负载型铜基催化剂组分间相互作用及其催化性能

͵Ͷ ȋʹͲͳ͵Ȍ ͺͷͳȂͺ͸Ͷۢौᆜᣛ ʹͲͳ͵ᒪ ㅢ͵Ͷভ ㅢͷᵕ ȁ Ǥ Ǥa v a i l ab l e a t w w w.sc i e n c ed i re c t.c o mj o u r n a l h o m e p a g e : w w w.e l s e v i e r.c o m /l o c a t e /c h n j cReview (Special Issue in Memory of the 80th Birthday of Professor Jingfa Deng)Interactions among supported copper Ǧbased catalyst components and their effects on performance: A reviewǡ ǡȗǡ ǡSchool of Chemistry and Chemical Engineering, Key Laboratory of Mesoscopic Chemistry of MOE, Nanjing University, Nanjing 210093, Jiangsu, ChinaCenter of Modern Analysis, Jiangsu Key Laboratory of Vehicle Emissions Control, Nanjing University, Nanjing 210093, Jiangsu, ChinaArticle history:ʹʹ ʹͲͳ͵ ʹ ʹͲͳ͵ ʹͲ ʹͲͳ͵Ǧ Ǥ Ǥ Ǥ ǡ ʹǡ x ͳ x ʹǡ ͵Ǧ ʹ Ǥ ǡ ǡ ǡ Ǥ Ǧ Ȁ ͵ǡ ǡ ǡ Ǥ̹ ʹͲͳ͵ǡ ǡ ǤǤ Ǥ ǤKeywords:ǦΪ͵Ϊ Ϊ ʹ1. IntroductionǦ Ǧ Ǥ Ȁ Ȁ ʹ ͵ǡ ȏͳȐǡ Ȁ ʹǡ ȋ Ǧ Ȍ ȏʹȐǡ Ǧ Ȁ ʹ ͵ǡ N Ǧ ȏ͵ȐǤ ǡ Ǧ Ǧ ȋ Ȍ ȏͶȐǡ Ǧ ȏͷȐǡ Ǧ ȏ͸Ȑǡ x ȏ͹Ȑǡ ȏͺȐǤǤ ǡ Ǧ ǡ ǡ Ǧ Ǧ ǤǦ ȏͻȐǤ Ǧ Ǥ Ǧ ȏͳͲȐ ͳͻ͹Ͳ Ǧ Ǧ ȏͳͳȐ ͳͻͺͲ ǡ Ǧȗ Ǥ ǣ Ϊͺ͸ǦʹͷǦͺ͵ͷͻʹʹͻͲǢ ǣ Ϊͺ͸ǦʹͷǦͺ͵͵ͳ͹͹͸ͳǢ Ǧ ǣ ̷ Ǥ ǤȋʹͲͺ͹͵Ͳ͸Ͳǡ ʹͲͻ͹͵ͲͻͳȌǡ ȋʹͲͳͲ ͹͵ʹ͵ͲͲȌǡ ȋ ʹͲͳͳͲͲ͵ͺͻȌ.ǣ ͳͲǤͳͲͳ͸Ȁ ͳͺ͹ʹǦʹͲ͸͹ȋͳʹȌ͸ͲͷͻʹǦͲ ȁ ǣȀȀ Ǥ Ǥ Ȁ Ȁ Ȁͳͺ͹ʹʹͲ͸͹ ȁ Ǥ Ǥ Ǥǡ Ǥ ͵Ͷǡ Ǥ ͷǡ ʹͲͳ͵ͺͷʹ DONG Lin et al. / Chinese Journal of Catalysis 34 (2013) 851–864Ǧ ǡ Ǥ Ǧ ȏͳʹȂͳ͸Ȑ ȏͳ͹ȂʹͲȐǡ Ú ȏʹͳȐǡ ȏʹʹȐǡ ȏʹ͵ȂʹͷȐǡ ȏʹ͸Ȃ͵ͲȐǤ Ǧ ǡ ǡ Ǥ ǡ Ǥ ȏ͵ͳȂ͵ͶȐ Ǥ ǡ ǡ Ǧ ǡ ǤǦ Ǧ ǡ Ǧ Ǧ Ǧ ǡ ǡ Ǥ ǡ Ǧ Ǧ ǡ Ǧ Ǥ ǡ Ǧ ǡ Ǧ Ǧ Ǧ Ǥ ǡ ȋ Ȍǡ Ǧ ȏ͵ͷǡ͵͸Ȑ Ǥ Ǧ ǣ ȋͳȌ Ǧ Ǧ Ǧ Ǣ ȋʹȌ ǡ Ǣ ȋ͵Ȍ Ǧ ǡ ͳǦͳǡ ͳǦʹǡ ʹǦͳǡ ͳǦ͵ǡ ʹǦ͵ǡ Ǧ Ǣ ȋͶȌ ȋ ǡ ǡ Ȍǡ ȋ ǡ JǦ ʹ ͵Ȍǡ ȋ ǡ ǡ ȌǢ ȋͷȌ ǡ ǡ ǡ Ǧ Ǥ ȋ ʹ ǡ ǡ ǡ ͵Ȍ ǡ Ǥ Ǧ Ǥ ǡ Ǧ ǤǤ ǡ ͵ ͵ ʹ ͷȀ ʹ x ͵ ȋ ͵Ǧ Ȍ Ǥ Ǧ ǡ ǡ ǤǦ Ǧ ȏ͵͹ȐǤ Ǧ ǡ Ǧ Ǧ ǡ Ϊ ͵Ϊ Ϊ ʹ Ǥ Ǧ Ǧ Ǧ ʹǡ x ͳǦx ʹǡ ͵Ǧ ʹǡ ǡ ǡ Ǧ Ǧ Ǥ Ǧ Ǥ2. CuO/CeO2ͳͻͺͲ ǡ ʹ Ǧ ȋ Ȍ Ǧ Ǧ Ǧ Ȁ ȋ Ȍ ǡ ȏ͵ͺǡ͵ͻȐǤ ͳͻͺͲ ǡ ȋ Ȍ ʹ ǡ ȋ Ȍǡ x ʹǡ ʹ ǡ ʹǤ ǡ Ǧ Ǧ Ǧ ȋε ͵ʹ͹ ι ȌǤ ǡDONG Lin et al. / Chinese Journal of Catalysis 34 (2013) 851–864 ͺͷ͵ǡ Ǧ Ǥ ǡ ǡ Ǥ ǦͳͻͻͲ Ǧ ʹ ʹǦ ʹǡ ǯ Ǥ ǡ Ǧ ͳͻͻ͹ǡ Ǥ ǡ ǡ Ǥʹ ʹǡ Ȁ ʹ Ǧ ȏͶͲȐǤ Ǧ ȋ ǡ Ǥ ͳȌ Ǧ Ǧ ȋ ǡ Ǥ ʹȌ ʹ ͳǤʹͲ ȀͳͲͲ ʹ ʹ ȋ ͹Ǥͳ ʹΪȀ ʹ ʹȌǤ Ǧǡ ȋͳͳͳȌ ʹ ʹΪ ͳǤʹʹ ȀͳͲͲ ʹ ʹǤ ǡ ǡ Ǧ Ǥʹ Ȁ ʹ ǡ ͶΪȀ ͵Ϊ Ǥ ȋ ȋ ͵Ȍ͵ȉ͸ ʹ ȋ ͶȌʹ ȋ ͵Ȍ͸Ȍ Ȁ ʹ ǡ ȏͺȐǤ Ǥ ͵ǡ Ǧ Ǥ ǡ ǡ ͵Ϊ ͶΪ Ǥ ͵Ϊ ǡ ΪǦĿǦ ͵Ϊ ȋ ȋ ȌȌǡ ǡ Ǥ ͶǤ ǡ ǡ Ǧ313335373941(5)(4)(3)(2)CuO (111)CuO (111)CeO 2(200)I n t e n s i t y2T /( o )(1)Fig. 1. Ȁ ʹ ʹΪ ͲǤͻͲ ȋͳȌǡ ͳǤʹͲ ȋʹȌǡ ͳǤͶͲ ȋ͵Ȍǡ ͳǤͷͷ ȋͶȌǡ ͳǤ͹Ͳ ʹΪȀͳͲͲ ʹ ʹ ȋͷȌȏͶͲȐǤ0.002.264.52 6.789.0411.3013.5615.820.00.20.4I C u 2p /I C e 3dTotal content of copper/nm2Fig. 2. Ȁ ʹ ȏͶͲȐǤ100200300400500T O F o f C O (s 1)Temperature (o C)Fig. 3. ȋ Ȍ Ȁ ʹ Ǥ ǡ Ǧ ȏͺȐǤCu +--Ce 3+Cu 2+-O-Ce 4+CO CO 2Cu +- -Ce 3+CO O O(Step 1) (Step 2)(S t e p 3)CO/O 2C O 2SSOVFig. 4. Ȁ ʹ ȏͺȐǤͺͷͶ DONG Lin et al. / Chinese Journal of Catalysis 34 (2013) 851–864Ǥ ǡ Ǥ Ǧ Ǥ ǡ ʹΪ Ǧ ʹ ǡ Ǧ ʹΪǦ Ǧ ͶΪ Ǥ ǡ Ǧ ʹΪǦ Ǧ ͶΪ Ǥ ǡ ȏͶͳȐǤ ǡ ʹΪǦ Ǧ ͶΪ Ǧ ǡ Ǥ 3. Bulk modification of the support: CuO/Ce x Zr 1Ǧx O 2Ǧ Ǥ ǡ ǡ ǡ Ǥ Ǧ Ǥ ǡ Ǥ ʹ ǡ Ǧ ȏ͵ͻǡͶʹǡͶ͵ȐǤ Ȁ ʹ ʹ Ǥ ǡ Ȁ ʹ Ȁ ʹ ȏͶͶȐǤ Ǧ ʹǦ ʹ ȏ͵ͻȐǤ ͶΪ ȋͲǤͲͺͶ Ȍ ͶΪ ȋͲǤͲͻ͹ Ȍǡ ͶΪ Ǧ ʹǦ ʹ Ǥ ǡ Ǧ ǡ ǡ Ȁ Ǧ Ǥ ǡ ʹǦ ʹ ʹȏͶ͵ǡͶͷȂͶ͹ȐǤǦ x ͳǦx ʹ ȋx η ͲǤͷȌ ǡ Ǥ ȏͶͺȐǤ ǡ x ͳǦx ʹ ȋx η ͲǤͷȌ ȋͳͳͳȌ ȋ Ǥ ͷȌǡ ʹ ȏͶͻȐǡ ʹΪ x ͳǦx ʹ ȋx η ͲǤͷȌǤͲǤ͸͹ ͲǤ͵͵ ʹ ȋ Ȁ Ȍǡ Ϊ ǡ ȏͷͲȐǤ Ǥ ͸ǡ ͲǤ͸͹ ͲǤ͵͵ ʹ ͲǤ͸͸ ͳǤʹ͵ǡ ͳǤʹͲǤ ǡ ͳǤʹ͵ Ǧ Ǥ ͹ ͲǤ͸͸ Ǧ ͲǤ͵͵ Ǧ ʹʹͶ ι ǡ ͶΪ ͵ΪǤ ͳǤʹ͵ Ǧ ǡ ͳǤ͸ͷ Ǧ ǡ Ǥ ͺ1020304050607080ƹCuOI n t en s i t y 2T /( o )0.33Cu-CZ0.66Cu-CZ 1.23Cu-CZ 1.65Cu-CZ ƹƹFig. 6. x Ǧ ȏͷͲȐǤ1001502002503003500.33Cu-CZ crystalline CuO231188145224187154Temperature (o C)H 2 c o n s u m p t i o n0.66Cu-CZ1.23Cu-CZ 1.65Cu-CZFig. 7. Ǧ ʹ ȋ ʹǦ Ȍ x Ǧ ȏͷͲȐǤLattice O 2–Ce 4+or Zr 4+Vacant siteʹ x ͳ x ʹ ȏͶͻȐǤDONG Lin et al. / Chinese Journal of Catalysis 34 (2013) 851–864 ͺͷͷǦ ǤǦ ǡ Ǧ Ǧ Ǥȋ Ȁ Ȍ Ǧ ͲǤͷ ͲǤͷ ʹ ȏͶͻȐǤ ȋ Ǥ ͻȌ Ǧ ͲǤͻ ȀͳͲͲ ʹ Ǥ ʹǦ ȋ Ǥ ͳͲȌ ͳ͹Ͳ ʹ͵ͷ ι ͲǤͻ ȀͳͲͲ ʹ ǡ ͵Ͳͻ ι Ǧ Ǥ Ǥ ͳͳǡ ͳǤʹ ȀͳͲͲ ʹ Ǥ Ȁ ʹǡ ǡ ȋ ȌǤ4. Surface modification of the support: CuO/MoO 3ǦCeO 2 Ǧ Ǧ Ǥ Ǧ ͵Ǧ ʹ ȋ ͵Ǧ ʹȌǤ ͵ Ǧ ǡ ǡ Ǧ Ǥ ǡ ͵ Ǥ ͵Ǧ ͵Ǧ ȋ Ǧ Ȍ Ǧ ͵ǡ Ǧ Ǥ ͵Ǧ ʹ Ǧ ǡ Ǧ2025303540455055(7)(6)(5)(4)(3)(2)R(1)I n t e n s i t y2T /( o)R CuORFig. 9. Ȁ ͲǤ͵ ȋͳȌǡ ͲǤ͸ ȋʹȌǡ ͲǤͻ ȋ͵Ȍǡ ͳǤʹ ȋͶȌǡ ͳǤͺ ȋͷȌǡ ʹǤͶ ȋ͸Ȍǡ ͵ǤͲ ȀͳͲͲ ʹ ȋ͹Ȍ ȏͶͻȐǤ889092949698100889092949698100 N 2 s e l e c t i v i t y (%)1.65Cu-CZ1.23Cu-CZ 0.66Cu-CZ N O c o n v e r s i o n (%)0.33Cu-CZ Fig. 8. ʹ x Ǧ ͵ͲͲ ι ȏͷͲȐǤ100200300400500(8)(7)(6)(5)(4)(3)(2)319263170234235172I n t e n s i t yTemperature (o C)(1)170231299210168165210299165205303309203163Fig. 10. ʹǦ Ȁ ͲǤ͵ ȋͳȌǡ ͲǤ͸ ȋʹȌǡ ͲǤͻ ȋ͵Ȍǡ ͳǤʹ ȋͶȌǡ ͳǤͺ ȋͷȌǡ ʹǤͶ ȋ͸Ȍǡ ͵ǤͲ ȀͳͲͲ ʹ ȋ͹Ȍǡ ȋͺȌ ȏͶͻȐǤ10203040506070C O c o n v e r s i o n (%)Copper oxide loading (mmol CuO/100 m 2CZ)Fig. 11. Ȁ ȏͶͻȐǤͺͷ͸ DONG Lin et al. / Chinese Journal of Catalysis 34 (2013) 851–864ȏͷͳǡͷʹȐǤ ǡ Ǥ ȏͷʹȐ ͵ ʹ Ǧ ͵Ȁ ʹ ǡ Ǧ Ǧ Ǧ Ǧ ǡ ͵ ǡ ͵ Ǧ Ǥ Ȁ ʹǤ ǡ Ǥ ȏͷ͵Ȑ ǡ Ǥ ͵Ȁ ʹǦ ʹ Ǧ ͵ ʹͲ Ψǡ Ǧ ǤǦ ͵Ǧ ʹ ͵Ǧ ȏͷͶǡͷͷȐǤ ȀͲǤͺ Ǧ ȀͲǤͶ Ǧ Ǥ ͲǤͺ Ǧ ͵ ʹǤ ǡ ʹ Ǧ ͸ΪǤ ǡ Ǧ ʹǤ ͲǤͶ Ǧ ǡ ʹ ǡ͵ ʹǤ Ǥ ͳʹȋ Ȍ ȋ ȌǤȀͲǤͺ Ǧ ȀͲǤͶ Ǧ Ǥ ͳ͵Ǥ Ǥ ͳ͵ȋ Ȍ ȋ Ȍ ʹǤͲ͸ ȀͳͲͲ ʹ ͵Ǧ ȋͲǤͺ Ǧ Ȍǡ Ǧ ʹ ȋͳǤʹͲ ȀͳͲͲ ʹ ʹȌǤ Ǧ ͵ Ǥ Ǧ ͵Ǥ(a)(b)Lattice oxygen Ce 4+VacancyCapping oxygen of Mo 6+Incorporated Mo 6+Capping oxygen of Cu 2+Incorporated Cu 2+Fig. 12. ȋͳͳͳȌ ʹ ͵Ǧ ȋ Ȍ ͵Ǧ ȋ Ȍ ȏͷͷȐǤ2030405020304050(6)(5)(4)(3)(2)(a)I n t e n s i t y2T /( o)xx CuOx (1)(b)I n t e n s i t y2T /( o)xx CuOx(6)(5)(4)(3)(2)(1)(7)(8)I C u O (111)/I C e O 2(111)I C u O (111)/I C e O 2(111)CuO loading (mmol/100 m 2 CeO 2)CuO loading (mmol/100 m 2 CeO 2)Fig. 13. x Ȁy Ǧ ͵ Ǥ ȋ Ȍ x ȀͲǤͶ Ǧ Ͳ ȋͳȌǡ ͲǤ͵ ȋʹȌǡ ͲǤ͸ ȋ͵Ȍǡ ͲǤͻ ȋͶȌǡ ͳǤʹ ȋͷȌǡ ͳǤͺ ȀͳͲͲ ʹ ȋ͸ȌǢ ȋ Ȍ x ȀͲǤͺ Ǧ Ͳ ȋͳȌǡ ͲǤ͵ ȋʹȌǡ ͲǤ͸ ȋ͵Ȍǡ ͲǤͻ ȋͶȌǡ ͳǤͺ ȋͷȌǡ ʹǤͶ ȋ͸Ȍǡ ͵Ǥ͸ ȋ͹Ȍǡ ͶǤͺ ȀͳͲͲ ʹ ȋͺȌǢ x ȀͲǤͶ Ǧ ȋ Ȍ x ȀͲǤͺ Ǧ ȋ Ȍ ȏͷͷȐǤDONG Lin et al. / Chinese Journal of Catalysis 34 (2013) 851–864 ͺͷ͹ǡ ʹǤͶͶ ȀͳͲͲ ʹǡ ǡ ǡ Ǧ Ǧ ͵Ǥǡ ʹΪ ͲǤͺ Ǧ Ǧ ʹΪ ʹǡ Ǧ Ǥ Ǥ ͳ͵ȋ Ȍ ȋ Ȍǡ ͲǤ͹͵ ȀͳͲͲ ʹ ʹ ͵Ǧ ȋͲǤͶ Ǧ Ȍǡ ʹ ȋͳǤʹͲ ȀͳͲͲ ʹ ʹȌǡ ͵ ʹ Ǧ Ǥ Ǧ Ǧ ʹȂ ͸Ϊ ʹǤ ʹ ͵ ͲͶ Ǧ Ǥ ʹǦ Ǧ ǤʹǦ ͲǤ͵ Ȁ ǡ ͲǤ͵ ȀͲǤͶ Ǧ ǡ ͲǤ͸ ȀͲǤͶ Ǧ Ǥ ͳͶǡ ͳ͹Ͳ ͳͻ͸ ι Ǧ ʹǡ ʹ͵ͷ ι Ǧ Ǧ Ǥ Ǧ ȋͲǤ͵ ȀͲǤͺ ǦͲǤ͸ ȀͲǤͺ Ǧ Ȍǡ Ǧ Ǧ ǡ Ǧ ͵ ʹ ʹǤ ǡ ʹ Ǥȋ Ȍ ͵ ʹ Ǧ α ͵ ǡ ͻʹͳ Ȃͳ ͲǤʹ Ȁ ͻ͸Ͷ Ȃͳ ͲǤͺ Ȁ Ǥ Ǧ ͵ Ǧ ȋ Ǥ ͳͷȋ Ȍǡ Ȍ ǡ Ǥ ͳͷȋ Ȍǡ Ǥ ǡ α Ǥ ͲǤͶ Ǧ ǡ ͲǤͺ Ǧ ǡ Ǧ Ȃ Ȃ Ǥ Ǥ ͳͷȋ Ȍ ȋ Ȍǡ Ǥα ȋ̱ͻ͸ͷ ȂͳȌ ȋ̱ͻͲͲ ȂͳȌ ȀͲǤͺ Ǧ ǡ ȋ Ǥ ͳ͸ȌǤ ͲǤ͵ ȀͲǤͺ Ǧ ǡ ͲǤ͸ ȀͲǤͺ Ǧ ǡ ͲǤͻ ȀͲǤͺ Ǧ150200250300350400(6)(5)(4)(3)(2)235196170I n t e n s i t yTemperature (o C)(1)Fig. 14. ʹǦ x Ȁy Ǧ Ǥ ȋͳȌ ͲǤ͵ ȀͲǤͶ Ǧ ǢȋʹȌ ͲǤ͸ ȀͲǤͶ Ǧ Ǣ ȋ͵Ȍ ͲǤ͵ ȀͲǤͺ Ǧ Ǣ ȋͶȌ ͲǤ͸ ȀͲǤͺ Ǧ Ǣ ȋͷȌͲǤ͵ Ȁ Ǣ ȋ͸Ȍ ͲǤͺ Ǧ ȏͷͷȐǤ(b)MoOOO O MoOOO MoOOO O O O Mo OOO O Mo OOOMo O O OO O OCuCuCu MoO O O OCuMo OOOO(a)Fig. 15. x ȀͲǤͶ Ǧ ȋ Ȍ x ȀͲǤͺ Ǧ ȋ Ȍ ȏͷͷȐǤ6007008009001000(4)(3)(2)965900800Raman shift (cm 1)I n t e n s i t y(1)Fig. 16. x ȀͲǤͺ Ǧ ǡ x Ͳ ȋͳȌǡ ͲǤ͵ ȋʹȌǡ ͲǤ͸ ȋ͵Ȍǡ ͲǤͻ ȀͳͲͲ ʹ ȋͶȌ ȏͷͷȐǤͺͷͺ DONG Lin et al. / Chinese Journal of Catalysis 34 (2013) 851–864ǡ ǡ ǦͲǤʹͲǡ ͲǤͳʹǡ ͲǤͲͷǡ Ǥ Ǧ Ǥ͵ Ǧ Ȁ Ǧ ȋ Ǥ ͳ͹ȌǤ Ú ȋ Ȍ ǡ ȋ ͳȌǤ Ǧ ȋ ʹȌǤ ͳ Ǣ ͲǤͶ Ǧ ͲǤͺ Ǧ ǡ ǤȀ ͵Ǧ ʹ ͵Ǧ Ǥ ͳͺǤ ǡ ͲǤͺ Ǧ ͲǤͶ Ǧ Ǥ ͳǡ ǡ ͵Ǧ Ǥ ʹͲͲ ʹͷͲ ι ǡ Ǥ ͵ͲͲȂ͵ͷͲ ι ǡ ǡǤΪ ͵Ϊ ʹ Ǥǡ Ǧ Ǧ x ͳǦx ʹ x ͳǦx ʹ ȋ Ȁ x Ǧ x ͳǦx ʹ ȏͷ͸Ȑǡ Ȁ x Ǧ x ͳǦx ʹ ȏͷ͹Ȑǡ Ȁ ͵Ǧ x ͳǦx ʹ ȏͷͺǡͷͻȐǡ Ȁ x ͳǦx ʹ ȏ͸ͲȐǡ Ȁ x Ǧ x ͳǦx ʹ ȏ͸ͳȐ ȌǤ Ǧ ǡ ǡ ǡ Ǥǡ ǡ Ǧ ǡ Ǥ ǡ1700160015001400130012001100170016001500140013001200170016001500140013001200T r a n s m i t t a n c e (%)T r a n s m i tt a n c e (%)Wavenumber (cm 1)Wavenumber (cm 1)13551255L1B1442(a)1630T r a n s m i t t a n c e (%)400 o C350 o C 300 o C250 o C 200 o C 150 o C 100 o CL2L11235125313451453(c)101624B400 o C350 o C 300 o C 250 o C 200 o C 150 o C 100 o C25 o C50 o C 101025 o C 50 o C 400 o C 13551221L2L112551447Wavenumber (cm 1)(b)1624B 350 o C300 o C 250 o C 200 o C 150 o C100 o C 25 o C50 oCFig. 17. ͵ Ǧ x ȀͲǤͺ Ǧ Ǥ ȋ Ȍ ͲǤͺ Ǧ Ǣ ȋ Ȍ ͲǤ͵ ȀͲǤͺ Ǧ Ǣ ȋ Ȍ ͲǤ͸ ȀͲǤͺ Ǧ ȏͷͷȐǤTable 1Ú x Ȁy Ǧ Ǧ ͵ ʹͷ ι ȏͷͷȐǤÚ ȋ Ȍ ȋ ͳ Ϊ ʹȌͲǤͶ Ȁ͸ͶͲ ͶͶ ͲǤ͵ ȀͲǤͶ Ǧ ͷ͵ͷ ͷ͵ͷ ͲǤ͸ ȀͲǤͶ Ǧ ͷͲ ͻ͹ͷ ͲǤͺ Ȁʹͷ͵Ͳ ͷͻ ͲǤ͵ ȀͲǤͺ Ǧ ͸͸Ͳ ͹Ͳ͹ ͲǤ͸ ȀͲǤͺ ǦͷͶͲ ͳͷͺͷ10203040506070N O c o n v e r s i o n (%)Temperature (o C)Fig. 18. ͵Ϊ Ϊ ʹ ȏͷͷȐǤDONG Lin et al. / Chinese Journal of Catalysis 34 (2013) 851–864 ͺͷͻǦ ǡ Ǥ ǡ Ǧ Ǧ Ǥ5. 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J Phys Chem B ǡ ʹͲͲͷǡ ͳͲͻǣ ͵ͻͶͻȏ͸ͲȐ ǡ ǡ ǡ ǡ ǡ ǡ ǡ ǡ ǡ Ǥ J Mol Catal A ǡ ʹͲͳʹǡ ͵͸ͷǣ ͺ͹ȏ͸ͳȐǡ ǡ ǡ ǡ ǡ ǡ ǡ ǡ ǡ ǡ Ǥ ACS Catal ǡ ʹͲͳͳǡ ͳǣ Ͷ͸ͺ䍕䖳ශ䬒ะۢौࡸ㓺࠼䰪⴮ӈ֒⭞਀ެۢौᙝ㜳Ⰾ 㑷a,b,*, 䄇㾂ㅎa , ⧣ 䢓aa㚰㈊⫔䁈⿐䁈⿐⹅䁈䊛, ㆊ⹼⿐䁈ㅭ䈞⤠䐹⮄㬖䂊㬳, ㅎ㯶㚰㈊210093 b㚰㈊⫔䁈㻷⫛⳷㹗䐱㾥, ㅎ㯶㬂〛Ⱀ⧖㸓㡙㸼㦟㋹䐧䐹⮄㬖䂊㬳, ㅎ㯶㚰㈊210093᪎㾷: 䍏䖭ර䬌สۜॆࡲഐަ㢟ྭⲴۜॆᙗ㜭઼⴨ሩվᓹⲴԧṬ൘䈨ཊ䟽㾱ᐕъۜॆ৽ᓄѝᗇࡠᒯ⌋Ⲵᓄ⭘. ᧒䇘䍏䖭ර䬌สۜॆࡲѝ㓴࠶䰤Ⲵ⴨ӂ֌⭘, ᴹࣙҾҶ䀓⴨ޣۜॆ֌⭘Ⲵᵜ䍘, Ѫ⧠ᴹۜॆࡲⲴ᭩䘋઼ᯠۜॆࡲⲴ䇮䇑ᨀ׋、ᆖ׍ᦞ. ᵜ᮷㔬䘠Ҷ䘁ᒤᶕᡁԜቡCuO ൘н਼䖭փкⲴ࠶ᮓǃ䬌⢙⿽઼䖭փⲴ᭩ᙗ৺ަ⢙⨶ॆᆖᙗ䍘ԕ৺ۜॆCO ᆼޘ≗ॆǃCO+NO ઼NH 3+NO+O 2৽ᓄᙗ㜭ㅹᯩ䶒Ⲵ⹄ウ䘋ኅ. 㔃᷌㺘᰾, CuO ൘ཊ⿽≗ॆ⢙䖭փ㺘䶒Ⲵ࠶ᮓ઼ᡰᗇ䍏䖭ර䬌สۜॆࡲⲴаӋ⢙⨶ॆᆖᙗ䍘ਟ৲㘳“፼ޕ⁑ර”ᗇࡠ䀓䟺, ᵜ᮷ѫ㾱䇘䇪ҶԕCeO 2,Ce x Zr 1 x O 2઼MoO 3-CeO 2Ѫ䖭փⲴаӋ䬌สۜॆࡲⲴ㓴ᡀ-㔃ᶴ-ᙗ䍘䰤Ⲵޣ㌫. ީ䭤䈃: 䍏䖭ර䬌สۜॆࡲ; 㺘䶒⴨ӂ֌⭘; ፼ޕ⁑ර; а≗ॆ⻣ᆼޘ≗ॆ; CO+NO ৽ᓄ; NH 3+NO+O 2৽ᓄ 㬶ⷆ㦶㠻: 2013-02-22. ㅴ㬽㦶㠻: 2013-04-02. ⨗⟇㦶㠻: 2013-05-20.*㵉䁗㑋㻖㦬. ⮈⿑: (025)83592290; ⪌䎇: (025)83317761; ⮈䓴㾦㼅: donglin@〚㆑㎕䊕: ⺛コ䓵㦜㋧䁈〚㆑(20873060, 20973091); ⺛コ䐹⮄〚⪂䁱㈠ⳃ䍚ェ⿏(973ェ⿏, 2010CB732300); ㅎ㯶㬂㋧ゝ䐈⧦ェ⿏⹅䄖㼏㚠(SBE201100389).⡟㸥⭥䇃㸥⮈䓴⟇䇪Elsevier ⨗⟇㪈䊻ScienceDirect 㩰⨗⟇(/science/journal/18722067).1. ࢃ䀶䍏䖭ර䬌สۜॆࡲഐަ㢟ྭⲴۜॆᙗ㜭઼⴨ሩվᓹⲴԧṬ㘼ᒯ⌋ᓄ⭘Ҿ䈨ཊ䟽㾱ᐕъۜॆ৽ᓄ. ֻྲ, CuO/ZnO/Al 2O 3ᱟⴞࡽ⭢䞷㫨≄䟽ᮤⲴѫ㾱ۜॆࡲ[1]; CuO/CeO 2ۜॆࡲ൘CO ᇼ≒≗ॆ৽ᓄѝ㺘⧠ࠪᶱ֣Ⲵۜॆᙗ㜭[2]; CuO-NiO/Al 2O 3ۜॆࡲ⭘ҾN -⭢สૼచਸᡀㅹㅹ[3]. 䲔ᐢᴹᓄ⭘ཆ, 䍏䖭ර䬌สۜॆࡲ䘈ᴹ䟽㾱Ⲵᓄ⭘ࡽᲟ, 䈨ྲ൘ᥕਁᙗᴹᵪ⢙(VOCs)⟳✗[4]ǃ≤⊭ਈᦒ[5]ǃ䞟㊫࣐≒[6]ǃNO x ⎸䲔[7]ԕ৺CO վ⑙≗ॆ[8]ㅹᯩ䶒Ⲵᓄ⭘. Ӿ࠶ᆀ઼৏ᆀ≤ᒣ⹄ウ䍏䖭ර䬌สۜॆࡲⲴ㺘䶒㓴ᡀǃ㔃ᶴǃᙗ䍘, ᧒䇘ۜॆ৽ᓄᵪ⨶, ሩ䘋а↕ᨀ儈↔㊫ۜॆࡲⲴᙗ㜭, ᤃᇭަᓄ⭘㤳ത, ᔰਁަ▌൘ᓄ⭘ԧ٬ާᴹ䟽㾱᜿ѹ.ӪԜᰙᐢ䇔䇶ࡠ൘䍏䖭රۜॆࡲѝ, 㻛䍏䖭⢙Ⲵᙗ䍘ᑨᑨнਟ䚯ݽൠਇࡠ䖭փⲴᖡ૽[9], ⹄ウ䍏䖭⢙о䖭փ䰤Ⲵ⴨ӂ֌⭘ᵜ䍘, ᐢᡀѪཊ⴨ۜॆѝཊᒤᶕᤱ㔝⹄ウⲴ✝⛩. 㠚20ц㓚70ᒤԓᵛᨀࠪ䠁኎о䖭փѻ䰤ⲴᕪGraphical AbstractChin. J. Catal.ǡ ʹͲͳ͵ǡ ͵Ͷǣ ͺͷͳȂͺ͸Ͷ ǣ ͳͲǤͳͲͳ͸Ȁ ͳͺ͹ʹǦʹͲ͸͹ȋͳʹȌ͸ͲͷͻʹǦͲInteractions among supported copper Ǧbased catalyst components and their effects on performance: A review ȗǡ ǡ Nanjing UniversityǦ ǡ Ǧ Ǧ Ȁ ʹǡ Ȁ x ͳ x ʹǡ Ȁ ͵Ǧ ʹ Ȁ ͵ǤCuO/CeO 2CuO/Ce x Zr 1–x O 2CuO/MoO 3-CeO 2CuOMoO 3 CeO 2ZrO 2⴨ӂ֌⭘(SMSI)[10]઼80ᒤԓࡍᨀࠪ≗ॆ⢙઼≗ॆ⢙䖭փѻ䰤Ⲵᕪ⴨ӂ֌⭘(SOOI)[11]ԕᶕ, 㖾ഭⲴBell઼Iglesia 䈮仈㓴[12~16]ԕ৺Wachs䈮仈㓴[17~20]ǃᗧഭⲴKnözinger 䈮仈㓴[21]ǃ᜿བྷ࡙ⲴColuccia䈮仈㓴[22]ǃঠᓖⲴReddy 䈮仈㓴[23~25]ԕ৺ഭ޵Ⲵୀᴹ⾪઼䉒ᴹ⭵䈮仈㓴[26~30]ㅹ൷ሩ䍏䖭ර≗ॆ⢙փ㌫ѝ䍏䖭⢙઼䖭փѻ䰤Ⲵ⴨ӂ֌⭘䘋㹼Ҷ⹄ウ, Ӿн਼䀂ᓖ⭘৽ᓄᵪ⨶ᡆ⁑රሩ䘉㊫⴨ӂ֌⭘࣐ԕ᧿䘠. ԕк⹄ウᡰ⭘≗ॆ⢙䖭փᑨᱟཊᲦ㊹ᵛ, ᆳԜоᇎ䱵ۜॆࡲᡰ⭘䖭փ⴨䘁, նᱟ⭡Ҿަཊ⿽Ღ䶒ޡᆈф∄ֻᵚ⸕, 䘉֯ᗇ䳮ԕ㔃ਸ䖭փⲴ㺘䶒㔃ᶴሩᴹޣ䰞仈䘋㹼ᇊ䟿Ⲵ᧒䇘. 䲿⵰㺘ᖱᢰᵟⲴ䘋↕, Goodman䈮仈㓴[31~34]࡙⭘ᢛ᧿䳗䚃ᱮᗞ䮌ㅹ᡻⇥㘳ሏҶ䍥䠁኎൘অᲦ≗ॆ⢙䖭փ㺘䶒Ⲵ࠶ᮓ㹼Ѫ, ᒦ䟷⭘⁑ර৽ᓄ⹄ウҶۜॆࡲ㺘䶒⍫ᙗ㓴࠶Ⲵᆈ൘⣦ᘱ઼ۜॆ⍫ᙗѻ䰤Ⲵޣ㌫. ᱮ❦, ቍ䈅ᢺ䍏䖭⢙Ⲵ࠶ᮓ㹼Ѫǃᡰᗇ㺘䶒⢙⿽Ⲵ㔃ᶴ઼ަۜॆᙗ䍘⴨ޣ㚄Ⲵа㌫ࡇ᧒㍒, ሩҾҶ䀓ۜॆ֌⭘ᵪ⨶ǃ᭩䘋ᐢᴹۜॆࡲԕ৺䇮䇑ᯠⲴۜॆࡲ䜭ᱟॱ࠶ᗵ㾱Ⲵ.о䠁኎-≗ॆ⢙䖭փ䰤⴨ӂ֌⭘⴨∄䖳, ⭡Ҿ㔃ᶴкⲴ৏ഐ, ਟԕ亴ᵏ≗ॆ⢙о≗ॆ⢙䖭փѻ䰤ᴤᓄ䈕ᆈ൘⿽⿽ѠᇼཊṧⲴ⴨ӂ֌⭘(ྲ: ᖒᡀ⴨ӂ֌⭘Ⲵ㺘䶒⢙⿽ǃᖒᡀപⓦփ઼⭏ᡀᯠॆਸ⢙), 㾱൘࠶ᆀ৏ᆀቲ⅑к᧒䇘䍏䖭⢙о䖭փⲴ⴨ӂ֌⭘ᗵ享⸕䚃䖭փⲴ㺘䶒㔃ᶴ, նᱟਟ⭘Ҿᇎ䱵⍻ᇊⲴ਴⿽≗ॆ⢙䖭փⲴঅᲦн᱃ᗇ, ᴹⲴнਟᗇ, ≗ॆ⢙оঅᲦ䖭փ⴨ӂ֌⭘Ⲵⴤ᧕㿲⍻ᴤ࣐ഠ䳮. 䪸ሩ䘉Ӌᛵߥ, Ѫ᧒䇘н਼㊫ර≗ॆ⢙оаӋᑨ⭘䖭փ䰤Ⲵ⴨ӂ֌⭘, ᡁԜӾ䖭փⲴᤙՈ᳤䵢Ღ䶒ޕ᡻, ᘭ⮕ޡ਼ᆈ൘ⲴަᆳᲦ䶒, ᗇࡠ਴ᑨ⭘䖭փⲴ㺘䶒㔃ᶴ, ޽㔃ਸ䍏䖭⢙ⲴḀӋ⢩ᙗ(ԧර઼⿫ᆀॺᖴㅹ), ᨀࠪҶ᧿䘠≗ॆ⢙о≗ॆ⢙䖭փ⴨ӂ֌⭘Ⲵ“፼ޕ⁑ර”(incorporation model)[35,36], ᆳⲴสᵜ㾱⛩ྲл: (1)䖭փ㺘䶒㾱ᴹ䘲ᖃⲴオսᆈ൘, 䘉ᱟ䠁኎⿫ᆀॆਸ⢙㠚ਁ࠶ᮓᗇԕ䘋㹼Ⲵส⹰; (2)䍏䖭ර⿫ᆀॆਸ⢙൘䖭փ㺘䶒кⲴ࠶ᮓᇎ䱵кᱟަ䱣⿫ᆀ䘋ޕ䖭փ㺘䶒オս㘼⴨դⲴ䱤⿫ᆀᇊսަк(ԕ؍ᤱ⭥ѝᙗ)Ⲵ㔃᷌; (3)н਼ԧරⲴ⿫ᆀॆਸ⢙, ྲ1-1රǃ1-2රǃ2-1රǃ1-3ර઼2-3රㅹ, ⭡ҾᆳԜᡰդ䲿Ⲵ䱤⿫ᆀᡰӗ⭏Ⲵቿ㭭᭸ᓄн਼, ഐ↔࠶ᮓᇩ䟿ਟ㜭ҏ਴н⴨਼; (4)⭡Ҿн਼䖭փ㺘䶒オս⿽㊫(ഋ䶒փսǃޛ䶒փսᡆ・ᯩփս)н਼, ਼⿽䖭փ㺘䶒ҏਟ㜭ᴹн→а⿽オս(ྲJ-Al2O3ᴹഋ䶒փս઼ޛ䶒փս)ᆈ൘. ഐ↔൘䇘䇪䱣⿫ᆀ䘋ޕオսᰦ㾱㘳㲁ᱟ੖Āਇ䱫ᡆᤙՈāⲴ䰞仈, ণ䱣⿫ᆀⲴॺᖴབྷሿоオսቪረⲴޣ㌫ԕ৺䱣⿫ᆀ䘋ޕオսਾަ䝽ս⣦ߥᱟ੖っᇊㅹ; (5)⭡Ҿн਼䖭փ㺘䶒オսⲴᇶᓖн਼, ഐ㘼਼а⿽䱤⿫ᆀ൘ަкᡰӗ⭏Ⲵቿ㭭᭸ᓄҏՊн਼, ൘䱤⿫ᆀቿ㭭᭸ᓄབྷࡠаᇊ〻ᓖᰦণՊࠪ⧠Ā㺘䶒ᇶ㖞অቲā. һᇎ㺘᰾, ൘ᇎ傼䈟ᐞ㤳ത޵, 䘉њ䘁լⲴ⁑ර㜭ᇊ䟿ൠ䀓䟺н਼ԧර≗ॆ⢙(ྲLi2O, NiO, CuO઼MoO3ㅹ)൘аӋ≗ॆ⢙䖭փ(Al2O3, CeO2, TiO2઼ZrO2ㅹ)кⲴ࠶ᮓᇩ䟿, ⨶䇪亴⍻оᇎ傼㔃᷌⴨ㅖ. 䈕⁑ර㜭䈤᰾ѪӰѸн਼Ⲵ䠁኎≗ॆ⢙൘਼а䖭փкՊᴹн਼Ⲵ࠶ᮓᇩ䟿, 㘼਼а⿽䠁኎≗ॆ⢙൘н਼䖭փкⲴ࠶ᮓᇩ䟿ҏн਼; 䘈䀓䟺Ҷվԧර䠁኎≗ॆ⢙൘≗ॆ⢙䖭փкнਟ㜭ࠪ⧠ᇶ㖞অቲ࠶ᮓㅹ䰞仈.൘䍏䖭රۜॆࡲѝ࣐ޕࣙࡲᑨᑨՊ᰾ᱮൠ᭩ਈަۜॆᙗ㜭, ֻྲ൘V2O5/TiO2ѝ␫࣐WO3ᡆMoO3Պᱮ㪇᭩ழަ൘NH3䘹ᤙᙗۜॆ䘈৏NO x (NH3-SCR)৽ᓄѝⲴվ⑙⍫ᙗ. 㲭❦䘉㊫йݳ䠁኎≗ॆ⢙փ㌫਴㓴࠶ѻ䰤Ⲵ⴨ӂ֌⭘∄Ҽݳփ㌫༽ᵲᖸཊ, նᆳᴤ᧕䘁Ҿᇎ䱵֯⭘Ⲵۜॆࡲ, ഐ↔ሩ䘉㊫ۜॆࡲփ㌫䘋㹼␡ޕⲴ⹄ウާᴹ䟽㾱Ⲵ᜿ѹ.ѻࡽᡁԜቡ䬌สۜॆࡲ⭘Ҿۜॆ⎸䲔CO䘋㹼Ҷㆰ㾱Ⲵ㔬䘠[37]. ѪҶ⹄ウᐕ֌ᴤާ㌫㔏ᙗ઼ޘ䶒ᙗ, ᵜ᮷᢬㾱㔬䘠ҶᡁԜ䘁ᒤᶕ൘Ҽݳ઼йݳ䍏䖭ර䬌ส≗ॆ⢙ۜॆࡲ⭘ҾCOᆼޘ≗ॆǃCO+NO઼NH3+NO+O2৽ᓄㅹᯩ䶒Ⲵᐕ֌. ѫ㾱䙊䗷ሩCuO䍏䖭൘CeO2, Ce x Zr1 x O2઼MoO3-CeO2ㅹ䖭փкᡰᗇа㌫ࡇṧ૱Ⲵ⢙⨶ॆᆖᙗ䍘઼ۜॆᙗ㜭Ⲵ㺘ᖱ, ᧒䇘≗ॆ⢙㓴࠶䰤Ⲵ⴨ӂ֌⭘઼ṧ૱Ⲵ㓴ᡀ-㔃ᶴ-ᙗ䍘ѻ䰤Ⲵ޵൘㚄㌫, ԕᵏѪ儈᭸䍏䖭ර䬌สۜॆࡲⲴ᧒㍒઼䇮䇑ᨀ׋аӋ、ᆖ׍ᦞ. л䶒ቡࠐњާᴹԓ㺘ᙗⲴփ㌫䘋㹼࠶㊫䇘䇪.2. CuO/CeO2։㌱㠚20ц㓚80ᒤԓԕᶕ, CeO2ഐާᴹ㢟ྭⲴۘ/䟺≗ᙗ㜭ԕ৺≗ॆ䘈৏ᙗ䍘㘼ᒯ⌋ᓄ⭘Ҿй᭸ۜॆࡲ(TWC)઼≤⊭ਈᦒㅹ亶ฏ, ᡀѪ〰൏≗ॆ⢙ᓄ⭘Ⲵᴰ䟽㾱ԓ㺘, ᕅ䎧ҶӪԜⲴᶱབྷޣ⌘[38,39]. ⴤࡠ80ᒤԓᵛ, й᭸ۜॆࡲ䘈བྷཊԕ䍥䠁኎(ѫ㾱ᱟRh઼Pt)Ѫ⍫ᙗ㓴࠶, ԕCeO2Ѫ䖭փ, ࣋≲ሶ⊭䖖ቮ≄ѝⲴCO, HCs (⻣≒ॆ⢙)઼NO xй㘵਼ᰦ䖜ॆѪCO2, H2O઼N2, Ѫ↔ᗵ享؍ᤱਸ䘲Ⲵ䘋ᯉ∄઼327 o CԕкⲴ儈⑙, 㘼⊭䖖㹼傦Ⲵޘ䗷〻ѝ䳮ԕ┑䏣䘉ӋᶑԦ, ቔަᱟߧ੟ࣘᰦ⟳✗нᆼޘ, Պᴹབྷ䟿⻣≒ॆ⢙ᧂࠪ, ޽࣐кᰕ⳺ѕṬⲴᧂ᭮㾱≲, ֯ӪԜሩ᭩䘋й᭸ۜॆࡲⲴ⹄ウаⴤ⋑ᴹ䰤ᯝ. ަѝањケࠪⲴ䘋ኅᱟ90ᒤԓѝᵏаӋ⊭䖖ޜਨ⭘CeO2-ZrO2ԓᴯCeO2䖭փ, ᱮ㪇ᨀ儈ҶۜॆࡲⲴ㙀✝ᙗ઼ۘ≗㜭࣋. 䈕ᢰᵟ㻛؍ᇶࡠ1997ᒤ᡽ᣛ䵢, ᕅ䎧ӪԜሩ䖭փ৺ަ᭩ᙗ⹄ウⲴᶱབྷޤ䏓. о↔਼ᰦӪԜҏ൘нᯝൠࣚ࣋ራ᢮ᰲ䍥〰㕪䍥䠁኎Ⲵᴯԓ⢙, བྷ䟿Ⲵ᧒㍒㺘᰾CuOᐢᱟᕅӪ⌘ⴞⲴሩ䊑.ѪҶ⹄ウCuO൘CeO2䖭փкⲴᆈ൘⣦ᘱǃ≗ॆ䘈৏ᙗ䍘ԕ৺CuOоCeO2䖭փѻ䰤Ⲵ⴨ӂ֌⭘, ᡁԜ䟷⭘⎨␽⌅ࡦ༷Ҷа㌫ࡇн਼CuOਜ਼䟿ⲴCuO/CeO2ۜॆࡲ, ᒦ⭘ཊ⿽䉡ᆖ᡻⇥䘋㹼Ҷ㺘ᖱ[40]. Xሴ㓯㹽ሴ(XRD, 㿱മ1)઼Xሴ㓯ݹ⭥ᆀ㜭䉡(XPS)⍻ᇊⲴᇊ䟿࠶᷀㔃᷌(㿱മ2)㺘᰾, CuO൘CeO2䖭փкⲴ࠶ᮓᇩ䟿㓖Ѫ1.20 mmol CuO/100 m2 CeO2 (7.1њCu2+/nm2 CeO2), о“፼ޕ⁑ර”᤹CeO2(111)Ღ䶒кᡰᴹⲴ䱣⿫ᆀオս䜭㻛Cu2+⿫ᆀঐᦞᡰՠ㇇Ⲵ(1.22 mmol CuO/100 m2 CeO2)⴨ㅖ. CuO䍏䖭䟿൘࠶ᮓᇩ䟿ԕлⲴṧ૱, CuOԕ儈࠶ᮓ⣦ᘱᆈ൘, ⴨ᓄⲴXRD䉡ѝнࠪ⧠CuOⲴ⢩ᖱጠ, 㘼䍏䖭䟿൘࠶ᮓᇩ䟿ԕкⲴṧ૱ѝࡉࠪ⧠Ღ⴨CuOⲴ㹽ሴጠ.ᖃCuO/CeO2⭘֌CO≗ॆۜॆࡲᰦ, CeO2ᰒᱟ䖭փ৸䎧⵰ࣙࡲⲴ֌⭘, 䘉⿽ࣙۜॆ֌⭘оṧ૱ѝCe4+/Ce3+Ⲵ∄઼ֻᆳԜ൘৽ᓄѝⲴ䖜ᦒᇶ࠷⴨ޣ. 䙊䗷⭘н਼ԧᘱCeⴀ(Ce(NO3)3·6H2O઼(NH4)2Ce(NO3)6)Ѫࡽ傡⢙, ࡦᗇа㌫ࡇCuOਜ਼䟿н਼ⲴCuO/CeO2ṧ૱, ᒦ㘳ሏަۜॆCOᆼޘ≗ॆⲴ৽ᓄᙗ㜭[8], 㔃᷌㿱മ3, Ӿѝਟԕⴻࠪ: ķ∄䖳ԧᘱн਼Ⲵࡽ傡⢙ᡰᗇєњ㌫ࡇⲴṧ૱ਟ⸕, ᖃCuO䍏䖭䟿⴨਼ᰦ, Ӿйԧ䫸ⴀᡰᗇṧ૱Ⲵۜॆ⍫ᙗ䜭∄ഋԧ䫸ⴀᡰᗇⲴ㾱儈. 䘉ਟ㜭ᱟ⭡Ҿࡽ㘵ѝCe3+ਜ਼䟿ᴤ儈, ᴹ࡙ҾCu+-Ƒ-Ce3+ॿ਼≗オս(SSOV)Ⲵᖒᡀᡰ㠤(㿱മ4).ĸ∄䖳֯⭘਼аࡽ傡⢙նCuO䍏䖭䟿н਼Ⲵṧ૱ਟ⸕, ަ⍫ᙗ䜭ᱟ䲿⵰CuO䍏䖭䟿Ⲵ໎࣐㘼໎࣐, ࡠᔰ࿻ࠪ⧠փ⴨CuOᰦ䗮ᴰ儈٬, ޽໎࣐CuOⲴ䍏䖭䟿, ṧ૱ѝࠪ⧠ᴤཊᲦ⴨CuO, ަ⍫ᙗ䲿ѻ᰾ᱮл䱽, о፼ޕ⁑රᡰ亴⍻Ⲵ⴨ㅖ: 䎧ࡍ䲿CuO䍏䖭䟿Ⲵ໎࣐, 儈࠶ᮓⲴCu2+䱶㔝ঐᦞCeO2㺘䶒Ⲵ䱣⿫ᆀオս, ࠪ⧠Cu2+-O-Ce4+Ⲵᵪ⦷䲿ѻ໎བྷ; 㘼ᖃ䍏䖭䟿䎵䗷࠶ᮓᇩ䟿ਾ, Ღ⴨CuOࠪ⧠, ᆳሩᖒᡀẕ㚄ⲴCu2+-O-Ce4+⢙⿽нՊᴹ᰾ᱮ䍑⥞, Ӿ㘼ሬ㠤᤹অњCu৏ᆀ䇑䟿ᡰᗇⲴ⍫ᙗ䱽վ. สҾ↔ᨀࠪҶ㺘䶒ॿ਼≗オս(SSOV)ۜॆ৽ᓄᵪ⨶[41]: ণ亴䘈৏ਆ䎠㺘䶒Cu2+-O-Ce4+⢙⿽ѝⲴ≗, ᖒᡀ㺘䶒ॿ਼≗オս, ᕅਁCO≗ॆ৽ᓄⲴ䘋㹼.3.䖳։Ⲻ։⴮᭯ᙝ: CuO/Ce x Zr1 x O2։㌱䖭փ᭩ᙗᱟᨀ儈ṧ૱ۜॆᙗ㜭ᑨ⭘Ⲵа⿽ᯩ⌅. 䙊䗷␫࣐䘲ᖃⲴ≗ॆ⢙ਟᗇࡠৼݳᡆԕкⲴ≗ॆ⢙പⓦփᡆቆᲦ⸣රᡆ䫉䫋ⸯ(ABO3)ර≗ॆ⢙ᡆ␧ਸ≗ॆ⢙ㅹ䗮ࡠ䈳ਈ䖭փᙗ㜭ⲴⴞⲴ. 䘉ᖃ❦઼䘉Ӌ≗ॆ⢙ѻ䰤ԕ৺ᆳԜ઼ᡰ䍏䖭Ⲵ⍫ᙗ㓴࠶ѻ䰤Ⲵ⴨ӂ֌⭘ⴤ᧕⴨ޣ. ᮷⥞ᣕ䚃Ҷབྷ䟿Ⲵㆋ䘹઼᧒ウ޵ഐⲴᐕ֌, ޵ᇩѠᇼ༽ᵲཊṧ. CeO2֌Ѫ䖭փ㲭ᴹཊ⿽Ո⛩, ն✝っᇊᙗᐞ, 儈⑙л᱃✗㔃, Ӿ㘼ѕ䟽ൠᖡ૽ަ৽ᓄ⍫ᙗ[39,42,43]. ᐢ⸕⭘ZrO2֌䖭փᰦCuO/ZrO2ҏᴹ㢟ྭⲴۜॆCO≗ॆᙗ㜭, ᒦф൘⭢䞷㫨≄䟽ᮤࡦ≒৽ᓄѝ, CuO/ZrO2Ⲵ㙀✝ᙗՈҾCuO/CeO2[44]. CeO2-ZrO2Ⲵ⴨മ㺘᰾൘⴨ᖃབྷⲴ⎃ᓖ४䰤є㘵ਟᖒᡀപⓦփ[39]; Zr4+ॺᖴ(0.084 nm)∄Ce4+(0.097 nm)ሿ, ൘ᇼ䫸ⲴCeO2-ZrO2പⓦփѝ, ⿫ᆀॺᖴᴤሿⲴZr4+䘋ޕCeO2Ⲵ㩔⸣ර・ᯩᲦṬ, 䜘࠶ਆԓሬ㠤Ღ㜎փ〟ԕ৺ᲦṬ৲ᮠ߿ሿ, Ӿ㘼ᨀ儈Ҷ䖭փⲴ✝っᇊᙗԕ৺փ⴨ᲦṬ≗Ⲵ䗱〫ᙗ઼ۜॆࡲۘ/䟺≗Ⲵ࣏㜭. ᇎ䱵к൘й᭸ۜॆࡲѝ, ✝っᇊᙗՈ㢟ⲴCeO2-ZrO2പⓦփ⧠൘ᐢ㓿ਆԓҶCeO2⭘֌䖭փ[43,45~47].XRD㔃᷌㺘᰾ᇼ䫸ⲴCe x Zr1 x O2(xı 0.5)പⓦփӽ❦؍ᤱCeO2Ⲵ㩔⸣ර・ᯩ㔃ᶴ, оAyastuyㅹ[48]Ⲵᣕ䚃а㠤. ᦞ↔, ྲ᷌ٷᇊCe x Zr1 x O2(xı 0.5)ⲴᤙՈ᳤䵢䶒઼CeO2аṧ, ҏѪ(111)Ღ䶒(㿱മ5)[49], ᡁԜቡਟԕሩCuO൘ަкⲴ࠶ᮓ઼Cu2+Ⲵ䝽ս⧟ຳ䘋㹼аӋ䇘䇪.ᡁԜሩCe0.67Zr0.33O2к䍏䖭CuOⲴ㌫ࡇṧ૱(ㆰ䇠ѪCuO/CZ)ѝCuOⲴ࠶ᮓǃ䘈৏৺ަNO+CO৽ᓄⲴۜॆᙗ䍘䘋㹼Ҷ㘳ሏ[50]. ⭡മ6ਟ㿱, Cu-CZṧ૱ѝCuOⲴ࠶ᮓᇩ䟿վҾ1.23㘼儈Ҿ0.66, ⨶䇪٬Ѫ1.20ᐖਣ; ൘1.23Cu-CZṧ૱ѝỰ⍻ࡠᲦ⴨CuOⲴᆈ൘. ⭡മ7ਟԕⴻࠪ, ൘0.66Cu-CZ઼0.33Cu-CZѝսҾ224 q CⲴጠ䶒〟བྷ㠤⴨ᖃ, ൷о㺘䶒Ce4+䘈৏ѪCe3+ᴹޣ; 㘼1.23Cu-CZṧ૱ѝ, 䈕ጠ䶒〟᰾ᱮ໎བྷ, 䘉ᱟ⭡ҾᲦ⴨CuOᖒᡀⲴ㕈᭵; ൘1.65Cu-CZṧ૱ѝ䈕ጠ䶒〟㔗㔝໎བྷ, ᖃоᴤཊⲴᲦ⴨CuOⲴᖒᡀᴹޣ, 䘉оXRDⲴ㔃᷌⴨੫ਸ. ྲമ8ᡰ⽪, 䬌ਜ਼䟿൘࠶ᮓᇩ䟿䱴䘁Ⲵۜॆࡲ⍫ᙗ઼䘹ᤙᙗ൷ᴰ֣.䘉Ӌ㔃᷌䘈䈤᰾, ൘䍏䖭රۜॆࡲⲴࡦ༷ѝ, ݵ࠶㘳㲁⍫ᙗ㓴࠶Ⲵ࠶ᮓᇩ䟿٬, ᒦ䙊䗷䘲ᖃ᡻⇥ࡦᗇ䈕ਜ਼䟿Ⲵ儈࠶ᮓṧ૱ሩҾᗇࡠᴰ֣᭸᷌Ⲵۜॆࡲ㘼н䙐ᡀ⍫ᙗ㓴࠶Ⲵ⎚䍩ॱ࠶䟽㾱.ԕCe0.5Zr0.5O2Ѫ䖭փ, ⭘⎨␽⌅ࡦᗇа㌫ࡇCuO䍏䖭䟿н਼Ⲵṧ૱(ㆰ䇠ѪCuO/CZ)[49]. XRD(㿱മ9)㔃᷌㺘᰾, CuO䍏䖭䟿൘0.9 mmol CuO/100 m2 CZᐖਣᰦࠪ⧠Ღ⴨CuOⲴ࠶⭼⛩, о↔⴨બᓄ, H2〻ᒿॷ⑙䘈৏(H2-TPR)㔃᷌(㿱മ10)ҏ䇱ᇎ䍏䖭䟿վҾ0.9 mmol CuO/100 m2 CZⲴṧ૱ѝਚࠪ⧠170઼235 q Cᐖਣ኎Ҿ儈࠶ᮓCuOⲴ䘈৏ጠ, 㘼൘309 q C䱴䘁⴨ᓄҾᲦ⴨CuO Ⲵ䘈৏ጠਚࠪ⧠൘CuO䍏䖭䟿ᴤ儈Ⲵṧ૱ѝ. 䘉Ӌṧ૱ⲴCOվ⑙≗ॆ৽ᓄ㔃᷌㿱മ11, ⍫ᙗᴰ֣ⲴѪ1.2 mmol CuO/100 m2 CZ. 䘉Ӌ㔃᷌ок᮷ሩCuO/CeO2Ⲵ䇘䇪а㠤, 䈤᰾࠶ᮓᘱⲴCuOᱟѫ㾱⍫ᙗ⢙⿽, 䗷儈Ⲵ䍏䖭䟿৽㘼֯ṧ૱᤹TOFՠ㇇Ⲵ⍫ᙗ䱽վ.4.䖳։Ⲻ㺞䶘᭯ᙝ: CuO/MoO3-CeO2։㌱䙊䗷≗ॆ⢙઼䖭փ㺘䶒Ⲵ⴨ӂ֌⭘ሩ䖭փ䘋㹼᭩ᙗҏᑨ㿱Ҿᓄ⭘. ᡁԜሶCuO䍏䖭Ҿ㓿MoO3᭩ᙗⲴCeO2䖭փ(MoO3-CeO2)к㘳ሏᡰᗇṧ૱Ⲵᙗ㜭. ѻᡰԕ䘹⭘MoO3ѫ㾱ᱟ㘳㲁ࡠMoO3൘ཊ⿽䟽㾱Ⲵۜॆ৽ᓄѝྲ✟⛳༽࠶䀓ǃ≗ॆ઼࣐≒༴⨶ㅹ, 䜭ᴹ䟽㾱ᓄ⭘, 㘼фMoO3ⲴTaman⑙ᓖվ᱃Ҿ൘≗ॆ⢙䖭փк࠶ᮓ, 䈳㢲⭘䟿ቡਟᗇࡠ൘䖭փк䜘࠶㾶ⴆᡆޘ㾶ⴆ(ণᖒᡀᇶ㖞অቲ)Ⲵṧ૱, ׯҾ㘳ሏ઼∄䖳ަᙗ䍘Ⲵਈॆ. ቡMoO3-CeO2փ㌫㘼䀰, ⴤ᧕⭘ҾۜॆCOվ⑙≗ॆ઼⭥䀓≤ࡦ≒ҏᐢ㿱䈨ᣕ䚃[51,52], ٬ᗇᤷࠪⲴᱟ, ൘ਾа亩ᐕ֌ѝHuangㅹ[52]⺞䇔൘ᡰࡦ༷ⲴMoO3/CeO2ṧ૱ѝMoO3ᒦᵚ䘋ޕCeO2ᲦṬ, ሶ⍫ᙗᖂഐҾ㺘䶒кMo-O-Ce⢙⿽Ⲵᖒᡀ, ᤷࠪۜॆ⍫ᙗԕ䍏䖭䟿᧕䘁ҾMoO3൘CeO2㺘䶒Ⲵ࠶ᮓᇩ䟿ণᖒᡀMoO3ᇶ㖞অቲᰦᴰ֣, 䘉а㔃᷌оᵜ᮷ޣҾCuO/CeO2ṧ૱Ⲵ⴨ޣ㔃᷌Ⲵ䇘䇪н䈻㘼ਸ. ↔ཆ, Rathodㅹ[53]൘⭘␧ਸ≗ॆ⢙ਆԓᴹᵪ৽ᓄѝᑨ⭘Ⲵǃᴹ∂᱃䙐ᡀ⊑ḃ৸䳮ԕഎ᭦Ⲵᰐᵪ䞨ۜॆࡲⲴ᧒㍒ѝ, ሶMoO3/CeO2-ZrO2⭘Ҿۜॆ㤟ᒦ૚ୁ㹽⭏⢙Ⲵਸᡀ, ᤷࠪ⍫ᙗԕ䍏䖭20wt.%ᐖਣMoO3Ⲵṧ૱Ѫᴰ֣, ۜॆࡲާᴹ᱃എ᭦, ਟ䮯ᵏ֯⭘ㅹՈ⛩.ᡁԜ⵰䟽㘳ሏҶCuO䍏䖭൘⭘MoO3᭩ᙗCeO2ᡰᗇ䖭փка㌫ࡇṧ૱Ⲵ⢙ᙗ৺ަ൘վ⑙NH3-SCR৽ᓄⲴۜॆᙗ㜭[54,55]. ṧ૱࠶࡛ㆰ䇠ѪCuO/0.8Mo-Ce઼CuO/0.4Mo-Ce; ަѝ0.8Mo-Ceᤷ൘CeO2кᐢ䍏䖭Ҷ⴨ᖃҾަ࠶ᮓᇩ䟿ⲴMoO3, ᤹⁑ර亴ᵏ↔ᰦCeO2㺘䶒ᖃᐢ㻛оMo6+դ䲿Ⲵ≗⿫ᆀᡰᖒᡀⲴᇶ㖞অቲᡰ㾶ⴆ, 䍏䖭൘ަкⲴCuOноCeO2ⴤ᧕᧕䀖; 0.4Mo-Ce㌫ࡇṧ૱ࡉਚ⭘ॺњঅቲⲴMoO3؞侠CeO2㺘䶒, 䍏䖭ަкⲴCuOᴹⲴо㺘䶒кⲴMoO3, ᴹⲴоᵚ㻛䚞ⴆⲴCeO2Ⲵ㺘䶒᧕䀖, ྲമ12(a)઼(b)ᡰ⽪.ሶCuO䍏䖭൘к䘠єњMoO3᭩ᙗⲴ䖭փк, XRD㔃᷌⽪Ҿമ13. Ӿമ13(b)઼(d)ਟԕⴻࠪ, ൘┑অቲMoO3᭩ᙗⲴ䖭փ(0.8Mo-Ce)к, CuOⲴ࠶ᮓᇩ䟿Ѫ2.06 mmol/100 m2, ᰾ᱮൠ儈ҾCuO൘ᵚ㓿᭩ᙗⲴCeO2кⲴ࠶ᮓᇩ䟿(1.20 mmol CuO/100 m2 CeO2). 䘉а㔃᷌ᤷࠪ┑ቲMoO3Ⲵ᭩ᙗ׳䘋ҶCuOⲴ࠶ᮓ, а⿽ਟ㜭Ⲵ䀓䟺ᱟ↔ᰦCuOᱟ࠶ᮓ൘MoO3ᡰᑖᶕⲴᇶ㖞অቲ≗ᡰᖒᡀⲴഋ䶒փオսк, 㤕ྲ↔, ਟՠ㇇ަ࠶ᮓᇩ䟿ᖃѪ2.44 mmol/100 m2, оᇎ⍻٬䖳᧕䘁ն᰾ᱮٿ儈, 䘉ਟ㜭ᱟ⭡Ҿ䍏䖭CuOՊሬ㠤㺘䶒MoO3ᇶ㖞অቲ㔃ᶴⲴਈॆ.᤹ԕк࠶᷀᧘⍻, ൘к䘠䖭փк࠶ᮓⲴCu2+ᱟ༴൘ഋ䝽սⲴ⧟ຳᓄᖃ∄࠶ᮓ൘ᵚ㓿᭩ᙗⲴCeO2кⲴCu2+(ӄ䝽ս)䖳䳮㻛䘈৏. ӾXRDമ13(a)઼(c)ਟԕⴻࠪ, ൘㓿ॺњঅቲMoO3᭩ᙗⲴ䖭փ(0.4Mo-Ce)к, CuOⲴ࠶ᮓᇩ䟿ਚᴹ0.73 mmol CuO/100 m2 CeO2, վҾᵚ᭩ᙗⲴCeO2 (1.20 mmol CuO/100 m2 CeO2). 㔃᷌㺘᰾䴦ᮓൠ䲿ᵪ࠶ᐳ൘CeO2кⲴMoO3ᰐࣙҾCuOⲴ࠶ᮓ, 䘉ਟ㜭ᱟ⭡Ҿнӵᵚᖒᡀާᴹഋ䶒փオսⲴᇶ㖞≗অቲ, 㘼фоMo6+դ䲿ⲴO2–䘈Պቿ㭭൘CeO2кⲴаӋオս, 㺘䶒кሶࠪ⧠ᰒоCeO2৸оMoO3⴨ӂ֌⭘Ⲵ䬌⢙⿽, ԕк䇘䇪ол䘠H2-TPR㔃᷌а㠤.ሩ∄മ14ᡰࡇH2-TPR㔃᷌ѝ0.3Cu/Ce, 0.3Cu/0.4Mo-Ce઼0.6Cu/0.4Mo-Ceйњṧ૱ਟԕⴻࠪ, 170઼196 q CⲴጠ৽᱐ҶCuO-CeO2⴨ӂ֌⭘⢙⿽Ⲵ䘈৏, սҾ235 q CⲴ㛙ጠࡉᓄᱟCu-O-Mo⢙⿽Ⲵ䘈৏ጠ. ٬ᗇ⌘᜿Ⲵᱟ, ൘㓿≗ᇶ㖞অቲ᭩ᙗⲴйњṧ૱ѝ, 0.3Cu/0.8Mo-Ce઼0.6Cu/0.8Mo-Ce൷ᵚࠪ⧠⴨ᓄҾCu-O-Ce⢙⿽Ⲵվ⑙䘈৏ጠ, 䈤᰾ᇶ㖞অቲⲴ≗ॆ䫬о≗ॆ䫸ѻ䰤Ⲵᕪ⴨ӂ֌⭘䱫䳄Ҷ䍏䖭ަкⲴCuOоCeO2Ⲵ᧕䀖, є㘵ѻ䰤Ⲵ⴨ӂ֌⭘ᐢн᰾ᱮ.◰ݹ᣹ᴬݹ䉡(LRS)㔃᷌㺘᰾, ᖃMoO3൘CeO2㺘䶒࠶ᮓᰦ, 䲿⵰䍏䖭䟿Ⲵ໎࣐, 儈࠶ᮓⲴMo=OㄟสጠՊੁᴤ儈⌒ᮠ〫ࣘ, Ӿվ䍏䖭䟿0.2Mo/CeᰦⲴ921 cm 1ࡠᖒᡀᇶ㖞≗অቲ0.8Mo/CeᰦⲴ964 cm 1, о↔⴨ᓄ, 㺘䶒儈࠶ᮓⲴ≗ॆ䫬⢙⿽Ӿᑨ㿱Ⲵঅњ䫬≗ഋ䶒փ⢙⿽(㿱മ15(a)ᐖ), 㚊ਸᡀѪޛ䶒փᶴරⲴ㚊≗ॆ䫬⢙⿽, བྷ㠤⽪᜿Ҿമ15(b)ᐖമ.൘䘉Ӌ᭩ᙗҶⲴ䖭փк䍏䖭CuO, ަ⴨ᓄⲴLRS䉡ਟ㿲ሏࡠMo=OጠᕪᓖⲴ߿ᕡ, ൘0.4Mo-Ceк䍏䖭Cu2+ਾ≗ॆ䫬⢙⿽੸ഋ䶒փ㔃ᶴ, 㘼൘0.8Mo-Ceкࡉ䘈Պᕅ䎧аӋMo O Mo䭞Ⲵࡺᕡ⭊㠣ᯝ㻲, Ӿ㘼⹤ൿ৏ᶕ䖳㿴ᮤⲴ㚊ޛ䶒փᶴර, བྷ㠤ྲമ15(a)઼(b)Ⲵਣॺമᡰ⽪.മ16ᱟ൘0.8Mo-Ceк䍏䖭н਼䟿CuOⲴLRS㔃᷌. Ӿѝਟᇊ䟿ՠ⍻䲿CuO䍏䖭䟿Ⲵ໎࣐, ṧ૱ѝޛ䶒փ(~965 cm 1)઼ഋ䶒փ(~900 cm 1) M=O䭞Ⲵਈॆ. ൘0.3Cu/0.8Mo-Ce, 0.6Cu/0.8Mo-Ce઼0.9Cu/0.8Mo-Ceṧ૱ѝ, 䲿⵰CuO䍏䖭䟿Ⲵ໎࣐, ޛ䶒փᡰঐ∄ֻ䱽վ, ׍⅑བྷ㠤Ѫ0.20, 0.12઼0.05. 䘉Ӌ㔃᷌㺘᰾, ⭡ҾCuO઼Mo ⢙⿽ѻ䰤ᆈ൘䖳ᕪⲴ⴨ӂ֌⭘, CuOⲴ࣐ޕՊᕅ䎧Mo⢙⿽Ⲵ㚊ਸᓖ䱽վ, ޛ䶒փⲴMo⢙⿽䙀⑀ੁഋ䶒փ㔃ᶴ䖜ਈ.Ѫ᧒䇘Cu/Mo-Ceṧ૱ѝн਼Ⲵਜ਼䫬⢙⿽઼㺘䶒䞨ᙗⲴޣ㌫, 䘋㹼Ҷ൘н਼⑙ᓖлаӋṧ૱кNH3੨䱴Ⲵ৏ս㓒ཆ⍻ᇊ(ྲമ17). 㔃᷌㺘᰾, 㚊ਸޛ䶒փ㔃ᶴⲴMo⢙⿽ᖒᡀ㺘䶒ⲴBrönsted䞨ս, 㘼ᆔ・ഋ䶒փ㔃ᶴⲴMo⢙⿽ࡉ൘ṧ૱㺘䶒ᖒᡀᕡLewis䞨ս(L1). CuOⲴᕅޕ֯B䞨ս᰾ᱮ߿ቁ, ᒦӗ⭏ҶᯠⲴ䖳ᕪⲴL䞨ս(L2). 㺘1㔉ࠪᇊ䟿㔃᷌, 0.4Mo-Ceо0.8Mo-Ceє㓴ṧ૱ᛵߥ⴨լնਾ㘵䞨ᕪᓖ઼䞨䟿䜭ᴤ儈.аӋCuO/MoO3-CeO2ṧ૱൘н਼⑙ᓖᰦNH3-SCR ৽ᓄⲴۜॆᙗ㜭⽪Ҿമ18. ᙫⲴᶕ䈤, 0.8Mo-Ce㌫ࡇṧ૱Ⲵ⍫ᙗ᰾ᱮ儈Ҿ0.4Mo-Ce㌫ࡇ. Ӿ㺘1ਟԕⴻࠪ, ࡽ㘵Ⲵ䞨䟿᰾ᱮ儈Ҿਾ㘵, 䘉㺘᰾৽ᓄѝ㺘䶒䞨ս䎧䟽㾱֌⭘. ৽ᓄ⑙ᓖ൘200઼250 q Cᰦ, 䍏䖭CuOՊᨀ儈৽ᓄ⍫ᙗ, 䘉ਟоṧ૱ѝL䞨սⲴ໎࣐⴨ޣ㚄; 㘼൘300~350 q C ⑙ᓖ४䰤CuOⲴ࣐ޕ৽㘼֯⍫ᙗл䱽, ↔ᰦਟ㜭B䞨ս䎧⵰ᴤ࣐䟽㾱Ⲵ֌⭘, 䘉Ӌ㔃᷌լѾᤷࠪ൘н਼⑙४“NO+NH3+O2”ۜॆ৽ᓄᴹн਼Ⲵ৽ᓄᵪ⨶.↔ཆ, ᡁԜ䘈ሩCuO䍏䖭൘㓿≗ॆ⢙᭩ᙗⲴCe x Zr1 x O2઼Ti x Sn1 x O2䖭փкᡰᖒᡀⲴཊݳ≗ॆ⢙փ㌫(ֻྲCuO/MnO x-Ce x Zr1 x O2[56], CuO/CoO x-Ce x Zr1 x O2[57], CuO/WO3-Ce x Zr1 x O2[58,59], CuO/Ti x Sn1 x O2[60]઼CuO/ VO x-Ti x Sn1 x O2[61]ㅹ)ѝ≗ॆ⢙㓴࠶䰤Ⲵ⴨ӂ֌⭘৺ަሩ⍫ᙗ㓴࠶઼䖭փⲴ㓴ᡀǃ㔃ᶴ઼ᙗ㜭Ⲵᖡ૽䘋㹼Ҷ㘳ሏ, ⢩࡛ᱟሩަCO≗ॆ઼༴⨶NOⲴۜॆᙗ㜭䘋㹼Ҷ⹄ウ.≗ॆ⢙㓴࠶䰤⴨ӂ֌⭘Ⲵ⹄ウ઼ᓄ⭘䶒ᒯ䟿བྷ, ਈॆ༽ᵲ, ਟ䈳ਈᑵᓖᖸབྷ, ൘⨶䇪઼ᇎ䱵ᓄ⭘(⢩࡛ᱟཊ⴨ۜॆ઼ᶀᯉࡦ༷)ᯩ䶒䜭ᴹ䟽㾱᜿ѹ. ࡽӪሩ㺘䶒⁑ර઼⴨ӂ֌⭘ᵜ䍘Ⲵ᧒㍒઼〟㍟, 䘁ԓ䉡ᆖ᡻⇥઼⨶䇪ᯩ⌅Ⲵ䘋ኅ, 䜭Ѫ൘䘉а亶ฏѝਆᗇ␡ޕⲴҶ䀓ᨀ׋ҶᶑԦ, ᡁԜ䘋㹼Ⲵᐕ֌ਚᱟ⋗⎧а㋏, 䴰㾱ᴤ࣐㌫㔏ॆ઼␡ޕ, 䘹ᤙᴤཊᴹ䟽㾱ᓄ⭘ࡽᲟⲴۜॆփ㌫, ㌫㔏ൠ⹄ウ⍫ᙗ㓴࠶઼䖭փⲴ䈳ਈ৺᭩ᙗѪᴹޣۜॆࡲⲴࡋࡦ઼ਁኅᨀ׋、ᆖ׍ᦞ.5.ᙱ㔉фኋᵑԕCuOѪѫ㾱⍫ᙗ⢙⿽, 㘳ሏҶަ䍏䖭ҾCeO2, Ce x Zr1 x O2઼MoO3-CeO2ㅹ䖭փ㺘䶒Ⲵ࠶ᮓ⣦ᘱ. สҾ“፼ޕ⁑ර”Ⲵสᵜ㘳㲁, 䖳ྭൠ䀓䟺ҶCuO൘н਼䖭փ㺘䶒Ⲵ࠶ᮓ㹼Ѫ৺⴨ޣ⢙⨶ॆᆖᙗ䍘Ⲵᐞᔲ. 䙊䗷ཊ⿽㺘ᖱ᡻⇥(वᤜ䜘࠶৏ս઼ॺ৏ս᡻⇥), ᒦ㔃ਸۜॆࡲ൘COᆼޘ≗ॆǃCO+NO઼NH3+NO+O2ㅹ⁑ර৽ᓄѝⲴۜॆᙗ㜭, ቍ䈅⵰ᔪ・Ҷަ൘ۜॆ৽ᓄѝⲴ“ᶴ᭸ޣ㌫”. ❦㘼ሩҾ↔㊫ۜॆࡲ൘䘉Ӌ৽ᓄѝⲴ৽ᓄࣘ࣋ᆖԕ৺⭡䬌⢙⿽ԧᘱਈॆᕅ䎧Ⲵ⭥ᆀ䖜〫ᗞ㿲ᵪࡦǃ৽ᓄᵪ⨶䘈нᱟᖸ␵ᾊ. ਼ᰦ, ሩۜॆࡲⲴޘ䶒䇴ԧ(वᤜᣇ≤ᣇ⺛ǃᣇ㘱ॆᙗ㜭ㅹ)ᴹᖵ䘋а↕ᆼழ. ഐ↔, ᡁԜӺਾሶ൘䘉Ӌᯩ䶒ڊаӋቍ䈅ᙗⲴᐕ֌.䱾ᠵ䱺⌞ ᒪ ᴾѰ㓠ᘫ䛉Ქਇᮏᦾ䙓ьжઞᒪ ᡇԢᴴ൞Ʌགྷᰜཝᆜᆜᣛ 㠠❬〇ᆜ⡾ Ɇਇ㺞Ҽćਂ䠇ኔ≝ौ⢟ૂ≝ौ⢟䖳։㓺࠼䰪Ⲻ⴮ӈ֒⭞Ĉжᮽ 䖢⵲ॷᒪᐨ䗽 ঍Ӣཝᆜ䘏ᯯ䶘Ⲻᐛ֒ѱ㾷⭧㪙᷍ᮏᦾ〇⹊㓺൞䘑㺂 ᓭᒪᮏᦾ౧᫦ᮽ ⧦⭧㪙᷍ᮏᦾ㩳ㅊᣋふ㓠ᘫᲥਇᮏᦾ䈔⭕ ઞᒪⲺщࡀ ԛ↚㺞䗴ᡇԢሯԌⲺ␧࠽ᘶᘫ。