Conjugated Porous Polymers Based on BODIPY and BOPHY Dyes in Hybrid Heterojunctions for Artificial Photosynthesis

Developing highly efficient photocatalysts for artificial photosynthesis is one of the grand challenges in solar energy conversion. Among advanced photoactive materials, conjugated porous polymers (CPPs) possess a powerful combination of high surface areas, intrinsic porosity, cross-linked nature, and fully π-conjugated electronic systems. Here, based on these fascinating properties, organic–inorganic hybrid heterostructures composed of CPPs and TiO₂ for the photocatalytic CO₂ reduction and H₂ evolution from water are developed. The study is focused on CPPs based on the boron dipyrromethene (BODIPY) and boron pyrrol hydrazine (BOPHY) families of compounds. It is shown that hybrid photocatalysts are active for the conversion of CO₂ mainly into CH₄ and CO, with CH₄ production 4 times over the benchmark TiO₂. Hydrogen evolution from water surpassed by 37.9-times that of TiO₂, reaching 200 mmol g_cat⁻¹ and photonic efficiency of 20.4% in the presence of Pt co-catalyst (1 wt% Pt). Advanced photophysical studies, based on time-resolved photoluminescence and transient absorption spectroscopy, reveal the creation of a type II heterojunction in the hybrids. The unique interfacial interaction between CPPs and TiO₂ results in longer carriers’ lifetimes and a higher driving force for electron transfer, opening the door to a new generation of photocatalysts for artificial photosynthesis.     

LD泵浦光在侧泵模块水冷结构传输中的偏振态变化和光强衰减分析

以LD泵浦光在侧泵模块水冷结构中的传输过程为研究内容,基于模块结构参数、光波传输特性及介质透光特性,系统分析了泵浦光在各介质表面和内部的偏振态变化、光强衰减过程及变化规律。重点分析了由介质表面菲涅尔效应和内部吸收效应等造成的光强衰减;计算了泵浦光在水冷结构中单次往返过程的损耗系数和偏振态变化矩阵。分析结果对于优化模块泵浦效率、增强散热效果等有一定借鉴作用。     

一种抗侧信道攻击椭圆曲线标量乘算法的设计与实现

有限域 上点乘运算是影响椭圆曲线密码实现效率的关键运算之一。为提高椭圆曲线密码算法计算的安全性和效率性,从分析固定基点梳形算法（Fixed-base Comb算法）的特点出发,在现有的边信道攻击和标量乘算法的基础上,提出了一种新的标量乘算法——DF-Comb（Distance Fixed-base Comb）算法。新的算法对私钥（ ）重新设计编码、分组计算,在预计算阶段和赋值阶段进行改进,能够极大地提高算法计算阶段的效率;此外,考虑到算法的抗侧信道攻击能力,通过引入乘数分解技术来隐藏算法中相关侧信道信息,引入一种同时多标量乘算法用来提高了抗侧道攻击力,从而增强算法的安全性。仿真实验结果显示,改进的DF-Comb算法算法可以在提高计算效率的同时降计算的存储量。经算法实验比较分析研究,表明该算法能较好地抵抗多种侧信道攻击。     

水电站大型地下厂房特殊部位开挖支护技术研究

以我国已建和在建的大型水电站地下厂房洞室施工实践为依据,系统总结了厂房顶拱、高边墙、母线洞等特殊部位的专项施工技术,并总结出了"先中后边、先软后硬","施工分层、一次预裂"及"先洞后墙、通层加固"的技术原则。随后运用三维有限元计算软件,对相关技术的施工效果进行仿真模拟,分析施工工艺对地下洞室施工开挖和围岩破坏的影响,有效地论证了施工技术的可靠性。     

边载和水平荷载作用下超长桩承载性状数值分析

采用有限元法,建立超长桩和土体共同作用的三维数值模型,研究受边载和水平荷载共同作用下超长桩的承载特性,分析超长桩侧摩阻力和桩身弯矩的变化规律。结果表明:水平荷载与边载比值k的增大可以有效改善桩侧负摩阻力,并且存在最优比值k=4。桩侧负摩阻力和桩身弯矩随着长径比的减小而减小;存在临界边载距离s=8 m,当边载距离s<8 m时,桩身负摩阻力随着边载距离的增大而减小,当s＞8 m时,边载对桩身负摩阻力几乎无影响。桩土刚度比的减小可有效提高超长桩承载力。同时应用多元非线性回归分析,得到最小桩侧摩阻力随不同因素变化的函数关系式。根据该式可预测不同因素组合下的最小桩侧摩阻力,有效避免桩侧负摩阻力的产生。     

需求侧多负荷协调能效优化评价指标体系的建立及应用

对电力需求侧能效资源进行有效管理,能够提高多负荷终端设备能效利用效率。针对电力需求侧能效资源的特点,从能源效率、环境效率、经济效率、社会效率和投资效率五方面构建需求侧能效资源开发效益综合评价指标体系,给出各评价指标的含义和测算方法,通过算例表明其有效性,为能效资源开发综合效益评价提供指标体系。     

静压桩荷载传递与承载性状试验研究

依托某实际工程 ,在对桩-土体系荷载传递机理分析的基础上 ,研究了现场静力压桩试验和载荷试验过程中桩侧阻力的变化规律及其承载特性.结果表明 :在竖向压力作用下静压桩穿越不同的土层时 ,需同时克服土体对桩侧阻力和端阻力作用 ,不同阶段桩顶荷载作用时的端阻和侧阻的发挥性状不同 ;随着压桩荷载增加 ,桩身上部摩阻力先于下部发挥作用 ,较先进入极限状态 ,体现了其异步性 ,桩基设计时桩身中上部应适当加强 ;地基土自身的强度会随地基土水环境的变化而改变 ,对桩侧摩阻力和桩端阻力发挥影响显著 ;正常工作阶段 ,桩基大都处于弹性变形阶段 ,然而超出此范围后 ,桩基破坏大都表现为沉降或不均匀沉降.     

贮氢合金催化共轭二烯烃类聚合物双键加氢的研究

研究了共轭二烯烃类聚合物在贮氢合金氢化物存在下双键加氢的情况。结果表明AB；型贮氢合金[包括LaNi5和MINi5-x(CoMnAl)8]可催化NBR、NR、BR、SBS等共轭二烯烃聚合物双键加氢，其氢化度分别可达33．5％、31．1％、45．8％、32．3％。采用IR、^1H NMR、碘量分析法等手段对加氢产物进行了分析，表明聚合物中双键加氢的同时，NBR中的-C≡N和SBS中的苯环不受影响。此外。研究结果还表明合金组成、表面处理方式等对贮氢合金催化共轭二烯烃类聚合物双键加氢活性有影响。合金氢化物在共轭二烯烃类聚合物双键加氢过程中具有提供氢源与催化双重功能。     

Synthesis of a high‐trans 1,4‐butadiene/isoprene copolymers with supported titanium catalysts

The copolymerization of butadiene (Bd) and isoprene (Ip) with a supported titanium‐triisobutyl aluminum catalyst system was studied. An analysis using differential scanning calorimetry, X‐ray diffraction, and ¹³C‐NMR spectra indicated that products with 25–60 mol % Bd units were random copolymers and that the melting temperatures and glass‐transition temperatures (Tg) were 30–40 and ?74°C (or thereabout), respectively, which were very similar to those of natural rubber. The chemical structure of these copolymers was characterized by a high‐trans 1,4‐configuration: the trans 1,4‐content of Ip units was greater than 98%, and the trans 1,4‐content of Bd units was greater than 90%. The reactivity ratio of Bd was greater than that of Ip (r_Bd = 5.7 and r_Ip = 0.17). The sequence distribution of the monomer units of the copolymers followed a first‐order Markov statistical model. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1800–1807, 2003     

A bipyridine-containing water-soluble conjugated polymer: Highly efficient fluorescence chemosensor for convenient transition metal ion detection in aqueous solution

A novel sulfonato-functionalized water-soluble conjugated polymer (WSCP), which containing 2′2-bipyridine units as receptors for transition metal ions in the main chain was successfully synthesized by Sonogashira-coupling reaction for the first time. This polymer could easily dissolve in water (5 mg/mL) and some polar organic solvents such as methanol. Its fluorescence in aqueous solution can be completely quenched upon addition of transition metal ions. The K_sv of different transition metal ions in aqueous solution were much higher than previous reports in organic solutions and showed highest selectivity to Ni²⁺. These results opened opportunities for developing novel chemosensors by introducing selective fluorescent chromophore into the water-soluble conjugated backbone.