离子液体催化大豆异黄酮醇解反应工艺研究

以离子液体为酸性催化剂,对天然产物大豆异黄酮糖苷在正丁醇溶剂中的醇解反应进行了研究.对离子液体的种类及用量、催化反应时间、温度等工艺条件进行了优化.确定最适宜的工艺条件是:采用[BIM]HSO4离子液体为催化剂,用量为0.036 g·mL-1;反应温度为(104±1)℃,反应时间为100 min.在此条件下,三种异黄酮糖苷的转化率均接近100%;另外,离子液体催化剂的稳定性测试结果表明,离子液体经3次循环使用,活性未见明显变化.采用浸渍法将离子液体固定化后用于催化醇解反应,结果表明,该固定化离子液体在首次使用时也具有较高催化活性,但稳定性差,难以重复使用,有必要进一步研究固定化离子液体的方法.     

磺化石墨烯固体酸催化剂的制备及活性评价

石墨烯是由碳原子以sp₂杂化连接的单原子层构成的新型二维碳原子晶体,由于含有众多具有反应活性的碳碳双键,石墨烯纳米片表面很容易进行化学修饰键合有机官能团而改变其性质。采用改良Hummers法制备氧化石墨烯,通过磺化反应制备磺化石墨烯固体酸催化剂,通过FT-IR、元素分析和XPS等对其结构进行表征。将制备的氧化石墨烯和磺化石墨烯应用于催化纤维二糖的水解反应,以纤维二糖糖苷键的水解反应为模型考察其酸催化性能。结果表明,氧化石墨烯和磺化石墨烯中含有-COOH、-OH和-SO₃H等官能团,磺酸根密度分别为1.0 mmol·g^-1和2.2 mmol·g^-1,氧化石墨烯和磺化石墨烯具有与H₂SO₄相比拟的酸催化活性,尽管酸性强度和密度较低,但催化活性与H₂SO₄相当。     

氨水改性氧化石墨烯高效催化 Knoevenagel缩合反应

通过浸渍法制备了氨水改性氧化石墨烯,考察了其在苯甲醛和丙二腈的Knoevenagel缩合反应中的催化性能。通过X射线粉末衍射(XRD)、拉曼光谱(Raman)、傅里叶变换红外光谱(FTIR)、NH3程序升温脱附(NH3-TPD)、元素分析等对催化剂进行了表征,考察了工艺条件对其催化剂性能的影响。结果表明:氨水改性氧化石墨烯可以有效地将NH4+固载于氧化石墨烯表面;氧化石墨烯经氨水改性后在苯甲醛和丙二腈的Knoevenagel缩合反应中表现出良好的催化性能,随着改性实验中氨水质量分数的增加,催化剂的活性不断增加。以质量分数5%的氨水为改性剂制备的催化剂(AW-GO-5%)在60℃、4 h下催化苯甲醛和丙二腈的Knoevenagel缩合反应,苯甲醛的转化率高达93.6%,产物苄亚基丙二腈的选择性为94.8%,该催化剂重复使用4次后催化活性仍较高。     

还原氧化石墨烯/BiVO_4复合材料的制备及其光催化性能

采用微波原位生长法制备了还原氧化石墨烯/BiVO4复合光催化剂。以四环素为模型污染物,对该催化剂在可见光(λ>420 nm)下的催化活性进行了评价。结果表明,还原氧化石墨烯/BiVO4复合光催化剂在可见光照射下对四环素的降解效率达到了85.3%明显高于纯BiVO423%的降解效率。     

磁性氧化石墨烯/TiO_2复合材料的制备及光催化降解染料废水的研究

为了提高TiO2的光催化性能,采用Hummers法自制氧化石墨、纳米TiO2、FeCl3等为原料制备了磁性氧化石墨烯/TiO2(磁性GO/TiO2)复合光催化材料。以活性艳红X-3B为模拟废水,对该催化剂在紫外光下的催化活性进行了评价。结果表明,TiO2/GO材料中GO含量为3%时光催化活性最好,磁性GO/TiO2复合材料GO含量为8%时在1.4 h时可以达到93%的降解率。     

石墨烯-二氧化钛纳米管催化剂的光解水制氢性能研究

为改善能源短缺,对新型光催化水解制氢材料进行了研究。通过改进Hummer法制备氧化石墨,溶胶-凝胶法制备锐钛矿型二氧化钛,采用浓碱法制得石墨烯-二氧化钛纳米管催化剂,考察了不同石墨烯的掺杂量对催化活性的影响。经过光解水制氢实验发现,掺杂不同质量分数石墨烯的催化剂催化活性得到了进一步提高,其中掺杂量为1%的产氢活性最好,产氢速率是纯二氧化钛纳米管的2. 5倍。通过BET、XRD、UV以及FT-IR等方法对催化剂进行了表征。结果表明,石墨烯与二氧化钛纳米管成功复合,并且石墨烯的掺杂在一定程度上提高了催化剂的BET比表面积;催化剂对可见光的响应范围得到进一步扩大,这为催化剂光解水制氢性能的提高提供了有力的条件。     

镍负载二氧化钛/PEI/石墨烯纳米复合催化剂的制备与研究

首先采用改进的Hummers法制备了氧化石墨烯(GO),再以聚乙烯亚胺(PEI)修饰的氧化石墨烯为载体,并以硫酸钛和氯化镍为前驱体,利用水热法在180 ℃下以PEI为交联剂制得镍负载的TiO2/PEI/石墨烯纳米复合催化剂。通过紫外可见分光光度计(UV-vis)、傅里叶变换红外光谱(FTIR)、扫描电镜(SEM)、透射电镜(TEM)、X射线衍射仪(XRD)等测试手段对催化剂进行了表征。结果表明,Ni-TiO2/PEI/RGO纳米复合催化剂中镍负载TiO2纳米粒子与石墨烯能够均匀复合,并具有较小的晶粒尺寸。以对硝基苯酚(4-NP)为降解目标物,考察了该催化剂在NaBH4存在下还原4-NP的催化活性。结果表明,镍负载的TiO2/PEI/石墨烯纳米复合催化剂具有良好的重复催化活性,其降解率为98%,催化剂重复使用10次后,降解率仍能保持90%以上。     

磁性氧化石墨烯负载离子液体催化碳酸二甲酯的合成

通过共价键接枝法制备以磁性氧化石墨烯为载体、咪唑盐型碱性离子液体为活性中心的负载型催化剂Fe_3O_4/GO-[bSIm]OH。通过FT-IR、TGA、XRD等手段对样品进行表征,考察了催化剂质量、原料摩尔比、反应时间、反应温度等条件对甲醇和碳酸乙烯酯合成碳酸二甲酯的酯交换反应的影响。实验结果表明,催化剂质量为0. 1 g、反应温度为90℃、n(Me OH)∶n(EC)=10∶1、反应时间为3 h时,DMC的收率达到95%,选择性达到99%。通过外部磁场将催化剂从反应体系中分离,重复使用5次后,催化剂仍能保持良好的催化活性。     

Pd/La0.5Pb0.5MnO3催化氧化甲苷合成葡萄糖醛酸

采用沉淀法制备了以钙钛矿型复合金属氧化物为载体的催化剂Pd/La0.5Pb0.5MnO3,催化氧化甲基葡萄糖苷合成甲苷酸钠,进一步水解反应生成葡萄糖醛酸. 利用XRD和SEM对催化剂进行了表征,考察了催化剂制备和氧化工艺条件对葡萄糖醛酸收率的影响. 结果表明,在Pd负载量为1%、原料与催化剂质量比为6:1、温度70℃、压力为常压、pH值9、时间5 h的条件下,葡萄糖醛酸的收率达到29.5%,反应选择性较好.     

石墨烯改性碳纤维基Pt–Sn直接燃料乙醇电池阳极催化剂

以静电纺丝技术制备的石墨烯改性碳纤维为载体,将Pt–Sn纳米催化剂原位负载在碳纤维上。利用X射线衍射、透射电子显微镜表征催化剂的微观结构,利用循环伏安、计时电流和交流阻抗等分析催化剂的电催化活性,研究石墨烯含量对燃料电池碳纤维基阳极催化活性的影响。结果表明:当石墨烯质量分数为3%时,催化剂表现出最佳的催化活性,循环伏安测试的峰电流密度达到119 mA/cm~2。     

Catalytic performance of sulfate-grafted graphene oxide for esterification of acetic acid with methanol

Graphene oxide possesses tremendous mechanical and electronic properties in combination with large surface area and accessible active sites leading to the development of novel innovative heterogeneous catalysts. The present study elaborates the catalytic activity of graphene oxide, enhanced by grafting active sulfate groups on its surface to result as a superior catalyst. The catalyst was evaluated in the model acetic acid esterification reaction with methanol in terms of acid conversion. Catalysts consisting of varied sulfate concentrations and calcination time were synthesized and optimized for its best catalytic activity. The prepared catalysts (GO-SO₄) were characterized using XRD, FT-IR, SEM-EDS, XPS, and BET. A 44% enhancement in catalyst activity was observed using sulfate-grafted graphene oxide (GO-SO₄) catalyst over bare GO due to the synergistic effect of sulfate ions. The catalyst can be separated out by simple filtration. Further, the influence of operating process parameters including catalyst loading, and the reaction temperature was evaluated toward the maximum acid conversion. In addition, the detailed kinetic study was also done in this system using Pseudo-homogeneous model.     

Simple preparation of nanoporous few-layer nitrogen-doped graphene for use as an efficient electrocatalyst for oxygen reduction and oxygen evolution reactions

We prepared nitrogen-doped graphene (NG) by simple pyrolysis of graphene oxide and polyaniline, which was selected as the N source. The resulting NG contains 2.4 at.% N, of which as high as 1.2 at.% is quaternary N. Electrochemical characterizations reveal that the NG has excellent catalytic activity toward oxygen reduction reaction (ORR) in an alkaline electrolyte, including a desirable four-electron pathway for the formation of water, large kinetic-limiting current density, long-term stability and good tolerance to methanol crossover. In addition, we demonstrate that the NG also has high catalytic activity toward oxygen evolution reaction (OER), rendering its potential application as a bi-functional catalyst for both ORR and OER.     

磁性氧化石墨烯固定化果胶酶

磁性氧化石墨烯固定化酶的研究鲜见报道,本实验采用水热沉淀法制备了铁磁性氧化石墨烯（magnetic graphene oxide,MGO）,通过交联剂固定化果胶酶。采用红外光谱和SEM表征了制备的MGO的活性基团和特性。结果表明MGO具有—OH等亲水活性基团,可以较好地分散在水相催化体系中。磁性氧化石墨烯的蛋白上载量可达1453mg/g MGO,远高于颗粒活性碳,硅藻土和粉末活性炭的上载量。并且研究了酶催化的动力学,酶的催化转化值7.41h?1,催化效率0.98mL/(h?mg),Km7.55mg/mL。固定化酶稳定性明显增强,且重复使用10次活性仍然可以保持在初始酶活的58％。     

磺酸磁性石墨烯固体酸的制备、表征及初步应用研究

以氧化石墨烯,Co（NO3）2·6H2O和Fe（NO3）3·9H2O为离子源利用水热法一步制备磁性石墨烯（Co Fe2O4-h GO）,用磺酸重氮盐将其重氮化制得磺酸磁性石墨烯固体酸,采用FT-IR、XRD、VSM和酸碱反滴定法测对其进行了表征。结果表明,链接石墨烯的Co Fe2O4为单相立方尖晶石结构,平均粒径为27 nm,饱和比磁化强度MS为29.7 A·m2/kg,其表面酸量为2.7 mmol/g。用乙酸与正己醇的酯化反应初步评估其催化性能：在90℃,乙酸与正丁醇摩尔比为1∶1,催化剂用量为3wt%,反应时间为4 h的条件下,乙酸转化率为59.1%。     

Reduced graphene oxide supported chiral Ni particles as magnetically reusable and enantioselective catalyst for asymmetric hydrogenation

A reduced graphene oxide (rGO) supported chiral-modified Ni catalyst was synthesized, characterized and employed for asymmetric hydrogenation. The prepared hybrid catalyst could produce each enantiomer with d- or l-tartaric acid as chiral modifier and exhibited a high TOF (20160 h⁻¹) and enantioselectivity (enantiomeric excess, 98.5%) for asymmetric hydrogenation of methyl acetoacetate. The high catalytic activity and enantioselectivity were mainly attributed to the unique properties of the support rGO, as it had a large specific surface area to sustain and stabilize Ni particles and its high charge carrier mobility could enable the readily transfer of electrons in the reaction process. Besides, the catalyst could also gain an enhanced reactant sorption with the support of rGO, thus achieved a greatly catalysis enhancement. The ferromagnetism of Ni made the catalyst easier for separation and reuse. The catalytic and recycling performance of the prepared chiral Ni catalyst demonstrated that rGO was indeed a promising support to improve activity, enantioselectivity and durability of catalysts, and the prepared catalysts were promising reusable heterogeneous catalysts for asymmetric hydrogenation.     

Suzuki–Miyaura reaction catalyzed by graphene oxide supported palladium nanoparticles

Pd supported on polyamine modified graphene oxide (GO-NH₂-Pd^2 +) was fabricated for the first time. The prepared catalyst was characterized by transmission electron microscopy, X-ray diffraction spectroscopy, X-ray photoelectron spectroscopy and infrared spectroscopy. The catalytic activity of the prepared catalyst was investigated by employing Suzuki–Miyaura coupling reaction as a model reaction. A series of biphenyl compounds were synthesized through the Suzuki–Miyaura reaction using GO-NH₂-Pd^2 + as catalyst. The yields of the products were in the range from 71% to 95%. The catalyst can be readily recovered and reused at least 10 consecutive cycles without significant loss its catalytic activity.     

磷钼杂多酸盐催化剂的制备及脱硫应用

采用十六烷基三甲基氯化铵、磷钼酸和乙醇为原料,制备磷钼杂多酸盐催化剂,然后对其脱硫性能进行考察.实验过程中考察了催化剂制备条件对催化剂催化脱硫性能的影响.从而确定了催化剂最佳制备条件:十六烷基三甲基氯化铵与磷钼酸的摩尔比为1:1;制备温度为60℃;反应时间为2h;干燥活化时间为10h.在上述的实验条件下,精制的磷钼杂多...