Chế tạo và đặc trưng hệ vật liệu mao quản trung bình chứa kim loại chuyển tiếp (v, ti, pt) làm xúc tác cho phản ứng oxi hóa một số hợp chất hữu cơ

da dong mot \ai iro v6 cung quan trong voi nhieu irng dung ti'ong cong nghe hap phu va xuc lac, su dung Irong nhieu eac qua trinh hoa hoe khac nhau.. hgp chal chira N, S hoac cac san pha

DAI HOC 01 OC GIA IIA NOI IRIJONC DAI HOC KlIOA HOC I i M l l K N

x v i v f x W K y r x x w x J f T C K X X X X ^ r x

Dfi lAI NGIIIKN Cl'j'U KIlOA HOC CAP DAI HOC QIJOC GIA IIA NOI

c m - : TAG VA DAC TRUNC HE VAT LIKIJ MAO QUAN

r R l l N ( ; BiNH ( IIIIA KIM LOAI CHUYKN TIKP (V,Ti, Pt) LAM XIJC l A C C l i O PI IAN IJN(; OXI HOA MOT SO HOP CHAT H C U CO

Ma so : QT-07-22 Clui tri cle tai : ThS.Nguyen Tlii Minli T/nr

OAI HOC QUOC GIA HA NOI

TRUNG TAM THONG TIN THU VIEN

Df/ HT

Ha N'oi-IOO?

DAI HOC QUOC GIA HA NOI IRLONC DAI HOC KIIOA HOC IL NHIKN

KKT QUA NC.IHKN CIJU 1)E TAI NCIHEN CUU KHOA HOC

CAP DAI HOC: QUOC CIA IIA NOI

Clui tri (Je tai : 7/^V Nguyen Thi Minh Thw

CACCAN BOTIIAM CIA

SV N<»iiytMi Anil I iisin KTV.Iran Hon<; Co

BAO CAO l O M TAT KE I QL A CUA DE TAI NCIHEN CIJ U

CAP OAI HOC QUOC CIA HA NOI QT-07-22

1.1 cn tie tai:

''Che tao vii clue trim}; he vat lieu mao qudn triint; hinh chiia k'un loai chuyen tiep (V, Ti, Pt) lam xuc tdc cho phdn I'm^i oxi hod mot so hop chat him co' "

Ma so: QT-()7~22

2.CI1U tri de tai: NCS, ThS, N^iiiySn Thi Minh Thir

3.Cac can bo tham gia:

- SV N<>uyen Anh Tudn

- KTV Iran lldnii Co'

4 IMuc tieii va noi tlun<^ n<5hicn ciVu:

4,1 Miic tien ni»hien ci'm\

Cuiiu \6"i SLi" phal iricii cua khoa hoc \at lieu ihi \ al lieu xuc lac doiig \ai

tm quail Irong Ironu sir phal Irien do Mien na\ nhTrug cong nghe sach C\'^)ng nghe than ihien luoi Iru'oug \ 6"i eac xuc lac "xanh" dang iiga_\ cang phal Irieii

nhain dap u'ug \eu cau cua new cong nghiep hoa chal hien dai Khoa hoc xuc lac

dang lurong \ ao \ lec lim ra cae chal xuc lac c6 hoal linh do chon Ipc cao mong nuion gop phan \ ao \ ice chuxcn hoa \ a long hop cac chal nioi cung nlur gop phan \ ao \ ic*-' h^io ^ C' n^oi iru'ong Song song \ oi cac xuc lac c6 cau Iruc /colil cac xuc u'lc di ihc ircn co" so" cac kirn k)ai chuyen liep niiu" V Pi Au C'e Mo dang la mol huong nghien ci'ru phal Irien manh do linh uu \ iel \ e kv ihual dieu che dcrn gian \ a hieu qua xuc lac cao Vice phan tan cac kirn loai chuyen liep U-en \at lieu nen niao quan Irung binh nham lao ra he \ al lieu xuc lac co nhieu ULi diem c!io phep cinixen hoa cac hop chal hCru co phan lu krong Ion cong kcnh nhu la eac lecpen caebohidraL lao ra cac hop chal co gia Iri

Muc liei! eua de lai \\i\\ la long hop \ a dae iru'ng eac he \ al heu niao quan imim

binh chua kini loai chu\en liep VX)^/ 1 i-MC'M-41: Pi MCM-41 \ a danh i^ia linii chal xue lar eua ehuiig lrt>ng phan I'rng oxi hoa o.-pinen niel\l oleal \ a ulucose

4,2.Noi (Inn}* n}ihien cim:

- long hop cac he val lieu MCM-41 Ti-MC:M-41 V : ( V r i - M C M 4 r ' va Pl/MCM-41

- Dae iruiig eac he \ al lieu long hop duoc bang eac pinrong phap \ al 1> \ a hoa 1> hien dai: XRl) SP.M 11.M ll.-TPR

- Danh i>ia linh chal xuc lac cua cac he \ at Heu Iron" phan unii oxi hoa a-pinen ( V , { V T i - M C M 4 ] ) elyl oleal (ri-MCM-41) glucose (V.O./1 i-MCM41 \ a Pl/MCM-41) San pham phan I'mg duoc phan lich bang eac phuo'ng phap: sac ky khi - khoi pho (CIC-MS) sac ky long-khoi pho (PC-MS) \ a sac ky l()ng hieu nang cao (I IP-I.C)

5 Cac ket qu:i n<^hicn ciVu da dat d n o c

5.LN}ihien cuu cohdn:

- Da long hop duoc cac he \ al lieu MCM-41 r i - M C M - 4 1 V.0s/Ti-MCM41 \ a

5.3Xdc san phdni khoa hoc:

- Da cong bo 0^' cong Irinh khoa hoc diroi dang bao cao khoa hoc lai Hoi nghi

Hap phu-Xue lac U)an quoe Ian ihir IV 2007 \ a Hoi nghi Khoa hoe \ a C OUL' nghe 1 loa 1 luu eo' loan quoe Ian ihir IV 2007

5.4 Ket (/na ilito tao:

- Iham uia dao lao 2 eu" nhan

6, Tinh hinh kinh phi ciia de tai:

Kinh phi duoc ca|): 20 trieu dong

Cac chi phi nhirsaii:

1 - 116a chal dune cu ihue khoan ehuven mon

t ^ • 2- Van phong pham in an lai lieu :

3- Chi phi kliac :

yen mon :

Cong :

17.6 trieu 0.8 Irieu 1.6 trieu

20 tricii

KIIOA QUAN LV

PGS.TS Nguyen Van Noi

nd noi J ngdy iSthdngJ^ndm 2007

Chii tri de tdi

I hS Nguyen Thj Minh Thu

IRUONC; DAI ll()( KIIOA HOC 11 NIIIKN

^\^iJ Tf^LTONG

/^G; B ^ i ^ i ^ ; i , ^ ^ , C ^ L j ^

S U M M A R I / E KKPORT OF THE PROJECT

OF VIETNAM NATIONAL UNIVERSFI Y HANOI

1 Title: Synthesis and charactirization mesoporoiis materials containin};

transitive metals (V, Ti, Pt) Stiidyin}> catalytic properties of those materials in

oxidation some ort^anic compounds

2.Codc: QC 11X04.01

3 Person of project: Ni^uyen Thi Minh Thu

4 Key implementers:

1 Nguyen Ihi Minh Ihu Director

2 Nguyen Anh Tuan Implemenler

3 1'ran Hong Co Implemenler

5 The lagets and the contents ol'stud) o l t h e project:

- S>nlheri/ing ihe malerial sxslems ri-MCM-41 V.O^H i-MCM-41 and

P i MCM-41

- Characleri/ing ihose malerial s_\slems b> melhods: XRD Raman

11-IPR SkM

Sludxing ealal}'iie properlies of ihose malerials in oxidalion some organic

compounds: u-pinen melh\ loleale and glucose

6 Main results:

-Results in science:

I Ihe suppor malerials i\'lCM-41 ri-MCM-41 were s\nlhcsi/ed 'and

characleri/ed

\ Dispered nano si/e \anadiun oxide on ri-MCM-41 and plalinium on

MC^M-41 eharaeleri/ed b\ chemi-pii\sieo techniques: XRD Raman 1

H-I PR, H-I H-I M

i SUidied llie ealaixlie properlies of ihe malerials sxslems in oxidalion

showed thai the V20s/'ri-MCM-41 is effective catahst for oxidalion pincn and melh> loleale Pt-MCM-41 is cffeeli\e catal\sl for oxidalion ulucose

Nguyen Thi Minh Thu

DAI HOC 01 OC CIA HA NOI IRIJONC DAI HOC KIIOA HOC TU NHIEN

BAO CAO TOAN VAN

KKT QUA NCHIKN CIJU DK TAI NCHIKN CUU KHOA HOC

CAP DAI HOC QUOC CIA HA NOI

TEN I)i: lAI:

Cllh TAO VA DAC IRUNCJ 111; VAT l.lHli MAO QUAN TRUNG B I N M

CIIU'A KIM l.OAl CHUYKN TIHP (V.IT Pt) l.AM XUC lAC CHO I'llAN

UNO OXI IlOA MOT SO HOP C H A T IIU'U CO

Ma so : QT-()7-22 CTiii tri dc (ai : ThS NguyC'ii Thi Minh Thu

CAC CAN BO THAM CIA

SV N<^iiytMi Anh fiian KTV I ran Hfing Co

MUC LUC

•anu

MO DAU 1

I T O N G Q U A N ^ 3

II MUC riHU VA N O I D U N G N G I I I K N C U U C U A DK lAI 16

IV CAC KHI QUA NGIIIHN CUU VA THAO LUAN 17

4.1 lonj^ hop vat lieu 17

4.1.1 long hop vat lieu mao quan Irung binh MCIVI-4I 17

4.1.2 long hop vat lieu ri-MCM-41 18

4.1.3 long hop vat lieu V20s/Ti-MCM-41 19

4.1.4 long hop vat lieu Pt/MCM-41 19

4.2 (^ae phu<)'n<5 phap tiac trunj^ vat lieu 20

4.2.1 Phu'cyng phap nhieu xa Ro'nghen (XRD) 21

4.2.2.Phu'o'ng phap pho tan xa Raman 28

4.2.3 Phuong phap khu I K theo ehuo'ng Irinh nhiel do 11:-1 PR 29

4.2.4 Phuo'ng phap ehup anh hien vi dien tu truyen qua 3 1

4.3 Danh "ia hoal (inh xiie tae 32

4.3.1 Phan u'ng oxi hoa a-pinen 32

4.3.2 Phan irng oxi hoa met}i oleat 38

4.3.3 Phan irng oxi hoa glueose 44

V.KI-T QUA Kl lOA I IOC VA DAO TAO S3

VI TAI Ml.U n i W l KIIAO 54

PIIU LUC 60

MO D A U

Hien nay nhu'ng cong nghe sach (il chal thai \'a khong doc hai) ha\ con goi la cong nghe than ihien moi truang vai cac xiic lac "xanh'' dang ngay cang phal Irien nham dap li'ng ycu cau cua ncn cong nghiep hoa chat hien dai Da co nhifiu nghien cu'u cai lien cong nghe, giam san phAm phu nang cao hieu sual cua qua Irlnh,

nghien cii'u nhu'ng ca scV khoa hoc cho vice xii If cac chat thai rdn long khi Che

lao ihanh cong nhu'ng val lieu xuc lac moi co hieu qua kinh Ic ky ihual cao du'Oc ung dung rong rai khong chi Irong ITnh \'u'c moi Iru'ong ma con Irong nhieu ITnh \uc khac nhu chat hoal dong bC mat, duoc phaim, my phalm, Huong lieu, thuoc bao ve ihu'c vat, polime

I km 40 nam qua, eac vat lieu /eolit va vat lieu tuang ty zcolit voi eac tinh chat axit, ba/o', oxi hoa khu, krong chue, da dong mot \ai iro v6 cung quan trong voi nhieu irng dung ti'ong cong nghe hap phu va xuc lac, su dung Irong nhieu

eac qua trinh hoa hoe khac nhau \u\ nhien, duong kinh mao quan va eac hoe rong

eua he vat lieu iia\ nho, khoanu 5,3 den 5,6 A chi thich ho'p cho viee ehuvcMi hoa eac phan tu nho khong the dap ung cho cae qua Irinh gom co nhieu phan lu Ian, eonu kenh

Dau thap nicMi 90, mot phat minh mang tinh dot pha cua hang Mobil la long hop ducK vat lieu mao quan trung binh (MQTIi) M41S He vat lieu nay voi kich thu'oe mao quan 20 - 500A, be mat rieng Ion 1000 1400m"/g va rat dong deu, co kha nang tao eac nhom ehue be mat khac nhau Thanh cong na\ da mo' ra co hoi day trien \'ong trong ITnh \ ire long hcyp xue tae, tao ra nhirng vat lieu nen, vat lieu xue lac cho phep ehii\en hoa cae hop chat eo phan tu krong Ion, cong kcnh kich ihuoe Ion nhir k\ cae teepen, cae hop chat eaebohidrat tao ra cae hop chat eo gia tri |6,7,8,9|

IVong nhfrng nam gan day, ben canh cae xue tae eo cau true /eolit trcn eo so" nhom silieat \ 6i tinh chat axit dae trung, cae xue lac di the tren eo' so cae kim loai chuyen tiep meialosilicat, kimloai qui hoac to hop eua chung : V, Pt, Au, Ce, Mo, dang la mol luro'iig nghiC'n ei'ru phal trieMi manh do tinh uu \'iet \ e ky thuat dieu ehe, linh da dang \ e kha nang xue tae \ a hieu qua xue tae cao | 4 | De khac phue

hgp chal chira N, S hoac cac san pham da ngimg lu, cung nhu lang do boat dong cua xuc lac, xu huang nghien cuu hien nay la phan Ian eac kim loai ehuven liep du'cVi dang cac hat co kich ihuoc nho, kich ihuac nano Ircn chal ncn hoac chat mang nham lang dien lich be mat cua val lieu, bien linh chiing de lao ra \'al lieu to hgp CO nhu'ng hieu ung vugt cong linh va lang do ben cua xuc lac

Huong nghien cuu eua de tai nay dua trcn y tuang kel hgp cac uu dicMii \ e hoal tinh xue lac eua cac kim loai chuyen tiep, kim loai quy vai cau true mao quan rong cung be mat rieng Ion cua \al lieu mao quan trung binh, nham lao ra he val lieu xue lac moi phu hgp cho eac qua Irinh oxi hoa nhCrng hgp chat hu'u co" eo phan

lu krgng Ion, cong kcnh: (x-pinen, melyl oleal va glueo/a ihanh cac hgp chat co gia

tri

da duge nghien cuu nhieu cae qua trinh xue lac trcn oxil kim loai da giiip khai pha nhung hieu biel moi ve moi quan he giCra cau true xue lac va co" che phan ung oxi hoa, mot van de bet sue phue tap trong phan ung dong the cung nhu phan ung di the I 10| Xue tae oxi hoa duge su dung rong rai trong cong nghiep hoa hoc, cong nghiep hoa dau, cong nghiep long hgp duge pham va long hgp hCru co tinh vi Theo so lieu thong ke nam 1991 cho thay trcn loan the gioi, gia Irj cac san pham hCru CO' di tir eac qua trinh xue tae oxi hoa chon loe chicm tren 40 ti USD trong long so 147 ti USD san pham cua cae qua trinh xue tae, chicm 1/5 vc khoi krgng trong loan bo eac nganh san xuat hoa chat Rieng doi \6i My, thj truang xue lac oxi hoa chieMu 105 trieu U'SD, xep thu 2 sau ITnh \ ire xuc lac polime hoa | 1 1 | Sir phat irien manh me Irong ITnh \ ire xuc tae oxi hoa gan lien voi eac xu huong cai tien cong nghe | 1 1 | Do la:

- Sir thay ihe eac ngii>en lieu tho: xu hirong tha\ the parafm bang olcHn hay eac

hgp chat tho'm (\ie iiua trinh dieu ehe anhidrie maleie tir butan ha\ pentan duac

tha\ the banu nuuxen lieu dau la ben/en, de san xuat acrylonitrin neuai la khong su dung propan ma dung propilen Cac nguycn lieu dau nay giup don gian hoa qui trinh cong nghe\ cho hieu sual cao \ a san pham tinh khict ho'n

- I loan thien eac he xiic tae eo san vai xu huong tha\' the eac he xuc lac dong the bang xiie tae di the d i a n g han tha\ he xuc tae PdCk/CuCk bang Pd'7Mo-V-P irong cae qua irinh ehu\ en hoa olefm thanh xelon

- Cjiam so giai doan eua qua trinh de tang hieu qua kinh te, \ i du su dung qua trinh oxi hoa xuc tae mot giai doan tir propilen thanh axit aer\ lie tha\ \ i phai di qua san pham trung gian acrolein truoc daw

- (jiam cae san pham phu tao ra nham tang hieu cjua kinh te do giam dirge chi

- Noi bat trong eac xu huong cai tien nay la \ice phal trien cac qua irinh moi: vice lien hanh trong eac dieu kicn sicu ban (supercrilical conditions), su phan

bo xuc lac tren chat mang, su dung eac chal phan ung duai dang mang mong (thin film) 11 1 | la nhung minh chung ve su phal Irien cac ky thuat moi de khac phue cac nhirge diem cua cac qua trinh truoc day

1.2 Phan ling oxi hoa tecpcn

1.2.1 Phdn iing oxi hod monotecpen

Tren the gioi va ca 6 Vici nam noi chung, monotecpen phan bo rong rai

trong lU nhien, trong dc) co ca trong cac ca the song, bao gom vi khucTin, nam, lao,

con trung va tham chi' ca o cac dong val bac cao ca sau, hai ly, [17| nhung chu yeu monolccpen van dirge san xuat rong rai luihuc val can No la thanh phan chinh

cua tinh dau cac loai hoa, cac loai tinh dau ihao moc Trong do dau thong chii'a hai

d6ng phan alpha \ a beta pinen la hai monotecpen chfnh Con trong cac linh dau khac nhu cam, chanh chua nhieu lecpen cung dong vai Iro quan Irong trong cong nghiep tao huong va nuoc hoa

Cac san phfim lu' monotecpen, hay cac hgp chat chua noi doi noi chung co gia Iri cao trong cong nghiep tao huong lieu va hucrng vi, la cac thanh phan Irong cong nghiep che lao dung moi, chat lay rua, hoa hoc nong nghiep xa trong nganh duoc lieu I l x p e n andehil, ancol \'a este thuong la nhu'ng chat quan Irong trong nhom thanh phan lao mui Iho'm Ion nhal | 8 | Trong hoa hoc lecpen, su epoxi hoa chon loe la rai ciuan trong Cac chal oxi hoa theo ti le hgp ihu'c dung cho phan ung nay ihudng la cac pcaxit hu'u eo phu'o'ng phap nay lao ra nhieu san phclm phe thai

va khong chon loe \o'i \iec dieu che epoxi nhay axil Tranh hien lugng nay, nhieu nizhien cuu sir ditiiu he XL'IC Uic bao izom eac ho'p chat cua x'onlVam, xuc tae nhom silieat mang lilan peroxolungslophotphat mt)l}'pden phu'c xanadi mangan da

duoc sir dung cho nhieu muc do thanh cong cung nhu la han che khac nhau

Patricia cung cong su da thu'c hien phan ting oxi hoa limone 3-carcn, dijng lac

nhan lUO tren he xiic lac (\)/SiO khac nhau cho siin phixm rat phii'c tap 118| Vf

du nhir khi dinig he xuc lac (AVSiO limonen ta(^ ra 3 san phAm chfnh: limoncn

oxil, earxeon, CcU\eol li'ong khi do caren lao ra hon hop san pham \a'\ dtVchon loe

ihap, nhu 3-caren 5 on \ a 3 earen-2.5-dion khong eo san pham epoxi hoa nhu sau:

1.2.2 Phdn im}^ oxi hod a-pinen: Due trimg vd ihi}^ ^/('"A'

Sir epoxi lioa cac olelln boi xiie tae la mot phan ung quan trong trong nghien cuu cung nhir trong cong nghe hoa chat do kha nang ehu\en hoa kinh te Cae san pham epoxi hoa la nhCrng hgp chat trung gian eo gia Irj trong ITnh vue long hgp eac hull CO' tinh \ i , lao ra cae hgp chat tinh khiet | 1 5 | a-pinen, la loai hgp chat co nhieu trong tir nhien no ki thanh phan chinh eua linh dau thong, mot loai ea> pho bien o Viet Nam Sir oxi hoa alpha pinen dirge quan tam Ian bo'i cae san pham eua

no CO nhieu ung dung quan trong irong cong nghiep cung nhu trong doi song, \ i du

lecpcnie andeh} I, rirgii esle va epoxi duge xem nhu cac chat dau dc long hgp duge

pham, chal lao miii Irong ehe lao my pham, nuoc hoa, chal lao huong \\ Dae

bicl la cae chal epoxi duge dung rong rai nhu* la cae nguycn lieu tho cho cac loai nhua epoxi, so'n, chal hoal dong be mal, eac chal trung gian Irong ITnh vue long hgp hu'u CO linh khict Tren the giai, vice nghien cii'u, che tao cac chal hoal dong

be mat dang chira nhom etilenoxil hoac nhom hidroxi tir cac dau thirc \at da duge ihue hien nhieu \ a i so lugng Ion Trong so rat nhieu cac che pham eua dau ihue vat, mot dan xuat dae trung va duge su dung rong rai nhal la cae san pham ehua oxi nhu eac hgp chat chua nhom etilenoxil hoac nhom hidroxi No la ihanh phan khong the thieu Irong nhieu san pham nhu chat lay rua, chal hoal dong be mat, lam

duo'c pham Iu\ nhicMi o Viet nam, van de na\' chua duoc dau tu mzhien cuu

nhieu

Cac san pham oxi hoa chira oxi eua a-pinen, cung vai monoglyxeril tir dau ihue vat tao ra nhirng to hgp chat boat dong be mat khong ion co nhieu irng dung Irong linh vue chat lay rua, chat tao nhu tuong, chat phu gia, dung nhieu trong san xual cong nghiep, cuoc song hang ngay,

Nhieu bao cao \ e sir oxi hoa tu dong eua cac monotecpen bao gom (/-pine, (]-pinen va limone trong sir eo mat eua Ti, / r , t r e n \'at lieu chira Si hoac Al da xuat hien nhieu uan d a \ C.^ac phan irnu huu co lru\en thonu dun^ eac chat phan ung phan irng theo ti le hgp thirc bo'i boat tinh sieu vict o nhiel do thap, nhirng san pham phire tap, nhieu san pham phe thai | I6| Nhom cae lac gia Maria K Lajunen,

va cac cong sir thirc hien phan irng oxi hoa a-pinen ircn xue lac Co(II) vai tae nhan

la oxi khong khi cho rat nhieu san pham \ o eiing phue tap nhu verbenol, verbenon, sorbrerol, p-xinien, eampholenie andehit, Khi chuyen hoa a-pinen bang xiie tae en/ym, Lindmark lienrikson \ a eac cong su cung thay rang phan ung lao ra rat nhieu cae san pham khac nhau: sobrerol xerbenol \erbenon nhu sau |LA,B|:

ihaeh thirc dau tien doi \ oi ncn cong nghiep san xuat hoa chat linh khict la phai lim

ra cac qua trinh sach eo hieu qua cao va han ehe toi da lugng san pham phu, hoac phai tao ra cae to hgp cong nghe sir dung san pham phu cua qua trinh nay la nguycn lieu cho qua trinh khac Vi du crackinh xiie tae eua qua trinh loe dau vai muc dich tang ham krgng xang, tang tii so oetan eua xang thuang co nhieu san pham olefin nhe, \ i \ a} phai eo cong nghe hoa dau di kem voi cac qua trinh san xuat PI- PP PVC, Mol trong cae phuo'ng phap do la su dung cac vat lieu xiie lac chon loe \oi lirng qua trinh

1.3 Phiin lin^ oxi hoa dau thuc vat va iin<> dung

1.3 J lin}^ (f{'fii! ^'ff^f ^/^/'' ^/'''^" 'T'^

Co xap \i 150 Irieii tan dau va mf)' du'Oc san xuat IrcMi loan the gioi \ao nam

2003 Thanh phan chinh cua dau thirc \'al la este ciia axit beo voi glixeri I'iiy theo

Trong dau dua va dau co co nhi^u axit beo mach ng^n va trung binh (chii yeu la C,

va C,,) rai ihfch hgp vai cac qua trinh phan ling sau hon ihanh chat hoaf dong be mat Dau dau tu'(mg, dau cai va dau huong duong chii'a cac axil beo mach dai (C,^) dirge dijng lam nguycn lieu iho cho li'ng dijng polime va chal boi Iron

Tu quan diem hoa hoc do, Iriglixcril se co hai lam hoal dong Do la lien ket doi trong chuoi axil beo khong no va nhom axit ciia mach axil do Phan li'ng di6u che dfin xual duge lien hanh 6 nhom cacboxylic duoc sii" quan Uim dae bicl (hon 90%), trong khi phan ung '\)leochemicar' co su tham gia ciia mach alkyl hoac lien

kel doi chi yeu cAu thap ho'n 10% De u'ng dung nh\6u hon, dfiu va ma phai duge

chia nho thanh cac san phan nhu: axit beo, glycerol, melyl este ciia axit beo cijng nhu cac cac san pham hydro hoa khac Tii' do nhieu san phslm mai duge san xual va

irng dung lam chat hoal dong be mat, chat nhu hoa, chat deo hoa cho polime xh

chai boi Iron

Chal hoal dong be mat ihu'Ong duge chia thanh 4 loai: chat boat dong be mat cation, chat hoal dong be mat anion, chat boat dong be mat khong ion va chat boat dong be mat lu'dng ifnh tuy thuoc vao loai va kha nang tuong tae voi moi truong nuoc Chat boat dong be mat duge dung rong rai Irong nhieu ITnh vue khac nhau, quan trong nhai la chat ta\' riia phan tan chong dong can, lao nhu-khir nhu, chong mai mon, my pham, hoa du'Oc (^hiing cung du'Oc diing Irong ITnh vue ihuc pham, bao ve mua mang, khai thac mo, chai luyen quang xa trong san xual son, thuoc nhuom va giay

Chat tao nhu duoc diing de che tao mot nhu tuong hoac lang do ben vu'ng ciia

nhu tuo'ng khac Monoglixerit daac diing trong cong nghe ihuc pham voi khoi lu'ong Ion do khii nang tao nhu tuong ciia he chat beo-nu6c-protein, thuc day kha

naniz lao cac hai dau beo don^ nhal cuni^ nhu tao ra cac hot khf ben tron^ he, lanu

kha nang bao boc cac boi khf ciia mang protein Do xay chiing duac dung hau hel

trong cac loai banh m\', banh ngot nhu mot chat chong dong ran ciic amilopeclin

ciia linh boi \'a gifr do xop lau dai Khi co mat cua 1% monoglixerit trong thanh phan keo dang cai'amcl sc ban che toi da sudfnh ncn giup cho x'iec dong goi \'a bao quan de dang hon Chiing ci)n dong \ai Iro nhu cac chat phii gia lam lang do tan

ciia huong lieu \ a phu gia khac khi dua \'ao he

1.3.2.Su oxi hod ddu thuc vat

Oxy boa xuc lac la mot cong nghe duge sii' dung rong rai dc san xual cac san pham chua oxi quan trong Irong cong nghiep, cong nghe hoa hoc, cong nghiep hoa '' dau, cong nghiep long hgp cac chat hUu ca tinh vi [21, 22, 27, 31] Cac cong nghe oxi hoa CO dien thuang gay 6 nhi6m moi truong vi sii* dung cac tae nhan oxi hoa nhu dicromat, pcmanganal Cac cong nghe do diin dan thay the boi cac cang nghe oxi hoa sach hon, hieu suai cao ban, cac chat xuc lac dong vai tro rat Ion.^Nhu'ng vice lua chon cac lac nhan oxi hoa cung hel sii'c can trong vi chiing quyel dinh khong nhij'ng hieu suai phan u*ng ma con lugng chat thai 6 nhiem moi truong

Trong cac phan u'ng nay, phai co phoi lii' bCn oxi hoa va no c6 the lam on dinh Irang thai hoa tri cao ciia cac tieu phan oxometal gio'ng nhu cac phoi lu" hii'u ca Do chfnh

la phuo'ng phap gan cac ion kim loai trong pha UCMT VO cct Oxi hoa xiic tae di the trong pha long voi chat xiic tae la cac ray phan tii" oxi boa khii' co nhu'ng ung dung

ro ret trong cac phan u'ng oxi hoa chon loe cac hgp chat hu*u co nhieu nhom chii'c phu'c tap, do ben nhict thap Ban than cac phan tii' loai nay cung ben trong moi truong oxi hoa, cau Iruc mao quan dong dCu, vi trf cac lam kim loai redox taeh bicl

han che su mal hoal do xiic tae, va co kha nang xiic lac chon loe hinh dang, he

thong ihiei bi cong nghe llurc hien theo phu'ong phap nay don gian \ a de dieu khicn ho'n

Oxi hoa dau thuc val la mot phan u'ng quan trong ve phucmg dien thu'o'ng mai

vi qua trinh nay cho nhieu san pham khac nhau co ting dung phong phii Dae biet la khi phan u'ng dirng lai cV giai doan epoxi tao cac epoxil co the lam lac nhan'men deo vii nhu'ng chai on dinh polime ngoai ra con duoc diing nhu nhu'ng chat trung gian trong vice san xiiai cac dan xual da dang boi vi ifnh boat dong cao ciia vong epoxi

bi cang ra Vf du rugu bac I, rugu bac 2, cac diolefin alkoxylalcohol, hydroxy lesler N-hydroxyalkyllamide, mercaptoalcohol aminoalcohol va

hydroxynitrile co the duo'c san xual theo duong mo vong epoxil \ a i cac chai phan

U'ng phii hgp | 2 I 22|

1 4 Cacbohidrat: dae trun<> \ a lin^ dun<y

Cacbohidral la mot hgp chat hiru eo* quan trong xuat hien trong thien nhien Ben canh eac axit nucleic, protein xa lipit, eacbohdrat la mot thanh phan ihiel yeu

eua sinh \al CaebohiLli'al co mat trong moi sinh \al \ oi \ai tro trung tam tj'ong sir

lieu Thuoc vao lap cacbohidral la eac chal nhu xenluloza, val lieu khung chu ycu

cua ihuc val, tinh boi, pectin va cae duong nhu glucoza va saccarozo 0 dong \ a t

bac cao, glueozo" la mot thanh phan quan Irong eua mau \ a xual bien duai dang

chat polymer glycogen trong gan va co Cacbohidral ton lai duai dang lien ket

Irong adenosin triphotphat, mot chat chia khoa trong su du Iru nang lugng sinh hoc

va van chuyen nang lugng trong ca ibe sinh val, va Irong cac axil nucleic la nhung

chal CO ehue nang luu giu' va truyen ma di Iruyen cung nhu dieu khicn su sinh long

hgp protein Cacbohidral la ticMi than lai yeu eua tat ca cae san pham trao doi chat

khac; duge tao thanh nguycn thuy boi qua trinh quang hgp Chung la nguon goe

eua tat ca cac hgp chat huu ca eua giai sinh vat

Thuat ngu" cacbohidral duge diing cho loan bo nhom cac san pham thien nhien co

lien quan vai cac duong dan gian Ta phan chia cacbohidral thanh cae duong va

cac polisaecarit C^ac dai dien cua cac nhom nay (vi du glucoza, saccarozo', linh

bot) deu la eac nguycn lieu cjuan trong eua cac qua trinh cong nghiep (cac-nguNcn

lieu lai sinh)

Trong khoang may ehue nam iro lai day, vice nghien cuu eaebohidrat da eo nhung

buac phal tricMi manh me, dae biet trong ITnh vue sinh hoe, eaebohidrat

(iilvcobiolouN ) hoac hoa sinh hoe cacbohidral (ulvcobiocbemistrv) Su tanu nhanh

cae kicn thirc \ e ITnh \ ue na\, bao gom ca nhirng hieu biet ve y nghTa sinh hoe eua

eaebohidrat eac loai doi \ oi moi sinh vat, lai cung kich thich vice nghien ciru khoa

hoe huu CO' ve eaebohidrat \ a irng dung cae phirong phap val li hien dai vao khao

sat cau tnic, dae biet la pho cong huxrng tir hat nhan va pho khoi lugng

1.4 L Phdn unt^ oxi hoa eaebohidrat

Cdc phironi: phdp oxi hoa co dien:

Cae duong co the bi oxi hoa bang cae con duong khac nhau 0 andozo',

nhom andehit la \'i tri nhay cam nhat Phuong phap oxi boa thong thuang la diing

Brom trong mot dung dich dem \ a i mot gia tri pi 1 tir 5-6 San pham 1^ cac axit

Tuang tu eac axit y va 5-hidroxicaeboxylie, cac axil onie ncu tren de taeh nuoc de lao thanh cac y hoac cS-lacton, vai su uu lien lao thanh y-laclon Su de bj oxi boa

cua cac andozo' da duac su dung cho nhieu phuong phap phan lich duong eo dicMi

duge cip di^ing pho bicMi truoc day, nhu thuoc thu l-elinh, thuoc thu Tolan

Dung djch T'elinh chira ion phire eua dong laetral, thuoc ihu nay khong ket lua mau

do gach eua CTbO khi oxi boa andozo" Trong moi truong kiem cae xetozo' bi

chuyen thanh i\ndo/.o\ va eac chat nay bi oxi hoa boi phue chat dong

Dung dich Tolan chira ion phire bac amoniacat va cho phan irng duong tinh \d\ 'dndo/.a \ a xetozcr

Cae axit andonie la cac hgp chat dau quan trong de long hgp cae xctozo" cao hon cung nhu de iboai bien thanh eac andozo* thap hon

Voi eac tae nhan oxi boa manh hon, thi du axit nitric dam dae, thi a andozo khong chi nhom andehit ma ca nhom ancol bac mot cung bi oxi boa thanh nhom cacboxxl San pham la cac axit andarie thi du D-glucozo" cho axit D-gluearic, D-mannozo'axit D-mannarie \ a D-galaclozo'axit galaetarie

H-HO

HO H-

Phdn im^ len men:

Nha lac dung cua cae enzim khac nhau, phan tu glucoza iham gia \ a a eac qua

trinh phan cat phiic tap (phan irng len men), lao thanh cae san pham cuoi 4:ung nhu

elanol, axil bul}rie, axil lactic, axit xitric , dong thai co giai phong ra san pham

khi nhu IN, CO2 Tii\' theo ban chat eua san pham thu duge ta phan biet cae phan

ling len men sau:

- Len men rugu: tao ra san pham la ancol elylie

1.4.2.Phdn mv^ oxi hoa D-}^lucozo'

Su oxi hoa gliicozo" la mot phan li'ng quan trong trong nghien cii'u cung nhu tronu

conu nnhc hoa chat do kha nanu chuxen hoa kinh le Cac san pham oxi hoa la

nhung hgp chal irung gian eo gia tri trong ITnh \ i^rc long hgp eac hiru eo tinh \ i, tao

ra cae hgp chal linh khiel | 15| (ikicozo la loai hgp chal eo nhieu Irong tu nhien,

rat pho bien o \'iei Nam Sir oxi hoa glucozo' duge quan tam Ion boi cae san pham

eua no eo nhieu ung dung quan trong trong cong nghiep cung nhu tronu doi sonn

HO \ NO- -^-COOH

OH

H 0 \ - - ~ C 0 0 H

o

2-keto-gKjconlc acid

Sir o x i hoa " l u c o / o " \i\ eac d a n x u a t t r c n cac x u c tae k i m loai

Ngay nay, sir oxi hoa glucozo' tao thanh cae axit cacboxylic, dieacbox} lie nhir axit sacearie, axit gluconic, tactarie, succinic, glucaric, la mot phan ung quan trong trong nghien cuu cung nhu trong cong nghe Cae axit cacboxylic nhan duge lu qua trinh na\ co the dirge sir dung de dieu ehe chat lay rua, tao phue lam phan bon qua

la, lam chat lao man cho gom sir, su dung trong thuc pham | 8 , 10, 15,| va dae biet gan da}', axit D-Cjlueonie, 13-glucarie eon duge su dung nhieu trong duge pham lam chat chong ung thir

Cac phan ung huu ca truxen thong dung cac chat phan ung phan ung theo ti le hgp thuc boi hoal linh cao a nhiel do thap, nhung san pham phue tap, khong ebon

loe 11 11 Nhirng thach thuc dau tien doi voi nen cong nghiep san xuat boa chal linh khict la phai tim ra eac qua trinh sach \ ai muc dich ban ehe toi da lugng san pham phu Mot Irong cac phirong phap do la su dung cac val lieu xiae tae ebon loe voi tirng qua li-inh

Nhieu bao cao \ e sir oxi hoa xue tae eua cac cacbohidral trong su co mat eua cac kim loai chuxCMi liep tren \at lieu chua Si hoac Al da xual bien nhieu, gan day

da CO mol so hiroim nuhien cuu trong \ ice diing xuc tae eo cau triic xae dinh ciino

vai hidroperoxil (I I2O2 hoac peroxit hun ca) nhu la chat oxi boa cho phan ung oxi hoa ebon loe

1,5 Xuc tae cho qua trinh oxi hoa chon loe

Oxi hoa xi^ic lac la mot cong nghe duge su dung rong rai de san xual eac san pham chira oxi quan trong trong cong nghiep Trong cong nghiep hoa dau \ a cong nghiep long hgp cac eac hgp chat hiru co' tinh vi, cac cong nghe oxi boa co dien sir dung cac tae nhan oxi hoa nhu diclomat, pcmanganal, thuang gay 6 nhiem moi

truong Do vay, eac cong nghe do dang dan dan duge thay the bang cac cong nghe

oxi boa sach, hieu sual cao hon | 3 |

Cac kim loai quv nhu ho Pt, Pd, Au ihuanu duo'c lua ebon lam xiie tae cho cac phan irng oxi hoii hoan loan |20'^| Vao cuoi nhung nam 1960, ngudi ta sir dung xiic tae Pl/Rd cho phan irng xu ly khi thai va xiic tae Pd cho phan irng axctoxyl hoa olelln Khi su dung cae he xiie lac kim loai quy nay de lien hanh oxi hoa chon loe can chii y phai ihire hien qua trinh trong dieu kicn khu (du hidreaebon

va thieu oxi), neu diing du oxi thi cae kim loai qui sc xiie tae cho phan irng oxi hoa

hoa loan nga} a nhiel do ihap (200 250"C^) Xiie tae Ag cung da dirge nghien ciru

\ a irnu duim lir rat lau cho cae phan irnu oxi hoa etilen thanh etilen oxit ha\ dehidro hoa elanol thanh axelaldehit Ag cung duo'c hang BASl' su dung thanh cong cho phan irng long hgp Ibrmandehit |2P^| I)a\ cung la xiic tae du\ nhal co

oxi-do chon loe cao cho phan irng oxi hoa chon loe etilen de tao hgp chal epoxi (etilen

oxit) trong pha khi '\\\\ nhieMi, hien na\ khi ma \ an dc moi truong dang ngay cang

"nong", \'iec ban ehe eac san pham phu, eac chat thai la mot yeu cau bat buoc doi vai cac qu\' trinh cong nghe hien dai huong nghien ciru su dung cac kim loai quy lam xiic tae cho cac phan irng oxi hoa lai diro'c quam lam nhieu bo'i uu diem cua

loai val lieu na>, do la linh ben do chon loe cao ban che cae san pham phu \ a kha

»

nang lai su dung nhieu Ian

Cian daN da co mot so lurong nghien ciru trong \iec dung xiic tae eo cau true

xae dinh eiing \oi hidi'operoxil (I b O : boae peroxit hCru eo') nhu la chat oxi hoa cho phan ung oxi hoa chon loe Vat lieu mao quan trung binh nhu la zcolit aluminophotpliat(AlP()) silieonakiminophotphal (SAPO) eiing \'ai su sap xep eo Irat tir cua cac kenh mao quan dang dirge nghien ciru rong rai Nhiing \at lieu na\

CO be mat Irong Ian va co cac lam dae trung la eac kim loai boat dong, su phan bo cao cua cac lam boat dong giiip cho qua trinh sieu ebon Ige Mot so qua Irinh cong nghiep moi dua Ircn muc lieu nay dang phal trien Mot vi du dae trung la TS-K mot dang silieat bien linh vai Ti la chat xiic lac cho qua trinh epoxi boa olefin, oxi hoa rugu va hydroxyl boa phenol Irong su eo mat cua I ^ O i da duge ihuo'ng mai hoa Mot van de chinh la nhung vat lieu xiic lac micropo mang eo kich ibuae nho (co khoang 5,4-5,6 A) nen TS-1 chi xue lac cho phan ung oxi boa cac hgp chat hCru

CO CO kich thiroc phan tu nho hon kich thuoc mao quan cua no, vi du nhu phenol, eac ancol mach thanu nho, cac anken, ankan, eac hop chat tham co khoi krone phan tu thap | 1X| Da eo nhung nghien ciru dua titan vao mang linh the cac zcolit

CO mao quan Ion ho'n nhir zcolit Y, mordenil Beta, nham long hop xiie tae oxi hoa cho eac hidroeaebon phan tu Ion song ket qua hien con rat ban che [24* |

Trong mot so nam gan day, Young va cong su 117| va mot so nha nghien ciru khac dang lam vice \6i cae dang mangan tren vat lieu silic mao quan trung

binh IVlCM-41 Xiao cimg cong dua ra vice long hgp va dae trung cua xiic tae

M'rS-9 cho do ebon loe cao trong phan irng epoxi boa styren va oxi hoa

trimetylphenol, do boat dong xiic tae eua chiing da cao h(m ban so \'ai cua

TS-1| I8|, eiing voi khong gian ba chieu 16 rong bo'n se cho phep giai quyel cac chat phan irng cong kenh

Nhirng nghien ciru moi su dung \al lieu mesopo chira kim loai chuyen tiep nhu ri-MCM-4 1 ,V-I IMS de chuyen hoa cae hgp chat huu co' kich thuoc khac

nhau da bat dau dwgc chii y 120,21 | Da\' la mot huong nghien ciru eo hieu qua va

nhieu ly ihii Vice phan lan kim loai chuyen tiep, kim loai quy hoac dua oxit kim loai vao mao quan cua \at lieu mesopo da tao ra he \at lieu mai eo nhieu tinh chat mai va eac uu diem virgi ti'oi Theo dinh huong na\ chiing toi thuc bien ehe tao eac

he xiic tae livn ca so* \ (il lieu mao quan trung binh chira eac kim loai chu\en tiep,

kim loai qui (V, li, Pt) su dung cho qua trinh oxi boa ebon loe mot so hgp chat huu eo: (x-pinen met> 1 oleal \ a glucoza voi muc dich tao ra nhirng san pham monu muon, co nhieu irng dung trong thuc ticMi

II MIJC TIEU VA NOI DIJNC NGHIEN CUU CUA DE TAI

LMuc tieu:

Muc lieu eua de lai nay la long hgp va dae trung cae be val lieu mao quan trung binh chira kim loai chuyen liep V 2 ( V r i - M C M - 4 1 ; Pl/MClVl-41 va danh gia tinh chat xuc lac cua chiing irong phan irng oxi boa a-pinen, melyl oleat va glucose

2.Cac noi dung nghien ciiu

- Tdng hgp eac he val lieu MCM-41, Ti-MCM-41, V ( V r i - M C M 4 l va

III PIIUONC PIIAP NCIHEN CIJU

1 Dieu che chat xuc tae:

- long hgp \at lieu lir eac tien chat \6 co\ template hCru co, bang eac

phirong phap tam, phirong phap sol-gel, ket tinh thuy nhiel trong autoekue,

2 Nghien cuu cac dae trung cau true eiia \ a t lieu xue tae :

- Phirong phap nhieu xa lia X (XRD): xae dinh dae trung cau triic eua \at lieu

- l^biro'ng i^hap pho hong ngoai (I- IIR): xae dinh cae dae trung lien ket

- Phuong phap quang pho Raman : xae djnh eac dae trung lien ket

- I^huong phap hien \ i dien lu quel (SI:M): xae dinh kich thuoc tinh the, kich thu'oe hai

- Phirong i^tliap hien \ i dien lu truyen qua ( ll-M): xae dinh \'al lieu mao quan nano, kim k)ai ha} oxil kim loai phan tan kich thirae nano

- Phuang phap khu hidro theo chuong trinh nhiel do ( rPR-H2): xae djnh trang thai ton tai cua kim loai chuyen liep monovanadat, polivanadat, \ anadat tinh ihc, kim loai qui Pt va su bien linh be mal, xae dinh kich ihuac nano cua \ at lieu

3.Nghien euu hoat tinh xiie tae trong phan ling oxi hoa eac hop chat huu eo': a-pinen, metyl oleat va glueo/o*

- Cac phan irng duge thuc hien a pha long trong dieu kicn cm diu, nhiel do tir

50 ~ 100 C, lac nhan phan iing la 112O2 va Oi khong khi

4.Phucng phap phan tieh danh gia san pham phan ung

- San pham eua phan irng oxi boa a-pincn, melyl oleal duge phan lich bang phuong phap sac ky khi kh6i pho (GC-MS) 1IP-6890 MS5973

- San pham cua phan irng oxi boa glucoza duge phan lich dinh tinh bang phuong phap sac ky long khoi pho (bC-MS) DTRAP 1 100 vai detccto khoi pho D i o r ARRAY, (\)t / O R B A X (^18 tai vicMi boa hoe thuoc vien khoa hoe va cong nghe Viet Nam \ a phan tieh dinh lugng bang phirong phap sac

ky long hieu nang cao (I IPkC)

IV.CAC KET QUA NCIHEN CUU VA T H A O LUAN

- Nguon silic: Telraelx lorlhosilical (TI:OS) (CdbOj^Si (Merck )

- Ispropanol lu>el doi (iPOIl); (CII,):C1 lOIl ( M e r c k )

- Dung dich anionihiroxil 2 5 ^ : NI1.^()H

- Nu'cVc cat

/)////•' cu: fail—.—

^ M I HOC Q U O C G I A HA NOI

May khay lii

Coc thuy linh

Pi pel

Cong \a hut

Binh nho gioi

Quv trinh tdn^^ ho'p:

Hoa tan CTAI3 vao hon hgp iPOH va nuoc duge dung dich I.Them mot lugng nhal dinh NHjOH vao dung dich 1 sao cho pH = 10 Khuay manh h6n hgp trcn trong 15

phut duge dung dich 2 co mau trong suot.Nho lir tu TEGS da duge Iron deu irong

isopropanol vao dung dich 2 Khi do qua trinh buib thanh gel sc bat dau Khuay manh trong 2h ihu gel co mau trang due Trong khi khuay Hen tuc chinh bang Nil,OH sao cho pi I khong doi khoang 10 Sau do dun hoi luu trong 1 ngay roi lam lanh tai nhict do phong

Loe ru*a san pham bang nuac cat den khi pH=7 De kho qua dem d nhict do phong roi say d I I()"C irong 5h Sau do nung duoi dong khong khf d nhict do 55()"(\ san

phiim thu dirge co man trang min Cau Iruc ciia mfiu duge xae dinh bang pho nhieu

xa Roughen (XRD), pho tan xa Raman

4.1.2 Ton}i hop Ti-MCM'41

Niiuxen lieu:

- Chat IIDBM: Ccl\ llrimelylamonibrt)mua (CTAB) C,,H,,(CH;J,NBr (Merck)

- Nguon Silic: lelraorlhosilical (THOS) (CJ-l,0),Si (Merck)

- Nguon Titan: Telraisopnipylortbotitanat (TlPOTi) (i-C3H.O)_,Ti (Merck)

- Tctrapropylainomhydroxit 40^r ( TPAOll): (C,I1 ),NOH (Merck)

- Ispropanol tuyct doi (iPOll): ( C I l J C l l O I l (Merck)

- Dung dich amonibiroxil 25''/: NlTiOIl

Binh nho gioi

Qui trinh ton,^ hop:

- Hoa lan CTAB vao hon hgp 1PA()H va nuoc duge dung dich 1 sao cho p H - 1 2

Khuay manh hon hgp trcn trong 15 phut duge dung dich co mau Irong suol Nho tiJf lu TbX)S da duge iron d6u trong isopropanol vao dung dich I duoc dung dich 2

Dong thai khay manh TlPOTi vai isopropanol duge dung dich 3

Nho that tu tu dung dich 3 vao dung dich 2 khuay manh, giu pH dung dich vfm khong doi

Chuyen gel \'ao binh cfiu cai hoi luu trong I ngay a nhict do 5()''C Sau do lam

lanh den nhict do phong Loe riia san pham cat toi pi 1=7

- De kho qua dem 6 nhiel do phong roi say o I l()"C trong 5h

- Nung Irong khong khf 6* 55()"C sc thu duoc boi mau trang min

- Cau true cua man duge xae dinh bang pho nhieu xa Rcrnghen (XRD), pho tan xa Raman

4.L3.7()n}4 hop \ 2O/H-MCM-4I

I loci chat:

Vanadi (V) oxit: Merck

Axit oxalic: Merck

Ti-M(^M-41 da ton^ hop

Nuoc cat

Ou\' trinh long hop:

1 loa lan xanadi (V) oxit a dang ran trong dung dich axit oxalic de thu duge dung

dich xanadi oxalat Tien haiih tam dung dich \'anadi oxalat len Ti-MCM-41 voi cac

ham lugng linh loan Man sau do diro'c say kho a 100 C xa tiep tuc nung o' 450"C

trong 5 gio de loai cae hgp chat huu co"

4.1.4 Idnii hop Pt/MCM-41

IbPtCl,: Merck

Quy trinh long hop:

Tien banh lam dung dich ri2PlCl6 len MCM-41 vai ham lugng 1% da duoc tinh

loan Sau do mau duge say kho a 1 10 " C Irong 5 gia va liep tuc mau duge nung a

500 'C trong 5 gia dc loai cac hgp chal hu*u co Xuc lac thu duge la Pl/MCM-41

4.2.Cae ket qua dae trung vat lieu

Tong hgp MCM-41 tu ticm chat Silic TCOS va chat dinh huong cau Iriic CTAB duge thuc hien kha thuan Igi Voi thanh mao quan siliconal v6 dinh hinh, \'at lieu nay thuong la chat ncn phan tan cac be cau lu xiic lac Vice dua Titan vao thay the dong hinh Silic trong vat lieu nen MCM-41 duge thuc hien theo ti Ic khac nhau (bang 2), lugng CTAB trong tat ca cac mfiu la nhu nhau bang 2,5 g Lugng vanadioxil mang trcMi Ti-M(rM-41 la 10% vc khoi lugng va lugng platin la 1%

Bang 1; Cdc mau veil lieu dur/c ton;^ hop

Nhiel do long hop ("O

^/^V.CVV15 Pl/MCM-41

Chal lao moi Iruong

NH.OH TPAOll TPAOll TPAOH TPAOH NH.OH TPAOll

Cac mAu lien tlii'Oc dae irii'ng bang ky thuat \al If bien dai XRD, RAMAN \a

danh gia hoal linh irong phan ung oxi hoa chon loe melyl oleat theo phU(mg phap

da neu trong chuong 2

4.2 l.Phivo'n}^ phdp nhieu xa Rongen (XRD)

Phuo^ng phap XRD thuong duge su dung de xae dinh cau triic cung nhu trang

thai don lap bci mat cua xiic lac Co rat nhieu oxil kim loai cung nhu kim loai co the

duge phan tan tren bC mat ciia chat mang d dang dan lap be mat Khi do chiing sc ton lai d trang thai phan tan cao hoac d trang thai v6 dinh hinh Khi chuyen sang

trang thai da lap be mat, trcn bC mat xiic lac sc xuat hien cac tinh the ciia oxit kim

loai hay kim loai hoal dong Do do tren ph6 XRD se xuat hien cac pic dae trung VI

MCM-41 CO thanh SiO, v6 dinh hinh nen XRD la cong cu de xae dinh cau triic mao

quan 110| Nho phucrng phap nay ma nhung nhan dinh ban dau va quan trong duge

xae dinh mot each nhanh chong va chmh xae

Gian do nhVeu xa Ronghen eiia mfiu Ml, M3, M4, M5 duge the hien trong

cac hinh sau day:

—^^-^^-^^^

n, 'i

/////// 12: (jicin do uhicu xa tia X ciia mau Ml

Tren gian do thay xuat hien cac pic cuang do lan 6 goe 29 ^ 2.2*' va 2 pic co cuong do nho lu'ong ling \d\ gc)e 20 ^ 4^' \a 20 ^ 5'' la dau hieu dae trung cho cau

true liic lang cua val lieu mat^ quan trung binh MCM-41 (Theo Kresgc va cac cong

sir pic d vung goe hep 20 <1()' dae trung cho cau triic hecxagonal) |5, 32J Nhung

pic nay chi mal [-than \a (chi so Miller) lu'ong ling la cac mat 100, 110 va 200 Di6u

nav kh;iniz dinh mau uSng hop duge ed cau triic deu dan 117,26, 28J

JSOO' -Ena 0(1000 -Sir-r 2b U 'C |l'.xim,-».iodr? Cu -Ci»Jtio^ 03.71 0 ' r J6JG

Hinh 13: (jicin do nhieu xa tia Xc ua mau M^_y

2 ihcta ScalQ

Hinh 14: (jidn do nhieu xa tia Xcua mau M'

y >^

2 Ihtita Scale

; i v 1 i i i - - i ^ d '.i.,n '.S0(> • t ' l a Siwxnj M.c 'i OJO L'lo i 0 3 1 ' 0' I82S 19

Hinh 15: G'/V//; do nhieu xa tia Xcua mau Mi f

Nhu tren da phan lich, \'iec thay the dong binh cac ion kim loai \'ao mang tu dien cung vol Silic qua licMi kel cau oxi phai tuan theo nguycn lac phii hgp v6 ki'ch thuoc ion r^,^, < 0.4 A Ma ban kinh ion cua Titan la r^,^, <().34A co the di xao mao quan

hecxagonal lao lien ket Ti-O-Si ma khong pha \d cau true 1^uy nhien so voi Si hay

Al, vice tonu hop MCM-41 co dua 1llan vao manu thuc bien kha kho khan do tien

chat chua Titan d dang monome lelraisopropyloctolitanat phai duge boa lan trong

dung moi lln'ch hop li'anh su thuy phan lire thai

Mat khac, duong UCMT 6 vung goe rong ciia cac mau M3, M4, M5 khong thay xuat hien cac tin hieu nhieu xa ciia titan oxit dang tinh the (anatas, brockil, rutin)

Trcn gian do cac dinh dae trung ciia MCM-41 sac nhon Vice thay doi ham lugng T\U\n cung khong gay anh huong gl den cau triic luc lang va do tral tu cua mao quan Qua irinh licii hanh ed hieu qua 6 50*'C Dc khao sat anh huong eiia kha nang kel hop lluiy nhiel lieii hanh thuc hien 6'nhict do thuong Ket qua nhu sau:

J r

.^-/'

fr-Hinh 16: Gidn do nhieu xa tia Xcua mau M ^ ^ y\^^\^

Hinh 17 : Cuin do nin'cu xa tia Xcua mauTi^CH^^/i [Tf/Xmi)

Kei cjiia XRD cung xuai bien cac pic dae Iru'ng tuy nhien do cudng do nho va doang Do d nhiel do thuong qua polime boa ngung tu silieat xay ra cham, mSu

chii'a Ti cuong do nhieu xa thap, dinh tu hon, cac goe 20 = 4" va 5" ro net mao quan khong tral lU

De so sanh anh huong cua moi truong bazo toi qua trinb long hgp

Ti-MC.M-41 tieii hanh ihuc hien khi chai chinh pi 1 la Nll4C)l 1 Ket qua gicin do tia X nhu sau:

"I'Ji- I- ,-.,.ir.- i ; t i „ - T,[ : i > / - i t - * ^ ^ i n i j s j c - t f i ' ^ V T Fi», : : ; 3 ' - V'-tir-« l O i ' - v ; s ; ' : i ' * o - , '

Hinh IS: G/V/// do nhieu xa Rojn^hen ciia man MQy~^

Su dung N I I O l l chai chinh p l l co uu diein la re lien, tuy nhien vice dieu chinh la rai kho khan, xae suai thanh cong tuong doi thap Hern nua amoniac lien

tuc bay hoi trong qua irinh long hgp khicn h6n hgp giam pH lien tuc Do do linh

dong deu kem hon so \ o i \ ice dung 1 P / \ ( ) I 1

Thu'c hien qua irinh lam Titan ICMI chai mang co bC mat rieng Ion la MCM-41 (mau M l )

? - I l K - r T - s - i ' c

Iliiili 19: (imii do iici Xcua lO'A li! MC!M-4I viin;^ ;j^6c In

''P

Hinh 20: (luin do tui Xciia l()7( Ti/ MCM-41 vuui^ go(^ rong

Qua hinh la thay tral tu mao quan co su tha\ doi do cuong do ifn hieu 6 goe

20 ^ 2,2*' khong con sac net nhu mau chua lam Nhu vay khi tam cac oxil kim loai len chai nen, cac oxit da phan bo ben trong mao quan lam kfch thuoc mao quan

thay doi va khong con dong deu d vung goe lo'n ton lai pha TiO the bien Irong gian do XRD qua cac nhieu xa o* g()c 20 bang 25.3", 37", 38", 38.5", 48", 54", 55",

62.5"

I; I

inh: Gian do XRD cua mau M i

Tren gian do nhieu xa Ktrnghen eua mau lOX'lOlM , khong con pie la nao khac nira chung to \ anadi oxil a dang \ 6 dinh hinh \ i the khong xual bien pie dae

trirnu cho tinh ihe \ anadi oxil Ciia tri di,,(, -khoang each gira 2 tam mao quan cua

val lieu V rO/MCM-41(28A) da th4p ban gia tri d,,,,, cua val lieu MCM-41 (-40A),

chung id vanadi oxit da chui vao trong mao quan \ a nam tren thanh mao quan lam

cho kich thuoc ong mao quan giam ban

I linh : Gian do nhieu xa XRD eua Ml^-viing goe hep (a) va goe Ion (b)

Qua pho XRD cua mau Pt/M("M-4K la nhan tha\' vat lieu \ a n giCr duge cau triic MQTH voi cac pie dae trung xuat hien trong vung goe hep, ngoai ra khong eo pha

la khac Tren gicin do XRD, eac pic dae trung cho tinh the Pt xual bien trong vung

20 =30** > 40" luy nhien tren pho XRD la khong thay su xuat hien cua eac pie

nay Dieu nay eo the duge giai thich la do ham lugng mang nho (1%), Pt chua the

hinh thanh dang linh the va no ion tai o dang v6 dinh hinh

Tuy nhien khoang each d|,,i,girra 2 lam mao quan da giam dan khi ehup nhieu xa o cung dieu kicn Ciia tri d|,„, cua Pt/MCM-41 da thap ho'n gia Irj di,,n cua vat lieu MCM-41 Dieu nay chiing to cac hat oxit platin bang phuang phap lam da dat

duge kich thiroe nho (<4 nano) moi eo the chui xao trong mang va nam tren thanh

mao quan lam cho kich ihiroe ong mao quan giam

Voi nghien ciiu dae irung \(il lieu bang Ronghen l V M C M - 4 1 (M3 M4, M5 M6 M7) cho thay kha nang bitan di vao mang Hi' dien, dong huih cung Silic, licMT kei

\oi Silic qua can oxi Cac man tren gian do dinh sac net, su che lap ciia anatas

khong xae nhan la ihu duge mesoporc l^uy nhien phuc^ng phap nay chua dae trung cho kha nang lha\ ihe lilan trong mang lii' dien Do do phai nhan dang Ti'^ bang

phuong phap Raman hay I J V - V I S V I pho UV-VIS khong nhay trong \icc phat

hien nhung vet Titan, do do chiing toi lien hanh do he xiic Uic V,Os/ Ti-MCM-4 being phmrng phap Raman

4.2.2.Phuv'n}f phdp phi) tdn xa Raman

Phuang phap pho tan xa Raman duge li'ng dung dc xae dinh li nam trong khung cau true bay Ti nam a ngoai mang Pho do quang pho tan xa Raman cua eac mau VI1, VI11 duge trinh bay a cac hinh tiep sau:

/////// 6.6 : pho Raman cua man VliL(stocks)

Cae dae trirnu dao dong eua cac lien ket trong \at lieu duige trinh ba\ trong bang 2

duoi da\:

Bdn}^ 2: Cdc ddc trung dao dong cua cdc lien ket tren pho Raman

tren pho do xuat hien eac pie 291, 972,1 co dinh sac nhon va cuong do Ion (Vlll),

day la cac dinh dae trung cho Ti nam trong khung cau true eua val lieu (4-t-| Ngoai

ra cung thay xuat hien eac dinh pho 146,1; 516,6; 639,5 dae trung cho Ti02 dang anatas Dieu nay mot lan nCra khang djnh nhu'ng ket luan lu pho XRD va IR vc cau triic vat lieu Do la vat lieu co can triic mao quan trung binh voi mot phan Ti nam trong khung can triic li'r dien, mot phan Ti nam ngoai duai dang oxit titan, anatas Con vanadi oxil xa ceri oxit phan tan tren nen vat lieu do

4.2.3.Phuo'ng phdp k/iw theo chwong trinh nhiet do (Hi-TPR)

Phuo'ng phap khu boa theo chuong trinh nhiet do cho ta cac thong so ve

trang thai ox) hoa khu eua be mat \ a khoi chat ran Qua trinh khu l b di^'gc tien hcinh o nhiel dp 25-700"C

Theo cac tai lieu|23 |, oxit vanadi o' dang kh6i(tinb the) khong mang trcn chal mang xuat bien 3 pic khu tai nhiel do 625,3; 656,7 va 726,8 'C , 3 pie nay ung vai qua Irinh khu V^' thanh V^' nhu sau: ^^^ - ^ ^ ' ' ^ -V^^ -V3^

Hinh 6.13: Phuo'ng phdp khic hod theo chuong trinh nhiet do cua man

V2()^ri-MCM-41

Ket qua tren gian do khu iheo chuong trinh nhiet do cua mau

IOV;)()>-/ r ( V M C M ^ 4 b cho thay hai pie o nhiet do thfip hon la 5 K V C va pie a A^(fC

luo'ng ung vol qua trmh khu *" va , va phan anh sir cung ton tai eua hai dang monovanadat biet lap (VOx) va pol\'vanadat (|V()x|) Dieu na\' cho thay: Khi la lam ham lugng V^O^ thap \ a o mao quan MCM-41 da dat ti'ang thai

don lop, V;()>l6n tai a dang monovanadat biet lap (VOx) va poKxanadat (| V()x|) , duge phan tan deu trcn be mat ncn de bi khu, la hai dang eo kha nang lam xue tae

tot cho qua trinh oxi boa

Doi voi mail Pl/MCM-41 khi dua Pt \cn chat mang, tuy thuoc vao ham lugng Pt

ma la eo the ihu duge eac dang oxit platin dan lop hoac da lop

Khi \irgt qua trang thai don lop, xuat hien dang \ o dinh binh \ a pha tinh the eua

Pt

30

K : 0 S^rM[(Auj- IPn

I linh 3.6: Gian do TPR ciia Pt/MClVl-41

Tren gian do phan tieh TPR cua mau Pt/MCM-41 chi thay xuat bien mot pic khu

sac nhon Theo Javier va cac cong su | | thi ed the day la qua trinh khu platin

l u d a n g P t ' > Pt

.11^-Mau vat lieu bat dau bi khu tai nhiet do 350 ( \ ket tbiic tai nhiet do 448 C Co the

nhan thay rang, sir khu Pt d\cn ra trong vung nhiel do trung binh Dieu na\ duge li giai la do Pt khong ton lai a dang tinh the ma la a dang nano, kich ihuac nho nen

nhiet do khu khong cao Ben canh do ta cung tha}' chi co mot pie khu duy nhat trcn gian do TPR, ehung to trang thai phan tan Pt dong deu, on dinh Khi Pt phan tan khong dong deu, trcn gian do se xuat hien nhieu pic kbu ung voi nhieu qua trinh khu khac nhau: P t ' > P t " , P t ' - > Pt

Nhu vay voi hinh anh IPR thu duge da chung to cac hat Pi long hgp bang phuo'ng phap tam da dat dirge kinh ihiroe nho, nano va do phan tan dong deu, on dinh

4.2.4.Phuong phdp ehup anh hien vi dien tw truyen qua (TEM)

Chup anh hien \ i dien lu trii> CMI qua cung la mot phuang phap cho phep nhan dinh

\i be mat eua \al lieu