Intercalated PtCo Electrocatalyst of Vanadium Metal Oxide Increases Charge Density to Facilitate Hydrogen Evolution.

Efforts to develop high-performance electrocatalysts for the hydrogen evolution reaction (HER) are of utmost importance in ensuring sustainable hydrogen production. The controllable fabrication of inexpensive, durable, and high-efficient HER catalysts still remains a great challenge. Herein, we introduce a universal strategy aiming to achieve rapid synthesis of highly active hydrogen evolution catalysts using a controllable hydrogen insertion method and solvothermal process. Hydrogen vanadium bronze HxV2O5 was obtained through controlling the ethanol reaction rate in the oxidization process of hydrogen peroxide. Subsequently, the intermetallic PtCoVO supported on two-dimensional graphitic carbon nitride (g-C3N4) nanosheets was prepared by a solvothermal method at the oil/water interface. In terms of HER performance, PtCoVO/g-C3N4 demonstrates superior characteristics compared to PtCo/g-C3N4 and PtCoV/g-C3N4. This superiority can be attributed to the notable influence of oxygen vacancies in HxV2O5 on the electrical properties of the catalyst. By adjusting the relative proportions of metal atoms in the PtCoVO/g-C3N4 nanomaterials, the PtCoVO/g-C3N4 nanocomposites show significant HER overpotential of η10 = 92 mV, a Tafel slope of 65.21 mV dec-1, and outstanding stability (a continuous test lasting 48 h). The nanoarchitecture of a g-C3N4-supported PtCoVO nanoalloy catalyst exhibits exceptional resistance to nanoparticle migration and corrosion, owing to the strong interaction between the metal nanoparticles and the g-C3N4 support. Pt, Co, and V simultaneous doping has been shown by Density Functional Theory (DFT) calculations to enhance the density of states (DOS) at the Fermi level. This augmentation leads to a higher charge density and a reduction in the adsorption energy of intermediates.

Experimentally revealed and theoretically certified synergistic electronic interaction of V-doped CoS for facilitating the oxygen evolution reaction.

Since electrocatalytic oxygen evolution (OER) is a four-electron transfer reaction with very slow kinetics, there is great competition to develop cheap, durable and efficient catalysts for oxygen evolution. A molecular model is designed for density functional theory (DFT) simulation calculations to guide the experiment, and this hypothesis is fully supported by the experimental data. Herein, regulating the composition and morphology of the bimetallic VCo and MoCo sulfide and monometallic sulfide nanoparticles (NPs) at the oil-water interface was achieved via a one-step hydrothermal method for efficient and durable OER electrocatalysts. Compared to CoS and MoCoS, the VCoS NPs show superior OER performance. By adjusting the atomic composition ratio of the VCoS nanoparticles, the VCoS NPs (1 : 2 : 1.5 mole ratio) showed a significant OER overpotential η = 255 mV (10 mA cm-2), and their outstanding stability was demonstrated after 48 h of continuous testing. The CoS and MoCoS NPs were also tested for comparison. Density functional theory (DFT) calculations showed that appropriate V doping (VCoS) can heighten the density of states (DOS) of the Fermi level, which generates more charge density and reduces the intermediate adsorption energy. This study not only provides efficient and powerful integrated catalysts, but also details a DFT calculation model guided by experiments to regulate the oxygen insertion technology, thus leading to the design of ideal materials and enabling more far-reaching applications in electrocatalysis.

Investigation of the local structure of molten ThF4-LiF and ThF4-LiF-BeF2 mixtures by high-temperature X-ray absorption spectroscopy and molecular-dynamics simulation.

The microscopic structures of ThF4-LiF and ThF4-LiF-BeF2 molten salts have been systematically investigated by in situ high-temperature X-ray absorption fine-structure (XAFS) spectroscopy combined with molecular-dynamics (MD) simulations. The results reveal that the local structure of thorium ions was much more disordered in the molten state of the ThF4-LiF-BeF2 salt than that in ThF4-LiF, implying that the Th and F ions were exchanged more frequently in the presence of Be ions. The structures of medium-range-ordered coordination shells (such as Th-F2nd and Th-Th) have been emphasized by experimental and theoretical XAFS analysis, and they play a significant role in transport properties. Using MD simulations, the bonding properties in the molten ThF4-LiF and ThF4-LiF-BeF2 mixtures were evaluated, confirming the above conclusion. This research is, to the best of our knowledge, the first systematic study on the ThF4-LiF-BeF2 molten salt via quantitative in situ XAFS analysis and MD simulations.

Carbon nanotubes as photoprotectors of organic dyes: reversible photoreaction instead of permanent photo-oxidation.

In this paper we report that single-walled carbon nanotubes (SWNTs) can protect surface adsorbed Rhodamine B (RhB) molecules from permanent photo-oxidation via a reversible reaction. Upon strong light irradiation at 514 nm, the SWNT-adsorbed RhB molecules were switched to a non-fluorescent form, which looked like ordinary bleaching behavior. However, after staying without light for several hours the non-fluorescent dye species turned back to the original fluorescent form. This on/off switching can be considered as a reversible photobleaching process of the dye molecules. Other irreversible photochemical pathways of RhB were strongly prohibited due to the presence of SWNTs, providing the dye molecules with a high resistance against permanent photodegradation. By determining the maximum number of reconvertable RhB molecules per unit length of the nanotubes, we have further proved that this effect only works for the first layer of adsorbed dye molecules on the SWNT surfaces.

Effects of ionic liquid [bmim][PF6] on absorption spectra and reaction kinetics of the duroquinone triplet state in acetonitrile.

The transient absorption spectra and photoinduced electron-transfer process of duroquinone (DQ) in mixed binary solutions of ionic liquid (IL) [bmim][PF6] and acetonitrile (MeCN) have been investigated by laser photolysis at an excitation wavelength of 355 nm. A spectral blue shift of 3DQ* was observed in the IL/MeCN mixtures compared to MeCN. At lower VIL(volume fraction of IL), the interaction between DQ and the solvent is dominant, and the decay rate constant (kobs) of 3DQ* increases steadily with the increasing of VIL; to the contrary, at higher VIL, the network structures due to the hydrogen bond and viscosity are dominant, and the decay rate constant decreases obviously with increasing VIL. A critical point (turnover) was observed at VIL = approximately 0.30. The dependence of the observed growth rate (kgr) of the photoinduced electron-transfer (PET) products on VIL is complex and shows a special change; kgr first decreases with increasing VIL, then increases, and finally decreases slowly with further increasing of VIL. It is speculated that the PET process in the mixture can be affected by factors including the local structure and the reorganization energy of the solvent and salt and cage effects. The change of local structure of [bmim][PF6]/MeCN is supported by following the steady-state fluorescence behavior of the mixture, in combination with the molecular dynamics simulation of the thermodynamic property. The results revealed that the degree of self-aggregation of monomeric cations (bmim+) to associated forms increases with increasing VIL. This is in good agreement with the laser photolysis results for the same solutions.

Noncovalently modified carbon nanotubes with carboxymethylated chitosan: a controllable donor-acceptor nanohybrid.

We report here the modification of multiwalled carbon nanotubes (MWNTs) with a kind of polysaccharide, carboxymethylated chitosan (cmCs), and their potential usage as donor-acceptor nanohybrids. The modified composites (cmCs/MWNTs) were characterized by high-resolution TEM, FT-IR, TGA and time-resolved spectroscopy. The time-resolved spectroscopic experiments revealed that interfacial electron transfer readily takes place between MWNTs and surface immobilized cmCs chains. The forward electron transfer is fast (< 20 ns) while the backward recombination is slow. The recombination process strongly depends on the chain length of carboxylmethylated chitosan, i.e. a shorter recombination lifetime (~1.1 micros) for the shorter-chain cmCs coated MWNTs against that of the longer-chain cmCs coated MWNTs (~3.5 micros). The results demonstrated that the cmCs/MWNTs composite may be applied as a controllable donor-acceptor nanohybrid.

[Laser photolysis study on photochemical reactions in mixed solutions of [bmim][PF6] and acetonitrile].

Laser flash photolysis study was carried out for the first time in the binary mixture of room-temperature ionic liquid (RTIL) and traditional organic solvent. Photochemical properties of the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate [bmim][PF6] and its binary mixed solutions with MeCN were investigated by laser photolysis technique at an excitation wavelength of 355 nm, using anthraquinone (AQ) as a probe molecule. It was indicated that [bmim] [PF6] itself participates in the reaction with 3AQ*. Moreover, along with the change in the ratio of RTIL to organic solvent, the decay reaction rate constant of 3AQ* changes regularly and a critical point was observed at chiRTIL = 0.06. Before the critical point, the decay rate constant increases rapidly with increasing chiRTIL; however, it decreases obviously with increasing chiRTIL after the critical point. The kinetic data are given, and the possible reaction mechanisms in mixed solutions are also speculated.

Structural investigation into physiological DNA phosphorothioate modification.

DNA phosphorothioate (PT) modification, with sulfur replacing a nonbridging phosphate oxygen in a sequence and stereo specific manner, is a novel physiological variation in bacteria. But what effects on DNA properties PT modification has is still unclear. To address this, we prepared three double-stranded (ds) DNA decamers, d(CG(PX)GCCGCCGA) with its complementary strand d(TCGGCG(PX)GCCG) (where X = O or S, i.e., PT-free dsDNA, [Sp, Sp]-PT dsDNA or [Rp, Rp]-PT dsDNA) located in gene of Streptomyces lividans. Their melting temperature (Tm) measurement indicates that [Rp, Rp]-PT dsDNA is most unstable. Their electron transfer potential detection presents an order of anti-oxidation properties: Sp-PT DNA > Rp-PT DNA > PT-free DNA. Their NMR structures demonstrate that PT modification doesn't change their B-form conformation. The sulfur in [Rp, Rp]-PT dsDNA locates in the major groove, with steric effects on protons in the sugar close to modification sites, resulting in its unstability, and facilitating its selectively interactions with ScoMcrA. We thought that PT modification was dialectical to the bacteria. It protects the hosting bacteria by working as antioxidant against H2O2, and acts as a marker, directing restriction enzyme observed in other hosts, like ScoMcrA, to correctly cleave the PT modified DNA, so that bacteria cannot spread and survive.