Immobilization of europium and terbium ions with tunable ratios on a dispersible two-dimensional metal-organic framework for ratiometric photoluminescence detection of D2O.

A two-dimensional zirconium-based metal-organic framework (2D Zr-MOF), ZrBTB (BTB = 1,3,5-tri(4-carboxyphenyl)benzene), is used as a platform to simultaneously immobilize terbium ions and europium ions with tunable ratios on its hexa-zirconium nodes by a post-synthetic modification. The crystallinity, morphology, porosity and photoluminescence (PL) properties of the obtained 2D Zr-MOFs with various europium-to-terbium ratios are investigated. With the energy transfer from the excited BTB linker to the installed terbium ions and the energy transfer from terbium ions to europium ions, a low loading of immobilized europium ions and a high loading of surrounding terbium ions in the 2D Zr-MOF result in the optimal PL emission intensities of europium; this phenomenon is not observable for the physical mixture of both terbium-installed ZrBTB and europium-installed ZrBTB. The role of installed terbium ions as efficient mediators for the energy transfer from the excited BTB linker to the installed europium ion is confirmed by quantifying PL quantum yields. As a demonstration, these materials with modulable PL characteristics are applied for the ratiometric detection of D2O in water, with the use of the stable emission from the BTB linker as the reference. With the strong emission of immobilized europium ions and the good dispersity in aqueous solutions, the optimal bimetal-installed ZrBTB, Eu-Tb-ZrBTB(1 : 10), can achieve the sensing performance outperforming those of the terbium-installed ZrBTB, europium-installed ZrBTB and the physical mixture of both.

Two-dimensional metal-organic framework for post-synthetic immobilization of graphene quantum dots for photoluminescent sensing.

Immobilization of graphene quantum dots (GQDs) on a solid support is crucial to prevent GQDs from aggregation in the form of solid powder and facilitate the separation and recycling of GQDs after use. Herein, spatially dispersed GQDs are post-synthetically coordinated within a two-dimensional (2D) and water-stable zirconium-based metal-organic framework (MOF). Unlike pristine GQDs, the obtained GQDs immobilized on 2D MOF sheets show photoluminescence in both suspension and dry powder. Chemical and photoluminescent stabilities of MOF-immobilized GQDs in water are investigated, and the use of immobilized GQDs in the photoluminescent detection of copper ions is demonstrated. Findings here shed the light on the use of 2D MOFs as a platform to further immobilize GQDs with various sizes and distinct chemical functionalities for a range of applications.

[Scale Effects of Landscape Pattern on Water Quality in Dongjiang River Source Watershed].

Based on water quality monitoring data and land use data, Dongjiang River source watershed water quality variation characteristics from 2017 to 2019 and the relationships between the landscape pattern of the Dongjiang River source watershed and water quality were analyzed using spatial analysis, correlation analysis, and redundancy analysis. The results showed that:① the water quality of the Dongjiang River source watershed improved overall, but the total nitrogen pollution was still severe. As of 2019, the annual average concentration of total nitrogen in all sampling points exceeded the type Ⅲ water quality standard. ② At the landscape level, water quality was positively correlated with landscape shape index, number of patches, and Shannon's diversity index but negatively correlated with largest patch index and aggregation index. Considering the land use type, construction land was the primary source of total nitrogen and total phosphorus. Landscape shape index and number of forest patches were positively correlated with NH4+-N. The number of forest patches was positively correlated with total phosphorus. However, the largest patch index and aggregation index of the forest were negatively correlated with total phosphorus. The number of patches of grassland was positively correlated with total phosphorus. The aggregation index of grassland was negatively correlated with total phosphorus. ③ It is suggested that management departments should focus on the optimization of the landscape pattern within the 2000 m buffer zone of monitoring points. The reasonable allocation of urban sewage-centralized treatment facilities, strengthening management of abandoned mining areas, improvement of intensive treatment of cultivated land, and construction of shelterbelt in areas where cultivated land is concentrated are beneficial for the water quality of Dongjiang River source watershed.

A Quantitative Study of Micro and Macro Mechanical Parameters Based on the PFC3D Flat-Joint Model.

The flat-joint model, which constructs round particles as polygons, can suppress rotation after breakage between particles and simulate more larger compression and tension ratios than the linear parallel-bond model. The flat-joint contact model was chosen for this study to calibrate the rock for 3D experiments. In the unit experiments, the triaxial unit was loaded with flexible boundaries, and the influence of each microscopic parameter on the significance magnitude of the macroscopic parameters (modulus of elasticity E, Poisson's ratio ν, uniaxial compressive strength UCS, crack initiation strength σci, internal friction angle φ and uniaxial tensile strength TS) was analysed by ANOVA (Analysis of Variance) in an orthogonal experimental design. Among them, Eƒ, kƒ has a significant effect on E; Cƒ and kƒ have a significant effect on ν; Cƒ, σƒ and kƒ have a significant effect on UCS; Cƒ; σƒ and Eƒ have a significant effect on TS; Rsd has a significant effect on σci; and φf, Eƒ, kƒ, µƒ, and σƒ have a significant effect on φ. Regressions were then carried out to establish the equations for calculating the macroscopic parameters of the rock material so that the three-dimensional microscopic parameters of the PFC can be quantitatively analysed and calculated. The correctness of the establishment of the macroscopic equations was verified by comparing the numerical and damage patterns of uniaxial compression, Brazilian splitting, and triaxial experiments with those of numerical simulation units in the chamber.

Metal-Organic Framework-Derived Electrocatalysts Competent for the Conversion of Acrylonitrile to Adiponitrile.

Electrochemical conversion of acrylonitrile (AN) to produce adiponitrile (ADN), the raw material for the production of Nylon 66, has become a crucial process owing to the increasing market demand of Nylon 66. Although the metallic Pb or Cd electrodes are commonly used for this reaction, the use of electrocatalysts or electrodes modified with catalysts has been barely investigated. In this study, nanoporous and electrically conductive metal-organic framework (MOF)-derived materials composed of Pb, PbO, and carbon are synthesized by carbonizing a Pb-based MOF through thermal treatments, and these MOF-derived materials are served as electrocatalysts for the electrosynthesis of ADN. The crystallinity, morphology, elemental composition, porosity, electrical conductivity, and electrochemically active surface area of each MOF-derived material are investigated. Mass-transport-corrected Tafel analysis is used to probe the enhanced kinetics for the electrochemical reduction of AN occurring at the electrode modified with the MOF-derived material. Electrolytic experiments at various applied potentials are conducted to quantify the production rate and Faradaic efficiency toward ADN, and the result shows that the MOF-derived materials can act as electrocatalysts to initiate the electrochemical reduction of AN to produce ADN at a reduced overpotential. The optimal MOF-derived electrocatalyst can achieve a Faradaic efficiency of 67% toward ADN at an applied potential of -0.85 V versus reversible hydrogen electrode─a much lower overpotential compared to that typically required for this reaction without the use of catalysts. Findings here shed light on the design and development of advanced electrocatalysts to boost the performances for the electrosynthesis of ADN.

Probing the electronic and ionic transport in topologically distinct redox-active metal-organic frameworks in aqueous electrolytes.

Three topologically distinct zirconium-based metal-organic frameworks (Zr-MOFs) constructed from redox-innocent linkers, MOF-808, defective UiO-66, and CAU-24, are synthesized, and the spatially dispersed redox-active manganese sites are post-synthetically immobilized on the hexa-zirconium nodes of these Zr-MOFs. The crystallinity, morphology, porosity, manganese loading, and bulk electrical conductivity of each material are studied. The redox-hopping-based electrochemical reaction between the installed Mn(III) and Mn(IV) occurring within the thin films of these MOFs in aqueous electrolytes is investigated, in the presence of various concentrations of Na2SO4 in the electrolytes. Cyclic voltammetry is used to qualitatively study the redox-hopping process, and chronoamperometry is used to quantify the electrochemically active fractions of manganese sites within the MOF thin film as well as the values of apparent diffusivity for the redox-hopping process. By adjusting the concentration of Na2SO4 in the electrolyte, the rate-determining step for the redox-hopping process can be tuned from ionic transport to electronic transport, and the Mn-decorated MOF-808, which possesses the largest pore size, can achieve the highest value of apparent diffusivity. Findings here shed light on the selection of Zr-MOF as well as the choice of electrolyte concentration for the applications of MOFs in supercapacitors and electrocatalysis relying on such redox-hopping processes in aqueous electrolytes.

Corrosion Performance of Nano-TiO2-Modified Concrete under a Dry-Wet Sulfate Environment.

This study compared the effects of the sulfate dry-wet cycle on the properties of ordinary concrete and nano-TiO2-modified concrete, including the mass loss rate, ultrasonic wave velocity, compressive strength, and XRD characteristics. In addition, a series of compression simulations carried out using the PFC2D software are also presented for comparison. The results show the following: (1) with an increase in dry-wet cycles, the damage to the concrete gradually increased, and adding nano-TiO2 into ordinary concrete can improve the material's sulfate resistance; (2) after 50 sulfate dry-wet cycles, the mass loss rate of ordinary concrete was -3.744%, while that of nano-TiO2-modified concrete was -1.363%; (3) the compressive strength of ordinary concrete was reduced from 41.53 to 25.12 MPa (a reduction of 39.51%), but the compressive strength of nano-TiO2-modified concrete was reduced from 49.91 to 32.12 MPa (a reduction of 35.64%); (4) after a sulfate dry-wet cycle, the nano-TiO2-modified concrete surface produced white crystalline products, considered to be ettringite based on the XRD analysis; (5) when considering the peak stress and strain of the concrete samples, the numerical results agreed well with the test results, indicating the reliability of the method.