多孔碳负载Cu_2O/Cu双相催化剂的制备及应用
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摘要
以硝酸铜和均苯三甲酸为原料,采用溶剂热合成法制备了金属有机框架材料(Cu-BTC),将其在氮气和空气气氛下焙烧制备了多孔碳负载的Cu2O/Cu催化剂Cu-BTC-1和Cu-BTC-2,并考察了其在对硝基苯酚催化还原中的催化性能。对Cu-BTC-1和Cu-BTC-2进行了XRD,SEM,TEM和BET表征。XRD表征结果表明:在氮气气氛中焙烧Cu-BTC可得到多孔碳负载的Cu2O/Cu双相纳米晶材料。SEM和TEM结果表明:相对于Cu-BTC-2催化剂,Cu-BTC-1双相粒子粒径较小,介于10~30 nm之间,比表面积较高,达200 m~2/g。对硝基苯酚催化还原实验结果表明:与Cu-BTC-2(表观速率系数kapp=0.0067 s–1)相比,Cu-BTC-1在对硝基苯酚的还原中具有更高的催化活性(kapp=0.0108 s–1)。
Cu-BTC metal organic frameworks were prepared by solvothermal method using copper nitrate and trimesic acid as raw materials. Then,porous carbon-supported Cu_2O/Cu dual phase catalyst(Cu-BTC-1) and Cu-BTC-2,can be obtained by calcining Cu-BTC precursor under nitrogen and air atmosphere,respectively. Meanwhile,the catalytic performance of Cu-BTC-1 and Cu-BTC-2 in p-nitrophenol reduction were investigated. XRD measurement indicated that porous carbon supported Cu_2O/Cu dual phase nanocrystals(Cu-BTC-1) could be obtained by calcinating Cu-BTC precursor in nitrogen atmosphere. SEM and TEM images showed that Cu-BTC-1 exhibits smaller crystal particles ranging from 10 to 30 nm and higher specific surface area up to 200 m~2/g compared with Cu-BTC-2 sample. The experimental results on p-nitrophenol catalytic reduction indicated that Cu-BTC-1 catalyst possesses much higher catalytic activity(kapp= 0.0108 s–1) compared with the Cu-BTC-2(kapp=0.0067 s–1).
Cu-BTC metal organic frameworks were prepared by solvothermal method using copper nitrate and trimesic acid as raw materials. Then,porous carbon-supported Cu_2O/Cu dual phase catalyst(Cu-BTC-1) and Cu-BTC-2,can be obtained by calcining Cu-BTC precursor under nitrogen and air atmosphere,respectively. Meanwhile,the catalytic performance of Cu-BTC-1 and Cu-BTC-2 in p-nitrophenol reduction were investigated. XRD measurement indicated that porous carbon supported Cu_2O/Cu dual phase nanocrystals(Cu-BTC-1) could be obtained by calcinating Cu-BTC precursor in nitrogen atmosphere. SEM and TEM images showed that Cu-BTC-1 exhibits smaller crystal particles ranging from 10 to 30 nm and higher specific surface area up to 200 m~2/g compared with Cu-BTC-2 sample. The experimental results on p-nitrophenol catalytic reduction indicated that Cu-BTC-1 catalyst possesses much higher catalytic activity(kapp= 0.0108 s–1) compared with the Cu-BTC-2(kapp=0.0067 s–1).
引文
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[4]Fang Y,Wang E.Simple and direct synthesis of oxygenous carbon supported palladium nanoparticles with high catalytic activity[J].Nanoscale,2013,5(5):1843-1848.
[5]Khodaveisi J,Dadfarnia S,Haji Shabani A M,et al.Artificial neural network assisted kinetic spectrophotometric technique for simultaneous determination of paracetamol and p-aminophenol in pharmaceutical samples using localized surface plasmon resonance band of silver nanoparticles[J].Spectrochim Acta,Part A:2015,138(2):474-480.
[6]Yu Huanhuan(余焕焕),Liu Fang(刘芳),Wang Shiqi(王士琦),et al.Preparation and characterization of silver-based montmorillonite nanocomposites and catalytic activity for 4-nitrophenol reduction[J].J Chin Ceram Soc(硅酸盐学报),2013,41(11):1581–1587.
[7]Zhao L,Zhang H,Xing Y,et al.Studies on the magnetism of cobalt ferrite nanocrystals synthesized by hydrothermal method[J].J Solid State Chem,2008,181(2):245-252.
[8]Kongarapu R J,Mahamallik P,Pal A.Surfactant modification of chitosan hydrogel beads for Ni@Ni O core-shell nanoparticles formation and its catalysis to 4-nitrophenol reduction[J].J Environ Chem Eng,2017,5(2):1321-1329.
[9]You J G,Shanmugam C,Liu Y W,et al.Boosting catalytic activity of metal nanoparticles for 4-nitrophenol reduction:Modification of metal naoparticles with poly(diallyldimethylammonium chloride)[J].J Hazard Mater,2017,324(2):420-427.
[10]Zhou Bo(周波),Liu Zhiguo(刘志国),Wang Hongxia(王红霞),et al.Hydrothermal preparation and visible photocatalytic activity of flower-like Cu2O/Cu nanocomposites[J].Acta Phys Chim Sin(物理化学学报),2009,29(9):1841-1846.
[11]Yang Caifeng(杨彩凤),Qin Lirong(秦丽溶),Zhao Jianwei(赵建伟),et al.Synthesis of Ni-foam-modified Cu/Cu O micro/nanostructures and their application in AA detection[J].J Southwest Univ(西南大学学报),2015,37(5):112-117.
[12]Krishna R,Fernandes D M,Ventura J,et al.Novel synthesis of highly catalytic active Cu@Ni/RGO nanocomposite for efficient hydrogenation of 4-nitrophenol organic pollutant[J].Int J Hydrogen Energy,2016,41(27):11608-11615.
[13]Zhao S D,Li Q M,Li F,et al.Synthesis of spinel Cu Co2O4nanoparticles and its application in p-nitrophenol reduction[J].J Sol-Gel Sci Technol,2017,81(2):544-555.
[14]You Jiayong(游佳勇),Zhang Tianyong(张天永),Liu Yanfeng(刘艳凤),et al.Rapid synthesis of metal-organic framework HKUST-1[J].J Chem Eng Chin Univ(高校化学工程学报),2015,29(5):1126-1132.
[15]Abdelhameed R M,Emam H E,Jo?o Rocha J,et al.Cu-BTC metal-organic framework natural fabric composites for fuel purification[J].Fuel Process Technol,2017,159(5):306-312.