一锅法制备磁性Ni-Ag纳米合金催化剂及其催化还原对硝基苯酚
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摘要
采用液相共还原一锅法制备了不同[Ni]∶[Ag]比例的磁性Ni-Ag纳米合金催化剂。利用XRD、SEM、TEM表征了催化剂的物相和形貌,利用XPS测试了催化剂表面元素价态,采用SQUID分析了催化剂的磁学性能;以对硝基苯酚的催化还原反应作为模型反应,研究了[Ni]∶[Ag]比例对磁性Ni-Ag纳米合金催化剂催化性能的影响,并考察了其循环使用性能。结果表明,磁性Ni-Ag纳米合金催化剂由直径50 nm左右的Ni-Ag合金颗粒组成,催化还原对硝基苯酚的催化活性随Ag含量的增加先增强后减弱,[Ni]∶[Ag]=1∶1的催化剂催化性能最好。该Ni-Ag纳米合金催化剂的饱和磁化强度为15.43 emu·g~(-1),具有很好的磁学性能,可实现磁回收和循环利用,循环使用5次后依然保持高催化活性和稳定性。
We prepared magnetic Ni-Ag nano-alloy catalysts with different ratios of [Ni]∶[Ag] by a one-pot liquid co-reduction method.Furthermore,we characterized the phase and morphology of the catalysts by XRD,SEM,and TEM,measured the valence state of the surface element of the catalysts by XPS,and analyzed the magnetic property by SQUID.Moreover,using the catalytic reduction of 4-nitrophenol as a model reaction,we studied the effects of the ratio of [Ni]∶[Ag] on the catalytic performance of Ni-Ag nano-alloy catalysts,and investigated the recycling performance.The results show that Ni-Ag nano-alloy catalyst consists of particles with a diameter of about 50 nm,and the catalytic activity firstly increases and then decreases with the increase of Ag content.Therein,the catalytic performance of catalyst with [Ni]∶[Ag]=1∶1 is the best.The saturation magnetization of the Ni-Ag nano-alloy catalyst is 15.43 emu·g~(-1),which has good magnetic property and can be magnetically recyclable for reuse.After 5 times reuse,the nano-alloy catalyst still has high catalytic activity and stability.
We prepared magnetic Ni-Ag nano-alloy catalysts with different ratios of [Ni]∶[Ag] by a one-pot liquid co-reduction method.Furthermore,we characterized the phase and morphology of the catalysts by XRD,SEM,and TEM,measured the valence state of the surface element of the catalysts by XPS,and analyzed the magnetic property by SQUID.Moreover,using the catalytic reduction of 4-nitrophenol as a model reaction,we studied the effects of the ratio of [Ni]∶[Ag] on the catalytic performance of Ni-Ag nano-alloy catalysts,and investigated the recycling performance.The results show that Ni-Ag nano-alloy catalyst consists of particles with a diameter of about 50 nm,and the catalytic activity firstly increases and then decreases with the increase of Ag content.Therein,the catalytic performance of catalyst with [Ni]∶[Ag]=1∶1 is the best.The saturation magnetization of the Ni-Ag nano-alloy catalyst is 15.43 emu·g~(-1),which has good magnetic property and can be magnetically recyclable for reuse.After 5 times reuse,the nano-alloy catalyst still has high catalytic activity and stability.
引文
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[2] ZHANG W,TAN F T,WANG W,et al.Facile,template-free synthesis of silver nanodendrites with high catalytic activity for the reduction of p-nitrophenol[J].Journal of Hazardous Materials,2012,217-218(3):36-42.
[3] SAHINER N,OZAY H,OZAY O,et al.A soft hydrogel reactor for cobalt nanoparticle preparation and use in the reduction of nitrophenols[J].Applied Catalysis B:Environmental,2010,101(1):137-143.
[4] PABLO H,MOIS S P L,LIZ-MARZ N L M,et al.Catalysis by metallic nanoparticles in aqueous solution:model reactions[J].Chemical Society Reviews,2012,41(17):5577.
[5] MISHRA A K.13.Reduction of 4-Nitrophenol as a Model Reaction for Nanocatalysis[M].John Wiley & Sons,Inc.,2014:333-395.
[6] LU W B,NING R,QIN X Y,et al.Synthesis of Au nanoparticles decorated graphene oxide nanosheets:noncovalent functionalization by Tween 20 in situ reduction of aqueous chloroaurate ions for hydrazine detection and catalytic reduction of 4-nitrophenol[J].Journal of Hazardous Materials,2011,197(6):320.
[7] LIU G,WANG Y J,XU C C,et al.Excellent catalytic effects of highly crumpled graphene nanosheets on hydrogenation/dehydrogenation of magnesium hydride[J].Nanoscale,2013,5(3):1074-1081.
[8] DARABDHARA G,DAS M R.Bimetallic Au-Pd nanoparticles on 2D supported graphitic carbon nitride and reduced graphene oxide sheets:a comparative photocatalytic degradation study of organic pollutants in water[J].Chemosphere,2018,197:817.
[9] HAI-LONG J,TOMOKI A,TAMAO I,et al.Synergistic catalysis of Au@Ag core-shell nanoparticles stabilized on metal-organic framework[J].Journal of the American Chemical Society,2011,133(5):1304-1306.
[10] MOHAMED M M,AL-SHARIF M S.Visible light assisted reduction of 4-nitrophenol to 4-aminophenol on Ag/TiO2 photocatalysts synthesized by hybrid templates[J].Applied Catalysis B:Environmental,2013,142-143(10):432-441.
[11] HAREESH K,JOSHI R P,SUNITHA D V,et al.Anchoring of Ag-Au alloy nanoparticles on reduced graphene oxide sheets for the reduction of 4-nitrophenol[J].Applied Surface Science,2016,389:1050-1055.
[12] KIM D K,ZHANG Y,VOIT W,et al.Synthesis and characterization of surfactant-coated superparamagnetic monodispersed iron oxide nanoparticles[J].Journal of Magnetism & Magnetic Materials,2001,225(1):30-36.
[13] SENAPATI S,SRIVASTAVA A S K,SINGHB A S B,et al.Magnetic Ni/Ag core-shell nanostructure from prickly Ni nanowire precursor and its catalytic and antibacterial activity[J].Journal of Materials Chemistry,2012,22(14):157-168.
[14] RAI R K,GUPTA K,BEHRENS S,et al.Highly active bimetallic nickel-palladium alloy nanoparticle catalyzed Suzuki-Miyaura reactions[J].ChemCatChem,2015,7(12):1806-1812.
[15] ZHAO C,GUO J H,YANG Q,et al.Preparation of magnetic Ni@graphene nanocomposites and efficient removal organic dye under assistance of ultrasound[J].Applied Surface Science,2015,357:22-30.
[16] FENG B,TAN F T,WEI W,et al.Facile preparation of Ag/Ni(OH)2 composites with enhanced catalytic activity for reduction of 4-nitrophenol[J].RSC Advances,2017,7(23):14283-14289.
[17] PRIETO P,NISTOR V,NOUNEH K,et al.XPS study of silver,nickel and bimetallic silver-nickel nanoparticles prepared by seed-mediated growth[J].Applied Surface Science,2012,258(22):8807-8813.
[18] WU X Z,XING W,ZHANG L,et al.Nickel nanoparticles prepared by hydrazine hydrate reduction and their application in supercapacitor[J].Powder Technology,2012,224:162-167.
[19] MA H Y,WANG H T,NA C Z.Microwave-assisted optimization of platinum-nickel nanoalloys for catalytic water treatment[J].Applied Catalysis B:Environmental,2015,163:198-204.
[20] ROY A,SRINIVAS V,RAM S,et al.The effect of silver coating on magnetic properties of oxygen-stabilized tetragonal Ni nanoparticles prepared by chemical reduction[J].Journal of Physics Condensed Matter,2007,19(34):346220.