A [001]-Oriented Hittorf's Phosphorus Nanorods/Polymeric Carbon Nitride Heterostructure for Boosting Wide-Spectrum-Responsive Photocatalytic Hydrogen Evolution from Pure Water

Red phosphorus is a promising photocatalyst with wide visible-light absorption up to 700 nm, but the fast charge recombination limits its photocatalytic hydrogen evolution reaction (HER) activity. Now, [001]-oriented Hittorf's phosphorus (HP) nanorods were successfully grown on polymeric carbon nitride (PCN) by a chemical vapor deposition strategy. Compared with the bare PCN and HP, the optimized PCN@HP hybrid exhibited a significantly enhanced photocatalytic activity, with HER rates reaching 33.2 and 17.5 μmol h⁻¹ from pure water under simulated solar light and visible light irradiation, respectively. It was theoretically and experimentally indicated that the strong electronic coupling between PCN and [001]-oriented HP nanorods gave rise to the enhanced visible light absorption and the greatly accelerated photoinduced electron–hole separation and transfer, which benefited the photocatalytic HER performance.     

Metal-Free Synthesis of Functional 1-Substituted-1,2,3-Triazoles from Ethenesulfonyl Fluoride and Organic Azides

The boom in growth of 1,4-disubstituted triazole products, in particular, since the early 2000’s, can be largely attributed to the birth of click chemistry and the discovery of the Cu^I-catalyzed azide–alkyne cycloaddition (CuAAC). Yet the synthesis of relatively simple, albeit important, 1-substituted-1,2,3-triazoles has been surprisingly more challenging. Reported here is a straightforward and scalable click-inspired protocol for the synthesis of 1-substituted-1,2,3-triazoles from organic azides and the bench stable acetylene surrogate ethenesulfonyl fluoride (ESF). The new transformation tolerates a wide selection of substrates and proceeds smoothly under metal-free conditions to give the products in excellent yield. Under controlled acidic conditions, the 1-substituted-1,2,3-triazole products undergo a Michael addition reaction with a second equivalent of ESF to give the unprecedented 1-substituted triazolium sulfonyl fluoride salts.     

Understanding the Origin of Highly Selective CO2 Electroreduction to CO on Ni,N-doped Carbon Catalysts

Ni,N-doped carbon catalysts have shown promising catalytic performance for CO₂ electroreduction (CO₂R) to CO; this activity has often been attributed to the presence of nitrogen-coordinated, single Ni atom active sites. However, experimentally confirming Ni−N bonding and correlating CO₂ reduction (CO₂R) activity to these species has remained a fundamental challenge. We synthesized polyacrylonitrile-derived Ni,N-doped carbon electrocatalysts (Ni-PACN) with a range of pyrolysis temperatures and Ni loadings and correlated their electrochemical activity with extensive physiochemical characterization to rigorously address the origin of activity in these materials. We found that the CO₂R to CO partial current density increased with increased Ni content before plateauing at 2 wt % which suggests a dispersed Ni active site. These dispersed active sites were investigated by hard and soft X-ray spectroscopy, which revealed that pyrrolic nitrogen ligands selectively bind Ni atoms in a distorted square-planar geometry that strongly resembles the active sites of molecular metal–porphyrin catalysts.     

Theoretical studies of the concentration dependences of d–d transition band,g factors,and local distortion for V4+ in Li2O–PbO–B2O3–P2O5 glasses

In this work, the g factors, d–d transition band, local distortion, and their concentration dependences for impurity V⁴⁺ in 20Li₂O–20PbO–45B₂O₃–(15 − x)P₂O₅:V₂O₅ (0 ≤ x ≤ 2.5 mol%) glasses are theoretically investigated by using perturbation formulas of g factors for a tetragonally compressed octahedral 3d¹ cluster. In the light of the cubic polynomial concentration functions for cubic field parameter D_q, covalency factor N, and relative tetragonal compression ratio ρ, the calculated concentration dependences of d–d transition band and g factors for V⁴⁺ show good agreement with the experimental data. With increasing x, N (≈0.7682–0.8165) displays the monotonously increasing trend, whereas ρ (≈6.5–4.2%) and D_q (≈1504.9–1481.1 cm⁻¹) exhibit the decreasing tendencies. The above concentration dependences can be ascribed to the modifications of the V⁴⁺–O²⁻ bonding and orbital admixtures around the impurity V⁴⁺ due to the effects of V₂O₅ doping on the stability of the glass network, the strength of local crystal fields, and the electron cloud distribution.     

Evaluation of alumina slurry dispersion by nuclear magnetic resonance relaxation as a comparison to conventional dispersion evaluation methods

In this paper, we evaluated the particle dispersion degree of alumina slurry containing a dispersant by solvent nuclear magnetic resonance (NMR) relaxation and compared it with conventional dispersion evaluation methods such as viscosity, particle size, and sedimentation height measurements. The dispersion of slurry was evaluated via numerical analysis of the transverse relaxation time (T₂). The effect of the changes in different parameters of the experiment in terms of milling time, solid loading, and dispersant amount was investigated by NMR relaxation as well as conventional methods. The results of NMR relaxation measurements revealed that T₂ correlates well with other dispersion evaluation methods; thus, it is an efficient technique to evaluate the dispersion of alumina slurry, specifically, when studying the effect of the change in milling time and dispersion amount.     

Two Optimal Value Functions in Parametric Conic Linear Programming

Journal of Optimization Theory and Applications - We consider the conic linear program given by a closed convex cone in an Euclidean space and a matrix, where vector on the right-hand side of the...     

A Delayed HIV Infection Model with the Homeostatic Proliferation of CD4+ T Cells

Acta Mathematicae Applicatae Sinica, English Series - In this paper, we investigate a delayed HIV infection model that considers the homeostatic proliferation of CD4+ T cells. The existence and...     

Synthesis of CO2-based functional poly(carbonate-co-lactide)

TPPAlCl-PPN⁺Cl⁻ binary catalyst (where TPPAlCl is 5,10,15,20-tetraphenylporphyrin aluminum chloride, PPN⁺Cl⁻ is bis[triphenylphosphine] iminium chloride, the molar ratio of TPPAlCl to PPN⁺Cl⁻ is 1 to 0.5) can initiate the effective one-pot/one-step ternary copolymerization of CO₂, lactide and 4-vinyl-1-cyclohexene-1,2-epoxide, and the quaternary copolymerization of CO₂, propylene oxide, lactide, 4-vinyl-1-cyclohexene-1,2-epoxide, to form multiblock poly(carbonate-co-lactide) products with pendant vinyl group. The ternary copolymerization product composes of polylactide (PLA) block and poy(vinylcyclohexylene carbonate) (PVCHC) block, and the quaternary copolymerization product composes of poy(propylene carbonate) (PPC) block, PLA block and PVCHC block, which are verified by ¹H NMR, ¹³C NMR, ¹H-¹H cosy, hetero-nuclear multiple bond correlation, DTG, and Gel permeation chromatography analysis. The functionality and glass-transition temperature of the products can be easily adjusted by the copolymerization variables, such as the molar ratio of comonomers, copolymerization temperature, pressure of CO₂, the concentration of the catalyst.     

Amorphous Manganese–Cobalt Nanosheets as Efficient Catalysts for Hydrogen Evolution Reaction (HER)

Catalysis Surveys from Asia - A facile and efficient electrocatalyst for hydrogen evolution reaction (HER) to produce hydrogen is very important for future energy. In this paper, amorphous...     

Correlating conductivity and Seebeck coefficient to doping within crystalline and amorphous domains in poly(3-(methoxyethoxyethoxy)thiophene)

Molecular doping of conjugated polymers (CPs) plays a vital role in optimizing organic electronic and energy applications. For the case of organic thermoelectrics, it is commonly believed that doping CPs with a strong dopant could result in higher conductivity (σ) and thus better power factor (PF). Herein, by investigating thermoelectric performance of a polar side-chain bearing CP, poly(3-(methoxyethoxyethoxy)thiophene) (P3MEET), vapor doped with fluorinated-derivative of tetracyanoquinodimethane FnTCNQ (n = 1, 2, 4), we show that using strong dopants can in fact have detrimental effects on the thermoelectric performance of CPs. Despite possessing higher electron affinity, doping P3MEET with F4TCNQ only results in a σ (27.0 S/cm) comparable to samples doped with other two weaker dopants F2TCNQ and F1TCNQ (26.4 and 20.1 S/cm). Interestingly, F4TCNQ-doped samples display a marked reduction in the Seebeck coefficient (α) compared to F1TCNQ- and F2TCNQ-doped samples from 42 to 13 μV/K, leading to an undesirable suppression of the PF. Structural characterizations coupled with Kang-Snyder modeling of the α–σ relation show that the reduction of α in F4TCNQ-doped P3MEET samples originates from the generation of low mobility carrier within P3MEET's amorphous domain. Our results demonstrate that factors such as dopant distribution and doping efficiency within the crystalline and amorphous domains of CPs should play a crucial role in advancing rational design for organic thermoelectrics.