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中文摘要：
甘油（GL）是一种重要的生物平台分子,通过催化选择氧化反应将其转化为具有高附加值化学品是可持续发展化学化工的重要课题之一.以Au为催化剂的GL水相选择氧化反应可以生成甘油酸（GLA）、二羟基丙酮（DHA）、羟基丙二酸（TTA）、羟基乙酸（GCA）和乳酸（LA）等多种产物.通常,该反应需要碱（NaO H）存在时才能进行,产物往往以GLA为主（选择性40%？70%）,副产物主要有GCA,TTA和草酸（OA）.一般认为,可溶性碱（OH？）是通过夺取GL分子中羟基上的质子而诱发反应的.尽管在Au催化的反应体系中从未检测到有甘油醛（GLD）生成,GLD和/或DHA被认为是该反应的中间物种.本课题组前期工作表明,氧化物（Ti O2,Al2O3,Zr O2,Cu O等）负载的纳米Au催化剂能够在无碱（无外加OH？）水溶液中选择性催化GL氧化生成DHA（而不是GLA）.因此,OH-的存在与否很可能会改变水溶液中Au催化剂上GL氧化反应的途径.本文试图回答当GL的水溶液中不存在Na OH时,Au催化剂载体的表面酸碱性质是否也会对GL氧化反应的选择性产生调控作用.我们选用Mg/Al比（x）不同的MgO-Al2O3样品为Au催化剂的载体,以尿素为沉淀剂,采用沉积沉淀法制备了相应的Au/MgO-Al2O3（x）催化剂样品.采用X射线衍射、电感耦合等离子体-原子发射光谱仪、透射电镜以及N2吸附-脱附等温线等对MgO-Al2O3（x）和/或Au/MgO-Al2O3样品的物相、元素组成、Au颗粒大小以及比表面积等进行了表征分析;采用NH3和CO2程序升温脱附（TPD）分别对MgO-Al2O3（x）载体表面的酸、碱性进行了测定.NH3-TPD和CO2-TPD结果表明,随着Mg/Al比x从0增加至4.8,MgO-Al2O3（x）的表面酸量从0.94降到0.20μmol/m2,而其表面碱量却从0.05剧增至0.80μmol/m2.因此,载体中MgO含量越多或Mg/Al比越大,其酸性越弱而碱性越强.在无碱水溶液中的催化反应结果表明,Au/MgO-Al2O3（x）上GL氧化反应的主?
英文摘要：
Glycerol（GL） valorization by catalytic aerobic oxidation in water over Au-based catalysts usually produces a number of products. A soluble base（usually NaO H） is often added to the reaction solution to promote GL activation and affect the product distribution. We report in this study the support effect on the catalysis of Au nanoparticles（NPs） for GL oxidation in base-free water on a series of supporting MgO-Al2O3 materials. The acid-base property on the surfaces of these MgO-Al2O3 supports were systematically varied by tuning the molar Mg/Al ratio（x） before they were loaded with the catalytic Au NPs. Au NPs on the most acidic and least basic MgO-Al2O3 exhibited the highest activity for GL activation and the highest selectivity for dihydroxyacetone（DHA） production. Increasing the surface basicity or lowering the acidity of the MgO-Al2O3 support results in continuously improved selectivity for glyceric acid（GLA） but lowered the selectivity for DHA. These correlations disclose for the first time that the support acid-base property inversely affects the formation of DHA and GLA, and demonstrate that the support acidity/basicity is a key to the selectivity control of their carrying Au NPs for GL oxidation.
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