Low Cost Transformation of Dioxins to Nontoxic Forms

二恶英低成本转化为无毒形式

• 批准号: 11555230
• 负责人: FUKUZUMI Shunichi
• 金额: $ 8.19万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B).
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-11555230/
• 关键词: Dioxins; Electron Transfer; Catalysis; Acridinium; Alcohol; NADH Analogues; Photocatalysts; Reaction Mechanisms; 無害化

The Low cost transformation of chlorinated compounds such as dioxins to nontoxic forms has been developed utilizing photocatalytic reductive dechlorination of chlorinated compounds by chemical reductants. This process is initiated by photoinduced electron transfer from the singlet excited state of the catalyst to chlorinated compounds, which is followed by the reduction of the oxidized catalyst by the chemical reductants. An NAD^+ analogue (10-methylacridinium ion) has been employed as an efficient photocatalyt for the reductive dechlorination of chlorinated compounds. The redox properties of NAD^+ analogues have been determined by examining the electron transfer reduction and the detection of the radical intermediates. The redox properties of the reduced forms, i.e., NADH analogues have also been determined by examining the electron transfer oxidation.The efficient and selective oxygenation of p-xylene to p-tolualdehyde is also initiated by photoinduced electron transfer from p-xylene to the singlet excited state of 10-methyl-9-phenylacridinium ion under visible light irradiation, followed by the deprotonation of p-xylene radical cation and the facile addition of oxygen to the deprotonated radical, leading to yield p-tolualdehyde exclusively as the final oxygenated product. The factors to improve the photocatalytic reactivity of the photocatalyst have been clarified.

利用化学还原剂光催化还原脱氯，可以低成本地将二恶英等氯代化合物转化为无毒的氯代化合物。该过程通过光诱导电子从催化剂的单重激发态转移到氯化化合物来引发，随后通过化学还原剂还原氧化的催化剂。NAD^+类似物（10-甲基吖啶离子）已被用作氯代化合物还原脱氯的有效光催化剂。NAD^+类似物的氧化还原性质已通过检测电子转移还原和自由基中间体的检测来确定。还原形式的氧化还原性质，即，NADH类似物也通过检测电子转移氧化来确定。对二甲苯有效和选择性氧化对甲苯甲醛也是通过在可见光照射下从对二甲苯到10-甲基-9-苯基吖啶离子的单重激发态的光诱导电子转移引发的，随后对二甲苯自由基阳离子的去质子化和氧容易地加成到去质子化的自由基上，导致仅产生对甲基苯甲醛作为最终氧化产物。阐明了提高光催化剂光催化活性的因素。

项目成果

Shunichi Fukuzumi et al.: "Catalytic Effects of Dioxygen on Intramolecular Electron Transfer in Radical Ion Pairs of Zinc Porphyrin-Linked Fullerenes"J.Am.Chem.Soc.. 123・. 2571-2575 (2001)

Shunichi Fukuzumi 等：“双氧对锌卟啉连接富勒烯自由基离子对分子内电子转移的催化作用”J.Am.Chem.Soc. 123·2571-2575 (2001)。

Shunichi Fukuzumi et al.: "100% Selective Oxygenation of p-Xylene to p-Tolualdehyde via Photoinduced Electron Transfer"Org.Lett.. 2・23. 3647-3650 (2000)

Shunichi Fukuzumi 等：“通过光诱导电子转移将对二甲苯 100% 选择性氧化为对甲苯甲醛”Org.Lett. 2・23 (2000)。

Shunichi Fukuzumi et al.: "Step wise Bond Formation in Photochemical and Thermal Diels-Alder Reactions of C_<60> with Danishefsky's Dienes"J.Am.Chem.Soc.. 122. 2236-2243 (2000)

Shunichi Fukuzumi等人：“C_<60>与Danishefskys Dienes的光化学和热Diels-Alder反应中的逐步键形成”J.Am.Chem.Soc.. 122. 2236-2243 (2000)

Shunichi Fukuzumi et al.: "ESR Spectra of Superoxide Anion-Scandium Complexes Detectable in Fluid Solution"J.Am.Chem.Soc.. 121. 1605-1606 (1999)

Shunichi Fukuzumi 等：“流体溶液中可检测的超氧化物阴离子-钪复合物的 ESR 光谱”J.Am.Chem.Soc.. 121. 1605-1606 (1999)

Shunichi Fukuzumi et al.: "Comparison between Electron Transfer and Nucleophilic Reactivities of Ketene Silyl Acetals with Cationic Electrophiles"J.Org.Chem.. 66・4. 1450-1454 (2001)

Shunichi Fukuzumi 等：“烯酮甲硅烷基缩醛与阳离子亲电子试剂的电子转移和亲核反应性的比较”J.Org.Chem. 66・4 (2001)。