Chemical characterization and ultrastructure study of pulp fibers

Understanding the ultrastructure and chemical characterization of pulp fibers is highly important in utilizing wood as a raw material in a wide scope of applications, such as forest biomass-based biorefineries and low-cost renewable materials. The observation of the ultrastructure is not possible without advanced microscopy and spectroscopy techniques. Therefore, this study focuses on exploring the ultrastructure of pulp fibers with helium ion microscopy (HIM) and scanning electron microscopy (SEM). For the analysis of chemical characterization in the pulp fibers, Raman spectroscopy, Fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS) were performed. For these studies, the pulp fiber samples were obtained mainly from three different wood species, i.e. spruce, birch and eucalyptus. They were received in the never dried state and dried with a critical point drier (CPD) to minimize pore collapse. The spectroscopy results showed a strong signal from crystalline cellulose and confirmed the absence of lignin after Kraft pulping and bleaching. However, with XPS about 2% of lignin was detected in eucalyptus pulp. The results obtained with the microscopy techniques are compared and indicating the nanofibril size, shape, surface roughness as well as their orientation in pulp fibers. To our knowledge, this is the first time that HIM is applied to study the ultrastructure of pulp fibers and compared against more conventional microscopy and spectroscopy techniques. The main differences between HIM and SEM were found to be related to the focusing and magnification. The individual nano- and microfibrils as well as their bundles were more easily visible with HIM than with SEM. Also, with HIM it was possible to get the total area in focus at once which was not the case with SEM. The increased understanding of the ultrastructure and chemical composition of wood pulp enhance the development of novel wood-based products and processes for their manufacture.     

Effective removal of cation dyes from aqueous solution using robust cellulose sponge

Cellulose sponge was proposed to an attractive bio-absorbent owing to its highly efficient, low-cost, biodegradable, and renewable sourcing. In this work, the wasted cotton linter as raw materials, the highly porous and lightweight cellulose sponges were synthesized via a facile chemical crosslinking and freeze-drying process. The resultant cellulose sponge (CA) exhibited an interconnected three-dimensional porous structure through crosslinked with N,N′-methylene bisacrylamide (MBA), which was beneficial to remove organic dyestuffs. The effects of various factors including solution pH, contact time, initial dye concentration, and ionic strength on the adsorption behavior were investigated in detail. Herein, Langmuir isotherm models were selected to determine the adsorption capacity, and the maximum theoretical adsorption capacity for Methylene blue (MB) and Crystal violet (CV) was 123.46 and 76.63 mg/g, respectively. Particularly, the results of kinetic and thermodynamic tests showed that the adsorption performance was a spontaneous endothermic reaction and the adsorption process followed the pseudo-second-order kinetic. Furthermore, cellulose sponges could maintain maximum adsorption capacity even after twelve cycles. Therefore, the eco-friendly cellulose sponge would be a promising adsorbent for effective wastewater treatment.     

Removal of multi-metals from water using reusable pectin/cellulose microfibers composite beads

Pectin (Pec) and cellulose microfibers (CF) extracted from orange waste were combined to form composite beads with enhanced adsorption capacity. Such beads were extensively tested in the removal of multi-metal ions from water. A factorial design approach was conducted to establish the optimum conditions for adsorption of Cd(II), Cu(II), and Fe(II) on Pec-CF beads. Batch adsorption experiments revealed that removal efficiency of such metal ions falls in the range of 94–58% and it followed the order Fe(II) > Cu(II) > Cd(II). The maximum Cd(II), Cu(II) and Fe(II) adsorption capacities calculated from the Langmuir isotherm were 192.3, 88.5 and 98.0 mg/g, respectively. FTIR analysis suggests that the functional groups on Pec-CF beads (binding sites) favor the adsorption of such metal ions. Desorption and reuse experiments demonstrated the beads could be used for at least five consecutive adsorption/desorption cycles. Our finds suggest the Pec-CF beads can serve as an efficient adsorbent for the removal of multi-metal ions from wastewater.     

Chiralcel OD-RH手性柱拆分卡维地洛对映体

采用Ch iralcelOD-RH(纤维素3,5-二甲基苯基氨基甲酸酯)手性固定相高效液相色谱法研究了乙腈-高氯酸钠缓冲盐体系对卡维地洛的手性拆分情况,讨论了流动相的各个因素(有机相的种类和比例、缓冲盐浓度、酸度等)对手性拆分的影响。在乙腈-高氯酸钠缓冲盐(pH 5.5,50 mmol/L)的体积比为35∶65的色谱条件下,卡维地洛对映体获得了基线分离。     

高温高压下氧化锌纳米晶的晶粒演化动力学

用GS-1B型六面顶压机研究了ZnO纳米晶高温高压下的晶粒演化动力学, 用MDI/JADE5 X射线衍射仪(Cu靶)和XL30S-FEG场发射扫描电子显微镜对高压样品的相组成、晶粒尺寸及微观形貌进行了表征. 实验发现300 ℃(包括300 ℃)以下, ZnO纳米材料中晶粒生长速率随着压力的升高先增大后减小, 1～3 GPa烧结体晶粒尺寸随着压力的升高而增大, 4～6 GPa烧结体晶粒尺寸随着压力的升高而减小. 利用高压下晶粒生长速率方程求出1～3 GPa, 4～6 GPa的激活体积分别为－5.82, 9.66 cm³/mol. 400 ℃(包括400 ℃)以上, 1～6 GPa烧结体的晶粒尺寸随着压力的升高而不断增大.     

富含纤维素类农作物秆与丙烯酸接枝共聚制备高倍率吸水树脂

用棉花秆、麦秆和玉米秆等富含纤维素类农作物秆与丙烯酸接枝共聚制备了高倍率的吸水树脂. 研究了不同水质(去离子水、自来水及雨水)对接枝产物吸水性能的影响. 采用棉花秆、麦秆、玉米秆与丙烯酸的接枝产物对去离子水的吸水倍率分别为930, 790和630 g/g, 对自来水的吸水倍率分别为670, 350和250 g/g, 用玉米秆/地瓜淀粉混合物制备的接枝产物对雨水的吸水倍率为540 g/g. 为棉花秆、 麦秆及玉米秆等富含纤维素的农作物秆的深加工与应用开辟了一条途径.     

纤维素纳米晶体手性复合材料:结构色的调控与应用

结构色在自然界中扮演了重要的角色,在昆虫外骨骼、鸟类羽毛以及植物果实中广泛分布.纤维素纳米晶体(CNCs)的水悬浮液达到一定浓度时会自组装形成左旋的手性向列液晶结构,这种手性向列结构在水分挥发后仍能保持并形成光子晶体虹彩薄膜,具有极强的手性和光子晶体的双重性质.膜内的周期性层状结构与光线产生干涉、衍射作用,表现出复杂的...     

温敏性纤维素/聚Ν-异丙基丙烯酰胺复合水凝胶的固体核磁共振表征及动力学研究

利用半互穿网络方法将具有温度响应的高分子聚N-异丙基丙烯酰胺( PNIPAM)与天然纤维素复合得到温敏性水凝胶。通过固体核磁共振的1 H,13 C CP/MAS(交叉极化/魔角旋转)和QCP(定量交叉极化)等实验手段对复合凝胶的结构进行了定性及定量研究,并利用固体静态变温核磁共振实验和偶极滤波-自旋扩散实验研究了复合凝胶中PNIPAM分子链段的动力学行为。     

多孔炭材料在纤维素催化转化中的应用

生物质作为自然界唯一可再生的有机碳资源,其利用受到了越来越多的关注。特别是随着能源和环境危机的日益加重,将生物质中非可食用部分催化转化为燃料及具有高附加值的化学品被认为是高效、环保、原子经济的绿色过程。同时,多孔炭材料具有丰富的孔道结构、优异的水热稳定性和大比表面积,是生物质催化转化反应中最常用的载体材料之一。兼之炭材料表面极性、亲疏水性的可调变性,及对酸碱溶剂的反应惰性,也使其无论在学术研究还是在工业应用中都具有特殊的优势。另外,随着纳米炭材料科学的飞速发展,合成孔径、形貌、及表面官能团可控的介孔炭和具有多级孔道结构的多孔炭材料成为可能,将其应用到纤维素催化转化过程中,对深入理解孔道结构、表面官能团对纤维素转化的作用,揭示催化反应作用机制,指导炭基催化剂的设计合成,均具有重要意义。在本综述中,我们首先对纤维素转化中多孔炭的孔道结构和表面官能团性质的独特作用进行了阐述。由于商业活性炭的孔径一般在微孔尺度,但纤维素及可溶低聚糖的分子体积较大,因而其在活性炭中的传质受到了极大的限制。通过模板法获得的介孔炭材料,可实现孔径在2–10 nm的可控合成,大大提高了反应物的扩散速率,使之能与催化活性位有效接触。但孔道过于狭长,在反应过程中堵塞的可能性增高,进而导致催化剂失活;因此,在介孔孔道的基础上,建立互通的多级孔道结构对反应物、中间物、和产物的扩散,及催化活性的保持更为有利。另一方面,炭材料表面的含氧官能团不仅具有加强1,4-糖苷键吸附的作用,还可以作为酸性活性中心催化水解反应的进行;尤其是在传统的水相纤维素催化转化过程中,亲水表面对多孔炭催化剂与反应物的接触非常有利。本文以纤维素水解及纤维素水解加氢反应为例,展开讨论了多孔炭作为固体酸及双功能催化剂载体的应用。在水解反应中,纤维素首先在热水中降解为可溶低聚糖,之后再与活性炭表面官能团反应;其中多孔炭的比表面积、酸量、及酸强度均是促进水解发生的正向因素。在水解加氢反应中,炭载贵金属催化剂作为最常用的加氢催化剂,可获得以六元醇为主的纤维素转化产物。除了加氢作用之外,贵金属小颗粒被证实可以通过氢溢流作用提供水解所需的H+,同时,正价的贵金属也可促进反应过程中的氢转移。另一方面,由于钨物种可催化逆羟醛缩合反应的发生,因此在反应体系中引入钨物种时,水解加氢的主要产物由六元醇变为乙二醇。需要特别指出的是,在纤维素催化水解加氢的过程中,多孔炭材料作为载体同样具有非常重要的作用：一方面,三维介孔的孔道结构不仅有利于反应物、产物的扩散,也有利于加氢金属催化剂的分散,进而提高金属的催化加氢能力;另一方面,当炭材料的表面化学性质改变时,也会影响产物的选择性分布,例如当炭表面显碱性时,由于异构化作用,丙二醇成为主要产物。本文最后,我们列举了一些新型多孔炭材料,包括杂原子改性的多孔炭材料和金属氧化物-炭复合多孔材料的合成方法及其在纤维素催化转化乃至生物质转化中的潜在应用。     

Chiral separation abilities of homogeneously synthesized cellulose 3,5-dimethylphenylcarbamates: Influences of degree of substitution and molecular weight

A series of cellulose 3,5-dimethylphenylcarbamates(CDMPCs) with different degrees of substitution(DS) and degrees of polymerization(DP) were homogeneously synthesized in 1-allyl-3-methylimidazolium chloride(Amim Cl). Then, the CDMPCs were coated on silica gel and used as chiral stationary phases(CSPs), and their chiral recognition abilities for seven racemates were evaluated by high performance liquid chromatography. The results showed that DS and DP of CDMPCs had a great influence on chiral recognition abilities of the CSPs. The CSPs with the DS ≈ 1 gives a low chiral recognition to most racemates. On the contrast, the CSPs with the DS ? 2 exhibited high chiral separation abilities. For example, six racemates could be separated on the CSP with CDMPC of DS ≈ 2(CSP-2). Especially, for the enantioseparation of 1-(2-naphthyl) ethanol and Tr?ger's base, CSP-2 gave the highest separation ability in all of CSPs. On the other hand, when the DP of cellulose was in a range from 39 to 220, the chiral separation abilities of CDMPCs increased as the DP increased. This work demonstrates that the structure of cellulose esters such as DS and DP has important effect on their chiral separation ability, and therefore provides a practical method to design and prepare desirable CSPs for different racemates.