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M u
Nhu cu nng lng trn th gii cng ngy cng cao cng vi s pht trin ca khoa hc-k thut, v vy i hi cc nh khoa hc khng ngng nng cao cht lng cc ngun nng lng thay th, c bit l cc loi pin v cqui. Oxit mangan l vt liu c dung lng ln nn c s dng ph bin ch to in cc trong cc ngun in. Hin nay, xu th trn th gii l ch to vt liu nano oxit mangan c dung lng rt ln (siu dung lng ). Siu dung lng ny xut hin do s tn ti ca loi t in in ha (gi t in ) trong qu trnh hot ng ca cqui v l ni tch tr nng lng trong qu trnh np in. Vt liu c kch thc cng nh th din tch b mt cng ln v do dung lng cng ln [5], [26]. C nhiu phng php tng hp oxit mangan nh: Phng php in phn, phng php ha hc, phng php thy nhitTheo nhiu nghin cu gn y th tng hp vt liu oxit mangan bng con ng thy nhit cho sn phm kt tinh tt, kch thc nh, v vy dung lng s ln hn. Cht oxi ha thng c s dng trong phng php ny l KMnO4, K2Cr2O7; cc cht kh c th l MnSO4, Na2SO3, NaHSO3, HCOOHTrong bn kha lun ny chng ti mun nghin cu vt liu tng hp bng phn ng oxit ha kh gia KMnO4 v etanol nhm dnh gi tnh cht in ha ca vt liu da trn dung lng ring C. V vy chng ti thc hin ti: Nghin cu cu trc v tnh cht in ha ca vt liu oxit mangan c iu ch bng phng php kh

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Chng 1 - Tng quan

1.1. Gii thiu chung v oxit mangan
Mangan l nguyn t a ho tr nn oxit mangan tn ti nhiu dng khc nhau nh MnO, Mn3O4, Mn2O3, MnO2 Trong t nhin khong vt chnh ca mangan l hausmannite (Mn3O4), pirolusit (MnO2) v manganite (MnOOH) [3]. Cc oxit mangan c rt nhiu ng dng trong thc t, mt trong s l s dng ch to cc dng trong pin kh. S hot ng ca pin da trn s chuyn ho ln nhau gia cc dng oxit ca mangan. V vy tu thuc vo loi oxit v thnh phn ca chng m kh nng hot ng ca in cc khc nhau.

1.1.1.

Mangan ioxit (MnO2) [7]

Mangan ioxit l mt trong nhng hp cht v c quan trng, c nhiu

ng dng trong thc t. Mangan ioxit c thnh phn ha hc khng hp thc. Trong hp cht mangan ioxit cha mt lng ln Mn 4+ di dng MnO2 v mt lng nh cc oxit ca Mn t MnO1.7 n MnO2. Do cu trc cha nhiu l trng nn trong tinh th ca mangan ioxit cn cha cc cation l nh K +, Na+, Ba2+, OH- v cc phn t H2O. MnO2 c cu trc phc tp do s sp xp khc nhau ca cc nguyn t mangan v oxi trong phn t. C nhiu kin khc nhau v cu trc ca MnO2. Hin nay l thuyt cho rng MnO2 c cu trc ng hm v cu trc lp c cng nhn ph bin nht. Theo l thuyt v cu trc ng hm (tunnel structures), mangan ioxit tn ti mt s dng nh -MnO2, -MnO2, -MnO2, MnO2Bng 1 cho thy mt s dng c bn ca tinh th MnO2. -MnO2

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-MnO2 hoc pyrolusite l nhng tinh th c cu trc n gin nht trong nhm hp cht c cu trc ng hm. Cc nguyn t mangan chim mt na l trng bt din c to thnh do 6 nguyn t oxi xp cht kht vi nhau

Bng 1: Cu trc tinh th ca MnO2

Hp cht Cng thc MnO2 MnO2 MnO2xOHx MnO2xOHx MnO2 Hng s mng Mng tinh th
Tetragonal Orthombic Orthombic Hexagonal Tetragonal a(pm) 440.4 4446 446.2 228.3 b(pm) 440.4 932 934.2 278.3 c(pm) 287.6 285 285.8 443.7 Kch thc ng hm [nxm] [1 x 1] [1 x 2]
[1x1]/[1x2]

0
90 90 90 90 90

Pyrolusite -MnO2 Ramsdellite -MnO2 -MnO2

90 90 90 90 90

90 90 90 90 90

[1x1]/[1x2] [2x2]

ging nh tinh th rutile. Nhng n v khuyt tt MnO6 to ra chui cnh bt din m dc theo trc tinh th c-axis. Cc chui lin kt ngang vi cc chui bn cnh hnh thnh gc chung. Cc l trng ny l qu nh cc ion ln c th xm nhp vo, nhng ln cho ion H+ v ion Li+. -MnO2 c th chp nhn thnh phn ng l MnO2.

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Hnh 1. Cu trc tinh th -MnO2 Ramsdellite Cu trc tinh th ca ramsdellite tng t cu trc ca pyrolusite, ch khc l cc chui n bt din trong tinh th -MnO2 c thay bng cc cp chui trong tinh th ramsdellite. Cc ng hm m rng dc theo trc tinh th ngn c-axis ca cu trc t phng (a = 446 pm, b = 932 pm, c = 285 pm), v th ramsdellite c kch thc ng hm rng hn ([1 x 2]) so vi -MnO2. Mt th tch mng ca ramsdellite c cu trc gn bng hai th tch mng ca -MnO2. Ramsdellite c cu trc ng hm nh, khng cho php cc cation l c kch thc ln xm nhp vo. Tuy nhin H+ v Li+ c kch thc rt nh nn c th khuch tn vo mng tinh th ca ramsdellite. Trong cu trc tinh th ca ramsdellite, cc nguyn t oxi v mangan nm nh ca 2 chp t din c chung cnh y, y ca chp gm 2 nguyn t oxi nm i din v 2 nguyn t mangan nm 2 nh cn li. Ramsdellite c cu trc khng bn vng, d bin i thnh -MnO2. Trong t nhin t khi tm thy cu trc dng ramsdellite. Lp K50A

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Hnh 2. Cu trc tinh th ca ramsdellite -MnO2 v -MnO2 Trong mt thi gian di cc nh khoa hc khng khng nh chc chn c cu trc ca -MnO2. De Wolff l ngi u tin a ra cu trc hp l nht ca -MnO2. Theo De Wolff, tinh th -MnO2 l s kt hp gia -MnO2 ([1 x 1]) v ramsdellitte ([1 x 2 ]). Tu vo mc ng gp ca hai thnh phn ny vo cu trc m gin XRD ca -MnO2 c s khc nhau. -MnO2 c cu trc ng hm [1 x 1] v [1 x 2], thm ch trong tinh th -MnO 2 cn tn ti ng hm ln [2 x 2]. Mt iu quan trng l trong cu trc ca -MnO 2 v ramsdellitte u c mt cc ion oxi sp xp trn mt phng ngang, nhng vi -MnO2 th ch c mt oxi xp nh hnh chp trong cu trc ca ramsdellitte.

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Hnh 3. Cu trc tinh th ca -MnO2 -MnO2 c cu trc da trn c s mng t phng ca -MnO 2 v ramsdellitte, tuy nhin n c cu trc hon thin hn, khng ph hu tnh t phng ca mng, tng khuyt tt v lm gim tnh trt t trong phm vi sp xp cc nguyn t mangan. Trong trng hp s sp xp cc nguyn t mangan tr nn km cht ch, xut hin nhiu khuyt tt ti v tr ca mangan, khi ta c cu trc dng -MnO2. Trong mu khuyt tt ca Dewoff c s m rng ca m hnh cation trng ca -MnO2. -MnO2 c tinh th ho thp hn -MnO2 (pyrolusite) v c mt lng ln khuyt tt trong cu trc. Ruetshi a ra mt s gi thit chng minh H2O v mt s ion l c mt trong tinh th MnO2: Cc nguyn t mangan kt hp vi nhau trt t hoc km trt t hn

ti l trng bt din trong cc l trng bt din do cc nguyn t oxi to ra. Mt phn x ca ion Mn4+ b thiu trong cu trc. V vy b li in tch th mi l trng Mn4+ kt hp vi 4 proton hnh thnh anion OH- ti v tr ca ion O2-. Mt phn y ca ion Mn4+ c thay th bng ion Mn3+. Vi mi ion Mn3+ c hn mt ion OH- trong mng thay th mt anion O2-

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Trong cu trc tinh th thy xut hin nhiu loi ion: Mn4+, Mn3+, O2-, OH- v cc l trng. Tnh dn in tng ln khi cc electron v cc ion dch chuyn trong ng hm hoc di chuyn t v tr ny sang v tr khc.

Hnh 4. Cu trc tinh th ca -MnO2 Ruetschin a ra cng thc chung ca -MnO2 nh sau: Mn4+1-x-yMn3+yO2-2-4x-yOH-4x+y Trong cng thc trn x, y c th tnh da vo cc phng trnh: x = m/( 2 + m ); Vi y = 4.( 2 n )/( 2+ m )

n: Ho tr ca kim loi trong cng thc MnOn m: T l mol ca H2O v Mn trong -MnO2

-MnO2 Tinh th ca -MnO2 bao gm cc ng hm c cu trc [ 2 x 2] v [ 1 x 1] m rng dc theo trc tinh th ngn c-axis ca mt n v t din. Nhng ng hm ny c hnh thnh t hai chui bt din MnO 6 c chung cnh vi nhau. Tri vi -MnO2, ramsdellite, v -MnO2, cu trc ng hm ln [ 2 x 2 ] ca -MnO2 rt ph hp cho s xm nhp ca cc ion l nh K+, Na+, NH4+ hoc nc. Lp K50A

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1.1.2.

Dng kh ca oxit mangan [7]

Bng 2: Cu trc tinh th mt s dng kh ca oxit mangan

Hp cht

Cng thc

Mng tinh th a (pm)

Hng s mng b (pm) c (pm) 571.0 458.0 90 90 90 90 90 90 0 0 0

Manganite Groutite

MnOOH MnOOH

Orthorhombic

880.0

525.0 289.0

Orthorhombic 1076. 0

Hausmannit e

Mn3O4 Mn2O3 Mn2O3

Tetragonal Cubic Tetragonal

814.0 943.0 815

814.0 943.0 815

942.0 943.0 815

90 90 90

90 90 90

90 90 90

Manganite ( MnOOH) Manganite c cu trc tinh th tng t cu trc pyrolusite khi c thm mt proton. Cu trc ca n gm cc n chui bt din Mn(O,OH)6, trong c 4 lin kt ngn ging nhau Mn O v 2 lin kt di Mn OH. Manganite l dng cu trc bn ca MnOOH, n c tm thy trong t nhin v ng thi cng rt d tng hp trong phng th nghim. N l sn phm kh in ha ca -MnO2. Groutite ( MnOOH) Groutite c cu trc tng t ramsdellite. S sp xp ca (MnO,OH) trong MnOOH rt ging vi ramsdellite. MnOOH l dng cu trc ramsdellite khi c thm mt proton. Cu trc ca n bao gm cc i chui bt din (MnO,OH), cc proton chim cc v tr trong tinh th xy dng nn mt mng li gii hn pha trong ng hm [2 x 1]. Trng thi ca MnOOH c th so snh vi hp cht LixMnO2, ion Li+ chim v tr trong ng hm ca mng ramsdellite c s. Trong c hai hp cht ny, lin kt Mn O b bin dng ln do s c mt ca cc cation l trong mng tinh th v s kh Mn4+ v Mn3+. Lp K50A

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(a)

(b)

Hnh 5. Cu trc tinh th ca MnOOH (a) v MnOOH (b) MnOOH Chng ta d dng thy rng s kt hp ca -MnO 2 v ramsdellite to nn cu trc dng MnO2. V vy c th gii thch cu trc tinh th ca MnOOH l s kt hp ca manganite v groutite. MnOOH l sn phm ca MnO2 khi phng in trong dung dch kim. Hp cht dng spinel Mn3O4 v Mn2O3 Mn3O4 v Mn2O3 u c cu trc kiu spinel t din lch. Hausmannite (Mn3O4) l mt oxit hn hp c cu trc (Mn2+)(Mn3+)2O4. Trong spinel t din ny, cation c ha tr hai Mn2+ chim l trng t din, cn ion Mn3+ chim cc l trng bt din gia cc ion O2- sp xp st nhau kiu lp phng. Ion Mn2+ c th c thay th bi cc ion c ha tr hai khc c bn knh tng t. (v d ZnMn2O4). Nu tng hp Mn3O4 bng phn ng oxi ha th gin nhiu x tia X thu c tng t nh gin ca hausmannite, nhng n ngha quan trng hn hausmannite. Verwey v De Boer cho rng Mn2O3 c thnh phn MnO1.39 MnO1.5. Goodenough v Loch cho rng tinh th Mn2O3 c cu trc spinel t din lch ca Mn3O4 nhng vi nhng khuyt tt quan trng ti v tr Mn3+ t din.

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Hnh 6. Cu trc tinh th ca Mn3O4 v Mn2O3

1.2. Cc phng php tng hp oxit mangan

C nhiu phng php c s dng tng hp oxit mangan: Phng php in phn [3]: Phng php ny c dng ph bin trong tng hp MnO2. Cc dung dch in phn c th dng l dung dch mui MnCl2, MnSO4, cc in cc c s dng l graphit, ch, titan v hp kim ca n, Sn phm ch yu ca qu trnh in phn l MnO2 c cu trc dng Akhtenskite vi mng tinh th Hexagonal (-MnO2). Phng trnh chung ca qu trnh in phn: (+) Anot: Mn2+ - 2e Mn4+ Mn4+ + H2O MnO2 + 4H+ (-) Catot: Phn ng tng : H+ + 2e H2 Mn2+ + 2H2O MnO2 + 2H+ + H2

Phng php ny c u im l sn phm to thnh c kh nng hot ng in ho cao, tuy nhin n cng c nhc im l hiu sut khng cao, tn km. Phng php ho hc: L phng php s dng cc phn ng ho hc quen thuc. Ph bin nht trong loi ny l s dng phn ng oxi ho kh vi cht oxi ho l KMnO4, K2Cr2O7; cht kh c th dng l MnSO4, MnCl2, Na2SO3, H2O2, CuCl, cc cht hu c nh HCOOH, toluen, CH3CH2OH [12], [24], [30], [31]. Lp K50A

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V d: S.Devaraj v N.Munichandraiah tng hp c tinh th -MnO2 c cu trc nan bng phn ng gia KMnO4 v MnSO4: [24] 3Mn2+ + 2Mn7+ 5Mn4+ Mn4+ + 2H2O MnO2 + 4H+ Nm 2002, H.Yagi, T.Ichikawa, A.Hirano, N.Imanishi, S.Ogawa, v Y.Takeda tng hp MnO2 bng cc phn ng gia KMnO4 vi cc cht kh nh sau: [12] 2KMnO4 + 3NaHSO3 = NaHSO4 + 2MnO2 + Na2SO4 + K2SO4 + H2O 2KMnO4 + 3Na2SO3 + H2O = MnO2 + 2KOH + 3Na2SO4 2KMnO4 + 3NaNO2 + H2O = 3NaNO3 + 2MnO2 + 2KOH 2KMnO4 + 3KNO2 + H2O = 3KNO3 + 2MnO2 + 2KOH Phng php ny c u im l n gin, hiu sut cao, tuy nhin li c nhc im l sn phm c kh nng hot ng in ho khng cao. Phng php thu nhit: Thc hin phn ng ho hc tng t phng php ha hc. iu khc bit y l c thm iu kin nhit v p sut cao. Yange Zhang, Liyong Chen, Zhi Zheng v Fengling Yang tng hp c -MnO2 bng phn ng thy nhit gia KMnO4 v CuCl 1800C trong 18h: [29] KMnO4 + CuCl + 4HCl MnO2 + KCl + CuCl2 + Cl2 + 2H2O Khi c nhit v p sut, hiu sut ca phn ng s tng ln, ng thi sn phm kt tinh tt hn. y l mt phng php hin i, c dng rt ph bin trong nhiu nm gn y. Phng php ny khng qu phc tp, hiu sut cao, cho kch thc ht ng u, kh nng hot ng in ho tt. 1.3.

ng dng ca oxit mangan

Oxit mangan c nhiu ng dng trong thc t nh: lm cht xc tc trong

tng hp hu c, x l mi trng (x l asen, hp th CO,), v c bit c Lp K50A

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s dng lm in cc trong pin v cqui. Mt s loi pin s dng in cc MnO2 nh: pin Zn-MnO2, Li-MnO2, Mg-MnO2.

1.3.1. Pin Leclancher: [4]

S in ha tng qut ca pin: (-) Zn/NH4Cl/MnO2 (+) E = 1.5 1.9V

C ch phng in ca in cc MnO2: Trong dung dch in li, mangan c ha tr 4, sau n b kh dn n ha tr thp hn. Cc phn ng xy ra trn in cc nh sau: MnO2 + 2H2O Mn(OH)4 Mn(OH)4 Mn4+ + OHMn4+ + 2e Mn2+ Mn2+ + 2OH- Mn(OH)2 Mn(OH)2 + MnO2 Mn2O3 + 2OH phn ng tng: MnO2 + H2O + 2e Mn2O3 + 2OHin th v dung lng ca in cc ph thuc vo b mt tip xc, c ngha l MnO2 hot ng ti nhng v tr tip xc ch khng phi ton b ht MnO2. iu ny mu thun vi lun im ca Lblang cho rng ion Mn 4+ t in cc chuyn vo dung dch. Muyl, Grun, Gunt, Sunxe a ra c ch sau: 2MnO2 + 2e Mn2O3 + O2O2 phn ng tng: + H2O 2OH2MnO2 + H2O + 2e Mn2O3 + 2OH2MnO2 + 2e 2MnO222MnO22- + 2H+ 2HMnO2 Lp K50A

Theo Keller c ch phng in l:

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Mn2O3 + H2O

Tuy nhin, cc c ch gii thch trn khng ph hp vi cc s liu thc nghim. Chnh v vy, Lukopxep gii thch c ch phng in ca MnO2 nh sau: Trong dung dch trung tnh hoc kim, trn b mt tip xc gia lp oxit vi dung dch cht in li xut hin lp in kp. Khi phng in, proton t dung dch i qua lp i qua lp in kp chuyn vo MnO 2 v n c trung ha bi in t t do v to thnh oxit c ha tr thp hn: MnO2 + H+ + e MnOOH Khi nng MnOOH trn b mt cc phn t hot ng ln th n tc dng vi dung dch in li axit yu to thnh Mn(OH)2 v Mn2+: MnOOH + H+ + e Mn(OH)2 Mn(OH)2 + 2H+ Mn2+ + 2H2O in th in cc ph thuc vo pH. Khi pH < 45 th th in cc cn ph thuc vo hot ca MnO2: =
0

+ 0.118lgaH+- 0.059lgaMn2+

Trong mi trng kim hoc trung tnh: =

0

- 0.059pH

Khi pin hot ng, H+ tham gia vo phn ng in cc nn nng ca n gim dn, pH tng ln v th in cc gim.

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Hnh 8. Cu to pin Leclancher

1.3.2. Pin Zn-MnO2 trong dung dch kim [9], [19] S sut in ng ca pin: (-) Zn/KOH/MnO2 (+)
Cc phn ng xy ra trong pin: Catot: Anot: Phn ng tng: MnO2 + H2O + 2e 2MnOOH + 2OHZn + 2OH- ZnO + H2O + 2e Zn + 2OH- ZnO + 2MnOOH

Pin kim l pin c th phng np nhiu ln, sut in ng ban u ca pin khong 1.5V. Nng KOH s dng trong pin khong 30% ( nng ny trnh c s th ng ca in cc Zn). C ch phng in ca in cc MnO2 gm 2 bc: Bc 1: Bc 2: MnO2 + H2O + e MnOOH + OHMnOOH + H2O + e Mn(OH)2 + OH-

C ch ny c gii thch phn trn. Trong qu trnh oxi ha kh chuyn Mn4+ thnh Mn3+, mt lng MnOOH to ra c th chuyn thnh Mn3O4 theo phn ng: MnOOH + e HMnO2HMnO2- + MnOOH Mn3O4 + H2O + OHMn3O4 l mt cht tr v mt in ha lm cho kh nng phng in ca pin gim. Pin Leclancher v pin Zn-MnO2 trong dung dch kim c s dng kh rng ri, v vy i hi chng phi lun c ci tin v cng ngh ch to v kh nng phng in.

1.4. Cc phng php nghin cu

1.4.1. Phng php nhiu x tia X (X-ray diffraction XRD)
Cho chm tia X truyn qua mt cht trng thi rn hoc kh, chm tia ny s tng tc vi cc in t trong cc nguyn t ca cht nghin cu hoc ngay c Lp K50A

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vi nhn nguyn t nu chm tia X c nng lng ln. Mt phn nng lng tia X s b mt do hiu ng tn x, phng truyn ca chm tia X s b thay i khi tng tc, khi tn x c th lm thay i hoc khng lm thay i bc sng ca bc x tia ti. Theo nguyn l cu to tinh th, mng tinh th c xc nh t cc nguyn t hoc ion phn b u n trong khng gian theo mt qui lut xc nh. Khi chm tia X ti b mt tinh th v i su vo trong mng li th mng li ny s ng vai tr nh mt cch t nhiu x c bit. Cc nguyn t, cc ion b kch thch bi chm tia X s tr thnh cc tm pht ra cc tia phn x. Theo phng trnh Bragg: = 2*d*sin Trong : d: Khong cch gia hai mt phng nguyn t thuc mng li tinh th phn tch. : Gc gia chm tia X vi mt phng phn x. Khi chiu chm tia X ln mu vi cc gc khc nhau ta thu c gin nhiu x tia X. Mi tinh th ca mt cht c mt b vch ph tng ng vi cc gi tr d v cng c trng. Vic tm ra trn gin s ging nhau c v v tr ln cng ca cht nghin cu v cht chun bit l c s ca php o nh tnh.

Hnh 9: S tia ti v tia phn x trn tinh th Lp K50A

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Trn hnh 10 trnh by s nguyn l ca mt my phn tch rnghen, chm tia X pht ra t ant ca mt ng pht mt chiu n mu mghin cu 2. Cc nguyn t ca nguyn t trong thnh phn mu b kch thch v pht ra cc tia c trng. Cc tia X vi di song khc nhau phn x trn mt mu, i qua h trc chun 3. Cc tia phn k theo cc phng khc nhau s hp th mt bn trong ca ng, cc tia xut pht t mu 2 s tch thnh cc vch trn gin ngha l phn b theo di bc song nh tinh th phn tch 4. Tia phn x t tinh th phn tch 4 qua h chun trc 5 s thu c bng detecter 6, sau c khuch i, chun ho, ri ghi li bng my ch th khc nhau.

Hnh 10. S nguyn l cu to my phn tch XRD

1.4.2. Phng php hin vi in t qut (SEM)

Chm tia in t i qua cc thu knh in t tiu t thnh mt im rt nh chiu ln b mt mu nghin cu. Khi cc in t ca chm tia ti va chm vi cc nguyn t b mt vt rn th c nhiu hiu ng xy ra. Cho chm tia in t qut ln mu, v qut mt cch ng b mt tia in t trn mt mn hnh. Thu v khuch i mt loi tn hiu no t mu pht ra lm thay i cng sng ca tia in t qut trn mn hnh, ta thu c nh. Trong knh hin vi in t qut c dng cc thu knh, nhng ch tp trung chm in t thnh im nh chiu ln mu ch khng dng thu knh phng i. Cho tia in t qut trn mu vi bin nh d (c micromet) cn tia in t qut trn mn hnh vi bin ln D (tu theo kch thc mn hnh), nh c phng i D/d. nh c phng i theo phng php ny th mu khng Lp K50A

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cn phi ct lt mng v phng, cho php quan st c mu k c khi b mt mp m. phng i ca knh hin vi in t qut thng thng t vi chc n vi trm ngn ln, nng sut phn gii ph thuc vo ng knh ca chm tia chiu hi t trn mu. Vi sng in t thng thng (dy si t hnh ch V), nng sut phn gii l 5nm i vi nh b mt bng cch thu in t th cp, do cho ta thy c cc chi tit th trong cng ngh nano.

1.4.3. Phng php dng - th tun hon (Cyclic Voltammetry CV)

Phng php dng - th tun hon, cn c gi l phng php o phn cc vng hay phng php volampe vng qut xung tam gic. Phng php ny c s dng nghin cu tnh cht in ho cng nh ng hc v c ch phn ng ca cht nghin cu trn cc in cc khc nhau. Phng php o ny cho php p t ln in cc nghin cu mt in th c dng xc nh c qut theo hng anot hay catot quan st dng tng ng. Trong phng php o ny, b mt in cc phi c phc hi trc mi th nghim, dung dch khng c s khuy trn, s chuyn khi c thc hin bng mt s khuch tn c bit. Phm vi in p ph thuc vo vic la cn dung mi, cht in li nn v bn cht in cc.

Hnh 11. Hnh dng ca ng cong phn cc ng cong phn cc vng l mt ng tun hon biu din mi quan h gia mt dng i (A/cm2) v th E(V). ng cong biu din quan h i-E c cc Lp K50A

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nh pc c trng ip,a ng vi Ep,a v ip,c ng vi Ep,c. Do khuch tn khng ch trong qu trnh thun nghch Ox + ne Re, Randle v Sensick a ra mi quan h gia dng in cc i vi tc qut th: ip = -n.F.A.C0.( .D0. )1/2. Trong = (nF/RT)* .t = (nF/RT)(E1 E) n: S electron tham gia phn ng : Tc qut th (V/s) A: Din tch in cc (cm2) C: Nng cht phn ng (mol/lit) D: H s khuch tn (cm2/s) ip : Mt dng pic (mA/cm2 Nh vy, dng cc i v th c tnh theo cng thc: ip = 2.99.105.n.( .na)1/2.A.Co.D1/2.v1/2 v: Epc = Eo RT/( cnaF).(0.78 + lnD1/2/ko + 1/2.lnb) : H s chuyn na : S electron trao i biu kin
( ,t)

Chng 2 - Thc nghim

2.1.

Ho cht v thit b
KMnO4 Etanol 96% Na2SO4 Loi AR ca Trung Quc Loi AR ca Trung Quc Loi AR ca Trung Quc

Ha cht

Bt Teflon Dupont - USA, mui axetilen. Dung dch m niken (II) sunphat. Lp K50A

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in cc thp khng g dng li. Thit b Cn phn tch 3 s. Bnh in phn vi 2 anot l in cc niken, catot l in cc thp khng g dng li. Bnh thu nhit (bnh Teflon), b p in cc. My chp nhiu x tia X-Siemen D5005, Khoa Ho hc, Trng i Hc Khoa Hc T Nhin, HQG H Ni v X-Siemen D5000, Vin Vt Liu, Vin Khoa Hc v Cng ngh Vit Nam, vi ng pht tia X bng Cu, bc sng 1.5406 A0. Thit b chp SEM Hitachi S-4800 ti Vin Vt Liu, Vin Khoa Hc v Cng ngh Vit Nam. My o Autolab 30 Eco chemie H Lan ghp ni vi my tnh ti phng th nghim in ho, Khoa Ho hc, Trng i Hc Khoa Hc T Nhin, HQG H Ni. H bnh o in ho 3 in cc gm: in cc lm vic l in cc nghin cu, in cc so snh l in cc bc clorua, in cc ph tr l in cc platin cng nhng trong dung dch in li.

Hnh 12. S o thit b Autolab 30 1. in cc ph tr (CE) l in cc platin Lp K50A

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2. in cc so snh (RE) l in cc bc clorua 3. in cc lm vic (WE) l in cc nghin cu

2.2. Mc ch ca ti
1. Tng hp vt liu oxit mangan bng phn ng kh KMnO4 bng etanol trong iu kin thy nhit. 2. Xc nh cu trc v kch thc ca vt liu tng hp c bng cc phng php vt l nh nhiu x tia X v SEM. 3. Kho st tnh cht in ha ca vt liu thu c trong mi trng cht in li.

2.3. Ni dung thc nghim

2.3.1. Chun b dung dch v in cc
Pha dung dch KMnO4 c nng 70g/l. Dung dch Na2SO4 vi cc nng khc nhau: 0.1M, 0.5M, 1M, 2M. Li thp khng g c ngm trong dung dch kim long loi du m, c ra sch v m mt lp mng Ni.

2.3.2. Tin hnh cc th nghim

Tng hp mu Va khuy va nh git t t dung dch KMnO4 vo etanol. Sau khi khuy

lin tc trong khong 2h th cho c hn hp vo bnh thu nhit. Tin hnh thu nhit mu nhit 1400C trong 10h. Vi mc ch nghin cu nh hng ca hm lng etanol trong hn hp

phn ng i vi dung lng ring C, chng ti tng hp cc mu theo bng di y. Bng 3: T l s mol etanol/KMnO4 trong cc mu Mu 1 2 3 4 5

Lp K50A

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T l s mol etanol/KMnO4

6.56

4.37

2.19

1.11

0.44

Chng ti tng hp mu trong 3 iu kin: thu nhit trong hn hp phn ng KMnO4 + C2H5OH, thu nhit trong nc v khng thu nhit nhm nh gi nh hng ca iu kin tng hp ti dung lng ring C. Sau 2h khuy u hn hp phn ng, mt phn hn hp phn ng tip tc c tin hnh thu nhit 1400C trong 10h, phn cn li em lc, ra sch v c chia lm hai: mt na sy kh (mu khng thu nhit) v na cn li tin hnh thu nhit trong nc cng iu kin.

Tt c cc mu sau khi thu nhit c lc, ra sch bng nc ct loi hon ton cc ion cn li t phn ng, cui cng c ra bng etanol. Sn phm sau c sy kh 800C trong 6h.

Trc khi chp XRD, SEM v nghin cu tnh cht in ha trong dung dch Na2SO4, sn phm c nghin nh trong ci m no.

Ch to in cc Cc in cc thp khng g sau khi ph Ni em cn xc nh khi lng m1. Bt p in cc c thnh phn theo khi lng l 70% mu nghin cu, 20% mui axetilen v 10% bt Teflon. Tt c c trn u, sau c p ln li thp khng g ph Ni, lc p khng i l 1 tn. in cc sau khi p c sy kh 800C trong khong 2h loi b hi nc hp ph. Sau em cn xc nh khi lng m2. Khi lng bt p trn mi in cc l: m = m2 m1 Khi lng thc t ca vt liu hot ng trong qu trnh phn cc l khi lng mu nghin cu: m = 70%.m Lp K50A

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o cc ng phn cc vng in cc ch to c o phn cc vng trn thit b Autolab 30 trong dung dch Na2SO4 xc nh dung lng ring C ca in cc. Khong th o vi tt c cc mu l nh nhau: t -0.2 0.8V.

Chng 3 - Kt qu v tho lun

3.1. Cu trc ca vt liu iu ch c
Kt qu nhiu x tia X cho thy sn phm thu c t phn ng gia KMnO4 v etanol ch yu c thnh phn gm -MnOOH (Manganite) v Mn 3O4 (Hausmannite).

Lp K50A

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220 210 200 190 180

Mau 2,1

160 150 140 d=2.765

Lin (Cps)

130 120 110 100 90 80 70 60 d=4.913 d=2.882 d=3.405

d=2.485

170

d=3.087

d=1.797

d=2.639

d=2.035

d=1.700

d=1.782

d=2.273

d=1.827

d=2.194

d=1.501

20 10 0 10 20 30

40

50

60

d=1.381

d=1.348 70

30

d=2.518

2-Theta - Scale
File: Chuyen K50A mau 2,1(2).raw - Type: Locked Coupled - Start: 10.000 - E nd: 70.000 - Step: 0.030 - S tep time: 1. s - Temp.: 25 C (Room) - Time Started: 18 s - 2-Theta: 10.000 - Theta: 5.000 - C 01-089-4837 (C) - Hausmannite, syn - Mn3O4 - Y: 81.88 % - d x by: 1. - WL: 1.5406 - Tetragonal - a 5.76300 - b 5.76300 - c 9.45600 - alpha 90.000 - beta 90.000 - gamma 90.000 - Body-centered - I41/amd 01-088-0649 (C) - Manganite - gamma-MnO(OH) - Y: 44.97 % - d x by: 1. - WL: 1.5406 - Monoclinic - a 5.30400 - b 5.27700 - c 5.30400 - alpha 90.000 - beta 114.380 - gamma 90.000 - Primitive - P21/c (14)

Hnh 13. Gin nhiu x tia X ca vt liu tng hp bng phng php thy nhit gia KMnO4 v etanol

(a)

(b)

Lp K50A

23

d=1.639

40

d=1.670

Khoa Ha Hc

d=1.439

50

d=2.459 d=2.413 d=2.365

d=1.575

d=1.543

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(c)

(d)

(e) Hnh 14. nh SEM ca cc mu c hm lng etanol khc nhau (a) Mu 1; (b) Mu 2; (c) Mu 3; (d) Mu 4; (e) Mu 5. T gin nhiu x tia X v hnh nh SEM i vi cc mu c t l s mol etanol/KMnO4 khc nhau ta thy: Mu 1 c t l s mol etanol/KMnO4 l 6.56: C cu trc tinh th l hausmannite Mn3O4, kt tinh tt, sn phm c dng que, kch thc tng i ln.

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Mu 2 , 3, 4 c t l s mol etanol/KMnO4 l 4.37, 2.19, v 1.11: Cu trc tinh th ca 3 mu ny tng t nhau, bao gm manganite -MnOOH v hausmannite Mn3O4, sn phm c dng si, kch thc nh. Mu 5 c t l s mol etanol/KMnO4 l 0.44: Cu trc tinh th ch c MnOOH. Sn phm kt tinh km, ht c kch thc ln. Phn ng gia KMnO4 v etanol c th xy ra theo cc phng trnh nh sau: 4KMnO4 + 3CH3CH2OH 4MnO2 + 3CH3COOK + KOH + 2H2O (1) 4MnO2 + CH3CH2OH + KOH CH3COOK + 4MnOOH 3MnO2 + CH3CH2OH + KOH Mn3O4 + CH3COOK + 2H2O (2) (2)

T kt qu trn chng t hm lng etanol trong hn hp phn ng nh hng n cu trc, hnh dng v kch thc ca vt liu. C th d on hm lng etanol thay i lm nh hng n sc cng b mt ca hn hp phn ng. Hm lng etanol cng ln lm gim sc cng b mt ca hn hp, nh hng n qu trnh kt tinh ca sn phm. Kt qu cho thy nu hm lng etanol qu ln th vt liu c xu th kt tinh di dng hausmannite Mn3O4 nhiu hn (phn ng 2 chim u th).

3.2. Tnh cht in ha ca vt liu oxit mangan

3.2.1. nh hng ca mi trng v qu trnh thy nhit ln tnh cht in ha ca oxit mangan Tin hnh o ng phn cc vng cc in cc ca 3 mu (cng c t l s mol etanol/KMnO4 l 2.19) tng hp 3 iu kin khc nhau: Khng thu nhit, thu nhit trong nc, thu nhit trong hn hp phn ng KMnO4 + C2H5OH, dung dch in li Na2SO4 1M, tc qut th 5mV/s, so snh vng qut th 5. Kt qu thu c nh sau:

Lp K50A

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Hnh 15. ng cong phn cc vng ca mu 3 tng hp cc iu kin khc nhau 1- Mu khng thu nhit 2- Mu thu nhit trong nc 3- Mu thu nhit trong hn hp phn ng KMnO4 + C2H5OH
M nO2

M nO 2

-1 0 .1 0 0 x1 0 -1 0 .0 7 5 x1 0 -1 0 .0 5 0 x1 0 -1 0 .0 2 5 x1 0

0 . 1 0 0 x -1 0 1 0 . 0 7 5 x -1 0 1 0 . 0 5 0 x -1 0 1 0 . 0 2 5 x -1 0 1 i/A 0 -0 .0 2 5 x-1 0 1 -0 .0 5 0 x-1 0 1 -0 .0 7 5 x-1 0 1

0 0 .2 5 0 E /V 0 .5 0 0 0 .7 5 0 1 .0 0 0

i/A

0
-1 -0 . 0 2 5 x 1 0 -1 -0 . 0 5 0 x 1 0 -1 -0 . 0 7 5 x 1 0 -1 -0 . 1 0 0 x 1 0 -0 .2 5 0

-0 .1 0 0 x-1 0 1 -0 . 2 5 0

0 .2 5 0 E /V

0 .5 0 0

0 .7 5 0

1 .0 0 0

(a)
M au MnO2 C o m p a re w i th sta n d a rd p l o t 0 .2 5 0 x 1-1 0 0 .2 0 0 x 1-1 0 0 .1 5 0 x 1-1 0 0 .1 0 0 x 1-1 0 0 .0 5 0 x 1-1 0 i/A 0 -0 .0 5 0 x1-1 0 -0 .1 0 0 x1-1 0 -0 .1 5 0 x1-1 0 -0 .2 0 0 x1-1 0 -0 .2 5 0 x1-1 0 -0 .2 5 0 0 0 .2 5 0 E / V 0.50 0 0 .7 5 0 1 .0 0 0

(b)

(c) Hnh 16. ng cong phn cc vng ca mu 3 tng hp cc iu kin khc nhau, trong dung dch NaSO4 1M, tc qut th 5mV/s: (a) Mu Lp K50A

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khng thu nhit; (b) Mu thu nhit trong nc; (c) Mu thu nhit trong hn hp phn ng KMnO4 + C2H5OH Bng 4: Dung lng ring C ca mu 3 tng hp trong cc iu kin khc nhau
Mu in lng Q(C) Khi lng mu m (mg) Dung lng ring C (F/g) Khng thu nhit 0.848 29.8 28.5 Thu nhit trong nc 0.871 28.7 30.3 Thu nhit trong hn hp phn ng KMnO4 + C2H5OH 3.037 34.6 87.8

T s liu trn ta thy: vi cc mu khng thu nhit v thu nhit trong nc th dung lng ring C rt nh, in cc hot ng rt km. iu ny c gii thch da vo cu trc, hnh dng v kch thc vt liu. Da vo kt qu nhiu x tia X v hnh nh SEM ta c:

(a)

(b)

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(c) Hnh 17. nh SEM ca mu 3 (t l etanol/KMnO4 bng 2.19) tng hp trong cc iu kin khc nhau: (a) Mu khng thy nhit; (b) Mu thy nhit trong nc; (c) Mu thy nhit trong hn hp phn ng KMnO4 + C2H5OH.

Hnh 18. Gin nhiu x tia X ca mu c t l etanol/KMnO4 Lp K50A

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bng 2.19 khng thy nhit

Hnh 19. Gin nhiu x tia X ca mu c t l etanol/KMnO4 bng 2.19 thy nhit trong nc

Hnh 20. Gin nhiu x tia X ca mu c t l etanol/KMnO4 bng 2.19 thy nhit trong hn hp phn ng KMnO4 + C2H5OH

Lp K50A

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Mu khng thu nhit: Sn phm gn nh cha kt tinh. Vt liu co cm vi nhau to thnh tng m c kch thc ln, cn tr qu trnh hot ng ca in cc, do vy in cc p t vt liu ny c C nh.

Mu thu nhit trong nc: Sn phm bt u kt tinh nhng cha nhiu. V vy, in cc ca vt liu ny cng c dung lng ring C nh.

Mu thu nhit trong hn hp phn ng KMnO4 + C2H5OH: Sn phm kt tinh tt, ht c dng si, c kch thc nh (7 15nm) v ng u, thnh phn gm -MnOOH v Mn3O4. in cc lm t mu ny c dung lng ring ln.

T kt qu trn c th kt lun: ht c dng si mnh, c kch thc nh th s c kh nng hot ng in ho cao. Mu thu nhit trong hn hp phn ng c dung lng ring C ln hn 2 mu kia v: thu nhit. So vi mu thu nhit trong nc th khi thu nhit trong hn hp Trong iu kin thu nhit c nhit v p sut cao hn, cc

nguyn t c sp xp trt t trong mng, vt liu kt tinh tt hn khi khng

phn ng, s hnh thnh tinh th cn ph thuc vo ion K+ c mt trong hn hp. Cc ion K+ to thnh nhng hc c tc dng c nh cc tinh th ging nh nhng ci khun. Do vy kh nng kt tinh ca vt liu cao hn so vi khi thu nhit trong nc. Mt khc, khi thy nhit trong hn hp phn ng th mi trng thy nhit cha etanol lm gim sc cng b mt ca hn hp, nh hng n qu trnh kt tinh ca sn phm. 3.2.2. nh hng ca hm lng etanol ln tnh cht in ha ca oxit mangan. Tng hp cc mu: Nng cht oxi ho trong cc mu l nh nhau (85ml KMnO4 70g/l), ch thay i hm lng etanol. Tin hnh o ng phn cc vng cc mu trn trong dung dch Na2SO4 1M, tc qut th 5mV/s, khong th qut t -0.2 0.8V. So snh cc mu vng qut s 5, thu c kt qu nh sau: Lp K50A

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Hnh 21. ng cong phn cc vng ca in cc t cc mu vi hm lng etanol khc nhau, trong mi trng Na2SO4 1M, tc qut 5mV/s 1- T l s mol etanol/KMnO4 l 6.56 2- T l s mol etanol/KMnO4 l 4.37 3- T l s mol etanol/KMnO4 l 2.19
M nO 2

4- T l s mol etanol/KMnO4 l 1.11 5- T l s mol etanol/KMnO4 l 0.44

M au M nO2 C o m p a re w it h sta n d a rd p l o t

0 .1 2 5 x 1 0 0 . 1 0 0 -2x 1 0 0 .0 7 5 x 1 0 0 .0 5 0 x 1 0 i/A i/A 0 . 0 2 5 -2x 1 0 0 - 0 . 0 2 5-2x 1 0 - 0 . 0 5 0-2x 1 0 -0 . 0 7 5 x 1 0 -0 .2 5 0

-2 -2 -2

-2

0 .2 0 0 x 1 0 0 . 1 5 0-1x 1 0 0 . 1 0 0-1x 1 0 0 . 0 5 0-1x 1 0 0 - 0 . 0 5 0-1 x 1 0 - 0 . 1 0 0-1 x 1 0 - 0 . 1 5 0-1 x 1 0 0 0 .2 5 0 0 .5 0 0 0 .7 5 0 1 .0 0 0 - 0 . 2 0 0-1 x 1 0 -0 .2 5 0 0 0 .2 5 0 0 .5 0 0 0 .7 5 0 1 .0 0 0

-1

E / V

E / V

(a)

(b)

Lp K50A

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M nO2

M nO 2

0 . 2 0 0 -x1 1 0 0 . 1 5 0 -x1 1 0 0 . 1 0 0 -x1 1 0 0 . 0 5 0 -x1 1 0 i/A i/A 0 - 0 . 0 5 0- 1x 1 0 - 0 . 1 0 0- 1x 1 0 - 0 . 1 5 0- 1x 1 0 -0 . 2 0 0 x 1 0 -0 .2 5 0

-1

1 0 . 1 2 5-x 1 0 1 0 . 1 0 0-x 1 0 1 0 . 0 7 5-x 1 0 1 0 . 0 5 0-x 1 0 1 0 . 0 2 5-x 1 0

0 - 0 . 0 2 5- 1x 1 0 - 0 . 0 5 0- 1x 1 0 - 0 . 0 7 5- 1x 1 0 - 0 . 1 0 0- 1x 1 0

0 .2 5 0

0 .5 0 0

0 .7 5 0

1 .0 0 0

- 0 . 1 2 5- 1x 1 0 -0 . 2 5 0

0 .2 5 0

0 .5 0 0

0 .7 5 0

1 .0 0 0

E / V

E / V

(c)
M nO2

(d)

0 . 2 0 0 x-1 0 1 0 . 1 5 0 x-1 0 1 0 . 1 0 0 x-1 0 1 0 . 0 5 0 x-1 0 1 i/ A 0 -0 . 0 5 0 x-1 0 1 -0 . 1 0 0 x-1 0 1 -0 . 1 5 0 x-1 0 1 -0 . 2 0 0 x-1 0 1 -0 . 2 5 0 0 0 .2 5 0 E / V 0 .5 0 0 0 .7 5 0 1 .0 0 0

(e) Hnh 22. ng cong phn cc vng ca cc mu trong mi trng Na2SO4 1M, tc qut 5mV/s vi t l s mol etanol/KMnO4 tng ng nh sau: (a) 6.56; (b) 4.37; (c) 2.19; (d) 1.11; (e) 0.44 Bng 5: Dung lng ring C i vi cc mu c hm lng etanol khc nhau Mu T l s mol etanol/KMnO4 in lng Q(C) Khi lng mu m (mg) 1 6.56 0.057 34.3 2 4.37 2.300 31.5 3 2.19 2.524 30.4 4 1.11 1.865 30.1 5 0.44 1.359 43

Lp K50A

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Dung lng ring C (F.g-1)

1.7

73.0

83.0

61.9

31.6

T nhng kt qu trn ta thy hm lng etanol trong hn hp phn ng c nh hng n dung lng ring C ca in cc ch to. Nng etanol qu ln (mu 1) th C rt nh, in cc gn nh khng hot ng. Khi gim hm lng etanol th C tng, kh nng hot ng ca in cc tng. Tuy nhin nu hm lng etanol qu nh (mu 5) th C li gim. C ln nht mu 3-khi t l s mol etanol/KMnO4 = 2.19.
Dung lng ring C (F/g) 100 80 60 40 20 0 0 2 4 6 8 T l s mol etanol/KMnO4

Hnh 23. th ph thuc gia dung lng ring C v hm lng etanol trong hn hp phn ng. S khc nhau v dung lng ring C l do s khc nhau ca in lng Q. Q cng ln th C cng ln. Gia cc mu c hm lng etanol khc nhau c s khc nhau v in lng Q, iu ny c lin quan n hnh dng v kch thc vt liu. T hnh nh SEM ca cc mu ta thy: Mu s 1: Ht c dng que, kch thc ln, khng ng u t 140 250nm. l l do gii thch ti sao kh nng hot ng in ho ca mu ny rt km. Mu 2, 3 v 4: Vt liu oxit mangan u c dng si rt nh, kch thc ng u, ng knh khong t 7 15nm. V vy cc mu ny c dung lng ring C cao hn hn 2 mu 1 v 5. Lp K50A

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Mu s 5: Ht c dng cu, kt tinh cha hon ton, kch thc vt liu t 120 160nm. Mu ny c kh nng hot ng in ho tt hn mu 1. Da vo cc kt qu trn chng ti nhn thy: Mu s 1 c hm lng etanol ln nht, sn phm c cu trc dng hausmannite Mn3O4. Theo cc nghin cu trc y v c ch phng in ca MnO 2 th Mn3O4 l sn phm kh cui cng trong qu trnh phng in ca MnO2, v vy Mn3O4 hu nh khng c kh nng hot ng in ha [6]. iu hon ton ph hp vi kt qu: Dung lng ring C ca mu 1 xp x bng khng. i vi cc mu c hm lng etanol nh hn th trong thnh phn ca vt liu tng hp c cha manganite -MnOOH l dng kh ca -MnO 2. Trong qu trnh phn cc MnO2 phng in to thnh MnOOH v ngc li, MnOOH np in to thnh MnO2. V vy, cc mu c thnh phn cha manganite MnOOH c dung lng ring C ln. Mu 3 (t l s mol etanol/KMnO4 bng 2.19) c dung lng ring C ln nht trong cc mu, nn trong nhng th nghim sau chng ti s dng mu 3 kho st. 3.2.3. nh hng ca nng cht in li ln dung lng ring ca vt liu mangan oxit Tin hnh o ng phn cc vng in cc ch to t mu 3 trong dung dch Na2SO4 c nng t 0.1 2M, tc qut th 5mV/s, so snh vng qut 5. Kt qu thu c nh sau:

Lp K50A

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Hnh 24. ng cong phn cc vng ca in cc p t mu 3 (T l s mol etanol/KMnO4 l 2.19) trong dung dch Na2SO4 c nng khc nhau, tc qut 5mV/s. 1- Dung dch Na2SO4 0.1M 2- Dung dch Na2SO4 2M 3- Dung dch Na2SO4 1M 4- Dung dch Na2SO4 0.5M

M nO2

M au M nO 2 C o m p a re w i t h st a n d a r d p l o t

0 . 1 5 0 x-11 0 0 . 1 0 0 x-11 0 0 . 0 5 0 x-11 0 i/A 0

-1 -0 . 0 5 0 x 1 0

-1 0 .2 0 0 x 1 0 -1 0 .1 5 0 x 1 0 -1 0 .1 0 0 x 1 0 -1 0 .0 5 0 x 1 0

i/A

0 - 0 . 0 5 0 -1 1 0 x - 0 . 1 0 0 -1 1 0 x

-1 -0 . 1 0 0 x 1 0

- 0 . 1 5 0 -1 1 0 x 0 0 .2 5 0 0 .5 0 0 0 .7 5 0 1 .0 0 0 - 0 . 2 0 0 -1 1 0 x -0 .2 5 0 0 0 .2 5 0 0 .5 0 0 0 .7 5 0 1 .0 0 0

-1 -0 . 1 5 0 x 1 0 -0 . 2 5 0

E / V

E / V

(a)

(b)

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M nO2

M au M nO2 C o m p a re w i t h sta n d a rd p l o t

0 .2 0 0 x 1 0
-1 0 .1 5 0 x 1 0 -1 0 .1 0 0 x 1 0 -1 0 .0 5 0 x 1 0

-1

0 .2 5 0 x 1 0 0 .2 0 0 x-11 0 0 .1 5 0 x-11 0 0 .1 0 0 x-11 0 0 .0 5 0 x-11 0 0 i/A

-1 -0 .0 5 0 x 1 0 -1 -0 .1 0 0 x 1 0 -1 -0 .1 5 0 x 1 0 -1 -0 .2 0 0 x 1 0 -1 -0 .2 5 0 x 1 0

-1

i/A

0 - 0 . 0 5 0 -1 1 0 x -0 .1 0 0 x 1 0 - 0 . 1 5 0 -1 1 0 x - 0 . 2 0 0 -1 1 0 x -0 .2 5 0 0 0 .2 5 0 0 .5 0 0 0 .7 5 0 1 .0 0 0
-1

-1 -0 .3 0 0 x 1 0 -0 . 2 5 0

0 .2 5 0 E / V

0 .5 0 0

0 .7 5 0

1 .0 0 0

E / V

(c)

(d)

Hnh 25. ng cong phn cc vng ca mu 3 vi nng dung dch in li khc nhau, tc qut 5mV/s: (a) Na2SO4 0.1M; (b) Na2SO4 0.5M ; (c) Na2SO4 1M; (d) Na2SO4 2M Bng 6: Dung lng ring C i vi mu 3 trong dung dch Na2SO4 c nng khc nhau, tc qut th 5mV/s Nng dung dch 0.1M 0.5M 1M 2M

in lng Q (C) Khi lng mu m (mg) Dung lng ring C (F/g)

1.767 34.3 51.5

1.973 33.9 58.2

2.524 30.4 83.0

2.033 35.0 58.1

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Nng dung dch o Na2SO4 c nh hng ti C. T bng 3 ta thy nu nng Na2SO4 nh (0.1M) th dung lng C rt thp. Dung lng C tng khi nng Na2SO4 tng t 0.1 n 1M, sau nng Na2SO4 tng th C li gim.
100 Dung lng ring C (F/g) 80 60 40 20 0 0 1 2 3 [N a 2S O 4 ] (M )

Hnh 26. th s ph thuc ca C vo nng Na2SO4 3.2.4. nh gi s nh hng ca tc qut th ln dung lng ring (C) o ng phn cc ca in cc p t mu 3 trong dung dch Na2SO4 1M, tc qut thay i, so snh ti vng qut 5, thu c kt qu nh sau:

Hnh 27. ng cong phn cc ca cc in cc t mu 3, trong dung dch Na2SO4 1M, vi cc tc qut khc nhau Lp K50A

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1- Tc 1mV/s 2- Tc 5mV/s
M nO2

3- Tc 10mV/s 4- Tc 20mV/s
M nO2

5- Tc 50mV/s

-2 0 .5 0 0 x 1 0

-1 0 .2 0 0 x 1 0 -1 0 .1 5 0 x 1 0

-2 0 .2 5 0 x 1 0

-1 0 .1 0 0 x 1 0 -1 0 .0 5 0 x 1 0

0 i/A i/A

0
-1 -0 .0 5 0 x 1 0 -1 -0 .1 0 0 x 1 0 -1 -0 .1 5 0 x 1 0

-2 -0 .2 5 0 x 1 0

-2 -0 .5 0 0 x 1 0

-2 -0 .7 5 0 x 1 0 -0 .2 5 0

0 .2 5 0 E /V

0 .5 0 0

0 .7 5 0

1 .0 0 0

-1 -0 .2 0 0 x 1 0 -0 . 2 5 0

0 .2 5 0 E / V

0 .5 0 0

0.750

1 .0 0 0

(a)
M au M nO2 C o m p a re w i t h st a n d a rd p l o t 0 . 1 5 0 x -1 0 1 0 .1 0 0 x 1 0 0 . 0 5 0 x -1 0 1 0 i/A -0 . 0 5 0 x-1 0 1 -0 . 1 0 0 x-1 0 1 -0 . 1 5 0 x-1 0 1 -0 . 2 0 0 x-1 0 1 -0 . 2 5 0 i/A
-1

(b)
M nO 2

0 .4 0 0 x -1 0 1 0 .3 0 0 x -1 0 1 0 .2 0 0 x -1 0 1 0 .1 0 0 x -1 0 1 0 -0 .1 0 0 x-1 0 1 -0 .2 0 0 x-1 0 1 -0 .3 0 0 x-1 0 1 0 0 .2 5 0 E / V 0 .5 0 0 0 .7 5 0 1 .0 0 0 -0 .4 0 0 x-1 0 1 -0 . 2 5 0 0 0 .2 5 0 E / V 0 .5 0 0 0 .7 5 0 1 .0 0 0

(c)
M nO2
-1 0 .5 0 0 x1 0

(d)

-1 0 .2 5 0 x1 0

i/ A

-0 . 2 5 0 x -1 0 1

-0 . 5 0 0 x -1 0 1 -0 .2 5 0

0 .2 5 0 E / V

0 .5 0 0

0 .7 5 0

1 .0 0 0

(e) Hnh 28. ng cong phn cc vng ca mu 3 trong dung dch Lp K50A

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in li Na2SO4 1M vi tc qut thay i (a) Tc qut 1mV/s; (b) Tc qut 5mV/s; (c) Tc qut 10mV/s; (d) Tc qut 20mV/s; (e) Tc qut 50mV/s; T ta c bng s liu sau: Bng 7: Dung lng ring C ca mu 3 vi cc tc qut th khc nhau Tc qut (mV/s) in lng Q(C) Khi lng mu m (mg) Dung lng ring C (F/g) 1 3.148 32.9 95.7 5 2.122 27.3 77.7 10 2.001 34.3 58.3 20 1.056 22.4 47.1 50 0.479 43.4 11.0

T bng s liu cho thy: dung lng ring C ph thuc vo tc qut th. Tc qut th cng ln th dung lng C cng gim. Ta c th gii thch kt qu trn nh sau: in lng chuyn qua trong qu trnh o ng phn cc: Q = I.t Trong : I: Cng dng in (A) t: Thi gian qut th (s) Khi tc qut tng th t gim nhanh (do cng qut trong khong th 1V), cn cng dng I th tng khng t l vi s tng tc qut. V vy m khi tc qut cng tng th Q cng gim. Dung lng ring C t l thun vi Q nn cng gim theo. Khi tc qut th l 1mV/s th C c gi tr ln nht. Tuy nhin tc ny l qu chm kho st, v th nhng th nghim sau ny chng ti s dng tc qut th l 5mV/s.

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Dung lng ring C (F/g)

1 20 1 00 80 60 40 20 0 0 20 40 60 T c q u t th (m V /s)

Hnh 29. th s ph thuc ca C vo tc qut th Theo cc ti liu [20], [21], [23], [24] th c hai c ch c a ra gii thch phn ng din ra trn b mt in cc magan ioxit v dung dch cht in li trong qu trnh phn cc: 1. C s chui vo v thot ra ca ion H+ hoc ion kim loi kim C+ (nh Na+, K+) trn in cc trong sut qu trnh phn cc: MnO2 + C+ + e- MnOOC 2. C s hp ph ca cc cation H+ hoc kim loi kim trong dung dch cht in li ln trn in cc: (MnO2)b mt + C+ + e- (MnOOC)b mt Trong th nghim ca chng ti: Khi tc qut thay i th nh hng rt ln n dung lng ring C, cn khi thay i nng cht in li th C thay i khng nhiu. C th d on c ch ca phn ng din ra trn b mt in cc trong trng hp ny l c ch th nht. Tc qut tng s tc ng trc tip n qu trnh khuch tn ca ion Na+ ln b mt in cc [23]. Khi tc qut ln, ion Na+ khng n st b mt in cc c, v vy qu trnh phng v np ca in cc gim, dn n dung lng ring gim. Tc qut cng chm th dung lng ring C cng ln. Trong thc t, c ch trn xy ra khi sc in cqui: Nu sc dng in nh (tng ng vi tc sc chm) th dung lng cqui Lp K50A

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cng cao nhng tn thi gian sc, nu sc vi dng in ln (tng ng vi tc sc nhanh) th dung lng cqui thp. V vy phi cn i gia thi gian sc v dung lng thu c. 3.2.5. nh gi s ph thuc ca dung lng ring C vo s vng qut

Hnh 30. ng cong phn cc vng ca in cc p t mu 3 cc vng khc nhau 1- Vng 2 2- Vng 5 3- Vng 10 7- Vng 30 4- Vng 15 5- Vng 20 6- Vng 25

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M nO 2

M nO2

0 . 2 5 0 x-11 0 0 . 2 0 0 x-11 0 0 . 1 5 0 x-11 0 0 . 1 0 0 x-11 0 0 . 0 5 0 x-11 0 i/A

i/A

0 . 2 5 0 x-11 0 0 . 2 0 0 x-11 0 0 . 1 5 0 x-11 0 0 . 1 0 0 x-11 0 0 . 0 5 0 x-11 0 0

-1 -0 . 0 5 0 x 1 0 -1 -0 . 1 0 0 x 1 0 -1 -0 . 1 5 0 x 1 0 -1 -0 . 2 0 0 x 1 0 -0 . 2 5 0

0
-1 -0 . 0 5 0 x 1 0 -1 -0 . 1 0 0 x 1 0 -1 -0 . 1 5 0 x 1 0

-0 . 2 0 0 x 1 0
-1 -0 . 2 5 0 x 1 0 -0 . 2 5 0

-1

0 .2 5 0 E / V

0 .5 0 0

0 .7 5 0

1 .0 0 0

0 .2 5 0

0 .5 0 0 E / V

0 .7 5 0

1 .0 0 0

(a)
M nO 2

(b)
M nO2

0 . 2 0 0 x-1 0 1 0 . 1 5 0 x-1 0 1 0 . 1 0 0 x-1 0 1 0 . 0 5 0 x-1 0 1 i/A i/A 0 -0 .0 5 0 x-1 0 1 -0 .1 0 0 x-1 0 1 -0 .1 5 0 x-1 0 1 -0 .2 0 0 x-1 0 1 -0 . 2 5 0 0 0 .2 5 0 E / V 0 .5 0 0 0 .7 5 0 1 .0 0 0

0 . 2 0 0 x11 0 0 . 1 5 0 x11 0 0 . 1 0 0 x11 0 0 . 0 5 0 x11 0

0 -0 . 0 5 0 -x1 1 0 -0 . 1 0 0 -x1 1 0 -0 . 1 5 0 -x1 1 0 -0 . 2 0 0 -x1 1 0 -0 . 2 5 0 0 0 .2 5 0 E / V 0 .5 0 0 0 .7 5 0 1 .0 0 0

(c)
M nO2

(d)
M nO2

0 . 2 0 0 x11 0

0 . 2 0 0 -1 1 0 x 0 . 1 5 0 -1 1 0 x 0 . 1 0 0 -1 1 0 x 0 . 0 5 0 -1 1 0 x i/A 0 -0 . 0 5 0-1x 1 0 -0 . 1 0 0-1x 1 0 -0 . 1 5 0-1x 1 0

0 .1 5 0 x 1 0 0 .1 0 0 x 1 0
0 . 0 5 0 x11 0 -1

-1

i/A

0 - 0 . 0 5 0 -x1 1 0 - 0 . 1 0 0 -x1 1 0 - 0 . 1 5 0 -x1 1 0 -0 .2 0 0 x 1 0 -0 . 2 5 0

-1

0 .2 5 0

0 .5 0 0

0 .7 5 0

1 .0 0 0

-0 . 2 0 0-1x 1 0 -0 . 2 5 0

0 .2 5 0

0 .5 0 0

0 .7 5 0

1 .0 0 0

E / V

E / V

(e)

(f)

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M nO 2

0 . 2 0 0 x -1 0 1 0 . 1 5 0 x -1 0 1 0 . 1 0 0 x -1 0 1 0 . 0 5 0 x -1 0 1 i/A 0 -0 . 0 5 0 x -1 0 1 -0 . 1 0 0 x -1 0 1 -0 . 1 5 0 x -1 0 1 -0 . 2 5 0

0 .2 5 0 E / V

0 .5 0 0

0 .7 5 0

1 .0 0 0

(g) Hnh 31. ng cong phn cc vng ca mu 3 trong dung dch in li Na2SO4 1M vi tc qut 5mV/s, so snh cc vng qut khc nhau: (a) Vng 2; (b) Vng 5; (c) Vng 10; (d) Vng 15; (e) Vng 20; (f) Vng 25; (g) Vng 30 Bng 8: Dung lng ring C ti cc vng qut khc nhau
S vng in lng Q(C) Khi lng mu m (mg) Dung lng ring C (F/g) 2 2.769 30.2 91.7 5 2.497 30.2 82.7 10 2.208 30.2 73.1 15 1.963 30.2 65.0 20 1.826 30.2 60.5 25 1.709 30.2 56.6 30 1.606 30.2 50.2

Dung lng ring C (F/g)

100 80 60 40 20 0 0 10 20 S vng qut 30 40

Hnh 32. th s ph thuc ca dung lng ring C vo s vng qut Lp K50A

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T bng s liu ta thy s vng qut cng ln th C cng gim. Chng t kh nng hot ng ca in cc gim theo thi gian s dng.

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Kt Lun
Sau mt thi gian nghin cu, tin hnh th nghim, chng ti t c nhng kt qu sau: 1. Tng hp vt liu oxit mangan bng phn ng gia KMnO4 vi etanol trong iu kin thu nhit. Kt qu cho thy vt liu ch to c ch yu c thnh phn gm manganite -MnOOH v hausmannite Mn3O4. 2. Kho st nh hng ca hm lng etanol, nng dung dch in li, tc qut th v s vng qut ti dung lng ring ca in cc. Kt qu cho thy mu c t l etanol/KMnO4 bng 2.19, thy nhit trong hn hp phn ng KMnO4 + C2H5OH, vi dung dch in li Na 2SO4 1M, tc qut th 5mV/s c dung lng ring ln nht. 3. ng thi cng chng minh c: vt liu tng hp theo phng php thu nhit trong hn hp phn ng c kh nng hot ng in ho cao hn hn so vi vt liu khng thu nhit v thu nhit trong nc.

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Ti liu tham kho

Ting vit
1. Nguyn Kim Giao (2004), Hin vi in t qut, truyn qua, NXB HQG H Ni. 2. Trn Hip Hi (2005), Phn ng in ho v ng dng, NXB Gio dc. 3. Hong Nhm (2000), Ho v c, tp 3, NXB Gio dc. 4. Trnh Xun Sn (2002), in ho hc, NXB i hc Quc Gia H Ni.

Ting Anh
5. Brian E. Conway (2003), Electrochemical capacitors, their Nature, function, and applications, Electrochemistry Encyclopedia. 6. Chengjun Xu, Baohua Li, Hongda Du, Feiyu Kang, and Yuqun Zeng (2008), Supercapacitive studies on amorphous MnO2 in mild solutions, Journal of Power Sources, 184, pp.691-694. 7. D. Linden (1994), Handbook of Batteries, McGraw-Hill, New York. 8. Daud K.Walanda, Geoffrey A.Lawrance, and Scott W.Donne (2005), Hydrothermal MnO2: synthesis, structure, morphology and discharge performance, Journal of Power Sources, 139, pp.325-341. 9. Dinesh Balachandran (2001), First principles study of structure, defects and proton insertion in MnO2, Master of Science in Materials Science and Engineering. 10. E.Beaudrouet, A. Le Gal La Salle, D. Guyomard (2009), Nanostructured manganese dioxides: Synthesis and properties as supercapacitor electrode materials, Electrochimica Acta, 54, pp.1240-1248.

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11. En-Hui Liu, Xiang-Yun Meng, Rui Ding, Ji-Cheng Zhou and Song-Ting Tan (2007), Potentiodynamical co-deposited manganese oxide/carbon composite for high capacitance electrochemical capacitors, Materials Letters, 61, pp.3486-3489. 12. H.Yagi, T.Ichikawa, A.Hirano, N.Imanishi, S.Ogawa, and Y.Takeda (2002), Electrode characteristics of manganese oxides prepared by reduction method, Solid State Ionics, 154-155, pp.273-278. 13. Jeng-Kuei Chang, Yi-Lun Chen and Wen-Ta Tsai (2004), Effect of heat treatment on material characteristics and pseudo-capacitive properties of manganese oxide prepared by anodic deposition, Sources, 135, pp.344-353. 14. Jianbo Wu, Hui Zhang, Xiangyang Ma, Ju Li, Feng Sun, Ning Du, and Deren Yang (2006), Synthesis and characterization of single crystalline MnOOH and MnO2 nanorods by mean of the hydrothermal process assisted with CTAB, Materials Letters, 60, pp.3895-3898. 15. Kenji Okitsu, Masaki Iwantani, Ben Naizai, Rokuro Nishimura, Yasuaki Maeda (2009), Sonochemical reduction of permanganese dioxide: The effects of H2O2 formed in the sonolysis of water on the rates of reduction, Ultrasonics Sonochemistry, 16, pp.387-391. 16. Laurie I.Hill, Alain Verbaere, and Dominique Guyomard (2003), MnO2 (-, -, -) compounds prepared by hydrothermal-electrochemical synthesis: characterization, morphology and lithium insertion behavior, Journal of Power Sources, 119-121, pp.226-23. 17. Lixia Zhang, Chengshuai Liu, Li Zhuang, Weishan Li, Shungui Zhou, and Jintao Zhang (2009), Manganeses dioxide as an alternative cathodic catalyst to platinum in microbial fuel cells, Biosensors and Bioelectronics. Journal of Power

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18.

M. Askar and H. Abbas, Chemical activated manganese dioxide for dry batteries, Journal of Power Sources, 51, pp.319-330.

19.

Minakshi Maniekam, Pritam Singh, Touma B. Issa, Stephen Thurgate, Roland De Marco (2004), Lithium insertion into manganese dioxide electrode in MnO2/Zn aqueous battery, Part I; A preliminary stydy, Journal of Power Sources, 130, pp.254-259.

20.

Mingdeng Wei, Yoshinari Konishi, Haoshen Zhou, Hideki Sugihara and Hironori Arakawa (2005), Synthesis of single-crystal manganese dioxide nanowires by a soft chemical process, Nanotechnology, 16, pp.245-249.

21.

P. M. Atkin (1998), Physical Chemistry, Oxford University Press, Oxford Melbourne Tokyo.

22.

Rongji Chen, Peter Zavalij, and M.Stanley Whittingham (1996), Hydrothermal synthesis and characterization of KxMnO2.yH2O, Chemistry of Materials, 8, pp.1275-1280.

23. Rongrong Jiang, Tao Huang, Jiali Liu, Jihua Zhuang, and Aishui Yu (2009), A novel method to prepare nanostructured manganese dioxide and its electrochemical as a supercapacitor electrode, Electrochimica Acta, 54, pp.3047-3052. 24. S.Devaraj and N.Munichandraiah (2007), Electrochemical supercapacitor studies of nanostructured -MnO2 synthesized by microemulsion method and the effect of annealing, Journal of the electrochemical society, 154, pp.80-88. 25. Thierry Brousse, Mathieu Toupin, Romain Dugas, Laurence Athouel, Olivier Crosnier, and Daniel Blanger (2006), Crystalline MnO2 as possible alternatives to amorphous compounds in electrochemical supercapacitors, Journal of The Electrochemical Society, 153, pp.2171-2180. 26. V.Subramanian, Hongwei Zhu, and Bingqing Wei (2006), Nanostructured MnO2: Hydrothermal synthesis and electrochemical properties as a Lp K50A

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supercapacitor electrode material, Journal of Power Sources, 159, pp.361364. 27. Wei Xiao, Hui Xia, jerry Y.H.Fuh, and Li Lu (2009), Growth of singlecrystal -MnO2 nanotubes prepared by a hydrothermal route and their electrochemical property. 28. Xueliang Li, Wenjie Li, Xiangying Chen and Chengwu Shi (2006), Hydrothermal synthesis and characterization of orchid-like MnO2 nanostructures, Journal of Crystal Growth, 297, pp.387-389. 29. Yange Zhang, Liyong Chen, Zhi Zheng, Fengling Yang (2009), A redoxhydrothermal route to -MnO2 hollow octahedrons, Solid State Sciences. 30. Yong Cai Zhang, Tao Qiao, Xiao Ya Hu, and Wei Dong Zhou (2005), Simple hydrothermal preparation of -MnOOH nanowires and their lowtemperature thermal conversion to -MnO2 nanowires, Journal of Crystal Growth, 280, pp.652-657. 31. Zhiqing Zhang and Jin Mu (2007), Hydrothermal synthesis of -MnOOH nanowires and -MnO2 sea urchin-like clusters, Solid State Communications, 141, pp.427-430.

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Ph lc

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