Dipole Moment and Built-In Polarization Electric Field Induced by Oxygen Vacancies in BiOX for Boosting Piezoelectric-Photocatalytic Removal of Uranium(VI).

Piezoelectric-photocatalysis is distinguished by its piezoelectricity as an external force that induces deformation within the catalyst to engender a polarized electric field compared to conventional photocatalysis. Herein, the piezoelectric photocatalyst BiOBr has been expertly synthesized via a plasma process and applied for piezoelectric-photocatalysis removal of uranium(VI) for the first time. The abundant surface oxygen vacancies (OVs) could induce a dipole moment and built-in electric field, which endows BiOBr with excellent separation and transport efficiency of photogenerated charges to actuate more charges to participate in the piezoelectric-photocatalytic reduction process. Consequently, under visible light and ultrasound (150 W and 40 kHz), the removal rate constant of OVs-BiOBr-30 (0.0306 min-1) was 2.4, 30.6, and 6 times higher than those of BiOBr (0.01273 min-1), ultrasound, or photocatalysis, respectively. The piezoelectric-photocatalytic synergy is also universal for BiOX (X = Cl, Br, or I) to accelerate the reduction rate of uranium(VI). This work highlights the role of piezoelectric-photocatalysis in the treatment of uranium-containing wastewater, which is of great significance for resource conservation and environmental remediation.

First-Principle Studies on Local Lattice Distortions and Thermodynamic Properties in Non-Stoichiometric Thorium Monocarbide.

Thorium monocarbide (ThC) is interesting as an alternative fertile material to be used in nuclear breeder systems and thorium molten salt reactors because of its high thermal conductivity, good irradiation performance, and wide homogeneous composition range. Here, the influence of carbon vacancy site and concentration on lattice distortions in non-stoichiometric ThC1-x (x = 0, 0.03125, 0.0625, 0.125, 0.1875, 0.25, or 0.3125) is systematically investigated using first-principle calculations by the projector augmented wave (PAW) method. The energy, mechanical parameters, and thermodynamic properties of the ThC1-x system are calculated. The results show that vacancy disordering has little influence on the total energy of the system at a constant carbon vacancy concentration using the random substitution method. As the concentration of carbon vacancies increases, significant lattice distortion occurs, leading to poor structural stability in ThC1-x systems. The changes in lattice constant and volume indicate that ThC0.75 and ThC0.96875 represent the boundaries between two-phase and single-phase regions, which is consistent with our experiments. Furthermore, the structural phase of ThC1-x (x = 0.25-0.3125) transforms from a cubic to a tetragonal structure due to its 'over-deficient' composition. In addition, the elastic moduli, Poisson's ratio, Zener anisotropic factor, and Debye temperature of ThC1-x approximately exhibit a linear downward trend as x increases. The thermal expansion coefficient of ThC1-x (x = 0-0.3125) exhibits an obvious 'size effect' and follows the same trend at high temperatures, except for x = 0.03125. Heat capacity and Helmholtz free energy were also calculated using the Debye model; the results showed the C vacancy defect has the greatest influence on non-stoichiometric ThC1-x. Our results can serve as a theoretical basis for studying the radiation damage behavior of ThC and other thorium-based nuclear fuels in reactors.

Ultra-fast uranium capture via the synergistic interaction of the intrinsic sulfur atoms and the phosphoric acid groups adhered to edge sulfur of MoS2.

In order to deal with the sudden nuclear leakage event to suppress the spread of radioactive contaminants in a short period of time, it is extremely urgent needed to explore an adsorbent that could be capable of in-situ remedial actions to rapidly capture the leaked radionuclides in split second. An adsorbent was developed that MoS2 via ultrasonic to expose more surface defects afterwards functionalized by phosphoric acid resulting in more active sites being endowed on the edge S atoms of Mo-vacancy defects, while simultaneously increased the hydrophilicity and interlayer spacing. Hence, an overwhelming fast adsorption rates (adsorption equilibrium within 30 s) are presented and place the MoS2-PO4 at the top of performing sorbent materials. Moreover, the maximum capacity calculated from Langmuir model is as high as 354.61 mg·g-1, the selective adsorption capacity (SU) achieving 71.2% in the multi-ion system and with more than 91% capacity retention after 5 cycles of recycling. Finally, XPS and DFT insight into the adsorption mechanism, which can be explained as interaction of UO22+ on the surface of MoS2-PO4 by forming U-O and U-S bonds. The successful fabrication of such a material may provide a promising solution for emergency treatment of radioactive wastewater during nuclear leakage events.

Modeling Uranyl Adsorption on MoS2/Mo2CTx Heterostructures Using DFT and BOMD Methods.

Uranium-bearing wastewaters exert a great threat to the ecological environment due to its high radiotoxicity level. The designing and fabrication of novel adsorption materials can be promoted for radionuclide elimination from wastewater. In this work, results from density functional theory and Born-Oppenheimer molecular dynamics simulations are reported for the uranyl adsorption behavior on the MoS2/Mo2CTx heterostructure in the gas phase and in an aqueous environment. Uranyl ions prefer to be adsorbed at deprotonated O sites on the Mo2COH surface and S sites on the MoS2 side of the heterojunctions, resulting in the formation of bidentate configurations. In addition to coordination interaction, H-bond and van der Waals interactions can also play an important role in binding configurations. More importantly, the oxidation state U(VI) can be reduced to U(V) and then to U(IV) caused by the strong reducibility of the Mo2COH surface at room temperature, whereas the uranyl complex can move freely on the MoS2 surface. However, the coordination number of U with respect to H2O in the first hydration shell on the Mo2COH surface remains unchanged and is found to be 3, which is similar to that on the MoS2 surface. This work provides novel nanosorbents for the removal of uranyl from wastewater. The present viewpoint provides valuable mechanistic interpretations for uranyl adsorption and will give a supplement to the experimental research.

Ultra-low thermal conductivity and high thermoelectric performance of monolayer BiP3: a first principles study.

The thermoelectric properties of monolayer triphosphide BiP3 are studied via first principles calculations and Boltzmann transport equation. First, the Seebeck coefficient, electrical conductivity and electron thermal conductivity at different temperatures are calculated using the Boltzmann transport equation with relaxation time approximation. It has been observed that BiP3 has a large power factor (265 × 10-4 W K-2 m-1, 700 K). Then, by analyzing the second-order interatomic force constant (IFCS), the atomic structure and phonon dispersion were studied, and the thermal conductivity of monolayer BiP3 was predicted in the temperature range of 300-800 K, and it was found that it had a very low thermal conductivity (2.13 W m-1 K-1) at room temperature. The thermal conductivity is mainly contributed by the branches of acoustics along in-plane transverse (TA). Finally, the maximum ZT value of monolayer BiP3 is 3.06 at 700 K, when the electron doping concentration is 2.35 × 1011 cm-2, which indicates that it is a promising thermoelectric material.

Quadruple-layer group-IV tellurides: low thermal conductivity and high performance two-dimensional thermoelectric materials.

Through first-principles calculations, we report the thermoelectric properties of two-dimensional (2D) hexagonal group-IV tellurides XTe (X = Ge, Sn and Pb), with quadruple layers (QL) in the Te-X-X-Te stacking sequence, as promising candidates for mid-temperature thermoelectric (TE) materials. The results show that 2D PbTe exhibits a high Seebeck coefficient (∼1996 µV K-1) and a high power factor (6.10 × 1011 W K-2 m-1 s-1) at 700 K. The lattice thermal conductivities of QL GeTe, SnTe and PbTe are calculated to be 2.29, 0.29 and 0.15 W m-1 K-1 at 700 K, respectively. Using our calculated transport parameters, large values of the thermoelectric figure of merit (ZT) of 0.67, 1.90, and 2.44 can be obtained at 700 K under n-type doping for 2D GeTe, SnTe, and PbTe, respectively. Among the three compounds, 2D PbTe exhibits low average values of sound velocity (0.42 km s-1), large Grüneisen parameters (∼2.03), and strong phonon scattering. Thus, 2D PbTe shows remarkable mid-temperature TE performance with a high ZT value under both p-type (2.39) and n-type (2.44) doping. The present results may motivate further experimental efforts to verify our predictions.

The Thermoelectric Properties of Monolayer MAs2 (M = Ni, Pd and Pt) from First-Principles Calculations.

The thermoelectric property of the monolayer MAs2 (M = Ni, Pd and Pt) is predicted based on first principles calculations, while combining with the Boltzmann transport theory to confirm the influence of phonon and electricity transport property on the thermoelectric performance. More specifically, on the basis of stable geometry structure, the lower lattice thermal conductivity of the monolayer NiAs2, PdAs2 and PtAs2 is obtained corresponding to 5.9, 2.9 and 3.6 W/mK. Furthermore, the results indicate that the monolayer MAs2 have moderate direct bang-gap, in which the monolayer PdAs2 can reach 0.8 eV. The Seebeck coefficient, power factor and thermoelectric figure of merit (ZT) were calculated at 300, 500 and 700 K by performing the Boltzmann transport equation and the relaxation time approximation. Among them, we can affirm that the monolayer PdAs2 possesses the maximum ZT of about 2.1, which is derived from a very large power factor of 3.9 × 1011 W/K2ms and lower thermal conductivity of 1.4 W/mK at 700 K. The monolayer MAs2 can be a promising candidate for application at thermoelectric materials.