Engineering hierarchical snowflake-like multi-metal selenide catalysts anchored on Ni foam for high-efficiency and stable overall water splitting.

The development of excellent bifunctional electrocatalysts is an effective way to promote the industrial application of electrolytic water. In this work, a free-standing W-doped cobalt selenide (W-CoSe300/NF) electrocatalyst with a snowflake-like structure supported on nickel foam was prepared by a hydrothermal-selenization strategy. Benefiting from the high specific surface area of the 3D snowflake-like structure and the regulation of tungsten doping on the electronic structure of the metal active center, W-CoSe300/NF shows remarkable electrocatalytic water decomposition performance. In 1.0 M KOH, the W-CoSe300/NF electrocatalyst achieved an efficient HER and OER at a current density of 50 mA cm-2 with overpotentials as low as 84 mV and 283 mV, respectively. More importantly, W-CoSe300/NF acts as both the anode and cathode of the electrolytic tank, requiring only a potential of 1.54 V to obtain 10 mA cm-2 and can operate continuously for more than 120 hours at this current density. This study proposes a new way for the design of high efficiency and affordable bifunctional electrocatalysts.

Advancing overall water splitting via phase-engineered amorphous/crystalline interface: A novel strategy to accelerate proton-coupled electron transfer.

Traditional phase engineering enhances conductivity or activity by fully converting electrocatalytic materials into either a crystalline or an amorphous state, but this approach often faces limitations. Thus, a practical solution entails balancing the dynamic attributes of both phases to maximize an electrocatalyst's functionality is urgently needed. Herein, in this work, Co/Co2C crystals have been assembled on the amorphous N, S co-doped porous carbon (NSPC) through hydrothermal and calcination processes. The stable biphase structure and amorphous/crystalline (A/C) interface enhance conductivity and intrinsic activity. Moreover, the adsorption ability of water molecules and intermediates is improved significantly attributed to the rich oxygen-containing groups, unsaturated bonds, and defect sites of NSPC, which accelerates proton-coupled electron transfer (PCET) and overall water splitting. Consequently, A/C-Co/Co2C/NSPC (Co/Co2C/NSPC with amorphous/crystalline interface) exhibits outstanding behavior for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), requiring the overpotential of 240.0 mV and 70.0 mV to achieve 10 mA cm-2. Moreover, an electrolyzer assembled by A/C-Co/Co2C/NSPC-3 (anode) and A/C-Co/Co2C/NSPC-2 (cathode) demonstrates a low drive voltage of 1.54 V during overall water splitting process. Overall, this work has pioneered the coexistence of crystalline/amorphous phases in electrocatalysts and provided new insights into phase engineering.

Integration of N, P-doped carbon quantum dots with hydrogel as a solid-phase fluorescent probe for adsorption and detection of Fe3.

In this work, a novel nitrogen-phosphorus co-doped carbon quantum dots (N, P-CQDs) hydrogel was developed utilizing the as-synthesized N, P-CQDs and acrylamide (AM) with the existence of ammonium persulfate and N, N'-methylene bisacrylamide (N-MBA). In consistent with pure N, P-CQDs, the N, P-CQDs hydrogel also shows a dramatic fluorescence property with maximum emission wavelength of 440 nm, which can also be quenched after adsorbing iron ions (Fe3+). When the concentration of Fe3+is 0-6 mmol l-1, a better linear relationship between Fe3+concentration and the fluorescence intensities can be easily obtained. Additionally, the N, P-CQDs hydrogel exhibits better recyclability. This confirms that the N, P-CQDs hydrogel can be used for adsorbing and detecting Fe3+in aqueous with on-off-on mode. The fluorescence quenching mainly involves three procedures including the adsorption of Fe3+by hydrogel, integration of Fe3+with N, P-CQDs and the transportation of conjugate electrons in N, P-CQDs to the vacant orbits of Fe3+and the adsorption process follows a pseudo-second-order kinetic model confirmed in the Freundlich isotherm model. In conclusion, this work provides a novel route for synchronously removing and detecting the metal ions in aqueous by integrating N, P-CQDs with hydrogel with better recyclability.

Synthesis of a Polyoxometalate-Encapsulated Metal-Organic Framework via In Situ Ligand Transformation Showing Highly Catalytic Activity in Both Hydrogen Evolution and Dye Degradation.

In situ molecular transformation under hydrothermal conditions is a feasible method to introduce distinct organic ligands and suppress competitive reactions between different synthons. However, this strategy has not yet been explored for the preparation of polyoxometalate (POM)-encapsulated metal-organic frameworks (MOFs). In this work, we designed and prepared a new compound, [Co2(3,3'-bpy)(3,5'-bpp)(4,3'-bpy)](H2O)3[SiW12O40] (1) (4,3'-bpy = 4,3'-dipyridine, 3,5'-bpp = 3,5'-bis(pyrid-4-yl)pyridine, and 3,3'-bpy = 3,3'-bis(pyrid-4-yl) dipyridine), via an in situ ligand synthesis route. The compound shows a novel POM-encapsulated MOF structure with two pairs of left- and right-handed double helixes. These left- and right-handed helical chains further lead to triangular and rhombus-like channels, respectively. Moreover, the as-synthesized title compound shows superior electrocatalytic activity toward the hydrogen evolution reaction (HER) in 1 M KOH aqueous solution with a low overpotential and Tafel slope of 92 mV and 92.1 mV dec-1, respectively, under a current density of 10 cm-2. Also, the compound exhibits a high activity for the photocatalytic degradation of the dye rhodamine B. The excellent performance of the compound may be attributed to the synergistic effect between W and Co elements and the presence of encapsulated POMs. The title compound proves that it is possible to prepare multifunctional MOFs with POMs and transition metals showing HER activity and dye degradation activity.

Maize starch derived boron doped carbon spheres via facile solvothermal route as the photoluminescence sensor for determination of pH and Cr(VI).

In this work, a kind of boron doped carbon spheres (B-CSs) was successfully synthesized utilizing maize starch as carbon source and boric acid as dopant via facile solvothermal method. The chemical structure of the prepared B-CSs was systemically investigated by TEM, FT-IR, XRD, XPS and EDS. The synthesized B-CSs feature spherical structure with average size of ∼254 nm and exhibit strong photoluminescence (PL) with maximum emission at a wavelength of ∼453 nm under irradiation at 350 nm, leading to a quantum yield of 6.2%. Furthermore, the aqueous pH and Cr(VI) has a significantly various impact on the PL intensity of B-CSs, which can be flexibly utilized as the PL sensor for detection aqueous pH and Cr(VI) in aqueous. Particularly, the B-CSs have a desirable sensitivity and selectivity for detection of Cr(VI) with a low detection limit of ∼0.34µmol l-1. Conclusively, our work provides a novel and dual-functional fluorescent sensor for detection of the pH and toxic metal ions in water environment.

Bimetallic FeNi-MIL-88-derived NiFe2O4@Ni-Mn LDH composite electrode material for a high performance asymmetric supercapacitor.

A simple continuous hydrothermal method was used to synthesize a NiFe2O4@Ni-Mn LDH/NF composite. The layered structure provides a large void to transfer the electron effectively, and the composite materials exhibit remarkable electrochemical performance including excellent specific capacitance (1265 F g-1 at 1 A g-1) and remarkable cycling stability (the specific capacitance remains at 80.9% after 5000 cycles). In addition, the asymmetric supercapacitor exhibits a high energy density of 96.2 W h kg-1 at a power density of 700 W kg-1, and there is an extraordinarily good cycling stability with a capacity retention rate of 92.5% after 4000 cycles. The outcomes indicate that the NiFe2O4@Ni-Mn LDH/NF composite electrode has potential application as a high-performance supercapacitor.

Facile synthesis of N, P-doped carbon dots from maize starch via a solvothermal approach for the highly sensitive detection of Fe3.

Nitrogen/phosphorus-doped carbon dots (N, P-CDs) with a quantum yield as high as 76.5% were synthesized by carbonizing maize starch via a facile ethanol solvothermal approach. Transmission electron microscopy (TEM) measurement shows that the as-prepared N, P-CDs displayed a quasi-spherical shape with a mean size of ca. 2.5 nm. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy disclosed the presence of -OH, -NH2, -COOH, and -CO functional groups over the surface of N, P-CDs. On the basis of excellent fluorescent properties with strong blue fluorescence emission at 445 nm upon excitation at 340 nm, these N, P-CDs were adopted as a fluorescent probe towards the effective detection of Fe3+ ions in water. The limit of detection (LOD) was as low as 0.1 µmol L-1 and showed a better linear relationship in the range of 0.1 ∼ 50 µmol L-1. In conclusion, these synthesized N, P-CDs can be efficiently used as a promising candidate for the detection of Fe3+ ions in some practical samples.

Design and performance evaluation of a 1000-year evapotranspiration-capillary surface barrier.

Surface barrier technology is used to isolate radioactive waste and to reduce or eliminate recharge water to the waste zone for 1000 years or longer. However, the design and evaluation of such a barrier is challenging because of the extremely long design life. After establishing a set of design and performance objectives, a package of design solutions was developed for 1000-year surface barriers over nuclear waste sites. The Prototype Hanford Barrier (PHB) was then constructed in 1994 in the field over an existing waste site as a demonstration. The barrier was tested to evaluate surface-barrier design and performance at the field scale under conditions of enhanced and natural precipitation and of no vegetation. The monitoring data demonstrate that the barrier satisfied nearly all objectives in the past two decades. The PHB far exceeded the Resource Conservation and Recovery Act criteria, functioned in Hanford's semiarid climate, limited drainage to well below the 0.5 mm yr-1 performance criterion, limited runoff, and minimized erosion and bio-intrusion. Given the two-decade record of successful performance and consideration of the processes and mechanisms that could affect barrier stability and hydrology in the future, the results suggest the PHB is very likely to perform for its 1000-year design life. This conclusion is based on two assumptions: (1) the exposed subgrade receives protection against erosion and (2) institutional controls prevent inadvertent human activity at the barrier. The PHB design can serve as the basis for site-specific barriers over waste sites containing underground nuclear waste, uranium mine tailings, and hazardous mine waste.

Gold nanorods contained polyvinyl alcohol/chitosan nanofiber matrix for cell imaging and drug delivery.

Gold nanorods (AuNRs) that contained polyvinyl alcohol/chitosan (PVA/CS) hybrid nanofibers with dual functions are successfully fabricated by a simple electrospinning method. The results of transmission electron microscopy (TEM), X-ray diffraction (XRD) and energy dispersive X-ray (EDX) spectroscopy indicate that AuNRs are indeed encapsulated into the PVA/CS hybrid nanofibers. FTIR spectra results demonstrate that the chemical structures of PVA and CS are not affected when the AuNRs are introduced into the fibers. In vitro cytotoxicity test reveals that the hybrid fibers involving AuNRs are completely biocompatible. The as-prepared fibers can be used as a carrier for anticancer agent doxorubicin (DOX), and the drug is delivered into the cell nucleus. The AuNRs and DOX incorporated fibers are effective for inhibiting the growth and proliferation of ovary cancer cells and they can also be used as the cell imaging agent due to the unique optical properties of AuNRs. The nanofiber matrix combining two functions of cell imaging and drug delivery may be of great application potential in biomedical-related areas.