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Patent 2367848 Summary

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(12) Patent Application: (11) CA 2367848
(54) English Title: METHOD FOR PRODUCING A CATALYST
(54) French Title: PROCEDE DE PREPARATION D'UN CATALYSEUR
Status: Deemed Abandoned and Beyond the Period of Reinstatement - Pending Response to Notice of Disregarded Communication
Bibliographic Data
(51) International Patent Classification (IPC):
  • B01J 37/34 (2006.01)
  • B01D 53/86 (2006.01)
  • B01D 53/94 (2006.01)
  • C25D 03/50 (2006.01)
  • C25D 05/18 (2006.01)
  • C25D 05/34 (2006.01)
  • F01N 03/28 (2006.01)
  • H01M 04/88 (2006.01)
(72) Inventors :
  • BERGINGER, ANDREAS (Germany)
  • BRITZ, PETER (Germany)
  • DAHLHOFF, ELLEN (Germany)
  • HOLDERLICH, WOLFGANG (Germany)
  • SCHNEIDER, MARTIN (Germany)
  • STAB, GABRIELE (Germany)
  • URBAN, PETER (Germany)
(73) Owners :
  • DAIMLERCHRYSLER AG
(71) Applicants :
  • DAIMLERCHRYSLER AG (Germany)
(74) Agent: KIRBY EADES GALE BAKER
(74) Associate agent:
(45) Issued:
(86) PCT Filing Date: 2000-03-04
(87) Open to Public Inspection: 2000-09-28
Availability of licence: N/A
Dedicated to the Public: N/A
(25) Language of filing: English

Patent Cooperation Treaty (PCT): Yes
(86) PCT Filing Number: PCT/EP2000/001914
(87) International Publication Number: EP2000001914
(85) National Entry: 2001-09-18

(30) Application Priority Data:
Application No. Country/Territory Date
199 12 896.0 (Germany) 1999-03-23

Abstracts

English Abstract


The invention relates to a method for producing a catalyst. Catalytically
active material is electrochemically deposited onto a substrate, whilst the
substrate is immersed in an electrolyte containing the catalytically active
material. A voltage is applied between the substrate and a counter-electrode,
whereby the catalytically active material is deposited onto a metal substrate
whilst the substrate which is to be coated is subjected to current or voltage
pulses of a predetermined amplitude and/or frequency, and whereby the
catalytically active material is directly and immovably fixed to the substrate.


French Abstract

Procédé de préparation d'un catalyseur, qui consiste à déposer de manière électrochimique une matière catalytiquement active sur un substrat par immersion dudit substrat dans un électrolyte qui contient la matière catalytiquement active, et à appliquer de la tension entre le substrat et une contre-électrode. La matière catalytiquement active est déposée sur le substrat métallique par le fait que ledit substrat à recouvrir est soumis à des impulsions de courant ou de tension d'amplitude et/ou de fréquence prédéterminées, la matière catalytiquement active adhérant ainsi immédiatement et solidement au substrat.

Claims

Note: Claims are shown in the official language in which they were submitted.


Claims
1. Process for producing a catalytic converter, in
which catalytically active material (6, 6.1) is
deposited on a substrate (4) as a porous or non-
cohesive layer, as a result of the substrate (4)
being immersed in an electrolyte (5) which
contains the catalytically active material (6) and
voltage being applied between the substrate (4)
and a couterelectrode (3), characterized in that
the catalytically active material (6, 6.1) is
deposited on a metallic substrate (4), and in that
an electric direct voltage (V dc), on which an
alternating voltage (V ac) is superimposed in such a
way that the sign of the sum voltage of direct and
alternating voltage (V ac, V dc) does not change, is
applied between substrate (4) and conterelectrode
(3).
2. Process according to Claim 1, characterized in
that the direct voltage (V dc) at least corresponds
to the deposition potential of the catalytically
active material (6, 6.1).
3. Process according to Claim 1, characterized in
that the substrate (4) is provided, on its surface
(4.1) which is to be coated, with a predetermined
surface roughness prior to the deposition.
4. Process according to Claim 3, characterized in
that the surface roughness is in the range from
0.3 µm to 10 µm.

5. Process according to Claim 1, characterized
that the catalytically active material (6) is
deposited as substantially spherical metal
clusters (6.1) as a result of the alternating
voltage component (V ac) being applied with a
frequency of over 50 Hz.
6. Process according to Claim 1, characterized in
that the catalytically active material (6) is
deposited as substantially dendritic metal
clusters (6.1) as a result of the alternating
voltage component (V ac) being applied with a
frequency of between 5 and 50 IIz.
7. Process according to Claim 1, characterized in
that the catalytically active material (6) used is
a precious metal or a mixture of precious metals
and/or catalytically active materials.
8. Process according to Claim 1, characterized in
that substantially spherical platinum clusters are
deposited on a stainless steel substrate from a
solution of a platinum compound in 0.1 M H2SO4 with
a platinum content of approximately 0.1 g/l as a
result of a modulated voltage comprising a direct
voltage (V dc) of approximately 1.3 volts
superimposed with an alternating voltage (V ac) with
a voltage swing (V ~~) of 0.3 1 volt and a frequency
of 50-100 Hz being applied between stainless steel
substrate (1) and counterelectrode (3).
9. Process according to Claim 1, characterized in
that substantially dendritic platinum clusters are
deposited on a stainless steel substrate from a
solution of a platinum compound in 0.1 M H2SO4 with
a platinum content of approximately 0.1 g/l as a
result of a modulated voltage comprising a direct
voltage (V dc) of approximately 1.3 volts
superimposed with an alternating voltage (V ac) with

a voltage swing (V pp) of 0.3-1 volt and a frequency
of 5-15 Hz being applied between stainless steel
substrate (4) and conterelectrode (3).
10. Process according to Claim 1, characterized in
that substantially dendritic rhodium clusters are
deposited on a stainless steel substrate (4) from
a solution of a rhodium compound in 0.1 M H2SO4
with a rhodium content of approximately 0.2 g/l as
a result of a direct voltage (V dc) of 1.4-1.6 volt
being applied between stainless steel substrate
and counterelectrode (3) and an alternating
voltage (V ac) with a voltage swing (V pp) of 0.3-1.5
volts and a frequency of 5-15 Hz being
superimposed.
11. Process according to Claim 8 or 9, characterized
in that the size of the platinum clusters is
between 2 nm and 1 µm.
12. Process according to Claim 1, characterized in
that the counterelectrode (3) is formed by
platinum-coated titanium.

Description

Note: Descriptions are shown in the official language in which they were submitted.


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Now preteJ, a 1
Process for produoina a c:dta~lYtic convwrter
The ~ nverztion relato~s to a proc:ees fox produri ng a
catalytic coziverter.
The diACloaurC JP-A-08 Z34 ~R2 has dQacribod as
eleotroplafiing procQaa for coatirxg a metallto substxa'Ce
with a smooth p.~waioua metal Zayer, in which an ~.xon~-
conzaining auhatrat~ ire provzd~d with a platinutri
aov~ring. The patent pL~ x97 3Z 170 C:2 has d'i,aeloaed a~
process for cov~r~inc~ a a~x'amia 8iC substrate in a
locally selective manner wlLh a p~.at3num aovwtine~, th~
10 surtr~ua of tnlhich m~tvhea the xough oQramic surtave, as
a r~oult of a direct voltac~a being applied b~el:ween the
aubat.cw~e and s countern7.eantrode. Th~ ooatcd aub~tsata
i.s thQn troated at elevated tampdi~atu=e Of over 4UU'~.
J~P-A-106 1.97, which formp the atartirrg point Zor thA
invention, has d:Cacloped a process for th~a el~etroahemical
deposition n~ a pozrou.a platinum layer . T'tie layer is
depoaitod on a ca~:bom ~r semioonduaror. aLtbatratQ. Tn thi,a
process. s otua-off high volta~go puls~o i~a applied between
substrate and couriterelaatrode. so that nueloi ax'!
deposited on the a~ohstrate. There thcn follows a prvlongsd
pulse at a lower voltage, during Whioh groral-.h of th~
nuclei l,r~kes place. US-A-4,273,624 hac disclosed au
cl~ctroplating proacaa in which a thin, oontinuo»R layax
3 0 of platinum is deposited on an SnOa substrate . JP-R-'7 80
has diaa~,oeed a catalytic wnverter i=i which a
metallic subt~i;rate is coated with a thizi, rion-porous layer
of precicu~ metal. Thha laclc of poroa u~saxzs that the
catalytic conv~swl.er is distinguished tay i high reoiotunce
3 3 t0 OXy!~e11.
AM~1~TDED Sl'ih7~T

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74.~Irlitioasl pn$e 1a
The obj~et of t:h.R invention ie to pzw~i.de a procea~a ~or
vva~.Szlg n metallic cub~tratn whieh all.owa the
depoei.t-.i.nn o~ a precious m~~a~l with. a large aur~aae
aLwa nizd good ndhcaion to a aubetrzte .
Thin object is achi~ved by t-.r~ teaturee of the
independprit claim.
A~c:nrdiag to the inverit;:~oil, a layer of catalyt3.enlly
active metallic mat~ri.~.l. is dey~o~ized on ~, v~~a1
substrate key meanp of electrochemival de8or~ition, the
oubEtrat~ being imnte~.r..~ed in an electzolyl.r~ which
1~ coriCain~s tam catalytically active rnota~l.lic material
AMENDED SH81ET

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aubatxate ass a porous or non-cohceive layer.
Ii.-. is part3cula~:ly advantageouo for the eubatraZ~ to ba
provic~.ed, on itA murfaac which :La Zo be routed, with a
prR~letermined aurfr~ce roughness prior I:o the
deposition, they surfs~ce roughness preferably lying in
the rang~ from 0, 3 bra to lU ~.un. A further preferred
range ~c~r the surface roughne~a is k~etWeen U . 3 ~tm and
3 ym. The surface rouc~hnesl~ is e~~cpadi~ntly generated by
to thermal ~xnd/or mechr~nieal and/or chemi~:r~l Zreatment .
The catalyLieally active mat~xial is preferably foamed
from metal clusters with a dla,mezer of hetw~ex~ a run arid
1 Nm, preferably between 2 nm and 300 nm.
18
Th~ pe,rticula~r advantage of the process ie that it
possible to depoaoit arrta,lytically active a ayerc with a
v~xy large surfaaa area and x~ relatively low level of
aatalytically ~aative ma~tcrial. They layers exhibit good
a.~lheaion and acre etable at high tAmpQrxturoo even aster
prolonged use.
Preferred catalytiaallly aotivc materai.a~ls are pr~cioua
m~talp. on~ au.itab~.e oat~xlytically avtive material l~s
35 platinum. A pxeterrwc~l eounterclectrode is formed by
platinum-coat~d titan~.um sheet . A ti~rthar profexred
countcrelecLrode consi~st.9 of platinum-coated nickel.
In a particularly pretwrred refinement of the
30 inven'Cion, platinum ire depvs~.zed with differcat
morpholog~.eo. Thla provides r~atalytio eonvQ~rtezw whioh
haves different. ael~vtivitie~s ~ow conver8ion of nwtter.
For o~.at~plo, it ire posa3lble fio produaa a preferred
platiixum o~talytir. aoavartex for a weforrrtir~ ra~.ctor
35 wh~lah, d~apito a high carbon monexi.d! aoneentration J.u
an Ha/CO mixture, bass a vontiauvualy high activity for
hydrogAn. ooriv~xaion iz~ operation.
Further advantages arid conf;iguraLionag of the invention

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will emerge from the fiurt-.hAr. claimw aid tho
description, Th~ ir~.vention io deocribnd in moms c~dt~til
below wll:~l reference to a drawing, in wh:i.ch:
Figure 1 shows au outline view of a structure i~or
carrying out the pros~ps aocording to tho irxvention,
higure 2 diagrammatically depicts a a0vtioa thx'ough a
coated surfiaee,
io
Figure~a 3a, b ahoo~r two acaiulliig-elnctromt~.orolscOpe
images of the surrace of a, or~t.alytie convert~r w~.th
dondritio platinum clusters, ,
Figure 4 shows a acsnniag electron microacoge image of
the ~urLt~ee of a catalytic converrwr w3.th spherical
platinum olu~t~ra,
Fir.~urQO Sa, b show two eoatmnir~g-clcctroa mivroacope
2 o images of tlzs auwr~c~r~ of a catalytic convertor with
dendritic plxti m.~m c.lustarm before (Figure sa) and
after (Figure 5b) a long-l,~,wu Lest,
Figures 6a, b chow a cornpa~~:ir~on of rc::uWti (Figure 6a)
arid smooth (Figure Rb) r~urfaes profile: of atoQl
eubatrateo prior to the coatirsg with catalyst nu~l.at~ial,
Figur~ '7 ahowp a meaa~uremerxt curve iridicating tam
lxyc3x~c~ett conversion achieved by a catalytic eonvextwr
with sph~rioal platir~,um cluotcra in e~ CO-containing
al:n:c~b~xieiw, and
Figure 8 a~aowd a measurement Curve iiluecrating the
rnnvPrr~-ton of hydrogen achi~vod by a catalytic
30 converter witlZ 3exidill.ic: platinum cluezere in a GO-
containing atmosphRr~.
b'igure 1 shows an arrangame~nt for carxyincg out the
proooco sccordirLg to the inver~,tion. A function
j

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generator l ,generates a modulated voltage which i~
' amplifinrl in as anipli~ier x arid i,s appli~d betw~ea an
ar~ode 3 and a nuk~strate 4 which iE to be corxi:vd in
depoeizion rath 8. A direct vu~.l;aae Vas is prs~~rably
superimposed with art alterriati ng voltage V~. Tl~s sum
voltage of direst voltage V~ a~c~d alternating voltage
V,~" ie also ye~erx;c~d zo below e9 the tnodul,atod woli.uge
V,~. The alLernat.inc~ voltage ie expediaiitly eirusoidal,
but may also adapt uLher forms, tar. example oawtooth ow
ZO scdu,~xwe-wave form.
The caLdlytioally active matorial 6 is depoa5.lted on the
substr.ats 4 in the form of vluete7co. Aee~rdirxg to the
311VCIltit711, the Cluagterra may hav~ different fvrrns wlzioh
can hR prs~dot4x~nir~cd by the deposition paremetera . The
oubatrate 4 which is rented with er~,tn7,ytically acCive
material 6 the~s forma the catalyl.ic converter_
The direac voltago V~ io prefera~rly apt least aae great
as the dopoaition pvtezztisl of the eatalytically activa~
nu~terial 6 on the substrate 4, particularly preferably
at ~nopt SO% higher. The precise levQl of thm direvt
voltage Vas is dependent on the conat~.tuemi;s and proeea~a
cond3tior~.a employed and may. ~'or exs~t~ple, adopt
2~ diL,Cerent values f.~r. differently pretreata~d substrates,
a7.t-.hough th4ae vahzea dv not u~ua~.ly differ greatly
from o~m another. When depositing rn~.xed syetomo as
catalytirally active material, it is also pnseibla for
the pre~erze~d direct voltage Vac to lie below Ltr,is
depos~i.tion pot~sitial.
Stain7.ws~s Ate~1, particularly C,r-N~, steel 1..A.~a41 or
CR-Ni eteol 1.4871 or Gr'Al stRwl. 1.4'767 io used as a
particularly a»i tablra substrate. Tt is ~xpedieriz fox'
tho a~otrdtQ to pe r~and'blasted or. roughen~d in some
ul.tier way, for ~xamplQ chQeni,eally, and i,o 'undergo
a11ca1inn degrcanixig prior Co the coatl.rag. This improves
thd adhesion of thw catalytically active mate~ri.al 6 zo
fibs substrate 4.
4

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=n a preferred embodiment, the altexia,atiisg voltatge V~
ha.t~ s maxi mum lroltagc awing Vap between minimum and
maximum which io lowex than the direct voltage V~, ao
that overall the sign of the cum voltage between
substrate ~4 and counterelectrode 3 doo~ not chango.
The current betw~~z~. substrate 4, whioh c~rvas as the
cathode during the depoe~.tivn, and anode ~ is recorded
and, xn accordance with Farada~r~ g law, is! used a: a
measure for determining the caudutll:y ~f c;uLalyt,'i.c$lly
aetiv~ mat~rial 6 dapoa~.tad, this material being
cont~.inda l.i~ l.h~s deposition oath; cu~:rent contxibutiona
which flow for thQ purpo~s of building up pnc7. brw~ek9ng
tit~wtl the eleotrolytic double layer on account of the
modul~.tien are expediAntJ.y ~1 i m5.nate~d, since they do
not originate from the reduction or oxidction o~
cations Or aniOnS.
zt is preferable zo deposit precious metals 1n order to
produce the aatalytio aoav~rter. Howev~r, it is alAv
possible to deposit mixtures of prev~.ous metall~. An
axpcdiont, ~.nexpenaive anodes il~ platirzum-eeatrd
titanium instead vt a c~tr~=ia~.z'c:~ r~acriticial anode made
2a~ trom solid platinum, which can be used to gaztieul.s~.rly
good erLeul, if platinum is to be depos~,ted ae
oatalytically active mat~rial. HOwevRr, nth.~r, pr.~aeioue
metals and ~l~r~ other metals can be depo'ited ire thxe
invvat itrs way .
The frA~mnry and/or the amplitude v~,r and/or the
voltage offset V~ of the modulated voltago caxi be
~d~umted in order to optimize the deposition pax'ameters
for the p~rtioular cyst~m. Th~ va~luos affect both the
~S size of the elusze~ag which are deposited vu Lhe
metallic ac~thode and th~aix morphology. Overall, the
elust~rs on the substrata 4 c;~~lai::Ltuta a large active
our~aa~s area for catalytic raactionn. The optimum
cluster size c;du Le stet im each cases for diifereat
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applieaticns by ~ami.fi.ably s~tleoting the deposit3os~
parameters end the duration of coe~tirig.
It is particularly etdvantageous for the surfaces of l,xid
substrate 4 which is to be coated to be roug~wttAra. prior
to the coating, for e~ampl.e by pickling ox oaad-
blasting. other methods for increasing the surface
roughness ar~ also potasibl~. This is illuotratod in
Figure z with reference to a diagrammatic side view of
1,0 a coated surface. A sub>ztrat~ 4 hats st rough~ned ~urf;ee
4.1 on which spherical metal cl.usz~rs 6.1 arc arranged
in reessa~sef . The metal clusters 6 .1 may a.lsao be
deposited o>,z the peaks or the flaizk~ ut Lk~d wraugtidand
armas_
i~
ThR inr..rw~pR~c1 pm.rt~~:A .ro~.tghnees has th9 advRntxtrds ths<t
deposited cluatexe G.x adhere mono auceessiully to the
substrate surface, arid and~sirable combining of the
clusters 6.1 ie ouppreaAed. A catalytically active
3u layer of individual clusters 6.1 is form~dr the layer
i~ preferably not aontinuouc, but rather is formed from
xsolat~d clusters 6.1.
Ttie ~ur.Cdc;d iwuc~lmaa~ is ptwfert~k~ly bwl.wdnri 0.3 ~t arsd
25 10 pm, particularly preferably bwtwewa 0.3 pm and 3 pn.
A large active surface eras. is formed from thr~ firmly'
distributed elustsrsa 6.1. A further advantage is that
the imcr~cascd aurfaee rougluzeass even also coi~tribut~ss
t~ i nrre~~r,~1 ng 1-.hw >;nrf~arr~ ~re~~ of rh~ t~mh~~hrate 4 and
30 therefore also the chemivally act~.ve surface area, At
the game time, the clusters 6.1 can be very small, so
that overall only a r:mall quantity of the expensive
catalytically active material 6 has to b~ deposited,
yet at the same time the eatalytio converter ice
35 distinguished, by a high catalytic atctivity.
The adheaivrz ofi the metallic c;lusLera~ 6.1 to the
substrat~ surfao~ 4.1 is v~ry good. This mak~s the
udt,alyal, layex mole resistanC to aro~siort,.
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A particular advantage over convv~emtioizal c:~t;alya~i.
- layer8 ie that, aceordtng t~ ~:na invention, good host
traastcr ~rom the cs~talyat layer to the substrate 4 ins
possible, since metallic clusters 6.1 are ~oinac7
metallic oubotrato 4, ey contrast, known, conventional
catalyst 7.ayers are produced, for exan~l~, with
supported catalyst matsxials, in which ceramic support
particles are coated with a precious metal. 1n this
ease, the heat trax~afQr b~tw~on aata~lytiaally act3.ve
p~.wc;iou~ u~at;dl a,rsd a substrate is siqnitioarttly worse,
r~ince the ceramic part~teles axrarlgQd bstw~.n them haves
only a low thermal conductivity. 2iz addltl~m, iu a
c:r~i-.a'l,yt-.i c! o~nvRrtRx which is produced according to the
1b invention, it is also possible to diepaaso with
standard adhesion promoter l~syaa~~, whi r..h have an
additional r~dverae e~~ect on the heat transfer
properties between eacalytically active material 6, 6.1
a.nd ssubatrate 4.
A subAtratw 4 which i~o coated according to the
invention is therefore particularly suitable for use as
an oxidation catalytic corm~rt~x for t~rextisig ~xhaust
gases iia tual cell syr~te~ys . A tu.~~l,xa~w expedient
application ip for various heterogenQOUSly catalysed
proceaaea . The catalytic comvexta~r accrrr~tirzr~ t;o l:~m
invention and the pros~r~a ~,ceord~,ruJ to the invention
are particularly advantageous iiz exhaust,gaa c$tal~r~lc
converters for vehicles.
35
r~igure 3 a~hows searuzing-electron microscope images of
prcfcrrcd catalytic converters With de~ndxitaLc platinum
clusters (Figures 3a, 3b), and w~.ch rhodium clusters
which are of substantially dendritic form.
Derldr~.tic platirmm clustexs ar~ profQrably dQpoeitnd oxz
a t~tr~~.mldd~s t~taal aub~rtrate a~ a result of a~ d~.reez
voltage V~" of 1.4 volts being superi~poR~d with axe
altornatizzg voltage V8e with Vpa~0.7S volt (peak-peals
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voltag~ swzr~g) and the modulated voltage b~slng applied
between a ataialeaa ote~1 Aubatrate and a
coaster~leCtrOGl9. The frequency ~t the alternating
voltage Vsc is ZO IIa. Tho eloetxolyta u~m~d i ~ platiniC
acid, in particular hexachloroplatiri,ic acid, r~r3.tk~, a
pl~~iylz,~,m content o~ 0 .1 g/l . The depr~r~i r.i.na preferably
takA~ place az room tampowa~uze.
platinum clusters praaesizt der~,dr~.tic growth, arid no
spherical platinum clu~t~rr~ axe observed. The prerd~wacl
Ga~.t~.:lyt~LC converter h~.p a high lovel of aotivity for
hydrogca aonvers.ion wen i n the nreserlce of c;arl~on
monoxide, carkwii monoxide alAO be~.ng aenvert~rd w~.th a
good yield at the samw time.
zn th~ selleted say~tem, dendritic; platinum cludtero are
tiepor~~.l.ad with frequcncieo of betw4en 5 ~vncl 15 Hz atld
an altern2~h ing voltage V,~ with a voltages awing Vry of
betwee~u 0.3-1 volt.
A further prcferrod catalytic aonve~rter is Droduced bY
depc~pi.t ion of x'hodium ors ataiialesa oteel , prei~rab~.Y
compriving etaitllaar~-steel ~aheet 1.4541 or 1.437x or
b'7. It is also podaible ~or mixed oatalycts of
z5 platinum to b4 deposited. ixi this waY or to c,~~podit
eatalyBts compriblng mixtures of precious metals and/or
catalytieally native matRrialg, such as for example
Ptlih, PtRu, PdPL .
3U Dep06itivti takes place fro~nn a anolution of 0.2 g/1 of
rhodium i.x~ c1.1 M lizbOa at room ~ampaxaturo with n sir~ct
voltac~~ Y,Ia of 1.4-1.6 volts and a super~.tctpoa~c.~
altarnar i ng voltage V~,o wi l.h Vap-1 volt (peak-p~a,k
amplitude) and a frecjuency of ~ ~ Hz . 'fhe formation c;W
derLdritic~ growth of zhe 'cluc~tera can be improvod ;still
further by vax~ying the voltage parameters.
A aatalytio co~n~rort~r of this tyre has a good activity
for methanol. A catalytic converter of thi.R type is
a

Str. sa. ~Idld1 11: ~eRM rRnI~IELL & MORINr LLP Nf_1.928 P.17
CA 02367848 2001-09-18
thereforA particularly suitable for use in fuel cell
vehicles operated with methanol, partivul~trly
pr~gprably in catalytic burners.
r'iguxe 4 shows a acanning~el~ci;;~'om ~tviw~oscope image of
c~ further pre~~rred ca,talytie oozwextar with aphRriQal
platinum clusters . 'Txm d~poaition takes place uair~g a
dir~ct voltage Vas of 1.2-1.56 v~lt~ and an alternating
voltage Via with VBp~O.~ volt a,nd 100 Hx; the deposition
~.0 ba.th othsrw~.sa! corresponds fi.n t-.r~t used for b'igure 3.
In this r~yAtAm, xn alternating voltage v°Q with
frequencina of more thar~ 50 Hz, preierubly up to
150 i~~, iR preferably used for the deposition of
~.5 spherical platinum eluctero . The dir~cst volt:ge V~
which i ~ applied varies with the substrata pweLi'ea1;11~1'~t
arid, for the dopos3tiorx of epho~'ioa,l alusot~rp, is
substantially equal to or tends to be all~x~t,~.y lower
than that used ~or bhe deposition of dendrit3e
U c~.uscera .
Figure 5 ahewr~ a ~:omparison of acanning,clectx'vn
micro:cop~ i.ma,g~s of s rr~ta:lytic converter with
deudrlt,i.c platinum clusters before (Figure 5a) and
aft~r (Figure 5b) a 7.o~lg-1'.e~rm test, iri whioh ~Che
c;~xl.a~lytie corsvextey ways eapoaed to an ~I,/GO mixture at
high temperatux.'A for. more than 200 h. Although eXposed
to high tempcraturaa of up to 600°C, the porous ox rrorr-
aohesive platinum layer ae catalyst remains stdblc~; th8
30 cluatexa Yemc~ia ~ixad in posit~.on and do not conv~re'~e.
The layer which has been deposited lii accordanoe with
the 3r~vet~tion domonot~'ates th~.t the elustox's is
practioe do riot change before z~nd af~~sr long-term uea.
35 Figure 6 shows a compariaroxi of rough (Figure 6a) and
smooth (Figures 6b) surface pr~fi l.ws et steel a9ubetraLes
whicxi have been used for the dopooition of th~
platinum. The adhAr~i.on et the platinum clusters to the
roughened e~ubatrnte is aignificaatly bettor than th~
9

5EP.14.2001 11:~M CRnhIELL & MnRIIVr LLP NQ.928
CA 02367848 2001-09-18
adhesion to the smooth subl~trats ~ the layers era wipe-
reair~tant, while the layers on ars ur~.tLented, smooth
Aubatr~.tR era nit wi pR-r~~i ~t~nt . They ~xm.rf~rp .r~mghnRaA
is preferobly botweea 0.3 dun and 10 ~.m, particulaxly
preferably between 0.3 dun and 3 pm.
'the catalytic activity and/or aeleotivity of the
catalytic convert~r diff4rs d~p~ading on the paxtiou~.ar
form of the clusters. A preferred catalytic converter
to with sph~ricxl platinum eluleters converts hydrogen in a
substantially selective manner. The catalytic converter
is poiaos~ed and has m greatly reduced activity in the
preseizce of carbon monoxide . A cectalytic converter of
thin type is preferalaly u.r~sr~. ~.mc3Rr ~arhnn mnn~xi dw-l~rwA
1S conditioni!t.
8y contraot~ a prefcryed catalytic converter with
dendritic platinum clusters tirezly has a hiqh
toley sate to carbon morxo~cide during the hydrogen
20 convsrs~.on and secondly has a ha.~h selectivity and high
activity both for the hydrogen vonv~r~aior~ and for the
carbon monoxide conversion.
Figure 7 shows a. ~ua~bu.~wusrs~~l. cu;we illu~strat:Lnq the
95 hydrogoa aonv~raion achieved by a pr~ferred catalytic
aonvortet~ w~,~l~ aplzerics,l platinum aluotcra. The
catalytic convartQx is~ exposed to an Hz/CO mixturA
u.czder standard operating cvnditxons. After even, a few
mi m~t:e~~, the hydrogen conversion in the pre9ence of CU
30 ~allcs to low levels.
Figure a shows a meas~uremo~nt curve illustrating the
hydrogen conversion achieved by a preferred catalytic
converter with dendtitia platinum oluAtQx~a. In thisc
35 case too, the catalytic converter i~ exposed to an
I~l/CO m~Lxtura and~r standard op~rating conditioaca.
However, the ntc~ar~u~~~u~smL cuzvrs slZOws tlu~t the
convwrsion of hydrog~n and for carbon monoxide remains
al; ~aWat,~xllLla~,ly coizstant high lo~rele~ over more than
l0

SEP.ia.200i 11:50AM CRnLIELL & MnRINr LLP NO.=~28 P.19
CA 02367848 2001-09-18
200 hours. The conversion can in each caQO bo unproved
furth.~r, since th~ operati~.g conditioxut have not been
_ optima.zed.
1i catalytic coizve,rl,er which has beAn produe~d in
accordance wi.rh. the inwr~tioa is particularly tw~istant
to erooioa, and itn prvc3uctivn sari be surc~es~sfully
reproduced. The clRposition para~metors of the
catalyt~,aally active mat~.c~l~l on Che substrate ea.n
3,0 easily be optimized for. diffaxent matsri~.lo which are
to be deposited by suitak~ly selecting the d~ rPat
vvltaQe vd~. alzet-nating voltac~! amplitude V~~ and/or
.frAquency. proceae control im simple, uzic3 the catalytic
comver~~i~ proper'Cies cats be resproduoibly sot by Aimple
modifi.oatiox~.~a to the depopition proceao, Thd yield oZ
material is qooa. so 'Chat, for examplQ fox highly
aetivp platir~um catalytic oonverter~s, relat.lvely small
quantities of they preciou' metal have to ha used.
30 A preferred use few a eat.~,lytie convertAr produced
according to thw inverstioxi is ucc in a CO-rich
~avironmcnt, is partivuldx~ in e.n exhaust-gas a~wr~nin~
system in a motor vehinl.e. A further prwferxcd uoe of a~
catalytic corivort~r according to L~ae i~ivenLion is~ a.ts
use in a fuel Cell syst~tn.
11

Representative Drawing
A single figure which represents the drawing illustrating the invention.
Administrative Status

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Event History

Description Date
Inactive: IPC from MCD 2006-03-12
Inactive: IPC from MCD 2006-03-12
Inactive: IPC from MCD 2006-03-12
Inactive: IPC from MCD 2006-03-12
Time Limit for Reversal Expired 2006-03-06
Application Not Reinstated by Deadline 2006-03-06
Deemed Abandoned - Failure to Respond to Maintenance Fee Notice 2005-03-04
Inactive: Abandon-RFE+Late fee unpaid-Correspondence sent 2005-03-04
Letter Sent 2003-01-15
Inactive: Single transfer 2002-11-19
Inactive: Courtesy letter - Evidence 2002-03-05
Inactive: Cover page published 2002-02-28
Inactive: Notice - National entry - No RFE 2002-02-27
Application Received - PCT 2002-02-12
Application Published (Open to Public Inspection) 2000-09-28

Abandonment History

Abandonment Date Reason Reinstatement Date
2005-03-04

Maintenance Fee

The last payment was received on 2004-02-17

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  • the late payment fee; or
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Please refer to the CIPO Patent Fees web page to see all current fee amounts.

Fee History

Fee Type Anniversary Year Due Date Paid Date
Basic national fee - standard 2001-09-18
Registration of a document 2001-09-18
MF (application, 2nd anniv.) - standard 02 2002-03-04 2002-03-04
MF (application, 3rd anniv.) - standard 03 2003-03-04 2003-02-21
MF (application, 4th anniv.) - standard 04 2004-03-04 2004-02-17
Owners on Record

Note: Records showing the ownership history in alphabetical order.

Current Owners on Record
DAIMLERCHRYSLER AG
Past Owners on Record
ANDREAS BERGINGER
ELLEN DAHLHOFF
GABRIELE STAB
MARTIN SCHNEIDER
PETER BRITZ
PETER URBAN
WOLFGANG HOLDERLICH
Past Owners that do not appear in the "Owners on Record" listing will appear in other documentation within the application.
Documents

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Document
Description 
Date
(yyyy-mm-dd) 
Number of pages   Size of Image (KB) 
Representative drawing 2002-02-26 1 8
Abstract 2001-09-17 1 23
Claims 2001-09-17 3 120
Drawings 2001-09-17 5 96
Description 2001-09-17 12 584
Reminder of maintenance fee due 2002-02-24 1 113
Notice of National Entry 2002-02-26 1 195
Request for evidence or missing transfer 2002-09-18 1 108
Courtesy - Certificate of registration (related document(s)) 2003-01-14 1 107
Reminder - Request for Examination 2004-11-07 1 116
Courtesy - Abandonment Letter (Request for Examination) 2005-05-15 1 166
Courtesy - Abandonment Letter (Maintenance Fee) 2005-05-01 1 174
PCT 2001-09-17 8 359
Correspondence 2002-02-26 1 24
PCT 2001-09-18 4 119