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.     

Classical solution for a nonlinear hybrid system modeling combustion in a multilayer porous medium

Combustion processes in porous media have been used by the petroleum engineering industry to extract heavy oil from reservoirs. This study focuses on a one-dimensional nonlinear hybrid system consisting of $n$ reaction–diffusion–convection equations coupled with $n$ ordinary differential equations, which models a combustion front moving through a porous medium with $n$ parallel layers. The state variables are the temperature and fuel concentration in each layer. Coupling occurs in both the reaction function and differential operator coefficients. We prove the existence of a classical solution, first locally and then globally over time, to an initial and boundary value problem for the corresponding system. The proof uses a new approach for combustion problems in porous media. The local solution is obtained by defining an operator in a set of Hölder continuous functions and using Schauder’s fixed-point theorem to find a fixed point as the desired solution. Using Zorn’s lemma, we extend the local solution to a global solution, proving that the first-order spatial derivative of the temperature in each layer is a bounded function.     

Photosensitive organic-inorganic hybrid structures based on porous silicon

Abstract

In this study, the photovoltaic organic-inorganic structures were created by deposition of poly(3,4-ethylenedioxythiophene) film doped by poly(styrenesulfonate) and reduced graphene oxide on the porous silicon/silicon substrate. Formation of the hybrid structure was confirmed by means of atomic-force microscopy and Fourier transform infrared spectroscopy. The current-voltage characteristics of the obtained structures were studied. It was found the increase of electrical conductivity and photo-induced signal in organic-inorganic structures. Temporal parameters and spectral characteristics of photoresponse in the 400–1100?nm wavelength range were investigated. The widening of spectral photosensitivity in a short-wavelength range due to light absorption in various layers of the multijunction structure in comparison with single crystal silicon was revealed.     

The double deflating technique for irreducible singular M-matrix algebraic Riccati equations in the critical case

As is known, Alternating-Directional Doubling Algorithm (ADDA) is quadratically convergent for computing the minimal nonnegative solution of an irreducible singular M-matrix algebraic Riccati equation (MARE) in the noncritical case or a nonsingular MARE, but ADDA is only linearly convergent in the critical case. The drawback can be overcome by deflating techniques for an irreducible singular MARE so that the speed of quadratic convergence is still preserved in the critical case and accelerated in the noncritical case. In this paper, we proposed an improved deflating technique to accelerate further the convergence speed – the double deflating technique for an irreducible singular MARE in the critical case. We proved that ADDA is quadratically convergent instead of linearly when it is applied to the deflated algebraic Riccati equation (ARE) obtained by a double deflating technique. We also showed that the double deflating technique is better than the deflating technique from the perspective of dimension of the deflated ARE. Numerical experiments are provided to illustrate that our double deflating technique is effective.     

Porous Molybdenum Carbide Nanostructures Synthesized on Carbon Cloth by CVD for Efficient Hydrogen Production

Molybdenum carbide (Mo₂C) is a promising noble-metal-free electrocatalyst for the hydrogen evolution reaction (HER), due to its structural and electronic merits, such as high conductivity, metallic band states and wide pH applicability. Here, a simple CVD process was developed for synthesis of a Mo₂C on carbon cloth (Mo₂C@CC) electrode with carbon cloth as carbon source and MoO₃ as the Mo precursor. XRD, Raman, XPS and SEM results of Mo₂C@CC with different amounts of MoO₃ and growth temperatures suggested a two-step synthetic mechanism, and porous Mo₂C nanostructures were obtained on carbon cloth with 50 mg MoO₃ at 850 °C (Mo₂C-850(50)). With the merits of unique porous nanostructures, a low overpotential of 72 mV at current density of 10 mA cm⁻² and a small Tafel slope of 52.8 mV dec⁻¹ was achieved for Mo₂C-850(50) in 1.0 m KOH. The dual role of carbon cloth as electrode and carbon source resulted into intimate adhesion of Mo₂C on carbon cloth, offering fast electron transfer at the interface. Cyclic voltammetry measurements for 5000 cycles revealed that Mo₂C@CC had excellent electrochemical stability. This work provides a novel strategy for synthesizing Mo₂C and other efficient carbide electrocatalysts for HER and other applications, such as supercapacitors and lithium-ion batteries.     

Synthesis of Organosilyl-Functionalized Cage-Type Germanoxanes Containing Fluoride Ions

Eight corners of a double-four ring cage-type germanoxane, containing a fluoride ion, were successfully silylated by the combination of chlorosilanes and silazanes. Three different silyl groups, trimethylsilyl, dimethylsilyl, and dimethylvinylsilyl, were attached on the corners of germanoxane cage. The solubility and reactivity of the cage modified with dimethylvinylsilyl groups were significantly increased, allowing for further reaction. Hydrosilylation reaction between dimethylvinylsilylated cage geramanoxanes and dimethylsilylated cage siloxanes afforded porous solids. Functionalization of the corners of germanoxanes with silyl groups should provide valuable building blocks in various functional materials.     

Highly Proton-Conductive Zinc Metal-Organic Framework Based On Nickel(II) Porphyrinylphosphonate

The design of new solid-state proton-conducting materials is a great challenge for chemistry and materials science. Herein, a new anionic porphyrinylphosphonate-based MOF ( IPCE-1Ni ), which involves dimethylammonium (DMA) cations for charge compensation, is reported. As a result of its unique structure, IPCE-1Ni exhibits one of the highest value of the proton conductivity among reported proton-conducting MOF materials based on porphyrins (1.55×10⁻³ S cm⁻¹ at 75 °C and 80 % relative humidity).     

Self-Assembly of C3 Symmetric Rigid Macrolactams into Very Polar and Porous Trigonal Crystals

Cyclohexane and cyclotri-β-alanyl have been used as scaffolds for the design of new C₃-symmetric rings incorporating conjugated alkenes and dienes. All three C₃-symmetric lactams share the same triangular shape and their crystal system is trigonal. They all belong to the R3 space group, R3m, R3 and R3c, for the increasingly large 12-, 18- and 24-membered rigid rings, respectively. All lactams stack on top of each other, through H-bonds and van der Waals noncovalent interactions, leading to endless supramolecular cylinders and tubes. The largest member of the family leads to tubes, the central pores of which is wide enough to let water in. A common feature of all the lactams is their very large dipole, of around 9 D, according to DFT calculations. Surprisingly, all the resulting cylinders and tubes pack side by side in the crystals, with all the dipoles pointing to the same direction. As a result, all three crystals are anisotropic and appear to be the first members of a new kind of highly polar crystals.     

Seeded Polymerization of an Amide-Functionalized Diketopyrrolopyrrole Dye in Aqueous Media

The self-assembly of an amide-functionalized dithienyldiketopyrrolopyrrole (DPP) dye in aqueous media was achieved through seed-initiated supramolecular polymerization. Temperature- and time-dependent studies showed that the spontaneous polymerization of the DPP derivative was temporally delayed upon cooling the monomer solution in a methanol/water mixture. Theoretical calculations revealed that an amide-functionalized DPP derivative adopts an energetically favorable folded conformation in the presence of water molecules due to hydration. This conformational change is most likely responsible for the trapping of monomers in the initial stage of the cooperative supramolecular polymerization in aqueous media. However, the monomeric species can selectively interact with externally added fragmented aggregates as seeds through concerted π-stacking and hydrogen-bonding interactions. Consequently, the time course of the supramolecular polymerization and the morphology of the aggregated state can be controlled, and one-dimensional fibers that exhibit a J-aggregate-like bathochromically shifted absorption band can be obtained.