Promoting Photocatalytic H2 Evolution through Retarded Charge Trapping and Recombination by Continuously Distributed Defects in Methylammonium Lead Iodide Perovskite

Inspired by its great success in the photovoltaic field, methylammonium lead iodide perovskite (MAPbI₃) has recently been actively explored as photocatalysts in H₂ evolution reactions. However, the practical application of MAPbI₃ photocatalysts remains hampered by the intrinsically fast trapping and recombination of photogenerated charges. Herein, we propose a novel strategy of regulating the distribution of defective areas to promote charge-transfer dynamics of MAPbI₃ photocatalysts. By deliberately designing and synthesizing the MAPbI₃ photocatalysts featuring a unique continuation of defective areas, we demonstrate that such a feature enables retardation of charge trapping and recombination via lengthening the charge-transfer distance. As an outcome, such MAPbI₃ photocatalysts turn out to achieve an impressive photocatalytic H₂ evolution rate as high as 0.64 mmol ⋅ g⁻¹ ⋅ h⁻¹, one order of magnitude higher than that of the conventional MAPbI₃ photocatalysts. This work establishes a new paradigm for controlling charge-transfer dynamics in photocatalysis.     

Continuous Flow Electrochemistry Enables Practical and Site-Selective C−H Oxidation

The selective oxygenation of ubiquitous C(sp³)−H bonds remains a highly sought-after method in both academia and the chemical industry for constructing functionalized organic molecules. However, it is extremely challenging to selectively oxidize a certain C(sp³)−H bond to afford alcohols due to the presence of multiple C(sp³)−H bonds with similar strength and steric environment in organic molecules, and the alcohol products being prone to further oxidation. Herein, we present a practical and cost-efficient electrochemical method for the highly selective monooxygenation of benzylic C(sp³)−H bonds using continuous flow reactors. The electrochemical reactions produce trifluoroacetate esters that are resistant to further oxidation but undergo facile hydrolysis during aqueous workup to form benzylic alcohols. The method exhibits a broad scope and exceptional site selectivity and requires no catalysts or chemical oxidants. Furthermore, the electrochemical method demonstrates excellent scalability by producing 115 g of one of the alcohol products. The high site selectivity of the electrochemical method originates from its unique mechanism to cleave benzylic C(sp³)−H bonds through sequential electron/proton transfer, rather than the commonly employed hydrogen atom transfer (HAT).     

Two-dimensional correlation analysis of continuous online in situ ATR-FTIR on the adsorption of butyl xanthate at the surface of a-PbO

The adsorption behavior of butyl xanthate on the surface of lead oxide was investigated using continuous online in situ attenuated total reflectance Fourier transform infrared（ATR-FTIR） spectroscopy technique and two dimensional（2D） correlation analysis.The adsorbed layer studied was prepared by coating α-PbO particles onto the surfaces of the ZnSe crystal.The appearance of spectral peaks at 1203 cm^-1,1033 cm^-1 and their red shift indicated the formation and aggregation of xanthate at the surface of α-PbO.According to 1R intensity changes after rinsing with deionized water and a NaOH solution,the adsorption was proved to be a chemisorption type.The competition between xanthate and OH for the surfaces leads to desorption of xanthate at higher pH.The technique of 2D correlation ATR-FTIR spectroscopy was used to evaluate the changing order of spectral intensities in the adsorption process,and the results indicated that xanthate micelles were formed at the surfaces.The adsorption kinetics of butyl xanthate was found to be a pseudo-second-order reaction model and the adsorption capacity of butyl xanthate at α-PbO was as high as 281 mg g^-1 after 150 min.     

Failure prediction of hybrid composite using Arcan's device and Drucker-Prager model

Hybrid composites are promising materials due the possibility of combining the properties of different fiber types with those of the polymeric matrix. The higher number of phases involved in this kind of material and the hydrostatic component of polymer behavior make it unfeasible to use classic models for failure prediction, like the Von Mises or Treska models. In this study, a modified Arcan's device was applied for mechanical characterization of a polymeric blend matrix composite reinforced with randomly oriented continuous fibers (a clutch disc) to generate combined loading conditions. Experimental results were applied in the Von Mises and Drucker-Prager theoretical models for failure prediction. Additionally, scanning electron microscopy (SEM) was applied to analyze the fracture surface. The failure envelope provided by the Drucker-Prager model fit the experimental results, making it a promising tool for predicting the behavior of this type of hybrid composite.     

基于连续光谱法联合测定NH3-N、COD方法研究

针对地表水中Ⅰ—Ⅴ类水域、地下水、工业废水对氨氮及化学需氧量准确快速联合测定的需求,融合光谱分析法中的连续光谱法与顺序注射技术（SIA）,基于地表水国家检测标准,以氨态氮（NH₃-N）、化学需氧量（COD）原位水质参数为检测对象,设计了一种小型微量原位水质NH₃-N、COD高效快速检测仪。该系统主要依据自主设计的基于紫外灯照射消解与加热密闭消解方法同时进行的消解池结构以及基于光谱扫描设计的的检测池结构,达到快速消解稳定检测的目的。同时系统基于分光光度法优化了检测流程,测定开始COD消解的同时,待检测池中的NH₃-N指数显色后的配位化合物进行光谱扫描测定,消解后,进行COD的测定,整个检测过程相比国标检测法缩短至少60 min,可以实现25min内自动完成NH₃-N及COD的测定,大大节约时间成本。绘制经光谱扫描显色反应后配位化合物的吸光度与连续波长曲线可得：NH₃-N、COD分别于690和445 nm处具有明显吸收峰,经读取峰的吸光度值,采用最小二乘法分别建立NH₃-N、COD回归建模,拟合回归方程并计算相关系数,绘制相应参数的吸光度-浓度工作曲线。实验结果表明：在0~2 mg·L-1浓度范围内,NH₃-N标准工作曲线相关系数r≥0.998 7,且浓度与吸光度成正相关。重复性相对标准偏差为1.36%~1.68%,加标回收率为97%~102%;在0~50 mg·L-1浓度范围内,COD标准工作曲线相关系数r≥0.997 8,浓度与吸光度呈负相关。重复性相对标准偏差为2.14%~2.48%,加标回收率为97.6%~102.95%。系统的测定结果准确、直线性与稳定性良好,具有较高的可行性与可靠性。基于SIA与连续光谱法联合测定NH₃-N、COD的方法研究,为拓宽光谱法在水质快速检测领域的应用、提高检测效率等方面的研究具有重大价值。     

A thermodynamic approach with internal variables using Lagrange formalism. Part II. Continuous symmetries in the case of the time–temperature equivalence

In the first part of this contribution, the Lie-symmetries of the principle of least action associated to the constitutive equations of the DNLR formalism of relaxation have been presented. We examine in this second part the continuous symmetries corresponding to the simple case of stress relaxation under isothermal conditions. The well-known principle of time/temperature equivalence is discussed in terms of variational symmetry for the Jacobi’s action functional, and connected to the Onsager’s relation near the thermodynamic equilibrium.     

Stabilization of Parametric Vibrations of a Nonlinear Continuous System

The purpose of the present paper is to solve an active control problem of nonlinear continuous system parametric vibrations excited by the fluctuating force. The problem is solved using the concept of distributed piezoelectric sensors and actuators with a sufficiently large value of velocity feedback. The direct Liapunov method is proposed to establish criteria for the almost sure stochastic stability of the unperturbed (trivial) solution of the shell with closed-loop control. The distributed control is realized by the piezoelectric sensor and actuator, with the changing widths, glued to the upper and lower shell surface. The relation between the stabilization of nonlinear problem and a linearized one is examined. The fluctuating axial force is modeled by the physically realizable ergodic process. The rate velocity feedback is applied to stabilize the shell parametric vibrations.     

A stochastic-structurally based three dimensional finite-strain damage model for fibrous soft tissue

A fully three dimensional finite-strain damage model for fibrous soft tissue is developed. The model assumes uncoupled contributions for the matrix and collagen fibers, and uncoupled bulk and deviatoric response over any range of deformations. A simple isotropic damage mechanism within the framework of continuum damage mechanics has been used to describe the softening behavior under deformation for the matrix. On the other hand, statistical aspects related to the length distribution of the reinforcing fibers lead to a damage model for the reinforcing material. As a result, a general theoretical framework for constitutive modeling of biological soft tissue with continuum damage is obtained. A theoretical example consisting of a biaxial test of a soft tissue reinforced with two families of collagen fibers has been considered to demonstrate the capabilities of the proposed model and to study the sensitivity to changes in the statistical parameters associated with the reinforcing material. Also, a preliminary numerical example is included to demonstrate the model on a inhomogeneous boundary value problem. Results show that the model is able to capture the typical stress-strain behavior observed in fibrous soft tissue and seems to confirm the soundness of the proposed formulation.