Chng 3.

Phng php Precursor Phan Vn Tng

Cc phng php tng hp vt liu gm NXB i hc quc gia H Ni 2007. Tr 27 33. T kho:Phng php ng kt ta, phng php Precursor nguyn t. Ti liu trong Th vin in t H Khoa hc T nhin c th c s dng cho mc ch hc tp v nghin cu c nhn. Nghim cm mi hnh thc sao chp, in n phc v cc mc ch khc nu khng c s chp thun ca nh xut bn v tc gi.

Mc lc
Chng 3 CC PHNG PHP PRECURSOR.............................................................2 3.1 Phng php precursor phn t ...............................................................................2 Phng php ng kt ta ...............................................................................2 Phng php precursor nguyn t (precursor ion)............................................5 3.1.1 3.1.2

Chng 3 CC PHNG PHP PRECURSOR

Trong phng php g m truyn thng, mc khuch tn cc cht tham gia phn ng di dng cc ht. Mc du vi thit b nghin hin i hin nay th kch thc cc ht cng ch ti khong 1 micromet, ngha l trong cc ht cng cha mt s rt ln cc phn t cht tham gia phn ng. phng php precursor ngi ta thc hin khuch tn cc cht tham gia phn ng mc phn t (precursor phn t) hoc mc nguyn t (precursor nguyn t). Hn hp ban u c g i l precursor c t l cc ion kim lo i ng theo hp thc ca hp cht ta cn tng hp.

3.1 Phng php precursor phn t

3.1.1 Phng php ng kt ta
V d chng ta cn tng hp g m noim ititanat Nd2Ti2O7. Theo phng php g m truyn thng chng ta trn hai oxit ban u theo t l mol Nd2O3/TiO2 bng 1/2 ri nung ln nhit cao thc hin phn ng gia cc pha rn Nd2O3 + 2TiO2 Nd2Ti2O7 Theo phng php ng kt ta chng ta chun b h n hp dung dch cha hai mu i noim v titan ri thc hin phn ng ng kt ta (di dng hiroxit, cacbonat, oxalat...) sao cho sn phm rn kt ta thu c, ng vi t l Nd/Ti nh trong sn phm g m mong mun Nd2Ti2O7. Cui cng tin hnh nhit phn sn phm rn ng kt ta . y chng ta phi lu 2 vn l: a) Bo m ng qu trnh ng kt ta ngha l kt ta ng thi c hai kim loi . V d vi hn hp cha hai ion Nd3+ v Ti4+, nu ta kt ta di dng hiroxit Nd(OH)3 v Ti(OH)4 th vic thc hin phi kt ta ng thi. Chng ta bit rng mui titan b thu phn rt mnh do phi gi trong dung dch rt axit trnh qu trnh thu phn. iu ny c ngha l pH ca hn hp hai mu i c gi tr rt b (pH khong t 0 n 1). Mt khc, pH kt ta Ti(OH)4 c gi tr khong 3,8 cn pH bt u kt ta ca noim c gi tr khong 6. Do , khi chng ta rt dung dch NH4OH vo hn hp c cha hai mu i NdCl3 v TiCl3 rt axit s xy ra tnh trng kt ta Ti(OH)4 trc v sau khi lng Ti4+ ch cn li rt t mi bt u qu trnh kt ta Nd(OH)3. Nh vy, chng ta khng thc hin ng s kt ta ng th i (xem hnh 13). thc hin kt ta ng thi th cn phi tin hnh ngc li. Ngha l rt dung dch cha hai mu i vo dung dch NH4OH.

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% mol
100
Ti4+,Nd

1 lng Ti

4+ 3+

Lng

3+

80

2 lng Nd

cn li 60 trong dung 40 dch 20

0
1

1 2

pH

Hnh 13. S ph thuc gia pH ca hn hp v lng Ti4+, Nd3+ cn li trong dung dch vo gi tr pH [36] b) Phi m bo trong precursor tc l hn hp pha rn cha hai ion kim loi theo ng t l nh trong sn phm gm mong mun. thc hin yu cu ny khng phi d dng. Chng ta bit rng tch s tan ca cc cht khc nhau rt khc nhau, do trong hn hp hai cht kt ta c th cha hai kim lo i khng ng nh hai kim loi trong dung dch chun b ban u. V d tng hp ferrit theo phng php g m truyn thng th thc hin phn ng nhit cao gia hai oxit: Fe2O3 + ZnO ZnFe2O4. Theo phng php ng kt ta, chng ta cho axit oxalic tc dng vi dung dch cha ng thi hai mu i sunfat st v sunfat km trong mi trng axit vi t l cation Fe2+/Zn2+ trong dung dch l 2/1. Nhng v tch s tan ca ZnC2O4 bng 2,75.108 cn tch s tan ca FeC2O4 bng 2.107 do trong pha rn kt ta t l Fe2+/Zn2+ thu c khng th ng nh yu cu ca sn phm g m. T chng ta thy rng vic chn iu kin thu c pha kt ta c t l cc cation kim lo i theo mun i h i phi tin hnh thc nghim, hoc bng tnh ton trc. V d h FeSO4-ZnSO4-H2C2O4 chng ti xc nh bng con ng thc nghim s ph thuc ca t l Fe2+/Zn2+ trong pha kt ta (y) v t l c trong dung dch chun b ban u (x) l: y = 0,933x 0,026 [1]. Vi h FeSO4-MnSO4-H2C2O4 chng ti xc nh bng con ng thc nghim v s ph thuc gia t l Fe2+/Mn2+ trong pha kt ta (y) v t l trong dung dch chun b ban u (x) l: y = 1,657x 0,084 [1]. Vic thc hin phn ng ng kt ta cha nhiu cation kim loi i h i phi tin hnh thc nghim, hoc tnh ton phc tp hn na. V d cn tng hp ferrit c cng thc l ZnxMn1xFe2O4 vi gi tr x hon ton xc nh chng ta phi tnh ton chun b dung dch sunfat st, sunfat mangan, sunfat km vi t l cation nh th no khi phn ng vi axit oxalic cho thu c pha rn kt ta ng vi cng thc ZnxMn1xFe2(C2O4)3.6H2O. gii quyt vn chng ti tin hnh ng thi hai phng php: Phng php tnh [2] C th tm tt m hnh bi ton nh sau:

SO 2 4

Hn hp dung dch + 2+ 2+ 2+ + 2SO4 , H , Fe , Mn , Zn A

Dung dch H2C2O4 B

H tng cng cha ion, phn t C

Dung dch Kt ta D

Hnh 14. M hnh bi ton Xem mt cch gn ng l qu trnh trn khng thay i th tch v nhit 25oC (VC = VA + VB). Lc t cn bng trong h D c cc phng trnh phn ng sau:
H2O H2C2O4
HC2 O 4

H+ H H H H + + + + + + + + + + + + + + + + + + + + + + +
+ + + +

+ + + + +

OH

(K1)
4

HC2 O
C2 O2 4

(K2) (K3) (K4) (K5) (K6) (K7) (K8) (K9) (K10) (K11) (K12) (K13) (K14) (K15) (K16) (K17) (K18) (K19) (K20) (K21) (K22) (K23) (K24) (K25) (K27) (K28) (K28)

H2SO4

HSO 4
SO 2 4

HSO 4
Fe
2+

C2O 2 4 C2O 2 4 C2O 2 4

C2 O 2 4 C2 O 2 4 C2 O 2 4

FeC2O4
Fe(C2 O 4 ) 2 2
4 Fe(C2 O 4 )3

FeC2O4
Fe(C2 O 4 ) 2 2

Zn

2+

ZnC2O4
Zn(C 2 O 4 ) 2 2 4 Zn(C 2 O 4 )3

ZnC2O4
2 Zn(C 2 O 4 ) 2

Fe Fe(OH)+ Fe(OH)2
Fe(OH)3

2+

OH OH OH OH OH OH OH OH

Fe(OH) Fe(OH)2

Fe(OH)3 Fe(OH) 2 4

Zn Zn(OH)+ Zn(OH)2
Zn(OH)3

2+

Zn(OH) Zn(OH)2

Zn(OH)3 Zn(OH) 2 4

Fe2+ Zn

2+ 2+

SO 2 4 SO 2 4 SO 2 4 C2 O 2 4 C2 O 2 4 C2 O 2 4 C2 O 2 4

FeSO4 ZnSO4 MnSO4 FeC2O4 ZnC2O4 MnC2O4

Mn(C2O4 )2 2

Mn Fe

2+

Zn2+ Mn
2+

MnC2O4 Mn Mn(OH)+
2+

OH OH

Mn(OH) Mn(OH)2

Vn t ra l tnh nng lc cn bng ca 35 phn t trong h D, da vo cc gi tr K trong ti liu tham kho. T cho php xc nh khi mun kt ta mt pha c cng thc ZnxMn1xFe2(C2O4)3.nH2O (vi gi tr x nht nh) th phi chun b dung dch ban u c t l bao nhiu.

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Phng php thc nghim [15] Nh chng ti ni khi nghin cu h ZnSO4-FeSO4-H2C2O4 ta c t l Fe2+/Zn2+ trong pha kt ta (y) ph thuc vo t l trong dung dch ban u (x) l y = 0,933x 0,026 v i h MnSO4-FeSO4-H2C2O4 s ph thuc l y = 1,657x 0,084. T hai phng trnh chun b hai dung dch: dung dch A c t l nng ban u ca Fe2+/Zn2+ sao cho trong pha kt ta c t l l 2, dung dch B c t l nng Fe2+/Mn2+ ban u sao cho trong pha kt ta c t l l 2. T hai dung dch A v B chun b dy ng phn t gam. Thc hin phn ng kt ta, tin hnh phn tch thnh phn kt ta ca tt c cc mu. Bng 7 cho bit kt qu thu c t hai phng php trn.
Bng 7. Kt qu thc nghim v tnh ton kt ta hn hp oxalat theo cng thc mong mun [15] Cng thc kt qu mong mun Nng cc mui ban u 2+ 2+ 2+ [ Fe ] [Mn ] [Zn ] Zn0,2Mn0,8Fe2(C2O4)3 0,1659 0,0991 0,0201 0,1403 0,0902 0,0193 Zn0,5Mn0,5Fe2(C2O4)3 0,1659 0,0612 0,0459 0,1403 0,0801 0,0294 Zn0,8Mn0,2Fe2(C2O4)3 0,1659 0,0716 0,0233 0,1403 0,0701 0,0394

Phng php Thc nghim Tnh ton Thc nghim Tnh ton Thc nghim Tnh ton

S sai khc gia hai phng php ny c th do cc nguyn nhn sau: Trong thc nghim c tin hnh nhiu cng on nh lc, ra, sai s ca php phn tch m ta khng lu n. Trong tnh ton u da vo cc gi tr tch s tan, hng s in ly... m cc ti liu tham kho khc nhau cho cc s khc nhau. Nhng iu ni ln tnh phc tp ca vn . Theo chng ti con ng thc nghim s cho kt qu ng tin cy nht trong thc t. Cng bng phng php ng kt ta chng ti tng hp c gm ititanat t him Ln2Ti2O7 khi dng dung dch amoni oxalat kt ta ng thi Ln3+, Ti4+ di dng (LnTiO)2(C2O4)5.7H2O [3].

3.1.2 Phng php precursor nguyn t (precursor ion)

Chun b pha rn ban u di dng tinh th trong c s phn b trt t cc cation kim loi mong mun v c thnh phn chnh xc. iu ny c thc hin bng hai cch: Tng hp phc a nhn hoc iu ch dung dch rn di dng cc mu i ng hnh. a) Precursor l phc a nhn V d iu ch g m ferrit mangan MnFe2O4 c th bt u bng vic tng hp phc oxoacetato ca st mangan ng vi cng thc Fe2 MnO(CH3COO)6(H2O)3.nH2O. Tin hnh phn hu nhit phc s thu c ferrit mangan c thnh phn chnh xc. iu c bit l th l phc ny c th cha nhiu ion kim loi chuy n tip khc nhau c cng thc tng qut

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Fe2MO(CH3COO)6(H2O)3.nH2O, trong M c th l Mn, Co, Ni, Zn... do , ta c th tng hp c nhiu loi ferrit khc nhau. Cc phc ny c th kt tinh li trong pyriin thu c sn phm tinh khit hn, lc c cng thc M3Fe6(CH3COO)17O3(OH).12C5H5N. Wickham [16] tng hp c cc phc rn ny vi M l Mg, Mn, Co, Ni di dng kh tinh khit. Sau tin hnh phn hu nhit phc r n M3Fe6(CH3COO)17O3(OH).12C5H5N s thu c gm ferrit c cht lng tt (xem bng 8). C th l t s Fe2+/M2+ tng i ph hp vi l thuyt, hng s mng li a kh ph hp vi ti liu tham kho, c bit l gi tr momen t bo ho nB (tr trng hp ferrit mangan) ph hp vi gi tr c cc tc gi cng nhn. Gi tr momen t bo ho rt nhy cm vi s sai lch vi cng thc ca ferrit v s phn b cation kim loi trong cc hc t v bt din ca spinen.
Bng 8. Thnh phn ho hc v tnh cht ca mt s ferrit thu c khi x l nhit phc pyriinat [10]

% khi lng Fe3+ Kt Tnh qu MgFe2 55, 55,84 69 O4 MnFe2 48, 48,43 32 O4 47, 47,60 CoFe2 O4 55 NiFe2O 47, 47,65 54 4 Ferrit

% khi lng M2+ Kt Tnh qu 12,41 12,16 23,68 25,24 25,03 23,82 15,12 25,05

T l mol Fe/M2
+

Nung (oC) 1000 1300 1000 1000

Hng s mng 8,384 0,001 8,512 0,001 8,388 0,001 8,338 0,002

1,954 2,008 1,990 1,997

Mom en t bo ho 1,37 4,5 3,57 2,12

Phng php ny cng c s dng tng hp g m cromit MCr2O4 c cu trc spinen. Nu tng hp gm cromit theo phng php g m truyn thng (phn ng trc tip gia hai oxit Cr2O3 v oxit kim loi MO) th giai on nghin trn rt lu v c bit l ph i nung nhit rt cao (14001700oC) m vn khng th thu c sn phm ng th v rng oxit crom v oxit kim loi ho tr 2 u c nhit nng chy cao v tng i tr v ho hc. Whipple v Wold s dng phng php precursor tng hp c mt s cromit (bng 9).
Bng 9. Tng hp mt s cromit theo phng php precursor [10] 3+ 2+ Cromit Precursor T l Cr /M MgCr2O4 (NH4)2Mg(CrO4)2.6H2O 2,010 0,002 NiCr2O4 (NH4)2Ni(CrO4)2.6H2O 1,999 0,002 MnCr2O4 MnCr2O7.4C5H5N 2,015 0,002 CoCr2O4 CoCr2O7.4C5H5N 2,012 0,002 CuCr2O4 (NH4)2Cu(CrO4).2NH3 2,000 0,003 ZnCr2O4 (NH4)2Zn(CrO4). 2NH3 1,995 0,0006 FeCr2O4 (NH4)2Fe(CrO4)2 1,995 0,003

Hiu sut % 70 75 90 90 43 77 80

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Nh c s phn b ion ca cc kim loi mt cch c trt t trong precursor, nn t l Cr3+/M2+ kh ph hp vi gi tr l thuyt v sn phm g m thu c hon ton ng nht. H. Tamaki, Z.J. Zhong,... tng hp c nhiu gm spinen MCr2O4 bng cch phn hu nhit phc {NBu4[MCr(OX)3]} [17]. Bari titanat BaTiO3 c hng s in mi cao, c s dng trong cc t in, thi gian u c tng hp theo phng php g m truyn thng bng cch nung hn hp bari cacbonat v cc oxit titan nhit cao. BaCO3 + TiO2 BaTiO3 + CO2 Nhng to c loi gm c tnh cht tt hn th sn phm phi c kch thc ht thch hp, mun th th phi tng hp bng phng php precursor bari titaninoxalat c cng thc l BaTiO((COO)2)2 ri phn hu nhit. Theo cch ban u tin hnh thu phn butoxit titan [16]. Ti(OBu)4 + 4H2O Ti(OH)4 + 4BuOH Ho tan kt ta trong axit oxalic
Ti(OH)4 + (COO) 2 TiO(COO)2 + 2OH + H2O 2

Rt t t dung dch BaCl2 vo s xy ra phn ng kt ta phc rn

+ TiO(COO)2 Ba[TiO((COO)2)2] Ba2+ + (COO) 2 2

Tin hnh phn hu nhit phc rn s cho sn phm Ba[TiO((COO)2)2]

BaTiO3 + 2CO2 + 2CO

Sn phm to thnh theo phng php ny g m nhng tinh th c kch thc rt b nn b mt ring kh ln, rt thun li cho vic s dng lm cht xc tc hoc lm t in. s dng lm vic khc th phi tin hnh nui n tinh th ln hn. b) Precursor l dung dch rn di dng cc mui ng hnh Theo phng php ny chng ta phn tn cc cation kim loi khc nhau vo trong mt pha ng th l dung dch rn ca cc mui ng hnh. V d mui mohr c cng thc (NH4)2SO4.MSO4.6H2O. Trong M c th l cation ha tr II ca st, niken, km, coban, mangan... c phn b ng u trong mng li dung dch rn. Cc thng tin v tnh tan ng nhit ca cc h mu i nc bc ba, bc bn... rt quan trng i vi k thut chun b cc dung dch rn kiu ny. Hnh 15 l gin tnh tan ng nhit ca h (NH4)2SO4.FeSO4.6H2O-(NH4)2SO4.ZnSO4.6H2O-H2O 30oC. T gin (hnh 15A) c th dng gin ng cong phn b Rozebom nh trn hnh 15B. V d chng ta mun tng hp ferrit km ZnFe2O4 th phi chun b dung dch rn ng vi cng thc (NH4)2SO4.(Zn0,333Fe0,666)SO4.6H2O, ngha l trong dung dch rn phi c t l Fe/Zn = 2. Mun th th trong dung dch rn phi c cha 66,666% (NH4)2SO4.FeSO4.6H2O ng vi im b ta phi chun b dung dch l ng ng vi im a v tin hnh bay hi ng nhit 30oC, s thu c dung dch rn c s phn b cc cation kim lo i hon ton c trt t. Tin hnh nhit phn dung dch rn s thu c ferrit.

(NH4)2SO4.FeSO4. 6H2O

b (A) M a N
(NH4)2SO4.ZnSO4. 6H2O

H2O
%(NH4)2SO4.FeSO4 trong pha lng a
80

60

(B)
40

20 20 40 60

66,66

80

%(NH4)2SO4.FeSO4.6 H2O Trong pha rn

Hnh 15. Gin tnh tan (A) v gin phn b (B) ca h o (NH4)2SO4.FeSO4-(NH4)2SO4.FeSO4-H2O 30 C

Rt nhiu mu i v c c kh nng to dung dch rn nh vy. V d phn nhm (NH4)M3+(SO4)2.12H2O trong M l cc cation Al3+, Cr3+, Fe3+, Co3+, Ga3+, In3+, V3+, Mn3+, Rh3+,... cc ihirat oxalat kim loi ho tr II MC2O4.2H2O (M l Fe2+, Ni2+, Mn2+, Zn2+, Co2+,...)...