【作者】 王峰； 罗能超； 黄志鹏； 王敏；

【Author】 Feng Wang;N.Luo;Z.Huang;M.Wang;Dalian Institute of Chemical Physics,Chinese Academy of Sciences;Zhang Dayu School of Chemisty,Dalian University of Technology;

【机构】 中国科学院大连化学物理研究所； 大连理工大学张大煜学院；

【摘要】 生物质是自然界中广泛存在的可再生碳资源,是光合作用的最终产物。生物质经处理可转化为粗化学原料,高附加值精细化学品或可再生燃料^[1]。生物质的能量密度（17 MJ kg-1）较低,因此将生物质转化为高能量密度的能源化学品,例如H₂,液体燃料和CH₃OH等,需要额外的输入能量以提高生物质产物的能量密度,并提高能源化学品的产率。光催化可以驱动吸热反应,并且可以在常温反应,因此如果使用太阳光或人造光源为能源有望将生物质转化为能量密度更高的生物质产物。本报告包括以下的研究工作。我们首先采用光催化的方法,通过断裂非预活化的C-H键,使生物质发生C-C键偶联并同时产生H₂^[2]。利用这种方法,可将生物质基甲基呋喃转化为柴油前体和H₂。柴油前体可通过加氢脱氧转化为含41%支链烷烃的C₁₀～C₂₀的柴油。我们还利用Pt/TiO₂光催化脂肪酸C-C键断裂,使脂肪酸转化为了柴油^[3]。通过引入H₂增加氢溢流的方法,可抑制碳链聚合反应,从而提高柴油碳数烷烃的选择性。TiO₂还被用于催化多元醇和糖类化合物的C-C键断裂,得到甲醇和合成气等C₁能源化学品[4]。我们也发现TiO₂上负载的Cu的状态影响了CO和过氧化产物CO₂的选择性。以上工作表明通过储存光能的方法,可将生物质转化为高能量的能源化学品。更多还原

【Abstract】 Biomass,abundantly present in nature,is ultimately produced from photosynthesis as the most abundant sustainable carbon source.Biomass,after proper modifications or transformation,can be used as raw chemical feedstocks,value-added fine chemicals or fuels.However,the relatively low energy density(17 MJ kg^-1) necessitates extra energy input to convert biomass into energy chemicals,such as liquid fuels,C₁ chemicals and H₂.Due to the potential to drive chemical reactions that are endothermic and conducted at r.t.,use of solar or artificial light to achieve biomass conversion by photocatalysis can storage light energy in biomass,thus,improving the energy density of bio-products.This report covers the following research works.We adopted photocatalytic method for C-C bond coupling to convert biomass feedstocks to H2 and diesel fuels via un-activated side C-H bonds cleavage.Using this chemistry,diesel fuel precursors and H₂ were coproduced from lignocellulose downstream feedstocks with the input of light energy.Diesel fuels were also produced from industrial fatty acids via platinized TiO₂ by C-C bond cleavage.The explosion of platinized TiO₂ to H₂ atmosphere can enormously improve the selectivity of diesel-range alkanes due to hydrogen spill over and enhanced capturing of carbon radical by hydrogen.TiO₂ was also used to cleave the C-C bond of polyols and sugars,delivering methanol and syngas as clean energy chemicals.We also found that the phase of Cu determined the ratio of CO and CO₂.The above works demonstrate photocatalytic methods in converting biomass to energy chemicals by light energy input.更多还原