NH3 Plasma Functionalization of UiO-66-NH2 for Highly Enhanced Selective Fluorescence Detection of U(VI) in Water.

Radioactive U(VI) in nuclear wastewater is a global environmental pollutant that poses a great threat to human health. Therefore, it is of great significance to develop a U(VI) sensor with desirable sensitivity and selectivity. Inspired by electron-donating group modification for enhancement of binding affinity toward U(VI), we report an amine group functionalization of UiO-66-NH2, using a low-cost, environmentally friendly, and low-temperature NH3 plasma technique as a fluorescence switching nanoprobe for highly sensitive and selective detection of U(VI). The resulting amine-functionalized UiO-66-NH2 (LTP@UiO-66-NH2) shows dramatically enhanced fluorescence emission and selective sensitivity for U(VI) on the basis of the quenching effect. The quenching efficiency increases from 58 to 80% with the same U(VI) concentration (17.63 µM) after NH3 plasma functionalization. As a result, the LTP@UiO-66-NH2 has the best Ksv (1.81 × 105 M-1, 298 K) and among the lowest LODs (0.08 µM, 19.04 ppb) compared with those reported in the literature. Intraday and interday precision and application in real environment experiments indicate stable and accurate U(VI) detection performance. Fluorescence lifetime and temperature-dependent detection experiments reveal that the quenching mechanism belongs to the static quenching interaction. The highly selective fluorescence detection is attributed to the selective binding of U(VI) by the rich functionalized amine groups of LTP@UiO-66-NH2. This work provides an efficient fluorescence probe for highly sensitive U(VI) detection in water, and a new strategy of tailored plasma functionalization for developing a practical MOF sensor platform for enhanced fluorescence emission, sensitivity, and selectivity for detecting trace amounts of radioactive species in the environment.

High-yield production of liquid fuels in CO2 hydrogenation on a zeolite-free Fe-based catalyst.

Catalytic conversion of CO2 to long-chain hydrocarbons with high activity and selectivity is appealing but hugely challenging. For conventional bifunctional catalysts with zeolite, poor coordination among catalytic activity, CO selectivity and target product selectivity often limit the long-chain hydrocarbon yield. Herein, we constructed a singly cobalt-modified iron-based catalyst achieving 57.8% C5+ selectivity at a CO2 conversion of 50.2%. The C5+ yield reaches 26.7%, which is a record-breaking value. Co promotes the reduction and strengthens the interaction between raw CO2 molecules and iron species. In addition to the carbide mechanism path, the existence of Co3Fe7 sites can also provide sufficient O-containing intermediate species (CO*, HCOO*, CO3 2*, and ) for subsequent chain propagation reaction via the oxygenate mechanism path. Reinforced cascade reactions between the reverse water gas shift (RWGS) reaction and chain propagation are achieved. The improved catalytic performance indicates that the KZFe-5.0Co catalyst could be an ideal candidate for industrial CO2 hydrogenation catalysts in the future.

Hydrothermal preparation of hierarchical ZIF-L nanostructures for enhanced CO2 capture.

A zeolitic imidazolate framework (ZIF-L) with hierarchical morphology was synthesized through hydrothermal method. The hierarchical product consists of ZIF-L leaves with length of several micrometers, width of 1 ∼ 2 µm and thickness of ∼300 nm cross connected symmetrically. It was found that the hydrothermal temperature is crucial for the formation of such hierarchical nanostructure. The formation mechanism was investigated to be a secondary crystal growth process. The hierarchical ZIF-L has larger surface area compared with the two-dimensional (2D) ZIF-L leaves. Subsequently, the hierarchical ZIF-L exhibited enhanced CO2 adsorption capacity (1.56 mmol·g-1) as compared with that of the reported two-dimensional ZIF-L leaves (0.94 mmol·g-1). This work not only reveals a new strategy for the formation of hierarchical ZIF-L nanostructures, but also supplies a potential material for CO2 capture.

Hydrothermal Synthesis of Metal-Polyphenol Coordination Crystals and Their Derived Metal/N-doped Carbon Composites for Oxygen Electrocatalysis.

Cobalt (or iron)-polyphenol coordination polymers with crystalline frameworks are synthesized for the first time. The crystalline framework is formed by the assembly of metal ions and polyphenol followed by oxidative self-polymerization of the organic ligands (polyphenol) during hydrothermal treatment in alkaline condition. As a result, such coordination crystals are even partly stable in strong acid (such as 2 m HCl). The metal (Co or Fe)-natural abundant polyphenol (tannin) coordination crystals are a renewable source for the fabrication of metal/carbon composites as a nonprecious-metal catalyst, which show high catalytic performance for both oxygen reduction reaction and oxygen evolution reaction. Such excellent performance makes metal-polyphenol coordination crystals an efficient precursor to fabricate low-cost catalysts for the large-scale application of fuel cells and metal-air batteries.

One-step fabrication of amino functionalized magnetic graphene oxide composite for uranium(VI) removal.

Amino functionalized magnetic graphene oxide composite (AMGO), a good sorbent for U(VI), was fabricated and characterized. The AMGO was applied as a magnetic sorbent for the U(VI) removal from aqueous solutions. The AMGO can be easily recovered from the solution with the magnetic separation within one minute. The kinetic data were well-described by the pseudo-second-order equation. The Langmuir model fitted the sorption isotherm data better than the Freundlich model. The maximum sorption capacity of the AMGO for U(VI) was 141.2mg/g, displaying a high efficiency for the removal of U(VI). It was found that the U(VI) sorption was accomplished mainly via chelation or ion exchange. The thermodynamic parameters illustrated that the sorption process was spontaneous and endothermic in nature. In addition, the excellent reproducibility indicate that the AMGO can be used as a potential sorbent for removal of U(VI) from large volumes of aqueous solution.

Rapid Construction of ZnO@ZIF-8 Heterostructures with Size-Selective Photocatalysis Properties.

To selectively remove heavy metal from dye solution, inspired by the unique pore structure of ZIF-8, we developed a synthetic strategy for rapid construction of ZnO@ZIF-8 heterostructure photocatalyst for selective reduction of Cr(VI) between Cr(VI) and methylene blue (MB). In particular, ZnO@ZIF-8 core-shell heterostructures were prepared by in situ ZIF-8 crystal growth using ZnO colloidal spheres as template and zinc source within 8-60 min. The shell of the resulting ZnO@ZIF-8 core-shell heterostructure with a uniform thickness of around 30 nm is composed of ZIF-8 crystal polyhedrons. The concentration of organic ligand 2-methylimidazole (Hmim) was found to be crucial for the formation of ZnO@ZIF-8 core-shell heterostructures. Different structures, ZnO@ZIF-8 core-shell spheres and separate ZIF-8 polyhedrons could be formed by altering Hmim concentration, which significantly influences the balance between rate of Zn(2+) release from ZnO and coordinate rate. Importantly, such ZnO@ZIF-8 core-shell heterostructures exhibit size-selective photocatalysis properties due to selective adsorption and permeation effect of ZIF-8 shell. The as-synthesized ZnO@ZIF-8 heterostructures exhibited enhanced selective reduction of Cr(VI) between Cr(VI) and MB, which may find application in the dye industry. This work not only provides a general route for rapid fabrication of such core-shell heterostructures but also illustrates a strategy for selectively enhanced photocatalysis performance by utilizing adsorption and size selectivity of ZIF-8 shell.

Incorporation of well-dispersed sub-5-nm graphitic pencil nanodots into ordered mesoporous frameworks.

Over the past few decades the direct assembly of optical nanomaterials into ordered mesoporous frameworks has proved to be a considerable challenge. Here we propose the incorporation of ultrasmall (sub-5-nm) graphitic pencil nanodots into ordered mesoporous frameworks for the fabrication of optoelectronic materials. The nanodots, which were prepared from typical commercial graphite pencils by an electrochemical tailoring process, combine properties such as uniform size (∼3 nm), excellent dispersibility and high photoconversion efficiency (∼27%). These nanodots were incorporated into a variety of ordered mesoporous frameworks (TiO2, silica, carbon and silica-carbon materials) by co-assembly, driven by hydrogen bonding, with the frameworks' precursors. The resulting materials showed a high degree of ordering, and a sharp increase in their optical performance (for example, photocurrent density). We envisage that the large-scale synthesis of ultrasmall carbon nanodots and their incorporation into ordered mesoporous frameworks may facilitate the preparation of materials with a variety of optical properties.

Self-curled coral-like γ-Al2O3 nanoplates for use as an adsorbent.

Biomimetic self-curled nanoplates assembled coral-like nanoporous γ-Al2O3 has been prepared by a solvothermal method using ethylene glycol (EG)H2O as the mixed solvent, followed by the annealing process. The resulting samples are composed of micro/nanostructured units (∼1.5 µm) with self-curled porous nanoplates on the surface. The volume ratio of EG to water in precursor solution is crucial for the formation of coral-like structure. The formation process is investigated to be an assembly process with self-curled nanoplates driven by adsorption of EG. Importantly, the coral-like porous γ-Al2O3 has high surface area of 64.18 m(2)/g and exhibits enhanced adsorption performance for efficient removal of heavy metal Hg(II) (49.15 mg/g). The removal capacity is higher than (∼2.5 times) those of commercial Al2O3 nanoparticles and hollow structured γ-Al2O3 prepared without EG (∼2.7 times). Further investigation shows adsorption behaviors of the coral-like γ-Al2O3 and the alumina hollow structure can be well described by Langmuir isotherm model, whereas that of commercial Al2O3 nanoparticles fits Freundlich isotherm model. This work not only provides an inspiration for high efficient biomimetic adsorbent but also presents a facile route for coral-like γ-Al2O3 preparation.

Impact of water quality parameters on the sorption of U(VI) onto hematite.

In this study, the sorption of U(VI) from aqueous solution on hematite was studied as a function of various water quality parameters such as contact time, pH, ionic strength, soil humic acid (HA) or fulvic acid (FA), solid content and temperature by using a batch technique. The results demonstrated that the sorption of U(VI) was strongly dependent on ionic strength at pH<6.0, and outer-sphere surface complexation may be the main sorption mechanism. The sorption was independent of ionic strength at pH>6.0 and the sorption was mainly dominated by inner-sphere surface complexation. The presence of HA/FA increases U(VI) sorption at low pH, whereas decreases U(VI) sorption at high pH. The thermodynamic parameters (ΔH°, ΔS°, and ΔG°) were calculated from the temperature dependent sorption isotherms, and the results suggested that U(VI) sorption was a spontaneous and endothermic process. The results might be important for the application of hematite in U(VI) pollution management.

Tower-like structure of ZnO nanocolumns.

The tower-like structure of ZnO nanocolumns grows normal to alumina substrates via pyrolysis and oxidation of ZnS, and is formed by stacking of ZnO nanocrystals layer upon layer.