多层次二氧化硅材料的仿生矿化研究进展

系统地介绍了仿生合成二氧化硅(SiO2)材料的研究进展,综述了仿生合成SiO2材料的模板分子特点及体外模拟方法,阐述了阴离子的存在、浓度、种类以及人工合成模板基质的不同类型对SiO2的尺寸和形貌的影响,并提出了新的实验思路,即设计合成具有催化活性的稳定的聚氨基酸多肽,在温和条件下,利用这种聚氨基酸多肽作为模板矿化SiO2材料,从而设计合成出具有特殊结构和性能的无机SiO2材料,并将此仿生材料应用到生物催化、药物载体等各个领域。     

Fe~(3+)诱导全氟羧酸的光化学降解:pH值及链长的影响

以全氟辛酸(PFOA)为代表的全氟化合物是环境水体中新出现的一类持久性有机污染物,Fe3+的存在促进了其在254 nm紫外光下的有效降解.在此基础上,主要考察了溶液初始pH值对Fe3+诱导PFOA光化学降解的影响,并以全氟丁酸(PFBA)、全氟戊酸(PFPeA)、全氟己酸(PFHxA)和全氟庚酸(PFHpA)为对象,研究了Fe3+诱导短链全氟羧酸(PFCAs)的降解,通过对降解中间产物的分析,进而推断了其降解机理.结果表明,强酸性条件有利于PFOA的降解,弱酸性或中性反应条件下,PFOA的降解和脱氟均受到明显地抑制,进一步证实PFOA的降解主要是溶解性铁作用的结果,此时Fe(OH)2+则是铁(III)-羟基配合物的主要分配形态.Fe3+诱导PFCAs的降解表明:当碳原子数大于5,长链的PFCAs更易于降解,但对于碳原子数小于6的PFCAs,其降解没有明显的规律.降解中间产物主要是链更短的PFCAs,由此推断,PFCAs的降解遵循逐级降解的规律.     

部分还原二氧化钛的NMR和EPR研究

Partially reduced TiO₂ nanomaterials have attracted significant interest because of their visible-light activity for catalysis and photodegradation. Herein, we prepared a partially reduced anatase TiO₂ (Re-A-TiO₂) nanoparticle material using a fast combustion method, demonstrating good activity toward decomposing methyl orange under visible light irradiation. The surface structure of the prepared material, after being surface-selectively ¹⁷O-labeled with H₂¹⁷O (¹⁷O-enriched water), was studied via ¹⁷O and ¹H solid-state magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy and electron paramagnetic resonance (EPR) spectroscopy, and the obtained results were compared to those of non-reduced anatase TiO₂ (A-TiO₂). The EPR results showed that the concentrations of paramagnetic species (i.e., oxygen vacancies (OV) and Ti³⁺) in Re-A-TiO₂ were much higher than that in A-TiO₂, while the former was associated with a higher OV/Ti³⁺ ratio. The intensities of the EPR signals were significantly affected by the adsorbed water, and this phenomenon was explored in combination with ¹H NMR spectroscopy. The ¹H species on Re-A-TiO₂ appeared at larger chemical shifts, denoting the increased acidity of the sample, and these ¹H species on Re-A-TiO₂ were more difficult to remove than those on A-TiO₂. On the other hand, different features were observed for the signals arising from the two-coordinated oxygen atoms (μ₂-O) in ¹⁷O NMR, suggesting a typical anatase TiO₂(101) surface on A-TiO₂, but a more complex surface environment for Re-A-TiO₂. Furthermore, a larger amount of hydroxyl groups (OH) were observed on Re-A-TiO₂ compared to that on A-TiO₂, indicating a larger proportion of exposed (001) facets on Re-A-TiO₂. However, the μ₂-O signals broadened and became similar when the drying temperature was increased to 100 ℃, indicating a non-faceted anatase TiO₂ surface in such conditions. Based on the EPR and NMR results, a significant fraction of the OH species is believed to be formed from the reaction of the paramagnetic centers and adsorbed water molecules. The ¹H→¹⁷O cross polarization (CP) MAS and two-dimensional heteronuclear correlation (2D HETCOR) NMR spectra were used to verify the spatial proximity of the hydrogen and oxygen species, confirming the spectral assignments of a strongly adsorbed water and one type of surface OH species. In particular, the ¹H NMR signals at approximately 11 ppm were ascribed to the hydrogen species in the intramolecular hydrogen bond. In summary, this study investigated the paramagnetic species and surface structure of anatase TiO₂ materials by combining EPR along with ¹H and ¹⁷O solid-state NMR spectroscopy. The differences in the surface structures of Re-A-TiO₂ and A-TiO₂ should be closely related to their different properties toward the photodegradation of methyl orange.     

Triton X-100/正戊醇/环己烷微乳液条件下BiOBr制备及其光催化性能

以TritonX-100为表面活性剂,正戊醇为助表面活性剂,环己烷为连续油相,0.20mol/LBi(NO3)3·5H2O(NaBr)为水相,在环己烷/Triton X-100/正戊醇/水相(体积比20:6:4:6)的微乳液介质条件下制备BiOBr(BiOBr-m)光催化剂.运用X射线衍射(XRD)、扫描电子显微镜(S...     

聚乙撑二氧噻吩阳极降解的研究

研究了聚乙撑二氧噻吩(PEDOT)膜在水溶液中的阳极降解过程. 研究发现PEDOT的阳极过程可以分为p掺杂区[电位范围－0.3～0.5 V (相对于饱和甘汞电极; vs. SCE)]、过渡区[电位范围0.6～1 V (vs. SCE)]、过氧化区[电位范围1.2～1.6 V (vs. SCE)]三个电位区域. 用电化学阻抗谱法、循环伏安法、红外光谱技术、膜电阻测量以及电子自旋共振技术分别研究了PEDOT膜在这三个电位区域的行为. 结果表明: PEDOT膜在这三个电位区域的性质有明显不同. 在p掺杂区PEDOT膜的官能团、共轭结构、导电性均保持, 即在这个电位区发生可逆的掺杂/脱掺杂反应, 膜几乎不降解. 在过渡区和过氧化区, PEDOT膜均发生了降解. 与传统的导电聚合物在高电位的阳极降解的过氧化过程不同, 我们认为膜在较高电位(过渡区)发生一个驰豫过程, 该过程使得膜的官能团改变, 但是膜的共轭结构和导电性均保持; 而在更高的电位区(过氧化区)膜的降解和一般意义的过氧化降解相同, 此时膜的官能团、共轭结构、导电性均发生不可逆的破坏.     

维生素C溶液有氧降解动力学

建立了一种恒温高压氧药物稳定性加速试验方法, 用这种方法可在较短的时间内求得药物氧化反应的动力学参数. 以10%维生素C溶液为例, 维生素C在有氧和无氧条件下均可降解, 总的降解速率常数k_t由两部分构成: k_t＝k_an＋k_ae, k_an为无氧降解速率常数, 可表达为k_an＝A_an•exp(－E_a,an /RT); k_ae为有氧降解速率常数, 可表达为k_ae＝A_ae•exp(－E_a,ae/ RT)• .     

阴离子交换固相萃取-气相色谱/质谱法分析人血浆中6种神经性毒剂降解产物

采用醋酸汞去除蛋白,实现了阴离子交换固相萃取-气相色谱/质谱法同时测定人血浆中6种神经性毒剂降解产物的三甲基硅烷衍生物。考察了不同溶剂的去蛋白效率和不同固相萃取柱对毒剂降解产物的保留行为,优化了阴离子交换树脂的洗脱条件。采用选择离子监测方式,6种降解产物在0.05~5.0 mg/L范围内呈良好的线性关系,最低检出限在22μg/L以内;RSD均小于9.7%。该方法检测灵敏度高,血浆样品干扰小,是一种理想的血浆中神经性毒剂降解产物的检测方法。     

壳聚糖混合膜酶降解的FTIR分析

生物可降解性是壳聚糖的重要性质之一,但利用傅里叶变换红外光谱(FTIR)研究降解过程中壳聚糖的变化则较少。文章制备了由高脱乙酰度壳聚糖(HDC)和中脱乙酰度壳聚糖(MDC)组成的混合膜。运用FTIR分析了壳聚糖混合膜组分变化对其红外谱图和脱乙酰度(DD)的影响,并研究了该混合膜在溶菌酶的降解作用下红外谱图和脱乙酰度的变化。发现壳聚糖混合膜材料的脱乙酰度与膜中MDC组分的比例呈线性关系;随降解的进行,混合膜的脱乙酰度增加。结果证实了溶菌酶对较低脱乙酰度壳聚糖的选择性降解作用,而且表明FTIR可用于分析壳聚糖混合膜降解过程中的化学变化。     

光助Fenton试剂氧化降解染料直接耐晒黑G的研究

文章研究了影响Fenton试剂氧化降解持久性有机污染物直接耐晒黑G的因素,如光源的选择、初始pH值、H₂O₂的用量、Fe2+的用量、阳离子交换树脂载体的引入等,通过研究确定了各因素的优化条件。研究结果表明：太阳光照能有效的促进直接耐晒黑G染料的降解脱色,大大缩短反应时间;引入阳离子交换树脂后,可增强Fenton氧化反应的活性,降解效果更好。