γ-MnO2掺杂修饰石墨电极电化学降解纤维低聚糖的研究-应用化学专业论文.docxVIP

河北工业大学硕士学位论文 河北工业大学硕士学位论文 γ-M γ-MnO2 掺杂修饰石墨电极电化学降解纤维低聚糖的研究 i i PAGE PAGE iv γ-MnO2 掺杂修饰石墨电极电化学降解纤维低聚糖的研究 摘 要 本文研究了电化学作用下纤维低聚糖的降解，通过沉淀法制备了具有催化活性的 γ-MnO2，掺杂修饰改性石墨电极作为工作电极，Pt 电极为辅助电极，饱和甘汞电极为 参比电极，电化学降解纤维低聚糖得到葡萄糖。考察了电极的制备条件、溶液 pH 值、 电解电位、反应时间和反应温度等因素对葡萄糖产率的影响。采用 X 射线衍射仪对 γ-MnO2 催化剂进行分析，并采用电子扫描电镜对制备的电极进行表征。 水热条件下，固体超强酸 SO42-/SnO2 作为催化剂对纤维素预处理得到纤维低聚糖溶 液，单因素考察了预处理时间，固体超强酸用量，固液比等因素对还原糖产率的影响， 结果表明预处理温度 190 ℃，催化剂 SO42-/SnO2 用量 0.4 g，固液比 4g/100mL，反应 4 h 时，纤维素降解率为 55%，纤维素预处理后的滤液中，低聚糖质量产率为 18.65%，葡 萄糖质量产率为 27.5%，其余为糠醛等小分子物质。对预处理后的纤维素进行红外分析， 结果表明纤维素结构上没有新的官能团产生，证明仍是未完全反应的纤维素。 电化学降解纤维低聚糖生成葡萄糖的较佳条件为 MnO2 (γ-MnO2 质量：石墨质量 =5% ) 掺杂修饰石墨电极为工作电极，Pt 电极为辅助电极，饱和甘汞电极为参比电极， 恒电位输出-1.0 V，溶液的 pH 为 3，60 ℃电化学降解 8 h，葡萄糖产率最高 72.4%，选 择性 100%。通过循环伏安曲线对电极行为的表征，还探讨了电化学降解纤维低聚糖的 机理。 关键词：纤维低聚糖，电化学降解，γ-MnO2，葡萄糖 STUDY ON THE ELECTROCATALYTIC DEGRADATION OF CELLULOSE OLIGOSACCHARIDES BY γ-MnO2 MODIFIED CARBON ELECTRODE ABSTRACT This paper has investigated the electrocatalytic degradation of cellulose oligosaccharides. The electrocatalytic degradation was studied in three electrode cylindrical cells which composed of a modified MnO2/graphite/PTFE electrode as work electrode, the platinum electrode as the auxiliary electrode and the reference saturated calomel electrode (SCE). For enhancement of glucose yield, optimal experiments about electrode preparation and cellulose degradation were conducted. The γ-MnO2 catalyst was analyzed using X-ray diffraction (XRD) and the surface morphology of electrodes was analyzed by SEM. The pretreatment of cotton cellulose was carried out under hydrothermal process to generate oligosaccharides. The reaction conditions of pretreatment time, reaction time, solid acid amount and solid-liquid ratio were studied for the yield of reducing sugar. The optimally experimental conditions were established as 190 ℃, 0.4 g SO42-/SnO2, 4g cellulose and 100 mL water and reaction time 4 h. The main components of the filtrate were found to be glucose and cellu