以精氨酸和卟啉组装体为模板构建具有对映选择性光催化能力的Pt/Pt-Au掺杂手性纳米结构  

Construction of Pt/Pt-Au doped chiral nanostructures using arginine and porphyrin assemblies as templates for enantioselective photocatalysis

作　　者：岳小勇 徐丽广 林恒伟 胥传来 李斯 Xiaoyong Yue;Liguang Xu;Hengwei Lin;Chuanlai Xu;Si Li(International Joint Research Center for Photo-responsive Molecules and Materials,School of Chemical and Material Engineering,Jiangnan University,Wuxi 214122,China;State Key Laboratory of Food Science and Technology,International Joint Research Laboratory for Biointerface and Biodetection,School of Food Science and Technology,Jiangnan University,Wuxi 214122,China)

机构地区：[1]International Joint Research Center for Photo-responsive Molecules and Materials,School of Chemical and Material Engineering,Jiangnan University,Wuxi 214122,China [2]State Key Laboratory of Food Science and Technology,International Joint Research Laboratory for Biointerface and Biodetection,School of Food Science and Technology,Jiangnan University,Wuxi 214122,China

出　　处：《Science Bulletin》2023年第16期1764-1771,M0004,共9页科学通报（英文版）

基　　金：supported by the National Natural Science Foundation of China(32101142);the Natural Science Foundation of Jiangsu Province(BK20221532);the Fundamental Research Funds for the Central Universities(JUSRP622037)。

摘　　要：具有不同功能的手性纳米材料已经被广泛探讨,但纳米材料的结构对其对映选择性催化能力的影响仍有待深入研究.本研究构建了具有不同形态和组成成分的手性铂和铂-金双金属纳米结构,并系统地研究了这些因素对手性纳米催化剂对映选择性光催化能力的影响.首先,本研究以L-/D-精氨酸(Arg)和单磺酸四苯基卟啉(H_(2)TPPS)为手性模板,通过控制Arg与H_(2)TPPS组装体系的pH、离子强度和反应时间,实现组装体形态和组成的调节,制备具有手性光学活性的铂和铂-金双金属纳米棒和纳米球.进一步地,以L-/D-二羟基苯丙氨酸(DOPA)为催化模型,系统地研究了手性纳米结构在可见光照射下的对映选择性催化能力,结果表明同手性构型的DOPA和铂纳米棒的氧化速率高约60%.该研究为构建形貌和组成可控的手性纳米催化剂提供了一种简单的策略,证明了纳米催化剂在手性有机物催化转化等方面的显著优势,将有助于构建发色团-蛋白质复合物的仿生材料,有利于高附加值手性分子的合成与转化.Chiral nanomaterials with different functions have been widely developed,but the deep understanding of the structural effects of nanocatalysts on enantioselective photocatalytic efficiency is still highly demanded.Herein,Pt and Pt-Au-bimetal-doped chiral nanostructures with various morphologies and compositions are facilely constructed using L-/D-arginine(L-/D-Arg)and mono-sulfonate tetraphenyl porphyrin(H_2TPPS)assemblies as chiral templates.Interestingly,these Pt and Pt-Au-doped chiral nanostructures,including nanorods(NR)and nanospheres(NS),can be well regulated by controlling pH,ionic strength,and reaction time of the assembling system of Arg and H_2TPPS.More impressively,specific Au growth direction along the Pt-doped chiral NR(L-/D-Pt-NR)is observed(from tip to middle)during the preparation of Pt-Au-bimetal-doped chiral NR(L-/D-Pt-Au-NR)and their compositions can be finely controlled by simply adjusting the concentrations of HAuCl_4.As expected,the chiral nanostructures exhibit superior enantioselective photocatalytic ability toward chiral organics under visible light:the oxidation rate of L-dihydroxy-phenylalanine(L-DOPA)catalyzed by L-Pt-NR(or D-DOPA catalyzed by D-Pt-NR)is about 60%higher than that of L-DOPA catalyzed by D-Pt-NR(or L-DOPA catalyzed by D-Pt-NR).This study provides a facile strategy to construct chiral nanostructures for the photocatalytic conversion of chiral organics.

关 键 词：四苯基卟啉 手性分子 对映选择性 纳米催化剂 蛋白质复合物 金属纳米结构 组装体 可见光照射 

分 类 号：TB383.1[一般工业技术—材料科学与工程] O643.36[理学—物理化学] O644.1[理学—化学]