17 4 2005 7 PROGRESS IN CHEMISTRY Vol. 17 No. 4 Jul., 2005 3 ( 300072), XRD EXAFS DSC SEM TEM XPS : O643136 ; TQ42618 : A : 10052281X(2005) 0420614208 Preparation and Application of Amorphous Alloy Catalyst Xiong Zhongqiang Mi Zhentao Zhang Xiangwen 3 ( Key Laboratory for Green Chemical Technology, School of Chemical Engineering & Technology, Tianjin University, Tianjin 300072, China) Abstract The development and applications of amorphous alloy catalyst are summarized. The most widely used techniques for the preparation of amorphous alloy catalyst are classified into rapid quenching method, chemical reduction method and impregnation2chemical reduction method. The reaction activity of the catalyst can be adjusted by changing the preparing condition, which including the calcination temperature, the metal load and the carrier. The amorphous structure, surface morphology and activity center can be determined and characterized by XRD, EXAFS, DSC, SEM, TEM and XPS. A detailed discussion of amorphous alloy catalyst in hydrogenation of unsaturated compound is presented. Key words amorphous alloys ; catalysts ; rapid quenching methods ; chemical reduction methods [2 4 ] : +, Fe2B Pd2Si Co2B2Si Ni2Fe2P2B ; +,, Ni2Zr Cu2Zr Pd2Zr, 1934, ;,, 1nm, 15nm 1980 Simth [1 ] 1nm,, 5 15nm : 2004 6, : 2004 9 3 e2mail :zliuying @public. tpt. tj. cn
4 615, ; (2),, ; (3),, ; (4), 011 1m 2 Πg, Ni2Al2P [8,9 ],,,, Ni2P Ni2B Ni2Cu2B 2.,,, PdΠC, 1986 van Wonterghem,, [5 ] 2 2,Ni2B : BH - 4 + 2H 2 O BO - 2 + 4H 2 (1), BH - 4 + 2Ni 2+ + 2H 2 O - 3 : 2Ni + BO 2 + 4H + + 2H 2 (2) BH - 4 + 2H 2 O B + OH - + 2. 5H 2 (3) 11 (2) (3) 1960 Duwez, Willens [6 ],, 106 Πs Al 2 O 3 Au 70 Si 30, (3) (2), B, [10 ] ; [11, ] Ni 2 B Ni 3 B, :, 2BH - 4 + 2Ni 2 + + H 2 O 30mΠs 5mm 30m Ni 2 B + HBO 2 + 2H + + 4. 5H 2 (4), [7 ] 5BH - 4 + 6Ni 2 + + 6H 2 O 2Ni 3 B + 7H + + 11H 2 (5) : (1) : ; (2), 2H 2 PO - 2 + Ni 2 + + 2H 2 O ; (3) 2H 2 PO - 3 + Ni + H 2 (6) : (1) Ni2B 200m 2 Πg,
616 17 [12 ] NaH 2 PO 2 6H 2 O CH 3 COONa, 10gΠL,, 90, 2h,,, 50 100 NiCoB Ni2BΠSiO 2 (10nm),,, SiO 2 NiCl 2, 8 ; Ni2B KBH 4,, 100 % 98 %,, PdΠC [18,19 ] (3) Ni2Co2B, : (1), [20 24 ], ; (2), ; (3) Ni2Co2B KBH 4 NiCl 2 CoCl 3,, KBH 4 = 5 2 (mol),,,, Deng [13 ] 1988, (4) Pd2BΠSiO 2,,,,, Yu [25 ] Pd2BΠSiO 2, PdCl 2 3., ( 100 ) ( 200 ), KBH 4, KBH 4, ( KBH, 4 Pd 2 + = 5 1 (mol) ) ( KBH 4 NaH 2 PO 3 ),,, (1) R2Ni2P Ni2Al2P,Li, [14 ] Ni :4812 %, Al :4817 %, P :311 %, 5mm 10 20nm 1. 200, Ni2BΠSiO 2, - Al BH 4 Ni 2 + Π [26, SiO 2, ] 17 ] (2) Ni2B (P) (110g SiO 2, 198mΠg, 40 60 ) [15,Ni2BΠSiO 2 NiCl 2,100 350,200
4 617, 1 1 Fig. 2 Effect of annealing temperature on conversion for benzene Fig. 1 Dependence of hydrogenation activity of hydrogenation over ultrafine NiP and NiB amorphous acrylonitrile on calcination temperature alloys XPS,, 1 400 350 30 %,, NiP 200,, 300 400,,400,Ni 2 + SiO 2 20 %, X (XAFS) X ;,Ni 2 + (XRD) (DTA) SiO 2,, ; NiB :, Ni 2 + SiO 2, 320 Ni 2 + BH - 4, NiB Ni 3 B 200 Ni 2 B ; 380 1 Ni, Ni 3 B Ni [29 ] Table 1 Dependence of mol ratio of surface Ni on NiP,300 calcination temperature calcination temperature ( ) 0 100 200 300 400 500 mol ( %) Ni 35. 26 38. 21 44. 17 33. 69 14. 72 6. 95 Ni 2 + 64. 74 61. 79 55. 83 66. 31 85. 28 93. 05 2. [27 ], Ni, ; NiP NiB NiP [28 ] :2gNiB, NiP 300 NiP, Ar, Ni 3 P Ni,, 2h 2 2 NiP NiB, NiP Ni Ni 3 P, 360 Ni 3 P Ni, Ni 3 B Ni 2 B NiB, 400, NiB 3.,NiB Ni 2 + BH - 4 Ni2B,350 Ni 2 + 63 %, 1 ;,3 Ni2BΠSiO 2
618 17, 3 Ni Fig. 3 Dependence of reduction percent on Ni content,, Ni 2 + ;,3. Ni 2 + BH - 4 X 614 % : 614 % (XPS),,,, Ni2B B Ni,Ni2P Ni, : P 34 ] ;Beilin [35 ] Ni P ; ; Tamaki [36 ] X ( XRD) X Ni2P RF :Ni2P ( EXAFS) ; P,P (DSC) ( TPR) 25 %, P Ni,P ; X 25 %,P Ni, Ni2B (XPS) B Ni ; (SEM2EDX) ( HRTEM) ; [5,11,30,31 ] 1. 2, 1. 3 : ; ( RDF) (3) (SAED), 1 2. (1) XRD XRD,, ;,, (2) EXAFS Wang, [39 ] Pd Pt Ni K,, [32,
4 619 2 Table 2 Amorphous catalyst in different hydrogenation reactions reaction reaction condition catalyst conversion( %) selectivity( %) benzene2cyclohexane liquid,150,4. 0MPa,4. 0h Ni2BΠAl 2 O 3 (1. 0g,20 %) 100 100 phemethylol2methylbenzene liquid,120,1. 0MPa,ethanol,4. 0h Ni2BΠSiO 2 (1. 0g,20 %) 10. 7 100 adipic dinitrile2hexamethylene diamine [37,38 ] liquid,120,410mpa,ethanol,4. 0h Ni2Co2BΠSiO 2 (1. 0g,20 %) 100 90 cyclopentadiene2cyclopentene [39,40 ] gas2solid,120,s. V. 10h - 1 Ni2BΠSiO 2 (1. 0g,5 %) 100 > 96 cyanobenzene2benzoic amine liquid,110,4. 0MPa,ethanol,4. 0h Ni2Co2BΠSiO 2 (1. 0g,20 %) 78 100 nitrobenzene2aniline liquid,110,1. 0MPa,ethanol,4. 0h Ni2BΠSiO 2 (1. 0g,20 %) 100 100 glucose2sorbitol [41,42 ] liquid,100,4. 0MPa,water,4. 0h 10 %Ni21 %W2BΠSiO 2 (1. 0g) 95 100,, 10h - 1, [39,43 47 ] Ni2BΠSiO 2 3, : 150 112 1 3 Ni2BΠSiO 2 Table 3 Properties of the amorphous Ni2BΠSiO 2 catalysts on cyclopentadiene hydrogenation samples S active (m 2 Πg Ni) S BET (m 2 Πg) V pore (cm 3 Πg) d pore (nm) Ni cont. (wt. %) B cont. (wt. %) conversion ( %) selectivity ( %) Ni2BΠSiO 2 70 183 0. 58 17. 0 4. 3 0. 31 100 96. 2 Ni2BΠSiO 2 a 58 160 0. 53 20. 0 4. 1 0. 29 81. 5 100 a catalyst used for 700h, Al 2 O 3 [48,49 ], Ni2P Ni2PΠSiO 2 Ni2BΠ SiO 2 94 %, 100 % [52 57 2. ] 10gΠg,, Pd2BΠSiO 2 [24,58 ] [59 ] 110MPa 30 [50 ] Ni 80 P 20 Pd2BΠSiO 2,, 98 % 95 %, 200,400, 90 % 8719 [51 ] Li [14 ], Ni2B Ni2Al2P, :C 2 H 2 1. 65 %, C 2 H 4 Al, 110MPa 30 95. 79 %, H 2 2. 56 %, 110 110MPa SiO 2,Cu Al 2 O 3 3.,Raney Ni 90 000h - 1 100 %
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