Surface charging behaviors of electrocatalytic interfaces with partially charged chemisorbates

The surface charge is a key concept in electrochemistry. Mathematically, the surface charge is obtained from a spatial integration of the volume charge along a particular direction. Ambiguities thus arise in choosing the starting and ending points of the integration. As for electrocatalytic interfaces, the presence of chemisorbates further complicates the situation. In this minireview, I adopt a definition of the surface charge within a continuum picture of the electric double layer. I will introduce surface charging behaviors of firstly ordinary electrochemical interfaces and then electrocatalytic interfaces featuring partially charged chemisorbates. Particularly, the origin of nonmonotonic surface charging behaviors of electrocatalytic interfaces is explained using a primitive model. Finally, a brief account of previous studies on the nonmonotonic surface charging behavior is presented, as a subline of the spectacular history of electric double layer.     

Theoretical study on the mechanism for the excited-state double proton transfer process of an asymmetric Schiff base ligand

Excited-state double proton transfer (ESDPT) in the 1-[(2-hydroxy-3-methoxy-benzylidene)-hydrazonomethyl]-naphthalen-2-ol (HYDRAVH₂) ligand was studied by the density functional theory and time-dependent density functional theory method. The analysis of frontier molecular orbitals, infrared spectra, and non-covalent interactions have cross-validated that the asymmetric structure has an influence on the proton transfer, which makes the proton transfer ability of the two hydrogen protons different. The potential energy surfaces in both S₀ and S₁ states were scanned with varying O-H bond lengths. The results of potential energy surface analysis adequately proved that the HYDRAVH₂ can undergo the ESDPT process in the S₁ state and the double proton transfer process is a stepwise proton transfer mechanism. Our work can pave the way towards the design and synthesis of new molecules.     

Effect of strain on charge density wave order in α-U

The effect of strain on charge density wave (CDW) order in $\alpha$-U is investigated within the framework of relativistic density-functional theory. The energetical stability of $\alpha$-U with CDW distortion is enhanced by the tensile strain along $a$ and $b$ axes, which is similar to the case of negative pressure and normal. However, the tensile strain along $c$ axis suppresses the energetical stability of CDW phase. This abnormal effect could be understood from the emergence of a new one-dimensional atomic chain along $c$ axis in $\alpha$-U. Furthermore, this effect is supported by the calculations of Fermi surface and phonon mode, in which the topological objects and the dynamical instability show opposite behaviors between strains along $a$/$b$ and $c$ axes.     

A general framework for describing photofission observables of actinides at an average excitation energy below 30 MeV

A reasonable prediction of photofission observables plays a paramount role in understanding the photofission process and guiding various photofission-induced applications, such as short-lived isotope production, nuclear waste disposal, and nuclear safeguards. However, the available experimental data for photofission observables are limited, and the existing models and programs have mainly been developed for neutron-induced fission processes. In this study, a general framework is proposed for characterizing the photofission observables of actinides, including the mass yield distributions (MYD) and isobaric charge distributions (ICD) of fission fragments and the multiplicity and energy distributions of prompt neutrons (n_p) and prompt γ rays (γ_p). The framework encompasses various systematic neutron models and empirical models considering the Bohr hypothesis and does not rely on the experimental data as input. These models are then validated individually against experimental data at an average excitation energy below 30 MeV, which shows the reliability and robustness of the general framework. Finally, we employ this framework to predict the characteristics of photofission fragments and the emissions of prompt particles for typical actinides including ²³²Th, ^{235, 238}U and ²⁴⁰Pu. It is found that the ²³⁸U(γ, f) reaction is more suitable for producing neutron-rich nuclei compared to the ²³²Th(γ, f) reaction. In addition, the average multiplicity number of both n_p and γ_p increases with the average excitation energy.     

Wave-based vibration control of large cable net structures

Large cable net structures have been widely applied in aerospace engineering due to the feature of light-weight, high packaging efficiency, and high thermal stability. Structural vibrations induced by a variety of disturbances are inevitable in the space environment, resulting in the requirement of effective vibration control strategies for large cable net structures. Since the large cable net structures have many closely spaced vibrational modes in the range of low frequencies, traditional modal based control may cause modal truncation and spillover problems. In this paper, a wave-based boundary control strategy is adopted and its effectiveness to control the vibration of cable net structures is investigated, by transfer function analysis and numerical methods. It is found that the structural vibration can be absolutely resisted by applying the wave-based boundary controllers onto all the exterior nodes, when disturbances come from the external boundaries of the cable net. Our results in this paper can provide a theoretical basis for the vibration control of large cable net structures.     

Facile synthesis of graft copolymers containing rigid poly(dialkyl fumarate) branches by macromonomer method

Graft copolymers show microphase separated structure as seen in block copolymers and have lower intrinsic viscosity than block copolymers because of a branching structure. Therefore, considering molding processability, especially for polymers containing rigid segments, graft copolymers are useful architectures. In this work, graft copolymers containing rigid poly(diisopropyl fumarate) (PDiPF) branches were synthesized by full free‐radical polymerization process. First, synthesis of PDiPF macromonomers by addition‐fragmentation chain transfer (AFCT) was investigated. 2,2‐Dimethyl‐4‐methylene‐pentanedioic acid dimethyl ester was found to be an efficient AFCT agent for diisopropyl fumarate (DiPF) polymerization because of the suppression of undesired primary radical termination, which significantly took place when common AFCT agent, methyl 2‐(bromomethyl)acrylate, was used. Copolymerization of PDiPF macromonomer with ethyl acrylate accomplished the generation of the graft copolymer having flexible poly(ethyl acrylate) backbone and rigid PDiPF branches. The graft copolymer showed a microphase separated structure, high transparency, and characteristic thermal properties to PDiPF and poly(ethyl acrylate). © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2474–2480     

Hybrid Isothermal Model for the Ferrohydrodynamic Chemically Reactive Species

A hybrid isothermal model for the homogeneous-heterogeneous reactions in ferrohydrodynamic boundary layer flow is established. The characteristics of Newtonian heating and magnetic dipole in a ferrofluid due to a stretchable surface is analyzed for three chemical species. It is presumed that the isothermal cubic autocatalator kinetic gives the homogeneous reaction and the first order kinetics gives the heterogeneous (surface) reaction. The analysis is carried out for equal diffusion coefficients of all autocatalyst and reactions. Heat flux is examined by incorporating Fourier's law of heat conduction. Characteristics of materialized parameters on the magneto-thermomechanical coupling in the flow of a chemically reactive species are investigated. Further, the heat transfer rate and friction drag are depicted for the ferrohydrodynamic chemically reactive species. It is evident that the Schmidt number has increasing behavior on the rate of heat transfer in the boundary layer. Comparison with available results for specific cases is found an excellent agreement.     

Ultrathin Silicon Oxide Film-Induced Enhancement of Charge Separation and Transport of Nanostructured Titanium(IV) Oxide Photoelectrode

The development of nanostructured semiconductor electrodes represented by a mesoporous TiO₂ nanocrystalline (mp-TiO₂) film is currently bringing great progresses in photoelectrochemical (PEC) devices for solar-to-electricity and solar-to-chemical conversion. Two serious losses can occur in PEC devices: 1) recombination between the conduction band (CB) electrons and valence band (VB) holes in the bulk and at the surface and 2) back reaction or electron trapping by oxidant in the electrolyte solution during transport to the electron-collecting electrode. Thus, the major challenge in common with the nanostructured semiconductor photoanodes is to achieve efficient charge separation and electron transport. In this study, an ultrathin SiO_x layer was formed on both the external and the internal surface of mp-TiO₂ using an original chemisorption-calcination technique employing 1,3,5,7-tetramethyltetrasiloxane as a starting material. The SiO_x surface modification of the mp-TiO₂ photoanode drastically prolongs the mean lifetime of CB-electrons in TiO₂ because of enhanced charge separation and electron transport by the negative charge applied in aqueous electrolyte solution. We have demonstrated that the performance of a one-compartment H₂O₂-photofuel cell using mp-TiO₂ as the photoanode is greatly boosted by the surface modification with the SiO_x layer. We anticipate that this methodology is widely applicable to nanostructured metal oxide semiconductor electrodes, contributing to the improvement in the performance of PEC devices.