Inducing a Synergistic Effect on Ptδ+/Electron-Rich Sites via a Platinization Strategy: Generating Hyper-High Current Density in Hydrogen Evolution Reaction.

Herein, we propose a platinization strategy for the preparation of Pt/X catalysts with low Pt content on substrates possessing electron-rich sites (Pt/X: X = Co3O4, NiO, CeO2, Covalent Organic Framework (COF), etc.). In examples with inorganic and organic substrates, respectively, Pt/Co3O4 possesses remarkable catalytic ability toward HER, achieving a current density at an overpotential of 500 mV that is 3.22 times higher than that of commercial Pt/C. It was also confirmed by using operando Raman spectroscopy that the enhancement of catalytic activity was achieved after platinization of the COF, with a reduction of overpotential from 231 to 23 mV at 10 mA cm-2. Density functional theory (DFT) reveals that the improved catalytic activity of Pt/Co3O4 and Pt/COF originated from the re-modulation of Ptδ+ on the electronic structure and the synergistic effect of the interfacial Ptδ+/electron-rich sites. This work provides a rapid synthesis strategy for the synthesis of low-content Pt catalysts for electrocatalytic hydrogen production.

Synergistic Activation of Inert Iron Oxide Basal Planes through Heterostructure Formation and Doping for Efficient Hydrogen Evolution.

Iron oxides have emerged as a very promising and cost-effective alternative to precious metal catalysts for hydrogen production. However, the inert basal plane of iron oxides needs to be activated to enhance their catalytic efficiency. In this study, we employed heterostructure engineering and doped nickel to cooperatively activate the basal planes of iron oxide (Ni-Fe2 O3 /CeO2 HSs) to achieve high hydrogen evolution reaction (HER) activity. The Ni-Fe2 O3 /CeO2 HSs electrocatalyst demonstrates excellent basic HER activity and stability, such as an extremely low overpotential of 43 mV at 10 mA cm-2 current density and corresponding Tafel slope of 58.6 mV dec-1 . The increase in electrocatalyst activity and acceleration of hydrogen precipitation kinetics arises from the dual modulation of Ni doping and heterostructure, which not only modulates the electrocatalyst's electronic structure, but also increases the number and exposure of active sites. Remarkably, the generation of heterogeneous structure makes the catalyst se. The Ni-doped catalyst has not only increased HER activity but also low-temperature resistance. These results suggest that the synergistic activation of inert iron oxide basal planes through heterostructure formation and doping is a feasible strategy. Furthermore, for efficient electrocatalytic water splitting, this technique can be extended to other non-noble metal oxides.

Constructing covalent organic frameworks with dense thiophene S sites for effective iodine capture.

Developing versatile sorption materials for radionuclides (e.g. iodine) capture has been a critical goal in nuclear energy and environmental science. At the same time, covalent organic frameworks (COFs), on account of their high porosity and functional scaffolds, have opened up a new way to develop adsorbents in recent years. Herein, two kinds of COF materials containing thiophene (TAPT-COF and TAB-COF), as iodine sorbents, are designed and synthesized by Schiff base reaction. Among them, TAB-COF has a higher surface area (TAPT-COF: 1141 m2 g-1, TAB-COF: 1378 m2 g-1), which is helpful for the physical iodine adsorption. More importantly, the COF backbone is rich in both N and S sites, which is advantageous to the chemical adsorption of iodine. These two features make the two COFs ideal iodine sorption materials. For example, TAB-COF has an excellent gaseous iodine adsorption capacity (2.81 g g-1) and is one of the most efficient iodine adsorption materials. Meanwhile, TAB-COF has an excellent adsorption effect on iodine in the cyclohexane system, which can reach 200 mg g-1. In addition, the DFT calculations proved that both imine N and thiophene S serve as active sites during the iodine adsorption. TAB-COF exposes more active sites on the premise of having a higher surface area, thereby leading to a higher iodine adsorption capacity. The results here indicate improved sorption efficacy by introducing thiophene in COFs for sorption applications in general and especially pave the way for developing stable and effective COF sorbents for iodine capture from various environments.

Improved Gaussian plume model for atmospheric dispersion considering buoyancy and gravitational deposition: The case of multi-form tritium.

Various types of radionuclides have different atmospheric dispersion characteristics, such as buoyancy and gravitational deposition phenomenon of light gas and heavy particles, respectively. Gaussian plume model was widely used to describe atmospheric dispersion behaviors of radioactive effluents, particularly for the purpose of engineering environmental impact assessment or nuclear emergency support. Nonetheless, buoyancy and gravitational deposition were rarely reported in previous work for tritium in particular, which might cause a deviation in evaluating near-surface concentration distribution and radiation dose to the public. Based on the multi-form tritium case, we made a quantitative description for the buoyancy and gravitational deposition phenomenon and discussed the feasibility of developing an improved Gaussian plume model to predict near-surface concentration distribution. Firstly, tritium concentration distribution near to the surface was predicted by using computational fluid dynamics method (CFD) and standard Gaussian plume model to reach consistency without consideration of buoyancy and gravitational deposition effects. Secondly, effects of buoyancy and gravitational deposition were identified by species transport model for gaseous tritium and discrete phase model for droplet tritium with integrating the buoyancy force caused by density variation of gaseous tritium and gravitational force of droplet tritium with enough size. Thirdly, buoyancy and gravitational deposition correction factors were obtained to modify the standard Gaussian plume model. Lastly, predictive results by improved Gaussian plume model were compared with CFD method. It was proved the improved correction method enables higher accuracy in predicting the atmospheric concentration distribution of gaseous pollutants with density variation or particles with gravitational deposition properties.