化工进展
化工進展
화공진전
Chemical Industry and Engineering Progress
2015年
11期
3938-3943,3950
,共7页
UiO-66(Zr)%吸电子基团%催化%二羟基丙酮%乳酸乙酯
UiO-66(Zr)%吸電子基糰%催化%二羥基丙酮%乳痠乙酯
UiO-66(Zr)%흡전자기단%최화%이간기병동%유산을지
UiO-66(Zr)%electron withdrawing groups%catalysis%dihydroxyacetone%ethyl lactate
以无水四氯化锆 ZrCl4和不同的有机配体,如苯二甲酸、2-硝基苯二甲酸和1,2,4-苯三甲酸为原料,DMF为溶剂,通过溶剂热法合成了一系列UiO-66(Zr)的金属有机骨架MOFs,并用于催化转化二羟基丙酮至乳酸乙酯的反应。UiO-66(Zr)的催化活性和乳酸乙酯的选择性可以通过在制备过程中采用含有不同吸电子基团的无机配体来调节。而且当使用反应中间产物丙酮醛作为起始反应物时,MOFs的活性有了显著的提高。材料表征结果显示, UiO-66(Zr)系列MOFs材料中Br?nsted酸的含量低但强度较大,而Lewis酸的含量则较高。本文对二羟基丙酮转化为乳酸乙酯的反应机理进行了详细分析,并实现了100%的二羟基丙酮转化率和乳酸乙酯选择率。
以無水四氯化鋯 ZrCl4和不同的有機配體,如苯二甲痠、2-硝基苯二甲痠和1,2,4-苯三甲痠為原料,DMF為溶劑,通過溶劑熱法閤成瞭一繫列UiO-66(Zr)的金屬有機骨架MOFs,併用于催化轉化二羥基丙酮至乳痠乙酯的反應。UiO-66(Zr)的催化活性和乳痠乙酯的選擇性可以通過在製備過程中採用含有不同吸電子基糰的無機配體來調節。而且噹使用反應中間產物丙酮醛作為起始反應物時,MOFs的活性有瞭顯著的提高。材料錶徵結果顯示, UiO-66(Zr)繫列MOFs材料中Br?nsted痠的含量低但彊度較大,而Lewis痠的含量則較高。本文對二羥基丙酮轉化為乳痠乙酯的反應機理進行瞭詳細分析,併實現瞭100%的二羥基丙酮轉化率和乳痠乙酯選擇率。
이무수사록화고 ZrCl4화불동적유궤배체,여분이갑산、2-초기분이갑산화1,2,4-분삼갑산위원료,DMF위용제,통과용제열법합성료일계렬UiO-66(Zr)적금속유궤골가MOFs,병용우최화전화이간기병동지유산을지적반응。UiO-66(Zr)적최화활성화유산을지적선택성가이통과재제비과정중채용함유불동흡전자기단적무궤배체래조절。이차당사용반응중간산물병동철작위기시반응물시,MOFs적활성유료현저적제고。재료표정결과현시, UiO-66(Zr)계렬MOFs재료중Br?nsted산적함량저단강도교대,이Lewis산적함량칙교고。본문대이간기병동전화위유산을지적반응궤리진행료상세분석,병실현료100%적이간기병동전화솔화유산을지선택솔。
A serious of Zr-terephthalates metal-organic frameworks [UiO-66(Zr)] were synthesized by solvothermal method starting from a solution of ZrCl4 and different organic ligands,such as terephthalic acid,2-nitroterephthalic acid,and 1,2,4-benzenetricarboxylic acid,dissolved in DMF. These materials were investigated as heterogeneous catalysts for the conversion of dihydroxyacetone into the valuable compound,ethyl lactate. The catalytic activity and selectivity towards ethyl lactate of UiO-66(Zr) materials can be easily tuned by using linkers with different electron withdrawing groups in the synthesis mixture. When pyruvic aldehyde,the intermediate product of the conversion reaction, was applied as the starting reagent,the activity of the MOFs was significantly improved. Characterization shows that the Br?nsted acid in the MOFs is strong but with low amount;however, the number of Lewis acid sites is higher. For the conversion of dihydroxyacetone,the reaction mechanism was fully explored and a complete substrate conversion with full selectivity towards ethyl lactate was achieved with the studied catalysts.