6 (C 1 ) 2013 38 CO 1,2, 1, 1 1,2 1*,, (1., 116023; 2., 100049) : Ce x Zr 1-x O 2, (DAE) Au/Ce x Zr 1-x O 2 X N 2 H 2, Au/Ce x Zr 1-x O 2 CO,,Zr CeO 2, Au Au/Ce x Zr 1-x O 2,Au/Ce 0.75 Zr 0.25 O 2 CO : ; ; ; ; :O 643 :A :1001-9219(2013)03-06-06 Ce x Zr 1-x O 2 CeO 2 [11,12] [13] (NO x ) [14] [15], (VOCs) [1],Ce x Zr 1-x O 2 [2-4] [5] [6] -, Ce x Zr 1-x O 2 Hori [2] [7] - (NH 4 ) 2 Ce(NO 3 ) 6 Ce,, [9, 11,12,14] [10,14,15] Ce x Zr 1-x O 2, Ce x Zr 1-x O 2 Rossignol [3] Ce(NO 3 ) 3 500 Ce Ce x Zr 1-x O 2,, 400,X CeO 2 ZrO 2,, [4], (DAE) [16],, HAuCl 4 CuO,, CO Ce x Zr 1-x O 2, Au [16], Au, -, 80 Haruta [7] Hutchings [8] Ce x Zr 1-x O 2, (DAE) Au/Ce x Zr 1-, xo 2 X N 2 H2 CO [9,10], CO 1 :2013-02-26; : (1985-),, 1.1, 0411-84379282, niext@dicp.ac.cn;* : (CP) Ce x Zr 1-x O 2 (x=0, 0.25,,,, 0411-84581234, xuhy@dicp.ac.cn
3 : CO 7 [17] 0.5, 0.75, 1) GC-8A (NH 4 ) 2 Ce(NO 3 ) 6 Zr(NO 3 ) 4 5H 2 O ( N2000, ), He, TDX- (NH 4 ) 2 CO 3 ( 01,TCD,, ) 200mL, 50mg~100mg, 40 ~60, 1L, ph 9~ 10, 55 2h,, : O 2 200, 1h 120,500 Ce x Zr 1-x O 2 4h, (DAE) Au/Ce x Zr 1-x O 2 [16] : 1 /min HAuCl 4 200mL, 70,, :1.67% CO 3.33% O 2 95% He, 15000mL g -1 h -1, (MFC), 2 2g Ce x Zr 1-x O 2, 1h, 50mL 25% 200mL, 2.1, 2.1.1 XRD Cl - ( AgNO 3 ),120, Ce x Zr 1-x O 2 XRD 1A, 300 4h, Au/Ce x Zr 1-x O 2, 2θ 25 ~33 1B Au 2% 28.5 ~29.5 1.2 (111) (JCPDS 03- XRD Philips 065-5923), Ce x Zr 1-x O 2 Zr X Pert PRO/PANalytical X, Ce x Zr 1-x O 2, Cu Kα (λ=0.1543 nm),, CeO 2 40kV, 40mA, 5 /min, 2θ= ZrO 2, 1 5 ~90 Scherrer Ce x Zr 1-x O 2 25 ~33 2θ, a Scherrer d Zr, Quantachrome NOVA 4000, a 2θ 110 350 a [18] 1h 3h, N 2 77K Zr 4+ BET N 2 (0.084nm) Ce 4+ (0.097nm), Zr BET ; BJH CeO 2 1, 32 N 2, Zr,Ce x Zr 1-x O 2,CeO 2 ZrO 2 12.2nm H 2 -TPR 12.3nm, Ce x Zr 1-x O 2 6.7nm 40mg, 500 8.2nm, Zr Ce x Zr 1-x O 2 Ar 30min, V(H 2 )/V(Ar)=5:95 H 2 -Ar, 10 /min, GC-8A, Ce 4+ Ce (TCD), (NH 4 ) 2 Ce(NO 3 ) 6 1.3 Ce 4+ [Ce(NO 3 ) 6 ] 2-, 8 mm ; Ce(NO 3 ) 3 Ce 3+,,
8 (C 1 ) 2013 38 [Ce(NO 3 ) 6 ] 2- Zr 4+, (NH 4 ) 2 Ce(NO 3 ) 6 Ce 1 1 CexZr 1-x O 2 XRD CexZr 1-x O 2, CeO 2 Ce 0.25 Zr 0.75 O 2,ZrO 2 2.1.2 N 2 3 CexZr 1-x O 2 2 CexZr 1-x O 2 N 2-2 Ce x Zr 1-x O 2 N 2 -, 2, ZrO 2,Ce x Zr 1-x O 2,, Ce 0.75 Zr 0.25 O 2 Ce 0.5 Zr 0.5 O 2 2 H1, Ce x Zr 1-x O 2 3 Ce x Zr 1-x O 2 N 2 -, Ce x Zr 1-x O 2 3nm~5nm, Ce 0.75 Zr 0.25 O 2 Ce 0.5 Zr 0.5 O 2 2 Ce x Zr 1-x O 2,, ZrO 2,Ce x Zr 1-x O 2 100m 2 /g, Ce 0.75 Zr 0.25 O 2 Ce 0.5 Zr 0.5 O 2, 133.0m 2 /g 135.8m 2 /g Ce x Zr 1-x O 2 3.38nm~ 4.06nm, CeO 2 ZrO 2, Ce x Zr 1-x O 2
3 : CO 9 Ce 0.25 Zr 0.75 O 2 >Au/ZrO 2,Au/Ce 0.75 Zr 0.25 O 2 Au/CeO 2,100 CO 4 Ce x Zr 1-x O 2 H 2 -TPR 4 Ce x Zr 1-x O 2 H 2 -TPR, ~900,ZrO 2 5, CeO 2 (453 ) (811 ), Ce 4+ Ce 4+ [19] Ce x Zr 1-x O 2 2.3, 2.3.1 XRD, Zr CeO 2 CeO 2 O 2-,Zr O 2-, CeO 2, Ce x Zr 1-x O 2, n(ce)/n(zr) n(ce)/n(zr) 3:1,Ce x Zr 1-x O 2,, 393,, n(ce)/n(zr) 1:1,Ce x Zr 1-x O 2 CeO 2, 456, n(ce)/ n(zr) 1:3,Ce x Zr 1-x O 2 6 Au/Ce x Zr 1-x O 2 XRD 491,Ce x Zr 1-x O 2 n(ce)/n(zr) 2.2 CO 6,Au/Ce 0.75 Zr 0.25 O 2 Au(111), n(ce)/n(zr), Au/Ce x Zr 1-x O 2 5, Au(111) Ce x Zr 1-x O 2 Au/ZrO 2,100 CO n (Ce)/n (Zr), [20] 12.9%, Au/ZrO 2 Au(111), Au/Ce x Zr 1-x O 2 CO Ce x Zr 1-x O 2 Au, Au, Ce x Zr 1-x O 2 n(ce)/ n(zr),au/ce x Zr 1-x O 2 2.3.2 N 2, :Au/Ce 0.75 Zr 0.25 O 2 >Au/Ce 0.5 Zr 0.5 O 2 >Au/ Au/Ce x Zr 1-x O 2 CO Au/Ce x Zr 1-x O 2 XRD 6
10 (C 1 ) 2013 38 3 Au/ Ce x Zr 1-x O 2, [20] n(ce)/n(zr),au/ce x Zr 1-x O 2, Au/Ce 0.75 Zr 0.25 O 2, Au/Ce x Zr 1-x O 2 CO 3 3 Au/Ce x Zr 1-x O 2 Ce x Zr 1-x O 2 3, n(ce)/ n(zr),au/ce x Zr 1-x O 2 Au,Au Ce x Zr 1-x O 2 Au/Ce 0.75 Zr 0.25 O 2,Au Ce x Zr 1-x O 2, Ce x Zr 1-x O 2 n(ce)/n(zr) Au Au CO Au/, Au/Ce x Zr 1-x O 2 Ce 0.75 Zr 0.25 O 2, 2.3.3 H 2 -TPR Au/Ce x Zr 1-x O 2 TPR 7, [1] Kaspar J, Fornasiero P. Structural properties and thermal stability of ceria-zirconia and related materials [M]// 7 4,Au/Ce x Zr 1-x O 2 Trovarelli A. Catalysis by Ceria and Related Materials. 50 ~250, London: Imperial College Press,2005:217-241. [2] Hori C E, Permana H, Ng K Y S, et al. Thermal stability, of oxygen storage properties in a mixed CeO 2 -ZrO 2 system, [J]. Appl Catal B, 1998, 16:105-117. n(ce)/n(zr) 3:1,Au/Ce x Zr 1-x O 2 [3] Rossignol S, Madier Y, Duprez D. Preparation of zirconiaceria materials by soft chemistry[j]. Catal Today, 1999,, 121,, 50:261-270. Au Au (NH 4 ) 2 Ce(NO 3 ) 6, [4],,,. 7 Au/Ce x Zr 1-x O 2 H 2 -TPR, CO [J]., 2009, [21] 30(10): 997-1000. Ce-O ; Ce x Zr 1-x O 2 [5] Zhang Y J, Deng J G, Zhang L, et al. AuO x /Ce 0.6 Zr 0.3 Y 0.1 O 2 Ce, nano-sized catalysts active for the oxidation of methane[c] // 3rd China-Japan Workshop on Environmental Catalysis and Eco-Materials, Beijing, China, 2007:29-36. [6] Dobrosz-Gomez I, Kocemba I, Rynkowski J M. Carbon monoxide oxidation over Au/Ce 1-x Zr x O 2 catalysts: Effects of moisture content in the reactant gas and catalyst pretreatment[j]. Catal Lett, 2009, 128: 297-306. [7] Haruta M, Kobayashi T, Sano H, et al. Novel gold catalysts for the oxidation of carbon-monoxide at a temperature far below 0-degrees-c[J].Chem Lett, 1987, 4: 405-408. [8] Hutchings G J, Joffe R. A novel process for the cosynthesis of vinyl-chloride monomer and sodiumcarbonate using a gold catalyst[j]. Appl Catal, 1986, 20:
3 : CO 11 215-218. noble metal catalysts[j].appl Catal B, 2010, 99: 198-205. [9] Wang L C, He L, Liu Y M, et al. Effect of pretreatment atmosphere on CO oxidation over alpha-mn 2 O 3 supported gold catalysts[j]. J Catal, 2009, 264: 145-153. [16] Ivanova S, Petit C, Pitchon V. A new preparation method for the formation of gold nanoparticles on an oxide support[j]. Appl Catal A, 2004, 267: 191-201. [10],,,. LaFeO 3 O 3 [17],,. Pt/Ce x Zr 1-x O 2 Au/Al 2 O 3 CO [J]. [J]., 2010, 31(10):, 2008, 29(6): 506-508. 1247-1252. [11],,,. [18] Fornasiero P, Di Monte R, Rao G R, et al. Rh-Loaded Au/CeO 2 [J]., 2009, 30(7): CeO 2 -ZrO 2 solid-solutions as highly efficient oxygen 666-672. exchangers: Dependence of the reduction behavior and [12] Boaro M, Vicario M, Llorca J, et al. A comparative study the oxygen storage capacity on the structural-properties[j]. of water gas shift reaction over gold and platinum J Catal, 1995, 151: 168-177. supported on ZrO 2 and CeO 2 -ZrO 2 [J]. Appl Catal B, 2009, 88: 272-282. [19] Yao H C, Yao Y F Y. Ceria in automotive exhaust catalysts(i): Oxygen storage[j].j Catal, 1984, 86: 254-265. [13] Ueda A, Haruta M. Nitric oxide reduction with hydrogen, carbon monoxide, and hydrocarbons over gold catalysts[j]. Gold Bull, 1999, 32: 3-11. [20],,. Au/Ce 1-x Zr x O 2 CO [J]., 2008, 29(2): 134-140. [14] Grisel R J H, Kooyman P J, Nieuwenhuys B E. Influence of the preparation of Au/Al 2 O 3 on CH4 oxidation activity [J]. J Catal, 2000, 191: 430-437. [21] Wei Y, Liu J, Zhao Z, et al. The catalysts of threedimensionally ordered macroporous Ce 1-x Zr x O 2 -supported gold nanoparticles for soot combustion: The metal-support [15] Santos V P, Carabineiro S A C, Tavares P B, et al. Oxidation of CO, ethanol and toluene over TiO 2 supported interaction[j]. J Catal, 2012, 287: 13-29. Preparation of ceria-zirconia solid solution and CO oxidation performance of Au/Ce x Zr 1-x O 2 catalyst NIE Xiao-tao 1,2, GE Qing-jie 1, MA Xian-gang 1, LI Wei-li 1,2, XU Heng-yong 1* (1. Dalian National Laboratory for Clean Energy (DNL), Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China; 2. University of Chinese Academy of Sciences, Beijing 100049, China) Abstract: A series of Ce x Zr 1-x O 2 composite oxide supports were prepared by co-precipitation method and their corresponding Au/ Ce x Zr 1-x O 2 catalysts were prepared by direct anionic exchange (DAE) method. The supports and catalysts were characterized by XRD, N 2 physisorption and H 2 -TPR, and the CO oxidation activity of the catalysts were measured in a fixed bed reactor. Results showed that single phase ceria-zirconia solid solution could be prepared using cerium (IV) ammonium nitrate as precursor. Addition of Zr increased the specific surface area of CeO 2 and changed the pore structure of the support. Loading of Au was beneficial to the reduction of ceria-zirconia solid solution, thus facilitated CO oxidation on Au/Ce x Zr 1-x O 2. Au/Ce 0.75 Zr 0.25 O 2 exhibited the best CO oxidation activity among Au/Ce x Zr 1-x O 2 catalysts. Keywords: cerium (IV) ammonium nitrate; precursor; ceria-zirconia solid solution; direct anionic exchange method; gold catalyst; carbon monoxide; oxidation!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! F-T - -, 10nm, 8nm 1nm, F-T, F-T UvA F-T,, Total S.A ( )