React. KJnet. Carol. Lett,, Vol. 15, No.

3, 377-382 (1980)

X-RAY DIFFRACTION STUDIES

OF REFORMING PLATINUM-ALUMINA CATALYSTS
IN A H I G H - T E M P E R A T U R E C H A M B E R
K. Richter, P. Borrnmann and N. M. Zeddman
W. Ulbrieht Leuna-Werke, Research Departmer~t, DDR
Institute of Catalysis, Novosibirsk, USSR
Received June 12, 1980
Accepted July 14, 1980

X-ray diffraction studies of platinum-alumina catalysts in a high-temperature

chamber indicate that in a stream of hydrogen starting from 550-600 K, platinum
is practically completely reduced. In several cases at higher temperatures a

platinum hydride is also formed.

PenTrenorpaqbe~ci~a~e r~ccne~oBaHr'~ anIOMOIL'IaTHHOBblXKaTa~HJaTolaOB B BblCOKO

reraneparypnoR KaMepe norce~a~-r~,~o B arMocqbepeBo~opoRa, HaqHHa~C550--600 K

Ha6~!aeTc~ npa~r~ec~cn nonHoeBoccra~oB~eHner~arr~m,~; B p~e enyqaeBnpH
6once BSICOKHXTe~epaTypax o6~apyx~BaeTe~ TaK~Keo6paJOBaHHe rn~pK/~artnaa-aHbi.

The valence and structure of platinum in supported platinum-alumina catalysts

under nearly reaction conditions (770 K, hydrogen) have not been studied in sufficient
detail In several studies / 1 ' 4 / t h e existence of charged platinum besides its zerovalent form was attributed to such properties as partial dissolution of platinum in mild
solvents and the formation of platinum compounds with supports. On the other,hand
/5, 6/, it was found that without contact of the reduced platinum-alumina catalysts
with air, platinum is not dissolved in mild solvents,
It is also k n o w n / 7 / t h a t after reduction of the catalyst (23 Ma % ~) by hydrogen,
a plafinurn hydride is formed which is stable in air. The above results indicate that
the interaction between platinurn-alumina catalysts and the reaction medium can lead
to significant changes in the valence and structure of Pt, which should be taken into
account,

377

RICHTER et al.: REFORMING CATALYSTS

Here we describe the results of X-ray diffraction studies of the interaction

between highly dispersed platinum species and the reaction medium under nearly
reaction conditions in a high-temperature chamber.

EXPERIMENTAL

A series of platinum-alumina catalysts (Table 1) were prepared via impregnation of 7-A120 3 in a solution of excess H2PtC16. Samples 1-4 and 5-8 ~ were prepared using alumina, Type 5788 (22 m2/g) and A-1 (t80 m2/g), respectively.
Temperatures of the thermal treatments in air after drying and of the reduction in
a stream of hydrogen are listed in Table 1.
X-ray diffraction studies were performed on an M-62 instrument (TUR, Dresden),
a PW 1050 (Phillips, Hamburg) vertical goniometer, and HTK-10 (PAAP,, Graz)
high-temperature chamber, a graphite monochromator crystal, a BDS-6 (Burevestnik,
Leningrad) scintillation counter and a measuring unit ("Messelektronik", Dresden).
The construction of sample carrier ensured good exchange with the gas flow (flow
rate 10 l/h).
The results of high-temperature measurements in the given media (air, hydrogen,
argon) and at room temperature after the respective high-temperature treatment were
the same, therefore, the measurements were performed mainly after cooling to room
temperature. The degree of platinum crystallization was measured from the relation
between the intensities of the diffraction lines Pt(Sll) of the initial sample and of the
same one after sintering at 900-10 000 K (100% crystallization). The size of platinum
particles were determined by the Sherrer equation. Each diffraction curve was recorded from 150 points with the accumulation of 10 000 pulses per 1 rain at each point,
which corresponds to an experimental error of 1%. In processing the results, the dif-

The authors are grateful to N. G. Kozhevnikova for the preparation of samples 5-8
378

RICHTER et al.: R E F O R M I N G C A T A L Y S T S

O
v

=O
e~

~
o

-1

~ ~

8
~..

02

O3
g~[~-

02

02

02

~['--

g'['--

[~~

QO

t~-

v-q

02

t~"
tO

~"
t~-

C~
L~tO

~ 02
g-"

r-~

Cx]

Cq

~~

'~0
O

Q)

E
~O

379

RICHTER et al.: REFORMING CATALYSTS

f r a c t i o n c u r v e of alumina was subtracted to correct for its content in the catalyst.

The experimental error of the integral Pt line intensity was +5%.

RESULTS AND DISCUSSION

After long storage in air, the degree of crystallization of all catalysts is greatly
below 100% (Table 1). After thermal treatment in a high-temperature chamber in
a stream of hydrogen, already at 623 K and without subsequent contact with oxygen
the crystallization degree of all samples was almost 100%. The decreased crystallization degrees of the samples contacted with air can be attributed to oxidation of a
significant portion of platinum on the crystal surfaces by 02. The possibility to
insert oxygen atoms into the disoriented layers of platinum particles in the platinumalumina cata!ysts was described in Ref. / 8 / .
After several successive treatments of sample 7 at various temperatures and in
different media, the crystallization degree falls in air and then in hydrogen is restored
to 100% (Table 1, Fig. 1, curves a and b)). Only after calcination at 1023 K in air,
is platinum sintered, its particles size becoming equal to 180 )~ and the crystallization
degree to 100%.
Another behavior, in a stream of hydrogen, is demonstrated by sample 3. As is
seen from Fig. ], with increasing temperature (starting from 673 K, curve c), the
intensity of the lines and the crystallization degree decrease and already at 903 K
attain 69% (curve e). Simultaneously with the above intensity decrease, the peak of
Pt(31I) is shifted, which corresponds to a change in the lattice parameter from 3. 923
for Pt to 3.880 ~.
The interpretation of the results illustrated in Fig. 1 leads to the following conclusions. In a hydrogen stream with increasing temperature, crystalline particles of
Pt are first formed via the reduction of platinum oxides in the upper level. At 623 K
the FCC lattice of Pt decomposes due to the insertion of hydrogen atoms. Similar
structural variations were described in Ref. /7/, where the X-ray diffraction pattern
380

RICHTER et aL: REFORMING CATALYSTS

,[
6000 L " " . . . . . . . . . . . . ' ' " ' ~ " ' % ~ . . .

h.

Id

6 ooo,L~-.~,,... . . . . .,...e
6 oo o L .-, -,--,.-,---,,--="'"
o t/
6
6000 I_.............................."
0L

60001- "'. ................ ". . . . .

0'-

~:.

-/

80001_ ............, -

8~176176 ........i.......
0

780

800
820
;tO"

84O

Fig. t. Fragment of the diffraction curve near Pt(311) under various conditions of
catalyst treatment; a, b - sample 7 after storage in air and hydrogen at
623 K, respectively, c, d, e, f, g, h - sample 3 after storage in air,
hydrogen at 623 and 903 K, argon (903 K) and air (723 K), respectively

was interpreted in terms of the structural model of PtH0.6' wherein half the platinum
atoms centered in the planes were substituted by hydrogen. Unlike in Ref. /7/, in
our case the phase of PtH0.6 was stable only in a hydrogen stream. According to
Fig. 1 (curve f), in argon Pt particles of FCC structure are reformed.
The conditions of platinum hydride formation upon the interaction of platinumalumina catalysts with the reaction medium are still unclear and should be studied
it, more detail.
T h e , the results indicate that starting from 550-600 K, in hydrogen practically
complete reduction of platinum is observed ; in several cases at higher temperatures
a platinumhydride is also formed.
381

RICHTER et al.: REFORMING CATALYSTS

Table 2
Platinum crystallization in sample 7 upon successive
thermal treatments in various media
Thermal treatment conditions
Medium

Air

Tempera-

Time

ture (K)

(h)

293

Crystalliz ation degree

several

X (%)
27

months

573

99

H2

778

98

air

373

73

air

523

air

623

50

air

1023

13

100

56

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382