Investigation of fluorescence characterization and electrochemical behavior on the catalysts of nanosized Pt-Rh/γ-Al<sub>2</sub>O<sub>3</sub> to oxidize gaseous ammonia

doi:10.1007/s11783-013-0517-0

Front Envir Sci Eng

2013, Vol. 7

Issue (3) : 428-434 https://doi.org/10.1007/s11783-013-0517-0

RESEARCH ARTICLE

Investigation of fluorescence characterization and electrochemical behavior on the catalysts of nanosized Pt-Rh/γ-Al₂O₃ to oxidize gaseous ammonia

Chang-Mao HUNG¹(

), Wen-Liang LAI², Jane-Li LIN²

1. Department of Vehicle Engineering, Yung-Ta Institute of Technology and Commerce, Pingtung 909, China; 2. Department of Environmental Science and Occupational Safety and Hygiene, Tajen University, Pingtung 907, China

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Abstract

This work describes the environmentally friendly technology for oxidation of ammonia (NH₃) to form nitrogen at temperatures range from 423K to 673K by selective catalytic oxidation (SCO) over a nanosized Pt-Rh/γ-Al₂O₃ catalyst prepared by the incipient wetness impregnation method of hexachloroplatinic acid (H₂PtCl₆) and rhodium (III) nitrate (Rh(NO₃)₃) with γ-Al₂O₃ in a tubular fixed-bed flow quartz reactor (TFBR). The characterization of catalysts were thoroughly measured using transmission electron microscopy (TEM), three-dimensional excitation-emission fluorescent matrix (EEFM) spectroscopy, UV-Vis absorption, dynamic light-scattering (DLS), zeta potential meter, and cyclic voltammetry (CV). The results demonstrated that at a temperature of 673K and an oxygen content of 4%, approximately 99% of the NH₃ was removed by catalytic oxidation over the nanosized Pt-Rh/γ-Al₂O₃ catalyst. N₂ was the main product in NH₃-SCO process. Further, it reveals that the oxidation of NH₃ was proceeds by the over-oxidation of NH₃ into NO, which was conversely reacted with the NH₃ to yield N₂. Therefore, the application of nanosized Pt-Rh/γ-Al₂O₃ catalyst can significantly enhance the catalytic activity toward NH₃ oxidation. One fluorescent peak for fresh catalyst was different with that of exhausted catalyst. It indicates that EEFM spectroscopy was proven to be an appropriate and effective method to characterize the Pt clusters in intrinsic emission from nanosized Pt-Rh/γ-Al₂O₃ catalyst. Results obtained from the CV may explain the significant catalytic activity of the catalysts.

Keywords ammonia (NH₃) nanosized Pt-Rh/γ-Al₂O₃ catalyst excitation-emission fluorescent matrix (EEFM) selective catalytic oxidation (SCO) tubular fixed-bed reactor (TFBR)

Corresponding Author(s): HUNG Chang-Mao,Email:hungcm1031@gmail.com

Issue Date: 01 June 2013

Cite this article:

Chang-Mao HUNG,Wen-Liang LAI,Jane-Li LIN. Investigation of fluorescence characterization and electrochemical behavior on the catalysts of nanosized Pt-Rh/γ-Al₂O₃ to oxidize gaseous ammonia[J]. Front Envir Sci Eng, 2013, 7(3): 428-434.

URL:

https://academic.hep.com.cn/fese/EN/10.1007/s11783-013-0517-0
https://academic.hep.com.cn/fese/EN/Y2013/V7/I3/428

Fig.1 Relationship of the ammonia conversion, N, NO and NO yield at various temperatures over the nanosized Pt-Rh/γ-AlO catalyst. Test conditions: 500 ppm NH in He, O = 4%, R.H. = 12%, = 423 K-673 K, GHSV= 92000 h

Fig.2 Contour plots of excitation-emission fluorescent matrix of (a) fresh and (b) after activity test nanosized Pt-Rh/γ-AlO catalyst. Test conditions: 500 ppm NH in He, O = 4%, GHSV= 92000 h

Fig.3 UV-Vis absorption spectra of the nanosized Pt-Rh/γ-AlO catalyst (a) before and (b) after the activity test. Test conditions: 500 ppm NH in He, O = 4%, RH= 12%, GHSV= 92000 h

Fig.4 Change in the particle size distributions of the nanosized Pt-Rh/γ-AlO catalyst (a) before and (b) after the activity test. Test conditions: 500 ppm NH in He, O = 4%, GHSV= 92000 h

Fig.5 Change in the zeta potential of the nanosized Pt-Rh/γ-AlO catalyst (a) before and (b) after the activity test. Test conditions: 500 ppm NH in He, O = 4%, GHSV= 92000 h

Fig.6 Cyclic voltammograms of the nanosized Pt-Rh/γ-AlO catalyst (a) before and (b) after the activity test in a 0.5 mol·L HSO electrolyte solution recorded at a scan rate of 50 mV·s

1	Galloway J N, Townsend A R, Erisman J W, Bekunda M, Cai Z, Freney J R, Martinelli L A, Seitzinger S P, Sutton M A. Transformation of the nitrogen cycle: recent trends, questions, and potential solutions. Science , 2008, 320(5878): 889–892 doi: 10.1126/science.1136674 pmid:18487183
2	Cui X, Zhou J, Ye Z, Chen H, Li L, Ruan M, Shi J. Selective catalytic oxidation of ammonia to nitrogen over mesoporous CuO/RuO₂ synthesized by co-nanocasting-replication method. Journal of Catalysis , 2010, 270(2): 310–317 doi: 10.1016/j.jcat.2010.01.005
3	Amblard M, Burch R, Southward B W L. A study of the mechanism of selective conversion of ammonia to nitrogen on Ni/γ-Al₂O₃ under strongly oxidizing conditions. Catalysis Today , 2000, 59(3-4): 365–371 doi: 10.1016/S0920-5861(00)00301-1
4	Wang W, Padban N, Ye Z, Andersson A, Bjerle I. Kinetic of ammonia decomposition in hot gas cleaning. Industrial & Engineering Chemistry Research , 1999, 38(11): 4175–4182 doi: 10.1021/ie990337d
5	Schmidt-Sza?owski K, Krawczyk K, Petryk J. The properties of cobalt oxide catalyst for ammonia oxidation. Applied Catalysis A, General , 1998, 175(1-2): 147–157 doi: 10.1016/S0926-860X(98)00206-3
6	Liang C, Li W, Wei Z, Xin Q, Li C. Catalytic decomposition of ammonia over nitrided MoNx/α-Al₂O₃ and NiMoNy/α-Al₂O₃ catalysts. Industrial & Engineering Chemistry Research , 2000, 39(10): 3694–3697 doi: 10.1021/ie990931n
7	Hung C M. Decomposition kinetics of ammonia in gaseous stream by a nanoscale copper-cerium bimetallic catalyst. Journal of Hazardous Materials , 2008, 150(1): 53–61 doi: 10.1016/j.jhazmat.2007.04.044 pmid:17517471
8	Brüggemann T C, Keil F J. Theoretical investigation of the mechanism of the selective catalytic oxidation of ammonia on H-form zeolites. Journal of Physical Chemistry C , 2009, 113(31): 13860–13876 doi: 10.1021/jp903720t
9	Zhang L, He H. Mechanism of selective catalytic oxidation of ammonia to nitrogen over Ag/Al₂O₃. Journal of Catalysis , 2009, 268(1): 18–25 doi: 10.1016/j.jcat.2009.08.011
10	Wang Z, Qu Z, Quan X, Wang H. Selective catalytic oxidation of ammonia to nitrogen over ceria-zirconia mixed oxides. Applied Catalysis A: General , 2012, 411-412(1): 131–138 doi: 10.1016/j.apcata.2011.10.030
11	Song S, Jiang S. Selective catalytic oxidation of ammonia to nitrogen over CuO/CNTs: the promoting effect of the defects of CNTs on the catalytic activity and selectivity. Applied Catalysis B: Environmental , 2012, 117-118(5): 346–350 doi: 10.1016/j.apcatb.2012.01.030
12	Hung C M, Lai W L, Lin J L. Removal of gaseous ammonia in Pt-Rh binary catalytic oxidation. Aerosol and Air Quality Research , 2012, 12(4): 583–591 doi: 10.4209/aaqr.2012.01.0015
13	Hung C M. Preparation, properties and cytotoxicity assessment of nanosized Pt-Rh composite catalyst for the decomposition of gaseous ammonia. Advanced Materials Research , 2011, 160-162: 1285–1290 doi: 10.4028/www.scientific.net/AMR.160-162.1285
14	Hung C M. Application of Pt-Rh complex catalyst: feasibility study on the removal of gaseous ammonia. International Journal of Physical Sciences , 2012, 7(14): 2166–2173 doi: 10.5897/IJPS12.0247
15	Hung C M. The study of catalytic oxidation ammonia reactivity using bimetallic PtRh particles as catalyst: electrocatalytic and electrochemical behavior. Advanced Science Letters , 2012, 8(1): 578–582 doi: 10.1166/asl.2012.2337
16	Ohno T, Amirbahman A, Bro R. Parallel factor analysis of excitation-emission matrix fluorescence spectra of water soluble soil organic matter as basis for the determination of conditional metal binding parameters. Environmental Science & Technology , 2008, 42(1): 186–192 doi: 10.1021/es071855f pmid:18350895
17	Henderson R K, Baker A, Murphy K R, Hambly A, Stuetz R M, Khan S J. Fluorescence as a potential monitoring tool for recycled water systems: a review. Water Research , 2009, 43(4): 863–881 doi: 10.1016/j.watres.2008.11.027 pmid:19081598
18	Tang Z, Yu G, Liu D, Xu D, Shen Q. Different analysis techniques for fluorescence excitation-emission matrix spectroscopy to assess compost maturity. Chemosphere , 2011, 82(8): 1202–1208 doi: 10.1016/j.chemosphere.2010.11.032 pmid:21129765
19	Anderson J A. Infrared study of CO oxidation over Pt-Rh/Al₂O₃ catalysts. Journal of Catalysis , 1993, 142(1): 153–165 doi: 10.1006/jcat.1993.1197
20	Choi J H, Park K W, Park I S, Nam W H, Sung Y E. Methanol electro-oxidation and direct methanol fuel cell using Pt/Rh and Pt/Ru/Rh alloy catalysts. Electrochimica Acta , 2004, 50(2-3): 787–790 doi: 10.1016/j.electacta.2004.01.109
21	Stoyanovskii V O, Vedyagin A A, Aleshina G I, Volodin A M, Noskov A S. Characterization of Rh/Al₂O₃ catalysts after calcination at high temperatures under oxidizing conditions by luminescence spectroscopy and catalytic hydrogenolysis. Applied Catalysis B: Environmental , 2009, 90(1-2): 141–146 doi: 10.1016/j.apcatb.2009.03.003
22	Hung C M. Fabrication, characterization, and evaluation of the cytotoxicity of platinum-rhodium nanocomposite materials for use in ammonia treatment. Powder Technology , 2011, 209(1-3): 29–34 doi: 10.1016/j.powtec.2011.01.023
23	Hu Z, Allen F M, Wan C Z, Heck R M, Steger J J, Lakis R E, Lyman C E. Performance and structure of Pt-Rh three-way catalysts: mechanism for Pt/Rh synergism. Journal of Catalysis , 1998, 174(1): 13–21 doi: 10.1006/jcat.1997.1954
24	Mulukutla R S, Shido T, Asakuru K, Kogure T, Iwasawa Y. Characterization of rhodium oxide nanoparticles in MCM-41 and their catalytic performances for NO-CO reactions in excess O₂. Applied Catalysis A: General , 2002, 228(1-2): 305–314 doi: 10.1016/S0926-860X(01)00992-9
25	Curtin T, Regan F O’, Deconinck C, Kn?ttle N, Hodnett B K. The catalytic oxidation of ammonia: influence of water and sulfur on selectivity to nitrogen over promoted copper oxide/alumina catalysts. Catalysis Today , 2000, 55(1-2): 189–195 doi: 10.1016/S0920-5861(99)00238-2
26	Sobczyk D P, de Jong A M, Hensen E J M, van Santen R A. Activation of ammonia dissociation by oxygen on platinum sponge studied with positron emission profiling. Journal of Catalysis , 2003, 219(1): 156–166 doi: 10.1016/S0021-9517(03)00191-X
27	Zhang S, Zhao Y. Facile preparation of organic nanoparticles by interfacial cross-linking of reversed micelles and template synthesis of subnanometer Au-Pt nanoparticles. Nano , 2011, 5(4): 2637–2646 doi: 10.1021/nn102666k
28	Larrivee E M, Elkins K M, Andrews S E, Nelson D J. Fluorescence characterization of the interaction of Al³⁺ and Pd²⁺ with Suwannee River fulvic acid in the absence and presence of the herbicide 2,4-dichlorophenoxyacetic acid. Journal of Inorganic Biochemistry , 2003, 97(1): 32–45 doi: 10.1016/S0162-0134(03)00239-3 pmid:14507458
29	Zhang Y, Geddes C D. Metal-enhanced fluorescence from thermally stable rhodium nanodeposits. Journal of Materials Chemistry , 2010, 20(39): 8600–8606 doi: 10.1039/c0jm01806f
30	Wu M L, Lai L B. Synthesis of Pt/Ag bimetallic nanoparticles in water-in-oil microemulsions. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2004, 244(1-3): 149–157 doi: 10.1016/j.colsurfa.2004.06.027
31	Xu R. Progress in nanoparticles characterization: sizing and zeta potential measurement. Particuology , 2008, 6(2): 112–115 doi: 10.1016/j.partic.2007.12.002
32	Du H Y, Wang C H, Hsu H C, Chang S T, Chen U S, Yen S C, Chen L C, Shih H C, Chen K H. Controlled platinum nanoparticles uniformly dispersed on nitrogen-doped carbon nanotubes for methanol oxidation. Diamond and Related Materials , 2008, 17(4-5): 535–541 doi: 10.1016/j.diamond.2008.01.116
33	Prasad K V, Chavdhari R V. Activity and selectivity of supported Rh catalysts for oxidative carbonylation of aniline. Journal of Catalysis , 1994, 145(1): 204–215 doi: 10.1006/jcat.1994.1024
34	Oliveira R T S, Santos M C, Nascente P A P, Bulh?es L O S, Pereira E C. Nanogravimetric and voltammetric studies of a Pt-Rh alloy surface and its behavior for methanol oxidation. International Journal of Electrochemical Science , 2008, 3(8): 970–979

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