纳米镍分子印迹催化剂的制备及选择性催化对硝基苯甲醇
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摘要
以对硝基苯甲醇(p-NBA)和六水合硝酸镍的络合物为模板分子,丙烯酰胺(AM)为功能单体,二甲基丙烯酸乙二醇酯(EGDMA)为交联剂,采用本体聚合设计制备了镍纳米粒子分子印迹聚合物(Ni-MIP),通过FTIR、UV-Vis、SEM和TEM等手段进行了表征。以非分子印迹聚合物Ni-NIP和空白非印迹聚合物NIP为对照,考察了Ni-MIP对p-NBA的催化活性和选择性。结果表明:以水为溶剂时,过氧化氢(质量分数30%)氧化p-NBA的反应中,Ni-MIP为催化剂,反应1 h时p-NBA转化率72%,高于Ni-NIP(64%),NIP没有催化效果;在p-NBA结构类似物邻硝基苯甲醇(o-NBA)的反应中,Ni-MIP的转化率仅为24%,明显低于Ni-NIP的转化率(64%),说明Ni-MIP催化剂具有与底物分子p-NBA相匹配的印迹空腔位点,可实现特异性识别催化。
With complex of p-nitrobenzyl alcohol(p-NBA) and nickel nitrate hexahydrate as template molecule, acrylamide(AM) as functional monomer and ethylene glycol dimethacrylate(EGDMA) as crosslinking agent, the Ni nanoparticle molecularly imprinted polymer(Ni-MIP) was prepared by bulk polymerization. The prepared Ni-MIP was characterized by FTIR, UV-Vis, SEM and TEM. Using non-molecularly imprinted polymers of Ni-NIP and NIP as comparison samples, the catalytic activity and selectivity of Ni-MIP for p-NBA were investigated. The results show that in the oxidation reaction of p-NBA with water as solvent and H_2O_2 as oxidant, the conversion of p-NBA reaches 72% after 1h with Ni-MIP as catalyst. The conversion rate of p-NBA is 64% with Ni-NIP as catalyst, and NIP has no catalytic effect. The catalytic efficiency of Ni-MIP is 24% for p-NBA structural analogue of o-nitrobenzyl alcohol(o-NBA), which is much lower than that of Ni-NIP(64%). It is indicates that the Ni-MIP catalyst has imprinted cavity matching the substrate molecule p-NBA, which can realize specific recognition catalysis.
With complex of p-nitrobenzyl alcohol(p-NBA) and nickel nitrate hexahydrate as template molecule, acrylamide(AM) as functional monomer and ethylene glycol dimethacrylate(EGDMA) as crosslinking agent, the Ni nanoparticle molecularly imprinted polymer(Ni-MIP) was prepared by bulk polymerization. The prepared Ni-MIP was characterized by FTIR, UV-Vis, SEM and TEM. Using non-molecularly imprinted polymers of Ni-NIP and NIP as comparison samples, the catalytic activity and selectivity of Ni-MIP for p-NBA were investigated. The results show that in the oxidation reaction of p-NBA with water as solvent and H_2O_2 as oxidant, the conversion of p-NBA reaches 72% after 1h with Ni-MIP as catalyst. The conversion rate of p-NBA is 64% with Ni-NIP as catalyst, and NIP has no catalytic effect. The catalytic efficiency of Ni-MIP is 24% for p-NBA structural analogue of o-nitrobenzyl alcohol(o-NBA), which is much lower than that of Ni-NIP(64%). It is indicates that the Ni-MIP catalyst has imprinted cavity matching the substrate molecule p-NBA, which can realize specific recognition catalysis.
引文
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[3]Zhu Yan(朱燕),Wu Guangwen(吴广文),Huang Yangang(黄艳刚),et al.Two step synthesis of m-nitrobenzaldehyde[J].Fine Chemicals(精细化工),2011,28(2):201-204.
[4]Liu C,Tan R,Yu N,et al.Pt-Pd bi-metal nanoparticles captured and stabilized by imine groups in a periodic mesoporous organosilica of SBA-15 for hydrogenation of nitrobenzene[J].Microporous&Mesoporous Materials,2010,131(1):162-169.
[5]Liang R N,Song D A,Zhang R M,et al.Potentiometric sensing of neutral species based on a uniform-sized molecularly imprinted polymer as a receptor[J].Angewandte Chemie International Edition,2010,49(14):2556-2559.
[6]Ya?ez F,Chianella I,Piletsky S A,et al.Computational modeling and molecular imprinting for the development of acrylic polymers with high affinity for bile salts[J].Analytica Chimica Acta,2010,659(1):178-185.
[7]Zhao Y,Zhao X,Hu J,et al.Multiplex label-Free detection of biomolecules with an imprinted suspension array[J].Angewandte Chemie International Edition,2010,48(40):7350-7352.
[8]Petcu M,Karlsson J G,Whitcombe M J,et al.Probing the limits of molecular imprinting:Strategies with a template of limited size and functionality[J].Journal of Molecular Recognition,2010,22(1):18-25.
[9]Danylec B,Schwarz L J,Harris S J,et al.The application of template selectophores for the preparation of molecularly imprinted polymers[J].Molecules,2015,20(9):17601-17613.
[10]Matsui J,Nicholls I A,Takeuchi T,et al.Metal ion mediated recognition in molecularly imprinted polymers[J].Analytica Chimica Acta,1996,335(1/2):71-77.
[11]Brunkan N M,Gagne M R.Effect of chiral cavities associated with molecularly imprinted platinum centers on the selectivity of ligand-exchange reactions at platinum[J].Journal of the American Chemical Society,2000,122(26):6217-6225.
[12]Li Y,Fan Y,Yang H,et al.Strong metal-support interaction and catalytic properties of anatase and rutile supported palladium catalyst Pd/TiO2[J].Chemical Physics Letters,2003,372(1):160-165.
[13]Tang Z,Li Q,Lu G.The effect of plasma pre-treatment of carbon used as a Pt catalyst support for methanol electrooxidation[J].Carbon,2007,45(1):41-46.
[14]Song J L,Gong S.A substrate-selective nanoreactor made of molecularly imprinted polymer containing catalytic silver nanoparticles[J].Advanced Functional Materials,2010,19(16):2601-2606.
[15]Zhang D,Li S,Li W,et al.Biomimic recognition and catalysis by an imprinted catalysts:A rational design of molecular self-assembly toward predetermined high specificity[J].Catalysis Letters,2007,115(3/4):169-175.
[16]Sun W,Tan R,Zheng W,et al.Molecularly imprinted polymer containing Fe(Ⅲ)catalysts for specific substrate recognition[J].Chinese Journal of Catalysis,2013,34(8):1589-1598.
[17]Stefankiewicz A R,Wa??sachorab M,Harrowfield J,et al.Selfassembly of transition metal ion complexes of a hybrid pyrazineterpyridine ligand[J].Dalton Transactions,2013,42(5):1743-1751.
[18]Richter F H,Meng Y,Klasen T,et al.Structural mimicking of inorganic catalyst supports with polydivinylbenzene to improve performance in the selective aerobic oxidation of ethanol and glycerol in water[J].Journal of Catalysis,2013,308(4):341-351.
[19]Menezes W G,Zielasek V,Dzhardimalieva G I,et al.Synthesis of stable AuAg bimetallic nanoparticles encapsulated by diblock copolymer micelles[J].Nanoscale,2012,4(5):1658-1664.
[20]Yuan X H,Liu T T,Gao L,et al.A convenient separation method for di(2-ethylhexyl)phthalate by novel superparamagnetic molecularly imprinted polymers[J].RSC Advances,2018,8(63):36191-36199
[21]Piletsky S A,Karim K,Piletska E V,et al.Recognition of ephedrine enantiomers by molecularly imprinted polymers designed using a computational approach[J].Analyst,2001,126(10):1826-1830.
[22]Sergeyeva T A,Piletsky S A,Brovko A A,et al.Selective recognition of atrazine by molecularly imprinted polymer membranes.Development of conductometric sensor for herbicides detection[J].Analytica Chimica Acta,1999,392(2/3):105-111.
[23]Richter F H,Meng Y,Klasen T,et al.Structural mimicking of inorganic catalyst supports with polydivinylbenzene to improve performance in the selective aerobic oxidation of ethanol and glycerol in water[J].Journal of Catalysis,2013,308(4):341-351.
[24]Sun W,Tan R,Zheng W,et al.Molecularly imprinted polymer containing Fe(Ⅲ)catalysts for specific substrate recognition[J].Chinese Journal of Catalysis,2013,34(8):1589-1598.