A hydrated amorphous iron oxide nanoparticle as active water oxidation catalyst

Developing efficient water oxidation catalysts (WOCs) with earth-abundant elements still remains a challenging task for artificial photosynthesis. Iron-based WOC is a promising candidate because it is economically cheap, little toxic and environmentally friendly. In this study, we found that the catalytic water oxidation activity on amorphous iron-based oxide/hydroxide (FeO_x) can be decreased by an order of magnitude after the dehydration process at room temperature. Thermogravimetric analysis, XRD and Raman results indicated that the dehydration process of FeO_x at room temperature causes the almost completely loss of water molecule with no bulk structural changes. Based on this finding, we prepared hydrated ultrasmall (ca. 2.2 nm) FeO_x nanoparticles of amorphous feature, which turns out to be extremely active as WOC with turnover frequency (TOF) up to 9.3 s^?1 in the photocatalytic Ru(bpy)₃²⁺-Na₂S₂O₈ system. Our findings suggest that future design of active iron-based oxides as WOCs requires the consideration of their hydration status.     

无烟煤氧化制苯多羧酸

对阳泉无烟煤进行了碱－氧气氧化研究。发现反应温度、碱的用量、反应时间以及氧初压是影响和控制水溶酸产率和反应速度的重要因素。最佳氧化条件为：温度２６０℃，碱煤比３．２８：１，反应时间２ｈ，氧初压５．５ＭＰａ。在最佳氧化条件下水溶酸的产率高达６６．０％，其中６７．４％为苯多羧酸。并采用红外光谱和气相色谱对反应产物进行了定性和定量分析。     

铟(Ⅲ)-芦丁极谱络合吸附波的研究

在pH6.0的乙酸盐缓冲底液中,用单扫极谱法可获得高灵敏度的铟(Ⅲ)-芦丁的络合吸附波,其检测下限达3.0×10~(-10)mol/L。成功地用于纯金属锌中10~(-5)％铟的测定。测得吸附电活性络合物的组成为:In(Ⅲ):芦丁=1∶2,条件稳定常数为1.8×10~(10)。电极反应是吸附络合物中的In(Ⅲ)还原为In(Hg)。测得电极反应的转移系数α=0.51,表面电化学反应的标准速率常数k_s=0.43/s     

The atomic-level structure of bandgap engineered double perovskite alloys Cs2AgIn1−xFexCl6

Although lead-free halide double perovskites are considered as promising alternatives to lead halide perovskites for optoelectronic applications, state-of-the-art double perovskites are limited by their large bandgap. The doping/alloying strategy, key to bandgap engineering in traditional semiconductors, has also been employed to tune the bandgap of halide double perovskites. However, this strategy has yet to generate new double perovskites with suitable bandgaps for practical applications, partially due to the lack of fundamental understanding of how the doping/alloying affects the atomic-level structure. Here, we take the benchmark double perovskite Cs₂AgInCl₆ as an example to reveal the atomic-level structure of double perovskite alloys (DPAs) Cs₂AgIn_1−xFe_xCl₆ (x = 0–1) by employing solid-state nuclear magnetic resonance (ssNMR). The presence of paramagnetic alloying ions (e.g. Fe³⁺ in this case) in double perovskites makes it possible to investigate the nuclear relaxation times, providing a straightforward approach to understand the distribution of paramagnetic alloying ions. Our results indicate that paramagnetic Fe³⁺ replaces diamagnetic In³⁺ in the Cs₂AgInCl₆ lattice with the formation of [FeCl₆]³⁻·[AgCl₆]⁵⁻ domains, which show different sizes and distribution modes in different alloying ratios. This work provides new insights into the atomic-level structure of bandgap engineered DPAs, which is of critical significance in developing efficient optoelectronic/spintronic devices.

Through Fe³⁺-alloying, the bandgap of benchmark double perovskite Cs₂AgInCl₆ can be tuned from 2.8 eV to 1.6 eV. The atomic-level structure of Cs₂AgIn_1−xFe_xCl₆ was revealed by solid-state nuclear magnetic resonance (ssNMR).     

太阳能光催化分解水制氢※

利用太阳能光催化分解水制氢是解决能源环境问题并实现太阳能有效转化和储存最有前途的技术之一, 这一“圣杯”式反应经过几十年不懈努力取得了诸多重要研究进展. 本文将综述光催化分解水制氢体系的基本概念、活性测试方法与注意事项、光催化材料种类等; 并从光催化分解水制氢的光吸收、光生电荷分离和表面催化反应等基本过程和关键科学问题的角度总结其重要研究进展, 最后对于太阳能光催化分解水制氢的挑战和潜在的发展方向进行分析和展望. 希望通过本综述的简要介绍能让刚从事光催化分解水制氢研究的青年科技人员清晰地了解掌握该领域的一些基本概念、操作规范、研究总体进展和现状等.     

Combining renewable gum rosin and lignin: Towards hydrophobic polymer composites by controlled polymerization

Rosin polymer–grafted lignin composites were prepared via “grafting from” atom transfer radical polymerization (ATRP) with the aid of 2‐bromoisobutyryl ester‐modified lignin as macroinitiators. Three different monomers derived from dehydroabietic acid (DA) were used for execution of grafting from ATRP, while DA was separately attached onto lignin by a simple esterification reaction. Kinetic studies indicated controlled and “living” characteristics of all monomer polymerizations. Thermal studies indicated that rosin polymer–grafted lignin composites exhibited glass transition temperatures in a broad temperature range from ～20 to 100°C. The grafting of both DA and rosin polymers significantly enhanced hydrophobicity of lignin. Static contact angle measurement of water droplets showed ～90° for all these rosin modified lignin composites. X‐ray photoelectron spectroscopy demonstrated that the surface of rosin–lignin composites was dominated with chemical compositions originating from the hydrocarbon rich rosin moiety. The impartation of hydrophobicity of rosin into lignin provided excellent water resistance of this class of renewable polymers, as all rosin‐modified lignin composites showed water uptake below 1.0 wt %. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Well Crystallized α-GaOOH Nanocrystals Synthesized through Hydrothermal Routes and Their Properties

A facile hydrothermal process involving Ga(NO₃)₃·H₂O·NaN₃ solutions led to the formation of α‐GaOOH nano‐platelets. X‐ray diffraction (XRD) pattern revealed that the synthesized samples belonged to an orthorhombic crystal structure with lattice constants a=0.4510 nm, b=0.9750 nm and c=0.2965 nm. Transmission electron microscopy (TEM) studies showed that α‐GaOOH displayed the morphologies of an eccentric platelet‐like structure with 60–120 and 200–300 nm in the short and long axes, respectively. The average thickness of products was about 70 nm through scanning electron microscopy (SEM) images. The ultraviolet absorption of the samples was at 214 nm. The prepared α‐GaOOH nano‐platelets exhibited a broad emission band from 220 to 400 nm with a maximum at 343 nm under short UV excitation of 200 nm. Fourier transform infrared (FTIR) spectrum confirmed the existence of Ga₂O and Ga–OH bending modes. A possible mechanism for the formation of α‐GaOOH nano‐platelets was discussed briefly.     

Br?nsted酸性离子液体催化缩醛化反应合成聚甲氧基二烷基醚

聚甲氧基二烷基醚(RO(CH2O)nR)具有高的十六烷值(CN)和含氧量,能显著改善柴油的燃烧特性,有效提高热效率,大幅减少碳烟和NOx排放,被认为是一种优良的环保型燃油组分.随着–R基碳链的增长,CN值、热值和闪点逐渐增大,密度和冷凝点逐渐降低.同时,该类化合物具有优异的溶解及渗透性能,能与许多有机溶剂互溶,低毒,可以用作溶剂或颜料分散剂.近年来,聚甲氧基二甲基醚(CH3O(CH2O)nCH3,PODEn,DMMn)的制备及应用研究受到广泛关注,而对封端基团(–R)碳数大于1的多醚类化合物的研究鲜有文献报道.本文以Br?nsted酸性离子液体为催化剂,对甲醛和二乙氧基甲烷或脂肪醇(碳数 ≥2)缩醛化反应制备聚甲氧基二烷基醚的反应性能进行了研究,考察了离子液体结构和酸性对其催化性能的影响.结果表明,–SO3H功能化的离子液体[MIMBs]HSO4在催化三聚甲醛与二乙氧基甲烷的缩醛化反应中表现出最好的催化活性.考察了催化剂用量、原料配比、反应温度、反应压力和反应时间等因素对反应性能的影响,并得到了最佳反应条件,在n([MIMBs]HSO4):n(DEM1):n(HCHO)=1:80:80,140°C下反应4 h,甲醛转化率达到了92.6%,DEM2–8选择性为95.1%.考察了不同甲醛源(三聚甲醛和多聚甲醛)与提供封端基团化合物(二乙氧基甲烷、乙醇、丙醇和丁醇)的缩醛化反应.结果发现,在反应过程中不生成水或不引入水的条件下,具有更高的反应转化率和产物选择性.分别采用静置分层和萃取实现了催化剂的分离与重复使用.推测反应机理认为,三聚甲醛首先在氢键作用下分解生成甲醛单体,甲醛和二乙氧基甲烷通过碳正离子反应机理实现了DEMn的链增长.     

多化学组份反应气体流动的Godunov格式

本文将单介质气体流动的Goduoov方法推广到多化学组份气体流动的计算中,建立了多化学组份气体的间断分解公式以及任意四边形网格下的Godunov方法的差分格式,提出了处理自由边界的虚相法,应用第二类网格,计算了超音速射流及其冲击问题的几个算例,并且同实验结果进行了比较。     

Interface Engineering of a CoOx/Ta3N5 Photocatalyst for Unprecedented Water Oxidation Performance under Visible‐Light‐Irradiation

Cocatalysts have been extensively used to promote water oxidation efficiency in solar‐to‐chemical energy conversion, but the influence of interface compatibility between semiconductor and cocatalyst has been rarely addressed. Here we demonstrate a feasible strategy of interface wettability modification to enhance water oxidation efficiency of the state‐of‐the‐art CoO_x/Ta₃N₅ system. When the hydrophobic feature of a Ta₃N₅ semiconductor was modulated to a hydrophilic one by in situ or ex situ surface coating with a magnesia nanolayer (2–5 nm), the interfacial contact between the hydrophilic CoO_x cocatalyst and the modified hydrophilic Ta₃N₅ semiconductor was greatly improved. Consequently, the visible‐light‐driven photocatalytic oxygen evolution rate of the resulting CoO_x/MgO(in)–Ta₃N₅ photocatalyst is ca. 23 times that of the pristine Ta₃N₅ sample, with a new record (11.3 %) of apparent quantum efficiency (AQE) under 500–600 nm illumination.