单分散掺硫碳微球的水热制备及其表征

以可溶性淀粉为碳源,采用硫辅助水热碳化法一步制备了平均粒径约为4 μm的单分散掺硫碳微球。利用扫描电镜、透射电镜、X射线衍射、氮气吸脱附、傅里叶变换红外光谱、X射线光电子能谱、固体核磁共振等手段对掺硫碳微球的结构和性质进行了表征。硫辅助水热碳化法可以在高浓度条件下高产量地制备分散性良好的掺硫碳微球,更重要的是硫原子可以同步进入碳的网络结构中。与传统水热碳化法相比,采用硫辅助水热碳化法制备的掺硫碳微球具有更高的比表面积,其可能的原因是硫原子的引入产生了大量的化学与结构缺陷:-S-S-、-S-、-SO₂-和-SO-等基团构成化学缺陷,而噻吩等五元环取代石墨六元环形成结构缺陷。     

单分散掺硫碳微球的水热制备及其表征

以可溶性淀粉为碳源,采用硫辅助水热碳化法一步制备了平均粒径约为4μm的单分散掺硫碳微球。利用扫描电镜、透射电镜、X射线衍射、氮气吸脱附、傅里叶变换红外光谱、X射线光电子能谱、固体核磁共振等手段对掺硫碳微球的结构和性质进行了表征。硫辅助水热碳化法可以在高浓度条件下高产量地制备分散性良好的掺硫碳微球,更重要的是硫原子可以同步进入碳的网络结构中。与传统水热碳化法相比,采用硫辅助水热碳化法制备的掺硫碳微球具有更高的比表面积,其可能的原因是硫原子的引入产生了大量的化学与结构缺陷:-S-S-、-S-、-SO2-和-SO-等基团构成化学缺陷,而噻吩等五元环取代石墨六元环形成结构缺陷。     

磁性碳基磺酸化固体酸催化剂的制备及其催化水解纤维素

以纤维素和硝酸铁为原料,发烟硫酸为磺酸化试剂,采用热解法合成了磁性碳基磺酸化固体酸催化剂(Fe/C-SO3H).利用扫描电镜(SEM)、透射电镜(TEM)、X射线衍射(XRD)、X射线光电子能谱(XPS)、傅里叶变换红外(FT-IR)光谱仪和振动样品磁强计(VSM)等手段对催化剂进行了表征,评价了催化剂在纤维素水解反应中的催化活性.结果表明,Fe是以γ-Fe2O3的形式存在于碳本体中,催化剂呈现超顺磁性.对于纤维素的水解反应,在优化条件下,纤维素的转化率可达40.6%.此外,催化剂可稳定分散于反应体系中,并在外加磁场作用下可快速与反应体系分离.但催化剂重复使用时催化活性有所下降,其失活原因经初步认定是由于表面部分磺酸基团在反应过程中脱落.     

纤维素水解研究进展

近年来纤维素的有效降解和转化问题已成为制约木质纤维素生物质有效利用的主要瓶颈之一。纤维素降解和转化方法的研究已成为当今科技界的一大研究热点,它对解决当前的资源、能源和环境问题都具有重要意义。将纤维素水解为葡萄糖等糖类物质是纤维素利用的重要途径。本文详细综述了目前有关纤维素水解的各种方法和相关研究进展。     

煤化程度对煤基固体酸结构及其水解纤维素性能的影响

利用煤具有缩合芳环、脂肪侧链及含氧官能团的结构特点,采用不同煤化程度的煤为碳源,在不同炭化温度下制备了煤基固体酸催化剂（CSA）。通过XRD、FT-IR、¹³C NMR对催化剂结构进行了表征。以还原糖和葡萄糖的产率为考察指标,探讨了煤化程度和炭化温度对煤基固体酸非均相催化水解纤维素的影响。结果表明,煤作为碳源具有传统碳源所不具备的结构优势,煤基固体酸碳层片上除含有磺酸基、酚羟基和羧基外,还含有传统碳基固体酸不具备的桥键（-O-、-CH₂-）和侧链（-CH₃、-OCH₃、-CH₂CH₃）。除磺酸基外,其余均由煤的结构演化而来。随着炭化温度的升高,催化剂的芳香度增大、活性基团的种类和数量减少、磺酸基密度逐渐下降,且随着煤化程度增加,煤基固体酸结构可调性降低,所需要的最佳炭化温度也逐渐降低。不同种类的煤基固体酸在水解纤维素过程中表现出了较高的活性,其中,霍林河煤基固体酸的活性最高。水解活性受催化剂芳香片层大小及堆叠高度、片层之间桥键和磺酸基密度等因素的影响,是众多活性基团协同作用的结果。     

秸秆纤维素的一步快速提取和水解

研究了秸秆纤维素的一步快速提取方法, 在醋酸和硝酸溶液体系中, 选择10种不同的反应条件, 进行了提取条件优选, 然后对提取的纤维素样品分别进行了水解. 结果发现, 纤维素提取的最佳条件为120 ℃, 固液比为1∶25, 在体积分数为80%的醋酸和10%的硝酸混合溶液中反应20 min, 纤维素的产率为38%. 纤维素样品的水解实验发现, 在最佳条件下提取样品的葡萄糖含量都大于90%, 水解率达到94%. 13C NMR和FTIR分析结果表明, 纤维素的分子结构未被破坏, 但纤维素Ⅰβ含量较高, 木质素和半纤维素的去除率都很高, 表明此方法是比较理想的制备高纯度纤维素的方法.     

微波辅助的金属氯化物Lewis酸催化纤维素水解

研究了微波辐射下四种金属氯化物Lewis酸的催化纤维素酸水解反应性能,发现CuCl₂的催化性能最好。反应温度、反应时间、微波功率、催化剂用量和酸种类对纤维素水解转化率、葡萄糖和5-羟甲基糠醛(5-HMF)的选择性均有明显影响。与传统热反应相比,微波辐射明显加快纤维素酸水解速率,提高葡萄糖的选择性。0.5g纤维素和15g水,在微波功率800W,温度到达225℃时立即停止反应的条件下,当CuCl₂用量为0.05mmol时,纤维素转化率和葡萄糖选择性达72.6%和62.3%;当CuCl₂用量为0.15mmol时,5-HMF的选择性最高为13.2%;当CuCl₂用量为0.30mmol时,纤维素的转化率高达90.6%,但葡萄糖选择性只有6.7%。     

固体酸催化合成马来酸二丁醋

制备了固体酸催化剂Zr(SO4) 2/SiO2,并用于合成马来酸二丁醋,考察了Zr(SO4)2负载量、焙烧温度、焙烧时间等催化剂制备条件对催化活性的影响.采用FTIR、XRD、TG等方法对催化剂进行了表征分析.通过正交实验设计优化了固体酸Zr ( SO4)2/SiO2催化合成马来酸二丁醋的工艺条件.实验结果表明,Zr(...     

固体酸催化合成马来酸二丁酯

制备了固体酸催化剂Zr(SO4)2/SiO2,并用于合成马来酸二丁酯,考察了Zr(SO4)2负载量、焙烧温度、焙烧时间等催化剂制备条件对催化活性的影响。采用FTIR、XRD、TG等方法对催化剂进行了表征分析。通过正交实验设计优化了固体酸Zr(SO4)2/SiO2催化合成马来酸二丁酯的工艺条件。实验结果表明,Zr(SO4)2/SiO2是合成马来酸二丁酯的良好催化剂,适宜的催化剂制备条件为:硫酸锆负载量57%,焙烧温度400℃,焙烧时间2 h。适宜的催化合成反应条件为:酐醇物质的量比为1∶2.5,催化剂用量为马来酸酐质量的6%,带水剂甲苯8 mL,反应时间2.0 h。在此条件下马来酸二丁酯的酯化率为98.5%。     

负载1-丁基-3-甲基咪唑氯的固体炭磺酸催化水解纤维素

纤维素作为可再生资源,其催化水解得到的平台化合物对缓解能源压力具有重要的意义。 本文以生物质竹子为原料选择700 ℃预碳化、150 ℃磺化得到的固体炭磺酸为基体,负载1-丁基-3-甲基咪唑氯后得到离子液体功能化固体炭磺酸催化剂。 结果表明,催化剂最优条件下水解纤维素得到的总还原糖产率相对于固体炭磺酸提升了15.2%,循环使用后,依然表现出良好的催化性能。     

High-yield Carbonization of Cellulose by Sulfuric Acid Impregnation

The carbonization of cellulose with sulfuric acid impregnation was studied by thermogravimetric analysis and scanning electron microscopy. The mass yield of carbon after 800°C treatment in nitrogen increased to 2–3 times by addition of small amounts of sulfuric acid. The sulfuric acid is considered to work as dehydration catalyst, thus suppressing the release of volatile organic substances. The shrinkage of the sample during carbonization was also significantly reduced by the addition of sulfuric acid.     

Electrical Double Layer as a Model of Interaction between Cellulose and Solid Acid Catalysts of Hydrolysis

Solid acid catalysts of cellulose hydrolysis in aqueous media attract considerable research interest because of the ease of their separation from the reaction products. The nature of interaction between the two solids is a relevant topic of ongoing research. One aspect of behavior of solid acids in water was not previously discussed in literature with regard to hydrolysis of cellulose: electrolytic dissociation and formation of electric double layers. In this work, on theoretical level, we consider the role of the double layer created by the solid acid when cellulose hydrolysis takes place. The diffuse layer of protons is regarded as the medium where the hydrolysis reaction occurs. Protonation of cellulose by these protons imparts positive charge onto its surface, and cellulose is electrostatically attracted to the polyanion of the catalyst. Thus, the two solid surfaces stay close to each other despite Brownian motion; this allows explaining the high activity of solid catalysts even when chemisorption of carbohydrates on a catalyst is not favorable.     

Chemical and Structural Properties of Carbonaceous Products Obtained by Hydrothermal Carbonization of Saccharides

Carbon‐rich‐quick scheme : A carbon‐rich solid product made up of uniform micrometer‐sized spheres of tunable diameter has been synthesized by the hydrothermal carbonization of saccharides. These microspheres possess a core–shell chemical structure based on the different nature of the oxygen functionalities between the core and the outer layer (see figure).

     

One‐step Preparation of Carbon‐based Solid Acid Catalyst from Water Hyacinth Leaves for Esterification of Oleic Acid and Dehydration of Xylose

Carbon‐based solid acid catalysts were successfully obtained via one‐step hydrothermal carbonization (HTC) of water hyacinth (WH) in the presence of p ‐toluenesulfonic acid (PTSA). Increasing the HTC temperature from 180 to 240 °C resulted in carbonaceous materials with increased sulfur content and less adsorbed water. The material obtained at 220 °C (WH‐PTSA‐220) contains the highest amount of acid sites and promotes the highest initial rate of two transformations, that is, methanolysis of oleic acid and dehydration of xylose to furfural. While all PSTA‐treated WH catalysts gave comparable fatty acid conversions (≈97 %) and furfural yields (≈60 %) after prolonged reaction times, the WH‐PTSA‐240 system bearing a relatively low acid density maintains the most favorable reusability profile. Higher HTC temperatures (220–240 °C) improved the catalyst reusability profiles due to graphitization and hydrophobicity of the carbon surface. The catalyst systems derived herein from biomass may have potential applications in biorefining platforms, utilizing the conversion of waste biomass to chemicals.     

水热炭化制备碳量子点及其应用

碳量子点作为新兴的“零维”碳纳米材料引起人们广泛的关注。水热炭化法是目前为止应用最广泛的碳量子点合成方法之一。水热炭化合成碳量子点取材广泛、过程简单,其最大的特点是合成的碳量子点表面含有丰富的含氧官能团,水溶性优异,在制备过程中即可对碳量子点进行表面功能化改性。此外,水热法合成的碳量子点具有石墨或无定形结构的碳核。水热碳量子点的结构和性质主要受原料种类及制备条件（水热炭化温度、时间及化学添加剂）的影响,产物在光催化技术、分析检测、活体成像和细胞标记、发光二极管（LED）及药物输送等领域展示出较好应用效果。本文综述了水热碳量子点的制备、性质、形成机理（包括原料的脱水、聚合、炭化及钝化过程）及发光机理（表面缺陷态效应和量子尺寸效应）,并对水热碳量子点的应用进行了总结。最后,对水热碳量子点发展过程中尚待解决的问题进行总结,对其未来的发展方向进行了展望。     

Hydroxymethylfurfural as an Intermediate of Cellulose Carbonization

Hydrogen bond donor solvents such as aromatic solvents inhibit the secondary degradation of cellulose-derived primary pyrolysis products. In a previous study, we found that the formation of solid carbonized products was completely inhibited during cellulose pyrolysis in aromatic solvents, with 5-hydroxymethylfurfural (5-HMF) recovered in certain yields instead. This indicated that 5-HMF is an intermediate in cellulose carbonization. To confirm this hypothesis, the thermal reactivity of 5-HMF was investigated. At 280 °C, pure 5-HMF polymerized into a hard glassy substance through OH group elimination, but further conversion was slow. When pyrolyzed in the presence of glycerol, a model of coexisting primary pyrolysis products from cellulose, a coupling reaction proceeded. Reactions characteristic of cellulose carbonization then occurred, including the formation of acidic groups and benzene-type structures in the solid products. These results confirmed the above hypothesis. The molecular mechanism of cellulose carbonization is discussed, focusing on the crystalline nature.     

酸水解法从菊芋中提取果糖

采用热水浸提法提取菊芋中的菊糖,并用磷酸水解为还原糖(大部分为果糖)。从固液比、提取时间、温度、水解时间、温度和菊糖液pH值等方面试验了对还原糖得率的影响,通过正交实验确定了最佳条件为:固液比1∶30,浸提温度80℃,浸提时间30min,水解温度80℃,水解时间30min,pH值为2,可以得到较令人满意的结果。     

微波水热改性制备S_2O_8~(2-)/Fe_2O_3-SiO_2固体酸及催化性能

对共沉淀法得到的Fe2O3-SiO2混合氧化物前驱物进行微波水热改性处理,经浸渍(NH4)2S2O8后再焙烧得S2O82-/Fe2O3-SiO2固体酸催化剂。用XRD、TEM、N2气吸附/脱附及化学分析方法对其进行了表征,用乙酸/丁醇酯化催化反应评估固体酸的催化性能,并与通常条件下制得的催化剂进行了比较。结果显示,引入SiO2会延迟Fe2O3晶体的形成与长大;对前驱物用250W的微波水热改性处理1.5h,制得的固体酸具有适中的比表面积、均匀的孔径分布,含硫量为6.02%,比表面积为37.1m2/g。该固体酸对乙酸丁醇酯化反应有很高的催化活性,催化酯化反应3h,乙酸的转化率高达97.7%。