温和条件下混合金属离子氧化木质素耦合电化学产氢  

Electrochemical hydrogen production coupled with lignin oxidation by mixed metal ions under mild conditions

作　　者：徐伟卓 周冰洁 李宁[1] 刘伟[4] XU Weizhuo;ZHOU Bingjie;LI Ning;LIU Wei(Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian 116023,China;University of Chinese Academy of Sciences,Beijing 100049,China;China Automotive Technology&Research Center Co.Ltd.,Tianjin 300300,China;School of Chemistry and Chemical Engineering,Central South University,Changsha 410083,China)

机构地区：[1]中国科学院大连化学物理研究所,大连116023 [2]中国科学院大学,北京100049 [3]中国汽车技术研究中心有限公司,天津300300 [4]中南大学化学化工学院,长沙410083

出　　处：《林业工程学报》2023年第5期130-137,共8页Journal of Forestry Engineering

基　　金：国家自然科学基金(22278446);湖南省自然科学基金(2022JJ10071)。

摘　　要：随着化石能源的枯竭以及温室效应的加剧,可再生资源的开发和利用已经成为全球关注的焦点。生物质是地球上最丰富的可再生资源,其可转化为化学品和燃料,具有广阔的应用前景。笔者提出一种简单、环境友好的电化学方法,在温和的反应条件下,利用廉价的混合过渡金属离子Fe^(3+)-Cu^(2+)作为电子转移载体和均相催化剂,将木质素的氧化与电化学产氢相结合,在降解木质素为芳香化合物的同时得到清洁、高能量密度的氢气。通过线性循环伏安曲线(CV)、极化曲线(I-V)、电压-时间曲线(V-t)、气质联用(GC-MS)、液相色谱(LC)以及分光光度法等测试方法研究了木质素氧化程度、产物、木粉含量变化以及电化学性能等情况。通过混合Fe^(3+)与不同的过渡金属离子Cu^(2+)、Cr^(3+)、Ni^(2+)及Co^(2+)协同氧化木质素,发现Fe^(3+)-Cu^(2+)的效果最为显著,木质素的降解率约48%,在100 mA/cm^(2)的电流密度下可以通电2.5 h。通过连续的化学-电解实验,未化学预处理原生木粉的降解率提高至62.8%,同时获得香兰素、葡萄糖和甲酸等有机小分子产物和氢气。With the depletion of fossil energy and the intensification of the greenhouse effect,it is urgent to develop and utilize renewable resources to effectively reduce the dependence on fossil energy.It is well known that biomass is the most abundant renewable resource on earth,with great potential for conversion into chemicals and fuels from a wide range of sources.A series of techniques has been developed for the conversion of biomass.However,native biomass contains complex chemical compositions,especially,lignin is the main component of cell walls of biomass with rigid structure,which is extremely difficult to convert and degrade.The conversion of lignin generally requires high temperature and high pressure.However,the harsh conditions would easily cause the deactivation of catalyst and side reactions.Electrocatalysis is a clean and efficient technology,which could control the chemical reactions by controlling the electrical input.In this study,a simple and environmentally friendly electrochemical method is proposed.Under mild reaction conditions,cheap transition metal ions Fe^(3+)-Cu^(2+)were used as the electron transfer carriers and homogeneous catalysts for lignin oxidation,and the regeneration of low valent metal ions was coupled with electrochemical hydrogen production.Through the chemical-electrolysis process,clean and high energy density hydrogen was obtained while lignin was degraded into aromatic compounds.The linear cyclic voltammetry(CV),polarization curves(I-V),voltage-time curves(V-t),gas-mass spectrometry(GC-MS),liquid chromatography(LC)and spectrophotometric method were used to investigate the degree of lignin oxidation,products,variation of content and electrochemical performance.By mixing Fe^(3+)with different transition metal ions Cu^(2+),Cr^(3+),Ni^(2+)and Co^(2+)for the synergistic oxidation of lignin,it was found that Fe^(3+)-Cu^(2+)had the most significant effect.During the heating process,about 48% of the lignin solids were solubilized and converted into aromatic compounds,such as vanillin a

关 键 词：混合金属离子 氧化木质素 电化学 产氢 

分 类 号：TQ35[化学工程]