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Joum[l.~ of N on-Cryst u :nille Sol ids 315 (200:1,) 2.97·-301

Nickel alumina composite aerogel catalysts with a high nickel load: a novel fast sol-gel synthesis procedure and screening of catalytic properties

S, Krompiec <I, J. Mrowiec . -Bialori ", K, Skutil '\ A. Dukowicz tI, L. Pajak c~

A.S. Jarzebski li,b,OI .

ri Fac!i/I;\' orClwmrSJr~', S:UIJ$'i'(W 1J11{~~r ~IIJI oj i!i,'lw()/ag)', "4·1.00 Gliw!"t!. Ks, .~'1. Slr:lli/jr 7. l'ul(j!ul b Institufe of Chemictl/.£ngiJ7ecriJlg, I'olish Ikademy of Sciences, 44:-JOO Gliwic.e. J1aiJ'l;kll S. Poland

Q Slle.rln" Um'l)usil r, .l1I$IIIII/.(: of I'h)'sl;::~ mltl (:hlJlnis/'f,11 oj'MI1IlII. , 4(}'041 Ku!"w{te. B~;Ik01va 12. (I:olaml

Received 23 October 2001; receililld in revised Conn 16 M:'l)/ 2002

.. \,bstr&;t

:Nickel-alurnina compcsitc aerogels wirh large nickel loadi;;g were synthesized using ,ill novel eomplextng agentassi$l«1 sol...gc1 prceedure to obtaln :malt'ri'l.i.s Jispluyinig v~ry :Iar.s~ and. open internal SUl'facl;l area,. ,easily aecessiba for large molecules and demonstrating excellent catalytic properties. Thty were tested in the following reactions: (i) hydJ'Q,!Y}lUltkm of propenQ and l-bmcae, (il) methanizatlon Qf carbon dioxide, (iii) isometization of l-butene, (iv) dehydrogenaslon of cyclohexane, ,(v) conversion of equimolar mixt1H~ of CO and NO to CO2 and Ni• Hill eenversions find 100% selectivities were ebialned in reaenens (i), Oil; iv) and (\!) and 311. equilibrium composition in reaction (iiD, These catalysts showed no pyrephorie activity on e'x.posifiS to a,mr even at Ni content as, large as, 50 wt%.

© 2003 Bl~evier Scienc~ B. v. ,All righi's reserved,

il .• Infrodu:ction

The ni:ckeI~basGd entalysts are of considerable industrial interest, especially for reactions such as hydrogenation of arom2lti,cs and unsatutarad hydrccarbons, COi!CH,j reforming and reduction offunct.i,onalgronps [1-5], and alumina is most often. used as nickel support, Quite often these

"Cor:responding a(li~o:r. Tel.JfaN: +48-32 231ID:HS. l.'~'ir11l (1ddr~51: ~.j!l.~~b@it(:h,gl \l\loo:pl (A.D. Janobsld).

catalyst conraiu a considerable nj'ckel load, wel] In excess of W% (w/w) [2,5], to ensure a proper surface density and s,izQ of metal clusters. F owever. carbon deposition over the metallic and the !lIcid sides of the support and NI partie.le: loss al1~ sirltering a.t high temperatures, facilitated by high nlekel loadings, lead to catalysts deacdvaden, 1'1 is wen documented that this 'carbon depositiu'" decreases with the increase ill base strength of the Gal rIb' ts and tbe addition of lantanium, rnagnesium 'Or molybdenium oxides has been found pa:rticulaJ'l)r useful to diminisll this ereOt [3;6 7],

00'22· O~310'3t$ • SIlC (,h)1\1 rnauer «') 2003 EliiQvilil' ~ience BY II rights reserved. f>H; 8(')0.22;· ~ 093{02}O 1!.509-5

But th wllakor sttcngth ;of surface acid centers of '¥~PI~OJ' obtained using the sol-gel method titan, ...;,f the normal 'OIl~S, plus stfOl1gel' inreraCiio~) between NiO and support, found in the sol-ge l rnateriala, was shown [8] to bequite effectiveto restrain carbon deposifion lmd theloss and! si:uering of nickel. Yet, under the reaction. conuh.bns 8500 0c) ibe y·AJ 0 phase tended to corveninto a,-Al10J, which resulted in a cOluidttabIo surface area decrease. Further unprovement in the thermal stability properties of ,/-.4.1103 could be obtained [8,9] by making use of 'the eomplexing al!:ent,·!~:ssis~'ed fsol-gcl mj,),lhod, which again demonstrated aconsiclerable porenliiiL or the sel-gel route to give efJ'ecti've: catslysts,

0 •. 1. the whole, aerogels appear io 'be quite attl'actiVi in catalytic and fI.bsorpl~ve applicaticus, due to their unique textural and morphological :propeliics [10-13], More nickel-alumina aerogels, prepared in two different W<l)IS, [14-l6].. have ben shown '10 be very eliectiveand stable caialyas in reactions of ~~formillg of methane and in the .liquid-pl:ul.schtydroge,na~ion of 'benzopheu.unc aod soybean oil. Yet, the preparation methods employed by those authors made no explioil 'lise Qf 'rije eom,p,lex:illg agent assisted sol-gel approach. Since the gelation of aluminum hydrm:ide occurs rapid I,)!, it is not easy to' obtain a uniform gel witb aluminum and the metal. Morem'~r,a continuous vigorous stirring of the reaction mixture, nCOOSS!liIY 1,0 obtain a. homogenous systern, precludes formation of a monolithic gel. A common strategy 'to tackle thig problem is LO slow down precursor's reactivity either by using a strong, rnineralacid [14;16] or by the use of chelacing ligands such as ethylacetoacetate (etac:) [17]" The 1 alter method, perhaps superior [0 the former OfH~ 1A>,1S more Lmtorollghly studied by Babonneau et al, (18] for the titania-sillca system, and las been found veryuseful togive high perfonnance aerogel catalysts with a I~rge density of Ti~O-Si s'"e~ U9,JO]. Th~s; it inay be of i:nt()lrest to ;inv!)stig:~rte pOlenlluls. of Ihis pre·pal'oi;, COIlO~-PI. to obtain a, new type of the highly porous tlickeljilumin,it ciludjlsts: ln the: following wei report the results of' preliminary investigacions addressing this is ue.

Four niokel,~a!l)!mil1aaero.gel, catalysts were prepared using nickel aceta.te. Nt fie), and alumiDum sec-butoxide, Al(OBu'), to. obtain samples with a uQmi.!llll15, 30! 4.0 or 50 wt% or NicQnt~!u in dry material (Ni + ;\12oQJ). The preparation of wet gels 'was as follows. First AI(OBuS)l W<lS mixed with etae under nH rogefl , in a glove box), either in 1: I or 1:.2 molar ratio, LO obtain two forms of' a .no(lifh~d alunsinum precursor, The firsl (l1')C was used to 0 btaia samples with 15% and ,301% of N i ( NIlS and Ni30; l:esl,octively) Rlld tile second one to 'synthesize Ni40 and Ni;iOr, Next the reactlon mJuure with the crli~ral1 eompositien AI:PrOH:l-f20:NHJ, = ]:10: 1 0:0,5 (mo-lar basis) was prepared in two steps. The procedure was aga:in slightly different for samples Ni15~Ni4iO than for Ni50. For the former one-s, in rbe first step half ef the lolal pl'opanol; a modified alumimun precursor and Ni(ac) were mixed for 10-20 min under reflux at 343 K to obtain a cIeRI' solution I(A) whidn wa cooled to room temperature, Then solutlon B (half of propanol + water + NH3) was slm Iy added to A undo.' vigorous siirrilll], to obtain a clear green sol, which gelled in about 2; min (samples N(IS and Ni30) or ill ~80 min (Ni40). Solution A used in Ute synthesis of Ni50, was prepared as ~OUClWS: Ilfst all PfO:I')(U)ol and Nilac) were mixed under reflux at 343 K until a clear solution was obtained, ana then this solution was cooled dOWll ro rO,M1 teml~er~l,lI:roC ~Htd a Mllodi·fi,ed aluminum precursor was added under stirring, AJterl,\!f!.rOg soluti.on 13 (water + NH,~) was added. 1O solution A under stirring to obtain ill clear green 50.1, which gelled in about 15 mill, As call be inIerred fr 111 the synthesis protoco(.)Js we used a dif· Iereet approach in the case of' Ni.40 and Ni50 from that used to obtain Nil:5 and Ni30. Indeed when iii modilied aluminium precursor of the first type ('1:1) was used In the I'i'l:pa.!,a~iOl) of Ni40 and Nf50, solllltiQnA was alwa'ys; clondy, which precluded as use in Ille further synthesis steps.

All wet 1;<:1$ were ag@d f,or 5 dil.yA at t'Ql)lJ1 temperature and then Were dried for'8 h. in a ;streHl\) 01" s.up$.fcr.itical carbon dio ide (3.33 K,

I ~ I1Pa) as <1cscTib~cJcal'lie;F (21). Pristine aerogels we,nal!y dried at 383 K for 5 hand were sl(J;ed in a desiccator.

hior 1,0 eharaeterization all, aerogels were grcnud into powder and then. were dried again at 3K3K fbr 1 h. This, powder was biter subjected also to tsermal treatmentin air, to achieve 823 Kin ,5 11 and was caloinGd for,~onal 5 h at this ternpec!ture. Nil.5alld. Ni50 aerogels were also treated Ill~1 stream of b>'droge:n, under 0.1 MFa al 773 K for:3 h, to obtain reduced materials, Catalytic proXll'ties (If Ni50 were later examined ill a numlJeroftestreactions" On the whole 0,.360 g of an acdie form was. obtained from 0,650 g of fresh snrlrple,

'Iexrusal prcperties, i.e, specific surface area, SnEll, total rnI!SOl'QI'C volume, Fr, ~lIid por~ size dis tribution (PSD) were determined the ni- 11"()~J1 adsorption isotherms fit 77 K, .recorded USil1@; a MicroI.1l1el'iti,c$ ASAP 2000 instrument,

lhe overall phase composition of the samples was determined by X-my diffraction (XRD) usi'l~g a Psilips instrument with Cu-Ka radi.JJ.ion,

2 .. '2, Screening o/wudJ',t i c proper lies

lEvai.uatiol1.of the catalytic peeperties of NiSO aeregel was performed ill the following reactions;

• fuydrogenatiol] ofpropeneend l-butene, .. metiulnizalh,n of curbon dloxide,

• i:!om~tii?;atIQn Of I-b'u,~ej}~~

• dehydr(!gl';natiot~ of cyo!Qbex.enc,

.. conversion ,of equilnolarmlxture CirCO and NO to CO~ and N 2'·

Catalytic tests were carried out in a How quartz reaetor (S ¢Jl1<\ 14 mm Ld.) uSing ~pp1"o);illlaroly 0.65 sofa catalyst preeurser, The reactor cfHlJ}Qut was- analyzed usieg two on-line gas chromatographs, One ac was equipped wjth FID~nd two columns: a packed column Om, deactivated AI.20~) and H ca:pillru)I colum» (15 iii, Tr·QPLOT), for the derenninationof hydrocarboos. The sec" (l'!]d G~ had TeD @;udi also two packed eolumns: 2, m, 5 A molecular sieve and 2 m, carbosieve, lor detection of inorganic compounds (Ieb: H!, al, COl, CO), The reaetorwas placed in: an lsotherma!


(67'< 1 K) s~cliofl of a. three-sectional electric Jumace, The reaction temperature was monitored by ~. th~I'irlOCO\llplcomb()ddcd in. H ql,umztube ~Hld placed in the catalyst. The f-eed gas mixtures were prepared in special I:IQltle$fUld their ccmposiuon was determined d.uomarogr!'lphically prior to experlmeats, AIl test reactions, except for the conversion 01 CO and NO, m~dc, us~ of the same catalyst sample, cooled down in 3J stream ofniIroglilo <373 K octwCl!C11 tbo tests and effectively cut offfrona the amblent, The reaeticas were carried aut in thesame Qrdel' as given ~bove~nd llJe catalyst was reaetivaredin a stream of hydrogen (623 K, $ h) onlycnce, before thadehydrcgenatton of eG'(periments,. Typically each experiment lasted 2-4 h, except for the reduction of NO Wllich was ,carried om COr' 6 I'i arid which made use of another catalyst sample redueed as describedabove, Condldeus of the spednc reactions were as follows;

• Hydrogena!.ion of propene and l-butene W8.S carried out ill the range of 3J5~73 K with the catalysts load of aboue 7.5 or 14,9 ml/kge,.UlI h.

• Methasrization of carbon dioxide (3.6 'iloL% in .hydrQgen) was ca.rriedl. out. in lhe temperature range of 523-623 K with the catalyst load of about 7.1, 14,8 and. 28.4m3Jkgh.

.' isoJ1:],erizadon of .I-hm.ene (0"87 VOl.%1 in nitrogen) was carried 'CHIt in the range of 41947~ Ka!lQ the eatalys1.1olld was aho!lt 7'.34 mJ/kg h.

•,geJi~.tiQ~ or eYGi!Qhexent to obtai!1 be:lleeneplus bydrogel)WlllS carried ,out ~t temperatures 513 and 62.3 K, cat!"\'lyst lo~d was ~1,3 m~1 kg and nitrogen saturated with oyclohexene vapor :.11 28,3 K (4. i \101.% or cycl{)hex,(lll~o) was a substrate.

• Conversion of NO ,H)d CO was hwestiga~¢dro.r the feed! gas mixture co:mpQscd Of 2,50% CO, 2..50% NO and. 95~% He (applied to facilitate tbe chrolu~uogmphic :Rli!llysjs) in the ruuge of 473-573 K with the catalyst!; load 0[6.7 m.!fkgh.

l. Re.!lults

As. expected, all fresh aerogels dlspl.ayed very ~~Hn\ct:ive' texture para11.i.eters i.e, pore volume, 'I~,


S. Kr(lll!pif~ 1:1 (II I JI}!lrIwl of Nml.('rp-wllilll' S(JJids .J1S (300J) J~7-J03

and sl.J'fa.ce areas, So _1', with somewhat lRll!,or values nown by the samples widl the lower «40 Wl%J :I:-kel contem (cf. Fiss, I a.!1.d 2). On the: whole nese values ate similar to or better than those "nickel-alumina aerogels reported before,

,s ex cted, calcinationappeared to have conside:r:a~ effec~ on both the surface area and pore vohnm:ilin cenrrasr to' tho reducuon PIi'\)CCS'S w:hich. affect these quantities much: less (cC data rotNj J' and Ni.SO ill Figs, I and 2), at least when

5.5 - s,e II.S

;.S: '\.0 '!'l

& 3.5 ~

'~ 3,0 -:s

,. 2.~


j:i., .HI

II,S 11.0



-1.- .fresh s.ampJes

-.-IIf1cr ealelnarien

liner ruduclion.

". ..


]0 40

N! lOld Iwt%1


Fig, I, 'IIIcsoJjiQt"¢ vo~"mG j.. ~.!lr08;els will! dif!'Qr~:fl1 Ilickd ·comiml, Lines are guides 10 the eye oilly_ Error bars « ±O.05 'ciIi~/m p;o;)\,cd 10 be SIi'JaJler than th~ symbols and for this reason Ib:y \V<lte Qml!~~d.


-:11- fi'<:.>M ~~ili11l'1C!S

-'.- u!:'tc:r ealeluation

-*- alll:r rt;."thll:tion





Ni IUHu II"t%1

Fig.. :2. Sp,edflc surface area in aefOge~ with. di.ffereUI nicke 1 ~mncill. ILin~~ nrc suklc~ 10 1110 e)'o onh'.

carried out ~u temperature ~l~ loy as 773 K, This trend, consistent with earlier observation ~21 can atsc be. soon in Fig. 3 showing rhe evolution or fSDs il} Ni.50 !ulI'Qgel after calcinatiorr, reduction and a series of test reactiens .. The XRD patterns of fresh aerogels, di.fTered dep~n.ding ,ot] (he nickel content (Fig. <Ii). ln Ni l5 only rhe presence of NiO was dCLi!C~ed in addition 10 amorphous ,~dun.linfl whereas in Ni50 the peaks pointed to the presence of AIOOa CaldtHlti.on or Nl 1.5 aerogel resulted in the formation of NiAiz04 spinel, which was not detected, in Ni50 where crystajline NiO phase

OJ.!! ...--------~~~~~~".,_."





,=0 0.20


Ii! ~



Q "C

;> 0.10


Q.ns E

().OO==~ 1



P,Ol"e dis:m.eter [!lim I

-ig. 3.1'80 in ii.1!~h NiSO sample (I), alter reduction e2l and a series (If ;esl reactions ~·3).






40 50 (jO


Fig. 4. X'RD jrl1l\l)rll$ rwm frCib. HilS ~md NiSO llerogcL


co d I)e seen instead (Fig, 5). The phase CQIT),J;lQSillll1 of both samples changed slighsly after redlJQ.ion;. :finc p!lr~.i.chl~ of nUltullic llick,GI were det.~c:ted in both aerogels, in addition to the phases alr(1!dy pOOS(lJ)l in the ealclned samples {Fig. 6).

(·ala.lytic ICS.iS cleady demonstrated that Ni50fleJogei is very active ~nd selective ill



:\0 ·4~ 50 6(} '1Q



Fig. S., )iRO p,IUetris Ct'o}m rili 1.5 <li!!d NiSO ~i~rog~ls il!!icr- C<l!~ilJ,a;iQtln.! &23 K.

~-iII!Q ~-!'ol

~ ollilAl,!),

• ~ ~ 00 'n _ ~


Fig. G .. X!l:O patterns fimn Nil 5 and NiSO :n~rogcls Ilfwr red\l~llioll ai '1n K.

Table I

COltdyUo IJlrtlP!!tt~~s QfNiSO ~l1J1!1\)rt.!.

~U 1he reactionsstudied and .. eq1.ulily important, it showed no pyrophoricaclivlt)' on exposing to air nft:er cUschnrgll1g from the reactcr. This is due to the prevalent presence or nickel i;1l an oxidized fo:rm. I u b oth byd I\()ge nation reac liorl s con vcrs ion of propeneaud J-buteae and selectivity to propane and l-butane reached ]00% in ~he wtvoic range of tem.p~ral.~m~s (Table I). In the merhantaation reaction under catalyst load of about 7_J ml/kg h full. conversion of' carbon cii.oxide Wl~S o~lili:ned only ~Il temperatures about ,623 Kalld decreased with temperature decrease, as shown in Fig. i; unlike selectb",ity W methane equal about 100% irrespeclive Qf the reaction teroperaturc. R('lsults of the J -bUMID.@ isom.~riza.tjo!~ srudles are shown ill Fig .. 8. Noteworthy is good. agreement of experimental dMn (filled symbols) obtaineollt 471 K wlth Ute eq uil ibrium composi t io 11 (open sym b ols) for this system at 4i3, K reported in [22,], aad a slight departure of experimental data from ~be- e<jl.liliDrhlm COi.tr1positlClnS observed at. 423 K. The-se results ind icatetha.t. the catalyst i 5~(\,t.i vein uh~ reactl 011 of a double bondmigration (If I-butene, yet no s,k,oletal isomerization. (~o isobutyl~ne) was observed, The aerogel cat,aJyst proved to be very effective in Uli.~ dehydrogenati.on reacrlon of cyclehexene to benzene and hydrogen (Tablel '). Conversion oi cyclobexaaewas full at both 623 and 573 K With benw,l~e boins the sole detected Ity. droearbonic product.

lluef~slitigly el~ougli;, Ni50 b~s alse proved capable mo alford a, qeantitative conversion of CO and NO fll 473 and 573 K to obtain l1iU"Qgen !Uld carbon dioside a.s the (july products, The content of NO was not determlned clu;o:lllat-ogfaphic-allll,. bu~ it was calc:1.1b\ted [l'on, tile nmomlt (If N •.. 'It was observed that below 213 Ktthe conversion of 00 was n(}~ qLl;lntit~lUve ~ndg.r:adually fell will1 the decrease in the reactiontemperature.

Hj!drog:en:'l:!i~!l OfprQ!'llln!1

I-l:yd rog,en<ltioll of 1-1J\l1<me De,hyd 1'1~!\~lIadCHI !if .;ycloheMne Convi:jr~iQIl. of GO .wd NO

P:rop;me !·julil.!'lC Oeilzen.e CO~ +Nl.

3·3:g.483· IOQ :nlC

33B47:) 100 100

m-(j2~ 100 100

473-m 100 100

.s. Krmllf1il'c III (II. I IOIJl"fU/,}ofNi'm-Cr',VSUlllim' S(}1id$ JI$ alJ'l}]) 197-J(}J"




Tc-mpera!llIt'll fel

l"ig. 1. <.an"VcI1l1ol1 .a.n.d s~lceIM!y intbe methauization reaejion III ·dilr~t1UH l~fliperalUTe~ fgr ~u!lly&t IO~l(! 1.1 rnllkllh: Error bit~s (±::I%) havl!' bcC:l~ onti'llecl as '[III"l.), we re of the size of !>ymbols:

:.. SO
Si Ill)
:"rit 31)2
1 .. /
." .20
:; 10
t,.l _-----+iO

~~....--- -I-I-bulen

~ -.- (lii)·2~b~lttin -*- (Z)-2-bu.teD


1 fQ 140 1.50 lijD 110 180 190 .20(1 Z10

li;jiflpQr:,1 ut~, rca

Pig. 8, "'lui,,! i<ul 'Of is,ol'Lu:r centent Willi 1,l1'rnJjlll rn.iiml i n the I· \li;l'!¢U¢ OOlilerlz.a~iQU r~aCLtml, &p~'r.iR.!!l!lU.1 d~tEl; ruled syml1o!s, ll::v:rtnOdYIHmli" dil!!t: Oplli! symbols,

4. Discussicm

The proposed precedure proved to be quite effeetive to give nickel-alumina composite aerogels wltb very attractive textural and catalytic properties in a broad range ofnickelloa(lings. The va.lue:s of specific surface area of reduced samples from the .range of 3S0~OO l11~tg are similar to those reported. by Sub et al. [14]alld larger than obtained by Osaki et al, [IS]. However, file corrcs~QndingmeSOPQre volumes gi.ven In Fig, 1 are

1<ll"ger than those reported so Jar inlplying 111m the in~e'rnal surface of these aeregel caia,lysts is even more easily accessible for bul.!.:.y reactants, and pointing to the attractive applications in UquidplHr e 'calaly is. Thisalsc accounts lor the excellent catalytic activity of these materials in tile perfonued test reactions, Compared to the preparalion procedure devised by Suh et AI. ill the procedure proposed we are not restricted to a small amount und a 1.11I.HOW range of'warer eontent to obtain ahard gel. Also compared to the method proposed by Osaki et al, there was Ill} need to subsaitute 501VeiU,f; (water and ethylene glyco 1.) wirh cthenol, in it: 'Lime consuming process, to obtain wet alcagels, sui'l.ablc rQr SUPQccriLical drying. These are important advantages of the applied procedure, which may still be optimized furrhof \0 obtain gels with the target nickel content and catalytic properties. AJu)lh!:!r lmportam property of the reduced aerogels is theirpvrophoric inactivi1.y on exposing to air, despite. : v ery large nickel lO;I.din.g, cOl1ttasting wi~h. lh~ b@i:l3lvio.!' of standard industrial. catalysis wicb. the same nickel content [~],. lhls can. be e-xphdned l:iy the phllS,e cO:lnposi .• tion of NiSo().

As could be expected the phase composltlon ·01' aerogels appeared to depend on tile nickel content. Interestingly enough, line particles of Nio were detected mil. both Nii5 aua N:i50 already artier rcduction at 773 K whereas ~hey were not detected in the nickel.-(II:utt1.imll sercgals ( .. "ith 10 wlV!o, of Ni) synthesized pre .... iou. s ly [14,16]. even after reduction with hydrogen at. mucb h.i.ghe~: temperetures. Whi.le the presence of metallic Iliok.el. i11 the reduced NiSO aerogel can be linked with the presence in tile calcined samples of the ea~jl)' reducible nickel oxide, the origin of fine particles of Ni() iII the reC;L\CCQ NilS acroS,cl is Mt quit.¢ clear. On the whole, this diffore-rlC(l in phase composition reflects a different degree of nlckel lnteractlon w1th th~ support i.e. weak interaeti III in Nj50 aerogel, resulting in the formation of easily reducible nickel oxide, .alld slroL1g intera,o"tion and very h.ilgh dispersity of nickel over .slllpport ill NiLS, yielding a NiAhOIl .spinel. This observation CJJH'Lliul'iively conforms to lffi:\at of Xu et al, (6), who found aclear signal, of (he NiO mkrocrystal phase presence in Nily-A1lOJ catalysts at loadings over 11.8 w1%


and ,'I) the recent repoets [8.2311 indicating the prcsU\ce of NlAl~Ol i11; 'lhecamlysts, with 1~)WC;I' li1ick~ conrent. To, obtain a deeper knowledge of the, rructural properties and und~rst,ancling of cutalrslsbehavior further more detailed investigaei cisare necessary,

ne nickel-a.lull.lina a~rogelS obtl1i!1Gd front the pr;opi),sed! comple;'i.lilg agent-,fl{Js>f.S'ted sol-gcl preeedure:::how very attractive properties, Their 'texrut\e parzlnQ!ers: specific surfacearea and P!)I.'C volume are sinilar or better than those of'thecorresponding a~j'o~els !,epor~ed I:lefon~alldl po:;iti"'~IY afr~ct the cafalrtic properties which appeared to be; excellent ill difcrent test reactions guCl). M: hydrcgenation of alket"ts, i$om.eriza~ion of l-buteae, dehydtosetlia. lion of cyclohexene, methaaization of carbon lind convenioli o,r CO .and NO to CO~ and N2. These catalysts, show no pyrophoric activity on el!:po~in.g to air at Nt eontem as large as 50 wt(VQ.

n J ,I\'. L~\ll(Judi" N. pg.P~:rf!iuwkl)$, Appl CU!!!I. A ~04 (2(100) 1~:;,

[4} M;, Twi&g. J,T; R;~oh<1Td~ol1. 1\~fJl. C~HaL 190A (2000) ,61, [3] V. TS~j}Oliriatl. Z. Zh,Ul!l., XJ!. Veljkios, 1. CalHL 179 {1~!)R) :28j·.

[II] R. MaUna,. G. P{>ncel'::l, J. Caml, 199 (2)00 l) 1611,

[511:;, K,Q'~~~OW~"~, I. Tonmsi~lVi¢~·Kw,\~" ,P~m, Chern, 'i7 (2) (I 99E} In

[61 Z. Xl). y, Li. J, ZI1~!lE!.I... Chung, It ZlwlJ. i;, lJ>,Ul. A])P;1.

Ca,!.lIi, A 21012(01)45-

[II L. :K~phiski. J}, 5t~~i!\$lq, t, Do~:()wic.cki. C~rbl.lfi rs (2001)) 1845<

(S:I v. Z!h~n!j, G, Xion.B. S, Shcl1S;.W. Yang" 0.11 a 1. l'od~\lI6) (2000) 511..

1.9) K. M~.s!l!li!, T. Sl:ltio, F. Mi,mkilnii, T. T\l"e~ki, K. K.m'lQ, Appl, Caial. B'; (1994JIB?

(10] G.M. Pajonk, i\pp1. CUtill, A 12 (1991.), 2.11.

[II] M. Scl1l1cid~r, .1\. B.t'liker, C<l1H1 .. R,e." Sti, Eng, 37 (1995) 515,

[12J Y.M. I'~~Ollk, Calal. Today 3:5 (199'1) .31'9'.

[1$] T, Mrow!~·.BiaIQIi. A,B. JarZ9bski. L. Pll.j~k, ban,ll'I\\ifl!i (1999) 6505.

(14) DJ. Sub, T.·), Park, J .• :li,Kim, K·L. Kim, 1, Non."Cl'

SQ.Ms ~'2S (!9~S) 1$8.

[1$1 T. Osaki, T, Horiuohi, T. Sugiyama, K. Snlold, "to Mort.

J. Nou·Crys!' Solids 225 (1998),

[Mil, D.J. Su.h, T.-J. Pa:rt" S;"I-t Lee" K..-L Kim, J. NOll.·Cry$t.

Solids 2~S (ZOOt) 309,

il7j F, Ba90JIlneau, J. Non.·CrystS9!id~ .121 (990)1 iss,

liS] L. D~I:\llre. ,. naJ~onlJeau. Ch .. m, MlIler. 9 (l'~~') 2lSS. ll9J R e , Hutter, 'r. Malia!, A. Baiker. 1. CaM .. 153 (1995)


[20J 0.1\. KhQld~e\'a> N.N. T:rukbafl, V.N. Romaoliikav, V,N. ~!1nm)l!, ,1, MrolY\~c..Ri<lI,~II., A,B. Jari~b~ki, Cil~U1. Tn(i(l)' 75 (lOOt.} 2m'.

[:nl J. Mrowlec.Biuloil. L.l';lJOJt •. .'\.B" Jiu~bski,. A.1. Lnehowski, 1.J. Mlllinowt>[.;J, J. NOJj·Crysl. Soli;;!s 22$ (199'8) us,

[221 LA., §all.oYskaja,Cb. ~achib~Jatov. Usp, Kb!m, jg (1970) ISQL

~:2,31 Z,X. Chen,g, X.G. ZhflO .. J.t. ti. Q.M.Zh'li. Aprl, CaI .. tA 205 (:1.001) 31.