium based QDs. InP QDs exhibit properties of direct band gap structure, low toxicity, and high mobility, which make them suitable for high-performance optoelectronic applications. However, it is still challenging to precisely regulate the components and crystal structure of InP QDs, especially in the engineered stable aliovalent doping. In this work, we developed our original reverse cation exchange strategy to achieve Cu+ doped InP (InP:Cu) QDs at lower temperature. A ZnSexS1-x shell was then homogeneously grown on the InP:Cu QDs as the passivation shell. The as-prepared InP:Cu@ZnSexS1-x core-shell QDs exhibited better fluorescence properties with a photoluminescence quantum yield (PLQY) of 56.47%. Due to the existence of multiple luminous centers in the QDs, variable temperature-dependent fluorescence characteristics have been studied. The high photoluminescence characteristics in the near-infrared region indicate their potential applications in optoelectronic devices and biological fields.
ABSTRACT
While biochar supported iron materials have been widely studied in advanced oxidation processes (AOPs), little is known about the effect and mechanism of goethite/biochar in sulfate radical (SO4-) based AOPs. Herein, a novel goethite/biochar composite was applied as peroxymonosulfate (PMS) activator for tetracycline (TC) degradation in the water. The superior catalytic efficiency of goethite/biochar was achieved through radical (OH and SO4-) and non-radical (1O2) processes according to the radicals quenching experiments and electron paramagnetic resonance analysis. Carbonyl group and Fe species were the main active sites on the surface of goethite/biochar, which was demonstrated by combining Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and reaction kinetic experiments. Furthermore, nine main by-products of TC degradation were detected by liquid chromatography-mass spectrometry and the reasonable degradation pathway was proposed according to the molecular structure analysis. Overall, the goethite/biochar materials could be applied to activate PMS for TC degradation, and this study will benefit the application of iron/biochar materials in practical water treatment.
Subject(s)
Charcoal , Peroxides , Iron Compounds , MineralsABSTRACT
Advanced oxidation technologies based on peroxymonosulfate (PMS) have attracted increasing attention because of their high reactivity and selectivity. Herein, we reported a novel CoFeLa-LDH catalyst, which exhibited excellent performance to activate PMS for tetracycline (TC) elimination. The influence of extra addition, simulation wastewater tests and the reusability experiments were investigated in detail. Remarkably, the quenching experiments and the results of EPR demonstrated the synergistic effect of radical and nonradical pathways in the TC degradation. Free radicals (SO4- and HO) played predominant roles in the first 1 min, and then both free and non-free radicals (1O2) interacted with TC. The possible TC degradation pathways were proposed on basis of the intermediates, which were analyzed by UPLC-QTOF-MS/MS. Finally, the reaction mechanisms of TC degradation in CoFeLa-LDH2/PMS system were proposed according to the comprehensive analysis.
Subject(s)
Peroxides , Tandem Mass Spectrometry , Catalysis , HydroxidesABSTRACT
A new nanocomposite based on chitosan (CS) and Mg-Al-layered double hydroxide (Mg-Al-LDH) was prepared using an emulsion-crosslinking method. CS was immobilized within the Mg-Al-LDH matrix to form the CS-LDH after crosslinking by epichlorohydrin. The characterization of XPS, SEM, TEM, FTIR, and BET analysis showed that the CS-LDH had a high specific surface area and contained many different functional groups. The adsorption capacity of the CS-LDH was evaluated by adsorbing Pb2+ and Cd2+ as representative heavy metals. Batch adsorption method was used to investigate the effects of the amount of adsorbent, pH of the initial solution, and contact time. We also examined the adsorption kinetics, isotherms, and mechanisms. The capacity of the CS-LDH for Pb2+ and Cd2+ adsorption was higher than that of CS and the Mg-Al-LDH, and the isothermal data followed the Langmuir isotherm model. The adsorption equilibrium was quickly achieved and the kinetic data obeyed the pseudo-second-order kinetic model. The adsorption process was almost not affected by solution pH above 3. The CS-LDH and heavy metals interacted via the following mechanisms: precipitation, surface complexation, and isomorphic substitution.