【作者】 朱明山；

【导师】 杨平；

【作者基本信息】 苏州大学 ， 物理化学， 2010， 硕士

【摘要】 卟啉环为“核”,稠环芳烃为树枝,通过共价键或氢键相连,构建成对称型共轭多枝分子。稠环芳烃为能量供体基团与卟啉环为“核”搭建的大分子结构在200-700 nm有很好的吸收,并具备有效的能量转移。以这些光敏性好的共轭多枝分子作为稳定剂,制备了金属/共轭有机分子纳米复合物催化剂,并研究了该纳米复合物光诱导分解水制氢的催化活性。具体工作如下:(1)以meso-5,10,15,20-四(对羟基苯基)卟啉(TPPH)为母体,在其外围引入不同取代位数萘基,合成出系列萘基卟啉和四取代位萘基卟啉(TPPNA)的Mg、Co、Cu、Zn金属卟啉配合物(TPPNA-M),并通过1H NMR、FT-IR、UV-vis等方法进行了结构表征。利用乙醇回流还原法成功制备了Pt@TPPNA纳米复合物,并用UV-vis、FTIR、TEM、XRD、荧光、光电流等手段对Pt纳米复合物进行了表征。制备的Pt纳米复合物平均粒径在2-4nm,在光照下激发态卟啉分子与Pt纳米粒子之间具有良好的电子传递作用。以EDTA为电子给体,Pt@TPPNA纳米复合物作为光敏剂和催化剂,在紫外-可见光照下可以将水分解成氢气。催化剂的量,体系酸度及纳米复合物中Pt/TPPNA的摩尔比能显著影响其催化性能。(2)以meso-5,10,15,20-四(对羟基苯基)卟啉(TPPH)为母体,在其外围引入不同取代位数蒽基,合成出系列蒽基卟啉(TPPAN),并通过1H NMR、FT-IR、UV-vis等方法进行了结构表征。利用乙醇回流还原法成功制备了Pt@TPPAN纳米复合物,并用UV-vis、FTIR、TEM、XRD、荧光、光电流等手段对Pt纳米复合物进行了表征。制备的Pt纳米复合物平均粒径在2-3nm,在光照下激发态卟啉分子与Pt纳米粒子之间具有良好的电子传递作用。以EDTA为电子给体,Pt@TPPAN纳米复合物作为光敏剂和催化剂,在紫外-可见光照下可以将水分解成氢气。催化剂的量,体系pH值及纳米复合物中Pt/TPPAN的摩尔比能显著影响其催化性能。(3)通过对芘的磺化,合成出芘磺酸(PSA),并通过1H NMR、FT-IR、UV-vis等方法进行了结构表征。为了模拟生物体系能量传递方式,考察了以氢键作为连接方式,自组装制备出芘-卟啉(TPPH-PSA)。利用乙醇回流还原法成功制备了Pt@PSA和Pt@TPPH纳米复合物,然后在Pt@TPPH里引入芘磺酸,制备出Pt@TPPH-PSA,并用UV-vis、FTIR、TEM、XRD、荧光、光电流等手段对Pt纳米复合物进行了表征。以EDTA为电子给体,Pt@TPPH-PSA纳米复合物作为光敏剂和催化剂,在紫外-可见光照下可以将水分解成氢气。催化剂的量,体系pH值及纳米复合物中Pt/TPPH-PSA的摩尔比能显著影响其催化性能。更多还原

【Abstract】 A series of architectural symmetry of porphyrins including porphyrin ring as the "core", polycyclic aromatic hydrocarbons for the "branch" through covalent or hydrogen bonds were synthesized. Substituting the fusedring aromatic compounds groups onto the porphyrin ring led the molecule to absorb over a broader range (200-700 nm) and to undergo efficient intramolecular/intermolecular energy transfer from the aromatic groups to the porphyrin ring. Porphyrins functionalized platinum nanocomposites were prepared, characterized and using the nanocomposites as photocatalyst for water splitting. Some corresponding researches were done as follows:(1) 5,10,15,20-tetrakis(4-(hydroxyl)phenyl) porphyrin (TPPH) bearing several naphthyl donor moieties 5,10,15,20-tetrakis(4-(naphthalen-1-ylmethoxy)phenyl) porphyrin (TPPNA-1~4), and a series of metalporohyrin (TPPNA-M M=Mg, Co, Cu, Zn) were synthesized and characterized by 1H NMR, FT-IR, UV-vis methods. The naphthylporphyrin functionalized platinum nanocomposites (Pt@TPPNA) have been successfully prepared with the alcohol reduction method and characterized with UV-vis, TEM, FTIR, XRD, Fluorescence spectroscopy and photo-electrochemical method, respectively. The diameter of the nanocomposites is range from 2-4 nm depending on the molar ratio of Pt to TPPNA. Under irradiation of UV-vis light, hydrogen was produced from photodecomposition of water using Pt@TPPNA nanocomposite as the catalyst in the presence of EDTA. The catalytic activity of Pt nanocomposite was influenced by the amount of catalyst, pH and the molar ratio of Pt/TPPNA.(2) 5,10,15,20-tetrakis(4-(hydroxyl)phenyl) porphyrin (TPPH) bearing several anthryl donor moieties 5,10,15,20-tetrakis (4-(anthracene-1-ylmethoxy)phenyl) porphyrin (TPPAN-1~4) was synthesized and characterized by 1H NMR, FT-IR, UV-vis methods. The anthrylporphyrin functionalized platinum nanocomposites (Pt@TPPAN) have been successfully prepared with the alcohol reduction method and characterized with UV-vis, TEM, FT-IR, XRD, Fluorescence spectroscopy and photo-electrochemical method, respectively. The diameter of the nanocomposites is range from 2-3 nm depending on the molar ratio of Pt to TPPAN. Under irradiation of UV-vis light, hydrogen was produced from photodecomposition of water using Pt@TPPAN nanocomposite as the catalyst in the presence of EDTA. The catalytic activity of Pt nanocomposite was influenced by the amount of catalyst, pH and the molar ratio of Pt/TPPAN.(3) Pyrenesulfonic acid (PSA) was synthesized by pyrene sulfonated and characterized by 1H NMR, FT-IR, UV-vis methods. To mimic photoinduced electron transfer processes in the natural photosynthetic reaction centre, constructing self-assembled pyrene-porphyrin conjugates (TPPH-PSA) held by hydrogen bonding will simplify the synthesis. The pyrene-porphyrin functionalized platinum nanocomposites (Pt@TPPH-PSA) have been successfully prepared with the alcohol reduction method and characterized with UV-vis, TEM, FT-IR, XRD, Fluorescence spectroscopy and photo-electrochemical method, respectively. Under irradiation of UV-vis light, hydrogen was produced from photodecomposition of water using Pt@TPPH-PSA nanocomposites as the catalyst in the presence of EDTA. The catalytic activity of Pt nanocomposite was influenced by the amount of catalyst, pH and the molar ratio of Pt/TPPH-PSA.更多还原