脱合金法制备Fe基纳米多孔材料及其催化性能
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摘要
近年来,纳米多孔金属材料成为催化和传感器等领域的研究热点。本研究将铁基非晶合金和脱合金工艺相结合,制备具有催化性能的纳米多孔材料。采用真空感应熔炼装置和真空急冷甩带装置制备宽1mm×厚25μm的Fe_(60)Pd_(20)P_(20)非晶合金条带,并借助X射线衍射仪(XRD)、扫描电镜(SEM)、能谱仪(EDS)对非晶合金条带进行表征。将Fe60Pd_(20)P_(20)非晶合金作为电化学脱合金的前驱体材料,在25℃、1mol/L H_2SO4电解液中进行1h恒电位脱合金处理,成功制备出具有均匀三维连通孔道结构的纳米多孔金属材料。经电化学测试表明,恒电位0.72V获得的纳米多孔材料,在0.5mol/L H_2SO4+0.5mol/L HCOOH溶液的循环伏安曲线中,较原非晶合金的氧化峰电压负移约0.4V,氧化峰电流密度提高约15倍,该纳米多孔材料对甲酸的分解有明显的催化性能。
Recently,nanoporous metal materials are the focus in catalysis and sensor fields.In this study,Fe-based amorphous alloy was chosen as a raw material,and the nanoporous materials with catalytic properties were prepared by dealloying.Fe_(60)-Pd_(20) P_(20) amorphous alloy ribbons with 1 mm in width and 25μm in thickness were prepared by vacuum melting and rapid solidification,and the amorphous alloy ribbons were characterized by XRD,SEM and EDS.The Fe60 Pd_(20) P_(20) alloy was used as a starting alloy for potentiostatic dealloying in 1 mol/L H_2 SO_4 solution at 25 ℃.The nanoporous amorphous alloy with an uniform 3-D interconnect structure was successfully prepared.The electrochemical tests showed that this nanoporous amorphous alloy exhibited high electrocatalytic activity for the decomposition of formic acid.Compared with the original amorphous alloy untreated by dealloying,the oxidation peak potential had a negative shift of 0.4 Vin 0.5 mol/L H_2 SO_4+0.5 mol/L HCOOH solution as well as the oxidation peak current density increased by 15 times.The nanoporous material has obvious catalytic activity for the decomposition of formic acid.
Recently,nanoporous metal materials are the focus in catalysis and sensor fields.In this study,Fe-based amorphous alloy was chosen as a raw material,and the nanoporous materials with catalytic properties were prepared by dealloying.Fe_(60)-Pd_(20) P_(20) amorphous alloy ribbons with 1 mm in width and 25μm in thickness were prepared by vacuum melting and rapid solidification,and the amorphous alloy ribbons were characterized by XRD,SEM and EDS.The Fe60 Pd_(20) P_(20) alloy was used as a starting alloy for potentiostatic dealloying in 1 mol/L H_2 SO_4 solution at 25 ℃.The nanoporous amorphous alloy with an uniform 3-D interconnect structure was successfully prepared.The electrochemical tests showed that this nanoporous amorphous alloy exhibited high electrocatalytic activity for the decomposition of formic acid.Compared with the original amorphous alloy untreated by dealloying,the oxidation peak potential had a negative shift of 0.4 Vin 0.5 mol/L H_2 SO_4+0.5 mol/L HCOOH solution as well as the oxidation peak current density increased by 15 times.The nanoporous material has obvious catalytic activity for the decomposition of formic acid.
引文
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11 Takeuchi A,Inoue A.Classification of bulk metallic glasses by atomic size difference,heat of mixing and period of constituent elements and its application to characterization of the main alloying element[J].Materials Transactions,2005,46(12):2817.
12 高胜利,杨奇,陈三平,等.化学元素周期表[M].北京:科学出版社,2017.
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14 Deng Z.A theis submitted in partial fulfillment of the requirement for the master of engineering[D].Wuhan:Huazhong University of Science and Technology,2014(in Chinese).邓珍.纳米多孔非晶合金的制备及其催化性能研究[D].武汉:华中科技大学,2014.
15 孙世刚,陈胜利.电化学[M].北京:化学工业出版社,2017.
2 Ding Y.Nanoporous metals:A new class of nanostructured energy materials[J].Journal of Shandong University,2011,46(10):121(in Chinese).丁轶.纳米多孔金属:一种新型能源纳米材料[J].山东大学学报,2011,46(10):121.
3 Erlebacher J,Aziz M J,Karma A,et al.Evolution of nanoporosity in dealloying[J].Nature,2001,410(6827):450.
4 Smith G B,Maaroof A I,Gentle A.Homogenized Lorentz-Drude optical response in highly nanoporous conducting gold layers produced by de-alloying[J].Optics Communications,2007,271(1):263.
5 Wang L J.Study on dealloying of Au-Ni alloys[D].Dalian:Dalian Jiaotong University,2007(in Chinese).王玲娟.Au-Ni合金的去合金化研究[D].大连:大连交通大学,2007.
6 Thorp J C,Sieradzki K,Tang L,et al.Formation of nanoporous noble metal thin films by electrochemical dealloying of PtxSi1-x[J].Applied Physics Letters,2006,88(3):1107.
7 Pugh D V,Dursun A,Corcoran S G.Formation of nanoporous platinum by selective dissolution of Cu from Cu0.75Pt0.25[J].Journal of Materials Research,2003,18(1):216.
8 Meyerheim H L,Soyka E,Kirschner J.Alloying and dealloying in pulsed laser deposited Pd films on Cu(100)[J].Physical Review B,2006,74(8):085405.
9 Wang B L.Electrochemical dealloying of icosahedron Al-Pd-M(M=Mn,Fe,Cr,Mg)quasicrystals[D].Dalian:Dalian University of Technology,2014(in Chinese).王宝林.Al-Pd-M(M=Mn,Fe,Cr,Mg)二十面体准晶电化学脱合金化研究[D].大连:大连理工大学,2014.
10 Ye H,Zhu S,Akihisa I.The development of Fe-based soft magnetic amorphous and bulk metallic glassy alloys[J].Journal of Functional Materials,2016,47(3):03027.
11 Takeuchi A,Inoue A.Classification of bulk metallic glasses by atomic size difference,heat of mixing and period of constituent elements and its application to characterization of the main alloying element[J].Materials Transactions,2005,46(12):2817.
12 高胜利,杨奇,陈三平,等.化学元素周期表[M].北京:科学出版社,2017.
13 Zhang X H,Dong X Z,Yang C L,et al.Multicomponent nanoporouspalladium with enhanced catalytic activity prepared by dealloying metallic glass[J].Journal of Functional Materials,2013,44(24):3634(in Chinese).张旭海,董小真,杨春雷,等.金属玻璃脱合金制备高催化性能的多元掺杂纳米多孔Pd[J].功能材料,2013,44(24):3634.
14 Deng Z.A theis submitted in partial fulfillment of the requirement for the master of engineering[D].Wuhan:Huazhong University of Science and Technology,2014(in Chinese).邓珍.纳米多孔非晶合金的制备及其催化性能研究[D].武汉:华中科技大学,2014.
15 孙世刚,陈胜利.电化学[M].北京:化学工业出版社,2017.