纳米纤维素基气凝胶的制备及其吸附性能研究进展

在可持续发展已成为全球各国共识的今天,合理且高效地研发及利用可再生生物质能源成为国内外各大课题组研究的热点及方向。而纳米纤维素作为典型的生物质可再生材料,将其应用到环境治理领域成为再好不过的选择。同时,以纳米纤维素为基体制备的气凝胶作为第三代气凝胶材料,具有高孔隙率、高比表面积、低密度、低介电常数和较高的吸附性等性能,在染料吸附、油污吸附、重金属离子吸附、CO 2气体吸附等吸附领域有着广阔的应用前景。综述了纳米纤维素的制备方法、纳米纤维素基气凝胶的制备工艺及其在吸附领域的应用,探讨了纳米纤维素基气凝胶在研发中存在的问题,展望了纳米纤维素基气凝胶在吸附领域的未来发展方向。     

纳米TiO2-ZnO复合材料的制备及其光催化性能

本文以TiO2纳米管阵列作为模板,利用溶胶-凝胶法制备ZnO@TiO2纳米复合材料,通过SEM等测试手段对其结构进行了表征,并进一步研究了该复合材料在紫外光下对亚甲基蓝溶液的光催化效率。发现ZnO@TiO2复合材料的光催化效率与模板孔深孔径有关,并且由于TiO2与ZnO间的电荷转移作用,使得纳米复合材料的光催化效率高于TiO2模板和ZnO@AAO光催化效率的线性加合。     

生物质炭/ZnO复合材料的制备及其吸附-光催化性能

以纳米晶纤维素（NCC）为形貌诱导模板,醋酸锌（Zn（CH₃COO）₂·2H₂O）为Zn源,采用原位聚合法制备NCC/ZnO纳米杂化物,再经550℃高温碳化,得到生物质炭/ZnO复合材料。采用TEM、XRD、BET、UV-Vis测试研究生物质炭与ZnO固体质量比（0.03:1、0.17:1、0.67:1）对生物质炭/ZnO复合材料形貌、晶体结构、孔结构及光吸收性能的影响。并进一步以亚甲基蓝（MB）为模型污染物,研究生物质炭/ZnO复合材料的吸附-光催化性能,阐明其吸附-光催化机制。结果表明,经550℃高温碳化后,NCC转化为具有石墨微晶结构的生物质炭,其骨架结构得以保留,纳米ZnO均匀负载在生物质炭表面,形成生物质炭/ZnO复合材料。与纯纳米ZnO相比,生物质炭/ZnO复合材料比表面积显著提高,具备优异的吸附性能,同时,NCC转化得到的生物质炭有效提高了ZnO的光生电子-空穴对的分离率。生物质炭/ZnO复合材料通过吸附-光催化协同效应去除水体中的MB,去除率显著增加。当生物质炭与ZnO的固体质量比为0.17:1时,生物质炭/ZnO复合材料的平均孔径为188.99 nm,比表面积为33.51 m2/g,在室温条件下,避光吸附30 min后,再使用500 W紫外灯照射20 min,即对MB降解率达到99.8%。      

磁控溅射制备Cu2O和Cu2O/TiO2复合膜及其光催化活性

采用直流反应磁控溅射的方法在普通玻璃上沉积得到Cu2O、TiO2和Cu2O/TiO2复合薄膜.用X射线衍射仪(XRD)、扫描电子显微镜(SEM)和X射线能谱仪(EDS)对薄膜的晶体结构、表面形态和薄膜元素组成进行了分析.XRD结果表明,当反应溅射时间为5 min时,Cu2O薄膜由单一的(111)晶面组成;反应时间的延长促进了Cu2O(110)和(220)晶面的生长.通过计算得出Cu2O(111)更有利于对O2的吸附.进一步使用氙灯作为光源,用薄膜对亚甲基蓝(MB)的降解率来表征光催化活性.结果表明,Cu2O/TiO2复合薄膜的光催化效果随着Cu2O含量的增加升高而后降低,当Cu2O含量为2.6mol%时,光催化活性最高.光催化效率的提高主要归因于Cu2O的加入引起光生电子-空穴的分离,而过量的Cu2O会延长光生电子迁移到Cu2O/TiO2界面和空穴迁移至表面所需要的时间,使电子和空穴复合的几率增大,从而降低了量子效率.     

纤维素纳米晶/聚乳酸复合材料的制备与性能

用酸解法制备了纤维素纳米晶(CNC),然后用醋酸乙烯酯和丙烯酸丁酯通过自由基聚合的方法对CNC进行包覆改性,制得改性纤维素纳米晶(m-CNC),再将m-CNC和聚乳酸(PLA)通过溶液浇注法制备复合材料。利用透射电子显微镜、红外光谱、扫描电子显微镜、广角X射线衍射、力学和降解性能测试研究了m-CNC/PLA复合材料的结构与性能。结果表明,酸解法制备的棒状CNC直径约为5 nm~26 nm,长度约为40 nm~380 nm。随着m-CNC含量的增加,m-CNC/PLA复合材料的拉伸强度呈上升趋势,当m-CNC的含量为8%时,m-CNC/PLA复合材料的拉伸强度与纯PLA的相比增加了43.3%。在PLA中加入适量的CNC或m-CNC,PLA的结晶度提高而晶粒尺寸减小。m-CNC的加入减缓了m-CNC/PLA复合材料在模拟体液中的降解速率,但加速了其在土壤中的降解。     

N掺杂TiO2陶瓷膜的制备及其光催化性能研究

采用溶胶-凝胶法制备N掺杂TiO2溶胶,用浸渍-提拉方法将溶胶涂敷在陶瓷膜表面,制备具有抗污染性能的光催化陶瓷膜。光催化与膜分离技术相结合,处理含盐直接耐酸大红4BS染料废水,考察了料液pH值、初始浓度、跨膜压差、膜面流速等因素对含盐染料废水处理效果的影响。结果表明,该复合陶瓷膜对4BS染料的截留率在99%以上,对无机盐的截留率低于1%,光催化膜分离耦合的膜通量较单一膜分离的通量提高90%。     

纳米TiO2 / 再生纤维素复合薄膜的制备及光催化性能

在1-烯丙基-3-甲基咪唑氯室温离子液体中, 将纳米TiO₂粉末与纤维素浆粕进行溶液共混, 所得纤维素用水再生后, 经过超临界CO₂干燥处理, 制备了不同TiO₂ 含量的纳米TiO₂ / 再生纤维素复合膜。通过扫描电子显微镜(SEM) 、X 射线衍射(XRD) 、傅立叶变换红外光谱( FTIR) 对所得薄膜的形貌、结构进行表征。利用PCC-2 型光催化活性检测仪测试薄膜在紫外光下光催化降解亚甲基蓝的能力, 评价薄膜的光催化活性。讨论了纳米TiO₂ 含量、超临界CO₂ 干燥和真空干燥对薄膜性能的影响。结果表明: 复合膜的光催化活性达到所用TiO₂粉体的90 %; 经超临界CO₂ 干燥处理所得复合膜的光催化活性明显高于真空干燥所得复合膜的活性; 纳米复合膜的光催化活性随TiO₂ 含量的增加先升高后降低, 含量为5 %时光催化活性最高。      

Cu2O-WO3复合物的制备及其光催化性质研究

采用室温液相还原法制备了Cu2O微米立方块和Cu2O-WO3复合物,利用XRD和FESEM对产物进行了表征。研究了太阳光照下氧化亚铜微米立方块对不同染料的光催化降解性能,结果表明合成产物对阴离子染料有较好的降解效果,对阳离子染料降解效果不明显。Cu2O-WO3复合物对阳离子染料亚甲基蓝的光催化活性明显高于纯的Cu2O,其中10%Cu2O-WO3复合物的光催化效果最好。借助荧光光谱分析了复合物提高阳离子染料亚甲基蓝的光催化效果的原因。     

纳米纤维素/聚酰亚胺气凝胶制备与性能研究

纳米纤维素气凝胶由于其良好的生物相容性、可再生性、可降解性以及较高的孔隙率等优异性能,在建筑隔热领域有着十分广阔的应用前景。为了更好地提升纳米纤维素气凝胶的保温隔热性能和力学性能,引入聚酰亚胺,制备了一种具有规则孔隙结构的复合纳米纤维素气凝胶。通过SEM、导热系数测试仪、红外成像仪等测试方法对其结构和性能进行表征。结果表明,当CNF∶PI的质量比为1∶1时,复合气凝胶的结构规则,孔径较小,在15～18μm左右,密度低至0.0413 g/cm³,压缩强度可达0.33 MPa,导热系数低至0.03159 W/(m·K),具有最优异的综合性能。     

Electrical and thermoelectric properties of Cu2Se and Cu2S

The electrical conductivity σ, Hall coefficient R_H and thermoelectric power Q of nearly stoichiometric Cu₂Se and Cu₂ S have been measured as function of temperature between 100 and 700 K. In the vivinity of phase transition temperatures, σ and Q undergo anomalous temperature dependence. A semiquantitative analysis of σ anomalies confirmes the existence of a two-phase region in Cu₂ Se for the α - to -β phase transition. The analysis also provides an evidence for the existence of a two-phase region between orthorhombic and tetragonal phases of Cu₂S.     

Synthesis and optical properties of Cu2O/SiO2 composite films via gamma-irradiation route

The Cu₂O particles or clusters dispersed mesoporous SiO₂ composite films were prepared by a new method: First the matrix SiO₂ films were prepared by sol-gel process combined with the dip-coating technique, and then they were soaked in Cu(NO₃)₂ solutions followed by γ-ray irradiation at room temperature and in ambient pressure. Thus prepared Cu₂O/SiO₂ composite films were examined by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy and optical absorption spectroscopy. Compared with the pure Cu₂O nanoparticles, an obvious blue shift existed in the obtained Cu₂O/SiO₂ composite films.     

Preparation and photoelectrochemical performance of TiO2/HS-CH2-COOH/Cu3Se2 composite film

In this paper, the TiO₂/HS-CH₂-COOH/Cu₃Se₂ composite film photoanodes were fabricated on conducting glass plates. Cu₃Se₂ nanoparticles were used as the sensitizer and the bi-functional modifier HS-CH₂-COOH was used at the interface between Cu₃Se₂ and TiO₂ films to improve the properties of the film photoanode. The characterization results show that the sol-gel prepared anatase TiO₂ film has a compact and uniform surface, while the tetragonal Cu₃Se₂ film has a coarse surface which is made up of uniform elongated particles. The photoelectrochemical experimental results indicate that the TiO₂/HS-CH₂-COOH/Cu₃Se₂ composite film photoanodes have a good photovoltaic property.     

Cu2ZnSnS4-CdS复合材料的制备及其在光催化制氢中的应用

为了进一步提高Cu₂ZnSnS₄的光催化制氢性能,首先通过水热法制备出Cu₂ZnSnS₄光催化材料,在此基础上加入Cd（CH₃COO）₂·2H₂O和Na₂S进行二次水热反应制备Cu₂ZnSnS₄-CdS复合材料。通过XRD、SEM、TEM、Raman及XPS等分析测试方法对Cu₂ZnSnS₄-CdS复合材料的物相结构、微观形貌和元素价态进行了表征。结果表明:成功制备了结晶性能较好的Cu₂ZnSnS₄-CdS复合材料。Cu₂ZnSnS₄-CdS复合材料是由球状和块状颗粒组成;Cu₂ZnSnS₄-CdS复合材料表面>95%的Cd和S原子（原子比为1:1）的存在说明块状颗粒Cu₂ZnSnS₄表面生长的球形颗粒为CdS;在氙灯下的光催化制氢性能表明,Cu₂ZnSnS₄-CdS复合材料的光催化制氢效果明显优于Cu₂ZnSnS₄和CdS,产氢效率为296.17 μmol（g·h）-1。      

聚吡咯/纳米二氧化钛的制备及电化学性能

采用化学原位聚合的方法制备了聚吡咯/二氧化钛(PPy/TiO_2)复合物,其中聚吡咯和二氧化钛的质量比分别为1∶1、2∶1、3∶1、4∶1,将其作为电化学超级电容器的电极材料,采用扫描电子显微镜和X射线衍射仪研究了PPy/TiO_2的形貌和相组成,通过电化学测试研究了PPy/TiO_2的电化学性能.结果表明:TiO_2均匀地包覆在PPy基体中,PPy/TiO_2的电化学性能明显优于纯PPy;当PPy与TiO_2的质量比为3∶1时复合材料的电化学性能最佳,即在2 A/g充放电电流密度下,其比电容达到了255.68 F/g,比纯PPy提高了2倍左右;在1 A/g充放电电流密度下,循环充放电1 000圈之后PPy/TiO_2的比电容保持率为87.2%,纯PPy的比电容保持率仅为46.9%.     

Cu2ZnSnS4纳米颗粒及其薄膜的制备与表征

采用热注入法,在油胺(OLA)中合成出Cu2ZnSnS4(CZTS)纳米颗粒,并在玻璃衬底上制备了薄膜,研究了不同合成温度对纳米颗粒生成的影响.通过X射线衍射仪、拉曼光谱仪、透射电子显微镜、扫描电子显微镜、紫外可见分光光度计对所得纳米晶材料的结构与成分、颗粒大小与形貌、光吸收谱进行了测试分析.研究结果表明:采用热注入法的最佳合成温度在260℃左右,该温度下生成的多晶CZTS纳米颗粒尺寸约10 nm,分散性良好,光学禁带宽度约1.5 eV.     

Preparation and super-hydrophilic properties of TiO2/SnO2 composite thin films

SnO₂-TiO₂ composite thin films were fabricated on soda-lime glass with sol-gel technology. By measuring the contact angle of the film surface and the degradation of methyl orange, we studied the influence of SnO₂ doping concentration, heat-treatment temperature and film thickness on the super-hydrophilicity and photocatalytic activity of the composite films. The results indicate that the doping of SnO₂ into TiO₂ can improve their hydrophilicity and photocatalytic activity, and the composite film with 1-5 mol% SnO₂ and heat-treated at 450°C is of super-hydrophilicity. The optimal SnO₂ concentration for the photocatalytic activity is 10 mol% and larger film thickness is helpful to reduce the contact angle of the composite films.     

Thermoelectric properties of Zn doped Cu2SnSe3

Zn doped ternary compounds Cu₂Zn_xSn_1−xSe₃ (x = 0, 0.025, 0.05, 0.075) were prepared by solid state synthesis. The undoped compound showed a monoclinic crystal structure as a major phase, while the doped compounds showed a cubic crystal structure confirmed by powder XRD (X-Ray Diffraction). The surface morphology and elemental composition analysis for all the samples were studied by SEM (Scanning Electron Microscopy) and EPMA (Electron Probe Micro Analyzer), respectively. SEM micrographs of the hot pressed samples showed the presence of continuous and homogeneous grains confirming sufficient densification. Elemental composition of all the samples revealed an off-stoichiometry, which was determined by EPMA. Transport properties were measured between 324 K and 773 K. The electrical resistivity decreased up to the samples with Zn content x = 0.05 in Cu₂Zn_xSn_1−xSe₃, and slightly increased in the sample Cu₂Zn_0.075Sn_0.925Se₃. This behavior is consistent with the changes in the carrier concentration confirmed by room temperature Hall coefficient data. Temperature dependent electrical resistivity of all samples showed heavily doped semiconductor behavior. All the samples exhibit positive Seebeck coefficient (S) and Hall coefficient indicating that the majority of the carriers are holes. A linear increase in Seebeck coefficient with increase in temperature indicates the degenerate semiconductor behavior. The total thermal conductivity of the doped samples increased with a higher amount of doping, due to the increase in the carrier contribution. The total and lattice thermal conductivity of all samples showed 1/T dependence, which points toward the dominance of phonon scattering at high temperatures. The maximum 1/TZT = 0.48 at 773 K was obtained for the sample Cu₂SnSe₃ due to a low thermal conductivity compared to the doped samples.     

SiO2/聚四氟乙烯复合薄膜的制备及力学性能

采用空气辅助干法共混、冷压烧结并车削成膜的方法制备了SiO₂填充量为35wt%、厚度为50 μm的聚四氟乙烯（PTFE）基复合薄膜。系统研究了SiO₂颗粒粒径对SiO₂/PTFE薄膜复合材料的孔洞缺陷和力学性能等的影响,并研究了SiO₂在PTFE中的分散情况及分子间相互作用对其性能变化的影响机制。结果表明,随SiO₂粒径的逐渐增大,其在PTFE中的分散趋于均匀,同时PTFE能更好地包覆粒子,因此SiO₂/PTFE薄膜孔洞缺陷逐渐减少,力学性能逐渐增强;当SiO₂的粒径D₅₀为12 μm时,其在PTFE中的分散均匀性最佳,SiO₂/PTFE复合薄膜孔洞缺陷最少,具有较好的力学性能,断裂伸长率达19.5%,拉伸强度达9.2 MPa。