Phm ta mt bi bo tru tng

Mt chin lc d di c pht trin cho s tng hp ca H-TS-Au

microspheres (MC) vi doubleshelled
kin trc rng v ph 5 nm Au ht nano (Au NP). Cc th tc lin quan n vic
tng hp
cc phng php sol-gel k mu h tr cho vic chun b ng phc hollowin rng
th bc
H-TS MC vi TiO2 / mSiO2 nh lng / v, v cc phng php lng ng kt
ta c o
qua trung gian vi Au (en) 2Cl3 tin cht cho xy dng ti ch cc k n nh Au
NP di mt lowtemperature
gim hydro. Vic tng hp H-TS-Au MC c c trng bi TEM, SEM, FTIR,
XRD, BET v UV-vis hp th quang ph. hot ng xc tc ca H-TS-u c
nh gi bng cch s dng gim
4-nitrophenol (4-NP) thnh 4-aminophenol (4-AP) bi NaBH4. Kt qu chng
minh rng H-TS-Au MC
s hu mt kch thc ln kin trc i v vi cu trc nguyn vn cao v mnh
m, m
hiu qu c th hn ch rt nhiu nh Au NP v hn ch chng t thiu kt hp
thm ch ln
tip tc nung 800 C. Do cu hnh cu trc thun li v hip ng
tc dng ca v i TiO2 / mSiO2, MC H-TS-u c chng minh trin lm
xc tc ng ch
hot ng v tnh n nh v bo tn cc hnh thi cn nguyn vn sau 6 gim lp
i lp li ca 4-NP.
1. Gii thiu
Cu trc vi cu rng a v (MC) c
kch thch insterests to ln v hp dn ca h
ng dng tim nng trong cc lnh vc khc nhau, chng hn nh cm bin, nng
lng
lu tr, xc tc v phn phi thuc [1-3]. cu trc iu ch nh vy
cung cp cc c im cu trc c o v c tnh hp dn
vi din tch b mt ring ln hn, ti trng ln hn, gim
khng khuch tn v multifunctionalities nng cao, cho thy
li th vt cht ng k i vi singleshelled thng thng
cu trc nano rng [4-8]. Nh vy, nhng n lc ng k
c dnh thit k phc tp rng a v
cu trc vi ti u ha / propertites ha hc vt l cho c th
cc ng dng. Mc d tuyn ng mu min ph bao gm ion

trao i phn ng, Ostwald chn v qu Kirkendall c

t c s ch ngy cng tng trong vi nm qua,
tng hp h tr da trn phng php mm v cng mu l vn l mt trong
nhng phng php hiu qu v thun tin nht xy dng cc kin trc ny vi
thnh phn ha hc v du dng ni definedshape thatdirectly tha k cc mu
[1,8-11]. v V d, Choi et al. bo co mt phng php n gin thit k mt
doubleshelled nanostrucutre silicate km vi ZnO2 nh mu [12]. Rattle loi bngtrong-bng V2O5 MC rng vi nng cao lithium thuc tnh lu tr c chun
b s dng hnh cu cha carbon mu nh cng [10]. Co3O4 Multi-v MC rng
vi PVP nh mu mm cng c ch to [13]. Mc d c s linh hot ca n
v hot ng n gin, vn cn nhng thch thc ln trong mu da trn tng hp,
pht sinh t cc cu trc vn khi loi b cc mu v chun b kim sot thng qua
mt qu trnh khun mu d di. Au NP vi kch thc siu nh c tm thy
trin lm v cng tnh cht xc tc cho qu trnh oxy ha u i ca CO, s
thay i kh nc phn ng, hydrocacbon t, xc tc v mi trng vv [14-16].
Tuy nhin, nng lng b mt cao lm cho h d dng hn tng hp hoc hnh
dng thay i trong phng php iu tr khc nghit v cc phn ng xc tc, kt
qu l gim ng k hot ng v chn lc [14,15,17]. gii quyt vn ny,
nhiu c lp
nanoreactors c thm d hn ch cc kim loi qu tc. Trong s , b mt
ng gi bng v oxit xp vi ni tht rng c xut nh l phng php
hiu qu, m c th lm tng hm lng Au-ti trong mi nanocatalyst cho hiu
qu xc tc cao hn [18,19]. Hn na, cc mao v nanoreactors hi cho cc loi
ha hc d tip cn hn n cc trang web hot ng v ni tht rng iu ch c
th lm giu s hin din ca h trong cc l rng, do c th tng tc xc tc
phn ng. c bit, nanoreactors rng a v vi kim loi qu tc kt vo ng c
lp v rt ph bin trong nhng nm gn y [4,5,17,20-22]. Cc embedment
u NP vo cu trc nano rng a v vi nhiu thnh phn v s to ra nhiu kim
loi-kim loi tng tc oxit v, dn n mt tc dng hip lc mnh m v do
ci thin ng k v hiu sut xc tc [5,21]. V vy, thit k hp l ca kin trc
rng a v tin tin l ht sc quan trng i vi s giam hm ca siu. mn u NP

vi hot ng cao v n nh nhit nng cao, y thc hin chc nng xc tc

ca h
Trong tc phm ny, chng ti m t mt chin lc tng hp mi ch to Aunp i v MC rng vi cao cu trc tnh ton vn v mnh m bng cch kt hp
cc k sol-gel phng php mu h tr v duy nht lng ng kt ta phng php
s dng Au (en) 2Cl3 tin thn l trung gian ha gii. cc th tc c minh ha
trong hnh. 1. u tin, resorcinol-formaldehyde (RF) lnh vc lin tip c gi
bi lp titanic, nha RF lp v silica / lp CTAB to thnh a v li-v
composit (RTRS). Sau , vic iu tr nhit c tin hnh ghi ra cc mu hu
c trong composit RTRS cho cc rng TiO2 lng / mSiO2 v MC (H-TS MC)
vi doubleshelled kin trc. Trong khi , mt tin cht vng Au (en) 2Cl3 l
chun b v c nh vo H-TS MC qua mt ha cht t qu trnh s dng cc
phn ng deprotonation ca ethlenediamin ligand trong iu kin c bn. Cui
cng, nhiu nh Au NP c in-situ hnh thnh trong kin trc H-TS do nhit
thp gim H2. tt nht ca kin thc ca chng ti, cc kim loi qu tc thng
c tr nm trong v bn trong ca MC i v thng qua mt lp-bylayerdepositionprocess.However, chng ti bt u ch to withthe ca cc i
v kin trc rng ca mt mt bc nha lu k qu trnh nung v sau tin
hnh cc postencapsulation Au NP bi mt qu trnh gim ti ch. Ngoi ra, bn
cht ca phng php lng ng kt ta c qua trung gian vi mt tin vng
cation [Au (en) 2] 3+ thay v anionicAuCl4 - cho vic chun b n nh cc k
nhit c h tr Au NP. Nh vy d di kt hp chin lc tng hp khng
c bo co. V nanocomposites u da trn tng hp trng by mt ni bt hot
ng xc tc v c th dng li gim lin tip 4-nitrophenol (4-NP) 4-aminophenol
(4-AP) bi NaBH4.
2. Thc nghim
2.1. ha hc
axit chloroauric (HAuCl4 3H2O, 99.9%) c mua
t Sinopharm (Thng Hi, Trung Quc). Ethylenediamine (en),
Cetyltrimethyl amoni bromua (CTAB) v 4-nitrophenol
(4-NP, 99%) c mua t Aldrich. Tetraethylorthosilicate
(TEOS), resorcinol, formaldehyde, tetrabutyl titanate (TBOT),
amoniac (28% trng lng), acetonitrile, v ethanol l tt c cc phn tch
lp, v mua t Sinopharm Ha cht thuc th Co., Ltd.

nc ct s dng trong tt c cc th nghim. Tt c cc ha cht l

s dng nh l nhn c m khng cn tinh ch thm.
2.2. Tng hp cc lnh vc RF keo Resorcinol-formaldehyde (RF)
hnh cu c tng hp thng qua phng php m rng Stober ca [23]. Tm
li, mt hn hp cha ethanol (8 ml), nc kh ion (20 ml), amoniac (0,1 ml,
28%), resorcinol (0,1 g), v formaldehyde (0,14 ml) l khuy qua m. Sau , s
kt ta c ly tm ra ngoi, ra bng ethanol v .
2.3. Tng hp RF @ TiO2 MC Cc lp titanic v nh hnh ng li trn mt cu
RF l chun b bng cch s dng phng php m t bi Liu et al. [24]. Thng
thng, cc dung dch keo RF trc (5 mL) c phn tn bng siu m thnh mt
hn hp c cha amoniac (0.2 mL, 28%), ethanol (15 ml) v acetonitril (8 mL).
Sau , mt gii php chng khon ca TBOT (0,5 ml) trong ethanol (5 ml) c
thm tng git. Sau khi khuy 6 h, cc cht keo c ly tm v ra vi ethanol
cung cp cho RF @ TiO2 MC. 2.4. Tng hp RF @ TiO2 @ RF MC Coating vi
lp nha RF polymer c h tr vi cc ng b mt cation CTAB [25]. Thng
thng, khi chun b RF @ TiO2 MC b phn tn trong mt hn hp cha nc
kh ion (50 ml), amoniac (0,15 ml, 28%), v CTAB (0,02 g) di sonication trong
30 pht. Sau , resorcinol (0,16 g) v formaldehyde (0,28 ml, 37%) c b
sung lin tc, v trng hp tin hnh qua m di khuy lin tc. Sau , RF @
TiO2 @ RF MC thu c, thu thp v ra sch bng ion nc-ru nhiu ln.
2.6. Tng hp cc H-TiO2 @ Au @ H-mSiO2 MC Au NP c ti ch ch gii
hn vo H-TS MC thng qua c o phng php lng ng kt ta qua trung
gian vi Au (en) 2Cl3 tin cht. u tin, Au tin cht (en) 2Cl3 c chun b bi
phn ng ethylenediamine vi HAuCl4 4H2O dung dch nc (1 mL, 0,24 mM)
v mt gii php nu minh bch c hnh thnh. Sau , tinh khit Au (en)
2Cl3 ta c thu thp bi cc ra vi ethanol severaltimes v invacuum
thendried. Cc hp cht driedpale vng c redispersed vo nc kh ion cung
cp cho mt ti Au (en) 2Cl3 gii php (3 mg L-1), trong gi tr pH c iu
chnh 9.0 ~ 10.0 bng NaOH (1 M). Sau , H-TS MC (20 mg) l m mnh siu
m vo Au (en) 2Cl3 gii php, tip bi qua m t tnh khuy. Cc trung gian thu

c (K hiu l H-TS-Auen MC) c ra sch vi nc ct, lm kh trong

chn khng, v cui cng c iu tr bng tinh khit hydro (99,99%) chy
150 C trong 1 gi, kt qu l sn phm ru vang H-TiO2 @ Au @ H-mSiO2
MC (k hiu l H-TS-Au MC).
2.7. gim xc tc ca 4-NP Vic gim 4-NP 4-AP c chn l mt phn ng m hnh
nghin cu hot tnh xc tc v s n nh ca cht xc tc. Tr thnh, 4-NP (30 L, 0,01 M)
c trn vi dung dch nc ti NaBH4 (0,5 ml, 0,25 M) v nc kh ion (2 ml) vo mt
cuvette thch anh, theo sau bng cch tim cc cht xc tc phn tn (80 L, 0,5 mg mL-1).
Trong ton b qu trnh gim, nng cc cht phn ng 4-NP v sn phm ca mnh 4-AP c
th c xc nh bng quang ph UV-vis. i vi cc bi kim tra th ti s dng, cht xc
tc c thu thp, ra sch vi nc ct v sy kh cho chu k tip theo.
2.8. c tnh knh hin vi in t truyn qua (TEM), phn gii cao knh hin vi in t truyn
qua (HRTEM) v chn in t khu vc nhiu x (SAED) c tin hnh trn mt knh hin
vi JEM-1230. knh hin vi in t qut (SEM) hnh nh c ghi li trn mt JEOL JSM-5600L
SEM c. Nng lng phn tn tia X quang ph (EDS) c s dng phn tch thnh
phn mu. tia X nhiu x (XRD) m hnh c ghi li trn mt Bruker D8 trc Nhiu x
(c) vi bc x Cu Ka (= 1.5406). Bin i Fourier hng ngoi (FT-IR) ph c ghi li trn
mt BRUKERALPHA FT-IR quang ph k. Phn tch nhit trng lc (TGA) c thc hin bng
cch s dng Rigaku ThermoPlus TG8120 h thng vi tc 10 C min-1 di khng kh.
UV-vis ph l thc hin trn mt Shimadzu UV 3600 quang ph k. nit isotherms hp ph-gii
hp c o trn cng sm cng tt nm 2020 (Micromeritics, M).
3. Kt qu v tho lun 3.1. Hnh thi v cu trc Cc hnh thi v kch thc ca mu khc
nhau trong tng hp qu trnh H-TS-Au MC c nghin cu bi cc k thut TEM v SEM
v kt qu c trnh by mt cch r rng trong hnh. 2 v 3. Monodispersed RF lnh vc
keo vi kch thc ca ~210 nm l chun b thng qua s trng hp ca resorcinol v
formaldehyde (Hnh. 2a). Cc RF @ TiO2 MC thu c bng phn ng sol-gel ca TBOT
vi hn hp dung mi c cha ethanol, acetonitrile v amoniac, deposite mt ~60 nm lp
titanic v nh hnh dy trn b mt ca mt cu, RF (Fig. 2b). sn Sol-gel ca RF @ TiO2 MC
vi lp nha RF cho RF @ TiO2 @ RF MC c h tr bi cc hot ng b mt cation
CTAB render b mt t tiu cc tnh [25,26]. Do lc y gim, RF nha polymer c th hp
th vo RF @ TiO2 MC v to ra ni difined v vi ~60 nm dy (Hnh. 2c). Vi ng lp rp
CTAB v TEOS trong phn ng sol-gel, ng phc lp silica mao vi ~100 nm dy l hnh
thnh trn RF @ TiO2 @ RF MC cho nhiu v li-v RTRS.
MC (Hnh. 2d). Sau khi nung nhit, cc mu hu c trong RTRS MC b t chy ra ngoi,
ni cc khoang trung ng v khong trng xen c xy dng cho cc rng i v H-TS
MC vi TiO2 / mSiO2 nh lng / v (Hnh. 2e). Hnh nh SEM trong hnh. 3c Validated H-TS

MC c xy dng bi hai hollowin rng c lp MC ng sn c phn tn tt, ni su rng

trung tm v khong trng xen c th c r quan st. Bn cnh , c cu phng v cng
c xc nh bi nhiu MC nt trong nhng hnh nh inset phng i. cc bn ngoi SiO2 MC
c ~820 nm ng knh vi ~90 nm trong dy v, trong khi TiO2 MC bn trong c ~420 nm
ng knh vi ~70 nm dy v. Cc kch thc xen rng l ~80 nm, trong khi cc kch
thc bn trong rng khong 230 nm. TG / DSC ng cong cho RTRS MC trong hnh. 4a tit
l mt giai on gim cn ch yu t 250-550 C, chim khong 42% trng lng. nh DSC
lin quan gn 324 C, cng vi cc cht ta nhit, ngh t hu c bao gm c nha RF v
CTAB c ng k xy ra nhit nung bu (500 C) cho H-TSMCs.Noticeably,
themagnifiedTEMimage (Hnh. 2f) verifiedthe knh mesopore t hng ring bit ca v ngoi
mSiO2, m ban cho cc khong trng i v rng vi kh nng tip cn cao i vi cc cht
ha hc.
Mt khc, Au NP ch gii hn vo cc khoang ca H-TS MC c ti ch xy dng thng
qua duy nht lng ng kt ta phng php s dng tin cht Au (en) 2Cl3 l trung gian ha
gii. Trc khi s hnh thnh ca tinh Au NP, cc cation vng phc tp Au (en) 2Cl3 hp cht
availably thm kin trc i v v bin i ha hc trn lng mang in tch m v v H-TS
MC thng qua mt qu trnh phn ng ha hc t, c lin quan n phn ng deprotonation
ethylenediamine ligand di c bn iu kin [27]. Au tinh (en) 2Cl3 cht rn (vng trn bng
vng du gch ngang) ang ni ln trong H-TS-Auen MC c quan st thy trong hnh. 3a,
khi s kh H-TS-Auen MC c redispersed thnh ethanol chun b cc mu TEM. Bn
cnh , vic phn tch EDS (Hnh. 3b) r rng xc nh 8,10% trng lng ca nguyn t N
pht sinh trong H-TS-Auen MC, hn na xc nhn vic c nh thnh cng ca Au (en) 2Cl3
tin cht vo H-TS MC. Trong gim hydro nhit thp, nhng goldprecursors
weredecomposedandconvertedintonumerous Au NP vi kch thc trung bnh 4,42 nm thng
nht hnh thnh trong H-TS MC, cho sn lng sn phm cui cng H-TS-Au MC (2g. Hnh v
ti). Cc u NP c nhng chc chn trn phn v bn ngoi bao gm cc b mt bn ngoi /
bn trong v cc knh mesopore, v phn lng bn trong t cc kin trc rng i v. Hn
na, khong cch interplanar cho ra li hin th trong HRTEMimage fromFig. 2h l 0,235
nmcorresponding n (111) my bay trong m hnh SAED, trong ch ra nhng mt i lp
phng tm cu trc vng vi tinh cao. Bn cnh , n cng c th c xem trong hnh nh
SEM (Hnh. 3d) rng sn phm cui cng H-TS-Au MC cho thy phn phi tt v duy tr cu
trc nguyn vn di truyn t H-TS MC. Cc EDS lp bn kt qu (3e hnh. V f) illustated
m H-TS-Au MC s hu cc yu t Au mi vi con- cao