CuFe_2O_4/纳米纤维素磁性复合材料的制备及催化性能
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摘要
采用简单易行的一锅溶剂热法原位合成CuFe_2O_4/纳米纤维素(CuFe_2O_4/CNC)磁性复合材料,并研究CuFe_2O_4/CMC磁性复合材料催化剂在NaBH4作用下催化还原4-硝基酚(4-NP)性能。结果表明:所制备的CuFe_2O_4/CNC磁性复合材料为单一尖晶石结构,具有超顺磁性,纳米颗粒尺寸约为10nm,其饱和磁化强度为33.15emu·g-1。与CuFe_2O_4纳米颗粒相比,CuFe_2O_4/CNC磁性复合材料的比表面积提高到89.9 m2·g-1(CuFe_2O_4纳米颗粒的比表面积为53.9m2·g-1)。CNC有助于改善CuFe_2O_4的单分散性,且对4-NP的吸附作用能加快反应的传质速率。将CuFe_2O_4/CNC磁性复合材料用于催化还原4-NP,反应符合一级动力学特征;当CNC的添加量为0.2g时,可以将4-NP(100μL,0.005mol·L-1)溶液在25s催化还原完全,表现出优异的反应活性。催化剂循环使用5次后,对4-NP的转化率仍能保持90%以上。
Magnetic CuFe_2O_4/cellulose nano crystals(CuFe_2O_4/CNC)composite was presented via a facile onestep solvothermal method.The catalytic reduction of 4-nitrophenol(4-NP)was tested with the addition of NaBH4.The results show that the prepared superparamagnetic CuFe_2O_4/CNC composite is a cubic spinel crystal structure with the nano particle size of 10 nm,presenting the saturation magnetization of 33.15 emu·g-1.Compared with CuFe_2O_4 nano particles,the CuFe_2O_4/CNC composite shows a higher specific surface area of 89.9 m2·g-1(the specific surface area of CuFe_2O_4 nano particles is 53.9 m2·g-1).The CNC helps to improve the monodispersity of CuFe_2O_4 nano particles and absorbs 4-NP to facilitate the mass transfer rate positively.The CuFe_2O_4/CNC composite is conducted to catalytic reduction of 4-NP.The dynamic kinetics of the catalytic reduction is the first order process.When 0.2 g CNC is added,CuFe_2O_4/CNC composite can catalyze the reduction of 4-NP(100μL,0.005 mol·L-1)within 25 s,showing a high catalytic activity.The conversion rate of 4-NP can still reach 90%even after 5 cycles.
Magnetic CuFe_2O_4/cellulose nano crystals(CuFe_2O_4/CNC)composite was presented via a facile onestep solvothermal method.The catalytic reduction of 4-nitrophenol(4-NP)was tested with the addition of NaBH4.The results show that the prepared superparamagnetic CuFe_2O_4/CNC composite is a cubic spinel crystal structure with the nano particle size of 10 nm,presenting the saturation magnetization of 33.15 emu·g-1.Compared with CuFe_2O_4 nano particles,the CuFe_2O_4/CNC composite shows a higher specific surface area of 89.9 m2·g-1(the specific surface area of CuFe_2O_4 nano particles is 53.9 m2·g-1).The CNC helps to improve the monodispersity of CuFe_2O_4 nano particles and absorbs 4-NP to facilitate the mass transfer rate positively.The CuFe_2O_4/CNC composite is conducted to catalytic reduction of 4-NP.The dynamic kinetics of the catalytic reduction is the first order process.When 0.2 g CNC is added,CuFe_2O_4/CNC composite can catalyze the reduction of 4-NP(100μL,0.005 mol·L-1)within 25 s,showing a high catalytic activity.The conversion rate of 4-NP can still reach 90%even after 5 cycles.
引文
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[3] CHEN R,WANG Q,DU Y,et al.Effect of initial solution apparent pH on nano-sized nickel catalysts in p-nitrophenol hydrogenation[J].Chemical Engineering Journal,2009,145(3):371-376.
[4] GAZI S,ANANTHAKRISHNAN R.Metal-free-photocatalytic reduction of 4-nitrophenol by resin-supported dye under the visible irradiation[J].Applied Catalysis B:Environmental,2011,105(3):317-325.
[5] MOHAMED M M,AL-SHARIF M S.Visible light assisted reduction of 4-nitrophenol to 4-aminophenol on Ag/TiO2photocatalysts synthesized by hybrid templates[J].Applied Catalysis B:Environmental,2013,142-143:432-441.
[6]何永珍,周雪飞,代朝猛,等.铁氧体及其复合材料去除水体中有机污染物的研究进展[J].材料导报,2015,29(5):16-19.HE Y Z,ZHOU X F,DAI C M,et al.Research progress on removal of organic pollutants in water by ferrite and its composites materials[J].Material Review,2015,29(5):16-19(in Chinese).
[7] GOYAL A,BANSAL S,SINGHAL S.Facile reduction of nitrophenols:Comparative catalytic efficiency of MFe2O4(M=Ni,Cu,Zn)nano ferrites[J].International Journal of Hydrogen Energy,2014,39(10):4895-4908.
[8] FENG J,SU L,MA Y,et al.CuFe2O4 magnetic nanoparticles:A simple and efficient catalyst for the reduction of nitrophenol[J].Chemical Engineering Journal,2013,221:16-24.
[9] IBRAHIM I,ALI I O,SALAMA T M,et al.Synthesis of magnetically recyclable spinel ferrite(MFe2O4,M=Zn,Co,Mn)nanocrystals engineered by sol gel-hydrothermal technology:High catalytic performances for nitroarenes reduction[J]. Applied Catalysis B:Environmental,2016,181:389-402.
[10] SU L,QIN W,ZHANG H,et al.The peroxidase/catalaselike activities of MFe2O4(M=Mg,Ni,Cu)MNPs and their application in colorimetric biosensing of glucose[J].Biosensors and Bioelectronics,2015,63:384-391.
[11] REN,Y M,LIN L Q,et al.Sulfate Radicals induced from peroxymonosulfate by magnetic ferrospinel MFe2O4(M=Co,Cu,Mn,and Zn)as heterogeneous catalysts in the water[J].Applied Catalysis B:Environmental,2015,165:572-578.
[12] TIAN C,FU S,LUCIA L A.Magnetic Cu0.5Co0.5Fe2O4ferrite nanoparticles immobilized in situ on the surfaces of cellulose nanocrystals[J].Cellulose,2015,22(4):2571-2587.
[13] ZHANG H,ZHAO Y,LIU W,et al.Preparation of magnetically separable Cu6/7Co1/7Fe2O4-graphene catalyst and its application in selective reduction of nitroarenes[J].Catalysis Communications,2015,59:161-165.
[14] ZHAO Y,HE G,DAI W,et al.High catalytic activity in the phenol hydroxylation of magnetically separable CuFe2O4-reduced graphene oxide[J].Industrial&Engineering Chemistry Research,2014,53(32):12566-12574.
[15]刘红玲,彭俊军,李明,等.玻璃固载TiO2/纳米纤维素复合薄膜的制备及其光催化性能[J].复合材料学报,2013,30(4):163-169.LIU H L,PENG J J,LI M,et al.Preparation and photocatalytic activity of TiO2/nanocrystalline cellulose catalytic composite films coating on glass[J].Acta Materiae Compositae Sinica,2013,30(4):163-169(in Chinese).
[16] ZHANG X,FENG M,QU R,et al.Catalytic degradation of diethyl phthalate in aqueous solution by persulfate activated with nano-scaled magnetic CuFe2O4/MWCNTs[J].Chemical Engineering Journal,2016,301:1-11.
[17] WU X,SHI Z,FU S,et al.Strategy for synthesizing porous cellulose nanocrystal supported metal nanocatalysts[J].ACS Sustainable Chemistry&Engineering,2016,4(11):5929-5935.
[18] REN Y,LI S,DAI B,et al.Microwave absorption properties of cobalt ferrite-modified carbonized bacterial cellulose[J].Applied Surface Science,2014,311:1-4.
[19]胡琼,曲雯雯,余明远,等.水热法制备纤维素基CdS纳米复合材料及其光催化性能研究[J].材料导报,2016,30(22):20-25.HU Q,QU W W,YU M Y,et al.Study on the preparation of cellulose based CdS nanocomposites and its photocatalytic properties by hydrothermal method[J].Material Review,2016,30(22):20-25(in Chinese).
[20]袁彩霞,罗卫华,袁光明,等.增容纳米纤维素/聚乳酸复合材料的制备与性能[J].复合材料学报,2016,33(12):2718-2724.YUAN C X,LUO W H,YUAN G M,et al.Preparation and properties of compatibilized cellulose nanocrystal/poly(lactic acid)composites[J].Acta Materiae Compositae Sinica,2016,33(12):2718-2724(in Chinese).
[21] XU S,SHEN D,WU P,et al.Fabrication of water-repellent cellulose fiber coated with magnetic nanoparticles under supercritical carbon dioxide[J].Journal of Nanoparticle Research,2013,15(668):1-12.
[22] HU Z,MENG Q,LIU R,et al.Physical study of the primary and secondary photothermal events in gold/cellulose nanocrystals(AuNP/CNC)nanocomposites embedded in PVA matrices[J].ACS Sustainable Chemistry,2017,5(2):1601-1609.
[23] ZHU M,MENG D,WANG C,et al.Facile fabrication of hierarchically porous CuFe2O4 nanospheres with enhanced capacitance property[J].ACS Applied Material Interfaces,2013,5(13):6030-6037.
[24] WOO H,JI W K,KIM M,et al.Au nanoparticles supported on magnetically separable Fe2O3-graphene oxide hybrid nanosheets for the catalytic reduction of 4-nitrophenol[J].RSC Advances,2015,5(10):7554-7558.
[25] DUAN B,LIU F,HE M,et al.Ag-Fe3O4nano-composites@chitin microspheres constructed by in situ one-pot synthesis for rapid hydrogenation catalysis[J].Green Chemistry,2014,16(5):2835-2845.
[26] XIONG R,WANG Y,ZHANG X,et al.In situ growth of gold nano particles on magneticγ-Fe2O3@cellulose nano composites:A highly active and recyclable catalyst for reduction of 4-nitrophenol[J].RSC Advances,2014,4(13):6454-6462.
[27] ZHOU Z,LU C,WU X,et al.Cellulose nanocrystals as a novel support for CuO nanoparticles catalysts:Facile synthesis and their application to 4-nitrophenol reduction[J].RSC Advances,2013,3(48):26066-26073.
[28] NASROLLAHZADEH M,BAGHERZADEH M,KARIMI H.Preparation,characterization and catalytic activity of CoFe2O4nanoparticles as a magnetically recoverable catalyst for selective oxidation of benzyl alcohol to benzaldehyde and reduction of organic dyes[J].Journal of Colloid and Interfaces Science,2016,465:271-278.
[29] ZHANG D,ZHANG G,WANG Q,et al.Dual-functional catalytic materials:Magnetically hollow porous Ni-manganese oxides microspheres/cotton cellulose fiber[J].Journal of Taiwan Institute of Chemistry Engineering,2017,77:311-320.