从废水到新能源:光催化燃料电池的优化与应用

随着经济的飞速发展,社会对能源的需求日益扩大,对工业废水的无害化处理也提出了更高的要求。光催化燃料电池 (photocatalytic fuel cell, PFC) 在燃料电池中引入半导体光催化材料作为电极,实现了有机污染物高效降解和同步对外产电的双重功能,在废水无害化与资源化利用方面具有潜在的应用价值。半导体光催化电极是PFC系统高效运行的核心组件,增强其可见光响应和光生载流子分离是提高PFC性能的关键策略。反应器结构设计和运行参数优化也有利于改善PFC性能。本文从PFC基本原理和应用入手,综述了PFC在环境污染物资源化处理中的研究进展,并详细阐述了提高PFC的污染控制性能和产电效率的优化手段,为进一步设计高效稳定的PFC系统并实现其在水污染控制和清洁能源生产中的应用提供理论指导。     

An improved LC–MS/MS method for determination of docetaxel and its application to population pharmacokinetic study in Chinese cancer patients

Because of its unpredictable side effects and efficacy, the anticancer drug docetaxel (DTX) requires improved characterisation of its pharmacokinetic profiles through population pharmacokinetic studies. A sensitive and rugged LC–MS/MS method for the detection of DTX in human plasma was developed and optimised using paclitaxel as an internal standard (IS). The plasma samples underwent rapid extraction using hybrid solid-phase extraction-protein precipitation. The analyte and IS were separated with an isocratic system on a Zorbax Eclipse Plus C₁₈ column using water containing 0.05% acetic acid along with 20 μM of sodium acetate and methanol (30/70, v/v) as the mobile phase. Quantification was performed using a triple quadrupole mass spectrometer through multiple reaction monitoring in positive mode, using the m/z 830.3 → 548.8 and m/z 876.3 → 307.7 transitions for DTX and paclitaxel, respectively. The range of the calibration curve was 1–500 ng/mL for DTX, and the linear correlation coefficient was >0.99. The accuracies ranged from −4.6 to 4.2%, and the precision was no higher than 7.0% for the analytes. No significant matrix effect was observed. Both DTX and the IS showed considerable recovery. This method was finally applied to the establishment of a population pharmacokinetic model to optimise the clinical use of DTX.     

Bimetallic Covalent Organic Frameworks for Constructing Multifunctional Electrocatalyst

Covalent organic frameworks (COFs) are a new class of crystalline porous polymers comprised mainly of carbon atoms, and are versatile for the integration of heteroatoms such as B, O, and N into the skeletons. The designable structure and abundant composition render COFs useful as precursors for heteroatom-doped porous carbons for energy storage and conversion. Herein, we describe a multifunctional electrochemical catalyst obtained through pyrolysis of a bimetallic COF. The catalyst possesses hierarchical pores and abundant iron and cobalt nanoparticles embedded with standing carbon layers. By integrating these features, the catalyst exhibits excellent electrochemical catalytic activity in the oxygen reduction reaction (ORR), with a 50 mV positive half-wave potential, a higher limited diffusion current density, and a much smaller Tafel slope than a Pt-C catalyst. Moreover, the catalyst displays superior electrochemical performance toward the hydrogen evolution reaction (HER), with overpotentials of −0.26 V and −0.33 V in acidic and alkaline aqueous solution, respectively, at a current density of 10 mA cm⁻². The overpotential in the catalysis of the oxygen evolution reaction (OER) was 1.59 V at the same current density.     

Boundedness of semilinear Duffing equations at resonance in a critical situation

In this paper, we propose a sufficient and necessary condition for the boundedness of all the solutions for the equation $\ddot{x}+n^{2}x+g(x)=p(t)$ with the critical situation that $|{\int }_0^{2\pi }p(t)e^{?int}dt|=2|g(+\infty )?g(?\infty )|$ on g and p, where $n\in {\mathbb{N}}^{+}$, $p(t)$ is periodic and $g(x)$ is bounded.     

Metabolic profiles of dioscin in rats revealed by ultra‐performance liquid chromatography quadrupole time‐of‐flight mass spectrometry

Dioscin (DIS), one of the most abundant bioactive steroidal saponins in Dioscorea sp., is used as a complementary medicine to treat coronary disease and angina pectoris in China. Although the pharmacological activities and pharmacokinetics of DIS have been well demonstrated, information regarding the final metabolic fates is very limited. This study investigated the in vivo metabolic profiles of DIS after oral administration by ultra‐performance liquid chromatography quadrupole time‐of‐flight mass spectrometry method. The structures of the metabolites were identified and tentatively characterized by means of comparing the molecular mass, retention time and fragmentation pattern of the analytes with those of the parent compound. A total of eight metabolites, including seven phase I and one phase II metabolites, were detected and tentatively identified for the first time. Oxidation, deglycosylation and glucuronidation were found to be the major metabolic processes of the compound in rats. In addition, a possible metabolic pathway on the biotransformation of DIS in vivo was proposed. This study provides valuable and new information on the metabolism of DIS, which will be helpful for further understanding its mechanism of action. Copyright © 2015 John Wiley & Sons, Ltd.     

Utilizing the Space‐Charge Region of the FeNi‐LDH/CoP p‐n Junction to Promote Performance in Oxygen Evolution Electrocatalysis

The modulation of electron density is an effective option for efficient alternative electrocatalysts. Here, p‐n junctions are constructed in 3D free‐standing FeNi‐LDH/CoP/carbon cloth (CC) electrode (LDH=layered double hydroxide). The positively charged FeNi‐LDH in the space‐charge region can significantly boost oxygen evolution reaction. Therefore, the j at 1.485 V (vs. RHE) of FeNi‐LDH/CoP/CC achieves ca. 10‐fold and ca. 100‐fold increases compared to those of FeNi‐LDH/CC and CoP/CC, respectively. Density functional theory calculation reveals OH^? has a stronger trend to adsorb on the surface of FeNi‐LDH side in the p‐n junction compared to individual FeNi‐LDH further verifying the synergistic effect in the p‐n junction. Additionally, it represents excellent activity toward water splitting. The utilization of heterojunctions would open up an entirely new possibility to purposefully regulate the electronic structure of active sites and promote their catalytic activities.     

QEPAS系统中石英音叉模态仿真计算与研究

对石英音叉增强型光声光谱(QEPAS)系统中常用的石英音叉进行了有限元模态计算，获得石英音叉前6阶振型与模态频率，认知了第4阶对称摆动振型为有效振动，利用单因素法分析了石英音叉的音臂长度l₁、音臂宽度w₁、音臂厚度t、音臂切角θ、音臂圆孔直径d及音臂圆孔高度h对低阶有效共振频率(Fre)的影响，敏感度依次为： l₁> w₁>d>θ>t>h，考虑实际设计情形，筛选出了l₁，w₁，d与h四个石英音叉设计变量，采用Box-Behnken实验设计方案与RSM(response surface methodology)方法，以Fre为函数目标，建立l₁，w₁，d与h的二次回归响应面模型，得到了参数之间的交互作用，利用Design-Expert软件对响应面模型进行设计参数反求，结果表明，在15 000 Hz≤Fre≤25 000 Hz计算区域内误差较小，基本满足QEPAS系统的计算需求，所提出的研究与设计方法具有一定通用性，可为QEPAS系统中石英音叉结构参数设计提供参考。     

Water-induced formation of an alkali-ion dimer in cryptomelane nanorods

Tunneled metal oxides such as α-Mn₈O₁₆ (hollandite) have proven to be compelling candidates for charge-storage materials in high-density batteries. In particular, the tunnels can support one-dimensional chains of K⁺ ions (which act as structure-stabilizing dopants) and H₂O molecules, as these chains are favored by strong H-bonds and electrostatic interactions. In this work, we examine the role of water molecules in enhancing the stability of K⁺-doped α-Mn₈O₁₆ (cryptomelane). The combined experimental and theoretical analyses show that for high enough concentrations of water and tunnel-ions, H₂O displaces K⁺ ions from their natural binding sites. This displacement becomes energetically favorable due to the formation of K²⁺ dimers, thereby modifying the stoichiometric charge of the system. These findings have potentially significant technological implications for the consideration of cryptomelane as a Li⁺/Na⁺ battery electrode. Our work establishes the functional role of water in altering the energetics and structural properties of cryptomelane, an observation that has frequently been overlooked in previous studies.

Water displaces potassium ions and initiates the formation of a homonuclear dimer ion (K²⁺) in the tunnels of hollandite.     

钙钛矿型Sr_（1－x）Bi_xFeO_（3－y）系列物的结构、电性及铁氧化态研究

在１１００℃制备了钙钛矿型非计量系列物Ｓｒ_（１－ｘ）Ｂｉ_ｘＦｅＯ_（３－ｙ），与文献相比，明显具有温度低、时间短、能耗少的特点。用化学分析方法测得其化学式及Ｆｅ离子的平均价态，用ＸＲＤ、交流阻抗、ＩＲ、Ｍｏｓｓｂａｕｅｒ谱等方法研究了其结构与性质，该类化合物具有Ｐｍ３ｍ对称性和半导体性质，铁离子会产生电荷歧化现象。     

Recursive partition and amalgamation with the exponential family: Theory and applications

The theory of tree-growing (RECPAM approach) is developed for outcome variables which are distributed as the canonical exponential family. The general RECPAM approach (consisting of three steps: recursive partition, pruning and amalgamation), is reviewed. This is seen as constructing a partition with maximal information content about a parameter to be predicted, followed by simplification by the elimination of ‘negligible’ information. The measure of information is defined for an exponential family outcome as a deviance difference, and appropriate modifications of pruning and amalgamation rules are discussed. It is further shown how the proposed approach makes it possible to develop tree-growing for situations usually treated by generalized linear models (GLIM). In particular, Poisson and logistic regression can be tree-structured. Moreover, censored survival data can be treated, as in GLIM, by observing a formal equivalence of the likelihood under random censoring and an appropriate Poisson model. Three examples are given of application to Poisson, binary and censored survival data.