Applied Catalysis, 2 (1982) 379-387 Elsevier Scientific Publishing Company,

379 Amsterdam - Printed in The Netherlands

CHARACTERIZATION

OF COPPER-SILICA

CATALYSTS

PREPARED

BY ION EXCHANGE

M. SHIMOKAWABE, Department Japan.

N. TAKEZAWA

and

H. KOBAYASHI Engineering, Hokkaido University, Sapporo 060,

of Chemical

Process

(Received

16 July 1981, accepted

18 January

1982)

ABSTRACT Copper-silica catalysts were prepared by ion exchange between the hydroxyl hydrogens on a silica surface and tetramnine copper (II) ions, and were characterized by a variety of analytical methods. It was concluded that copper ammine complexes held on the surface can exist in three different states, i.e. isolated and clustered diammines and free tetramnine copper (II) nitrate. The relative amounts of these species were strongly dependent upon the amount of copper loaded onto the silica. These ammine complexes decomposed around 300C. The clustered species transformed into highly dispersed CuO clusters at 300C in air and then further crystallized into bulk CuO at aroun 720C. The isolated species, on the other hand, remained in part as isolated Cu B + ions on the support after calcination at temperatures above 3oo"c, while the tetrammine copper(II)nitrate rapidly transformed into bulk CuO at 500C. Based on these results, a surface phase diagram of the catalyst was tentatively presented as a function of copper loading and calcination temperature.

INTRODUCTION The elucidation of a catalyst of the effects of preparation importance upon the nature or the structure design. A precise characterfor

is of considerable prepared

for catalyst conditions

ization of catalysts this purpose

under various work,

is, therefore,

required

[l]. In previous

it was shown that copper-containing

catalysts

were fairly active hydrogen converted catalysts atoms

for methanol

steam reforming, molecule,

CH30H + H20 + CO2 + 3H2, so that are effectively or supported

in the methanol hydrogen

as well as in water,

into gaseous

[4 - 81. The activity copper

of support-free

which were prepared affected

by kneading

hydroxide

with various metal oxides and the amount of that anions and inhibited

was markedly copper

by the pH of preparation

of the hydroxide precursor

loading.

Characterization material

of the catalyst were strongly

revealed

in the copper the reaction

starting

held in the catalyst was prepared

to a great extent when the hydroxide held markedly

at lower pH. On the was

other hand, the amount of anions prepared

decreased

when the hydroxide copper formed

at higher pH. The particle decreased appreciably therefore,

size of the metallic when the copper depended markedly

in the course The

of the reaction activity

loading was decreased. upon the copper

of the catalyst,

loading. catalysts

More recently

[6], some experiments by ion exchange

were carried between

out over copper-silica

which were prepared

hydroxyl

protons on a silica gel surface

OlSS-9~34/82/0000-0000/$02.76

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Publishing Company

380
and tetrammine the activity catalysts. copper (II) cation. It was shown that the selectivity affected by the preparation as well as of the to

of the reaction was strongly

In connection with these results, the present work was undertaken

which were prepared by an ion exchange and we show how the states of the catalyst in the preparation, varied with the temperature

study the states of catalysts various conditions involved

method at

parameters copper

such as the calcination

and

loading on silica.

EXPERIMENTAL Catalysts The catalysts complex complex Chromato were prepared by an ion exchange from copper nitrate with hydroxyl method. Tetrammine copper(I1) and the (Nihon

solution was prepared cation was exchanged

and aqueous ammonia,

protons on a silica gel surface

Ind. Co., surface area = 413 m2 g-') at a pH of 11 - 12. The catalysts were dried at 110C in air for 3 h. Copper contents in the catalysts

thus prepared varied

in the range 0.5 - 11.1 wt %. Some experiments prepared by the impregnation method.

were carried out over a thus prepared contained

catalyst

The catalyst

21.1 wt % copper.

Characterization

of catalysts were carried out in air or nitrogen with the aid of DTA

DTA and TGA experiments equipment

(Rigaku Denki 8441 Al) and an electrobalance

(Cahn Model RG), respectively. programmed reduction)

The heating experiments,

rate was 5 - 10C min -'. In the TPR (temperature a hydrogen-nitrogen

at a total flow rate of 50 ml min by gas chromatography of the catalysts spectrophotometer

mixture (4 % hydrogen) was passed over the catalyst -1 and the hydrogen consumption was determined Co., Model 701). Diffuse reflectance spectra

(Ohkura Electric

in the UV/VIS/NIR

regions were recorded with a Hitachi Model 330 sphere (Hitachi 210-2101) was attached. infrared for

to which an integrating

Infrared spectra of the catalysts spectrophotometer. the determination on the surface. energy reference

were recorded

with a Hitachi Model 260-50 ESCA 3) was employed

XPS spectroscopy of the valence

(Vacuum Generators

state of copper or for the assignment

of ammonia

The 2p binding energy of Si (103.6 eV) in silica was used as the line for the XPS spectra. The presence of cupric oxide or

cristobalite

was confirmed

by XRD (X-ray diffraction,

Rigaku Denki 2114). The number by reaction with ethyl ethane [91.

of surface hydroxyls magnesium

on the silica gel surface was estimated determination

bromide and subsequent

of the amount of evolved from the concentration The tetrammine

The amount of copper on the support was estimated ion in the solution

of cupric

before and after the ion exchange.

copper

(II)

solution was titrated with EDTA solution pyridylazo)-2-naphthol as an indicator.

of known concentration

using PAN l-(2-

381 RESULTS AND DISCUSSION 1 illustrates the DTA curves of copper-silica An endothermic catalysts which were dried 100C while peak becomes were carried

Figure

at 110C prior to the experiments. two exothermic appreciable

peak is seen around

peaks are seen around 265 - 300C. The latter exothermic 5 wt %. When the experiments

when the copper loading exceeds or helium atmosphere, revealed

out in a nitrogen although

only the peak around

100C was observed, at 100C and around

gas analyses

that water and ammonia

desorbed

265 - 3OO"C, respectively. were observed oxidation

Since exothermic

peaks around

265 - 300C and 720C to the

only in the presence ammonia.

of oxygen,

these would be ascribable

of copper and/or

:: w

i =;

! 8 6 in air static

FIGURE

DTA curves of Cu/Si02 catalysts

dried at 110C in air.

Figure 2 illustrates

XPS spectra of the catalyst.

A peak due to N 1s of ammonia

is seen around 400 eV. However, if nitrate was present. around

there is no peak at 407 eV as would be expected The satellite peak which is characteristic of Cu 2+ is seen copper around 936.4 eV. 2p3,2 is estimated to be 0.47 which agrees [lo]. This strongly suggests The ratio of ammonia of XPS of a sharp in

945 eV, together with the Cu 2P 3,2 peak of divalent for a number of cupric compounds

The peak ratio Cu2+ (satellite)/Cu2+ well with that obtained that divalent copper

ions exist predominantly

on the surface.

to copper was estimated tetrammine decrease copper

to be 2.07 on the basis of the intensities nitrate. From TG or OTA analysis both around

(II)

of the catalyst,

in the weight was observed

100C and 300C. As described

382

410

405 Binding energy

400 eV

395

FIGURE 2

XPS spectra of Cu/Si02 catalyst

(IO wt %).

the results of gas analyses, the latter estimated

the former

is due to the desorption

of water while lost was the

is due to that of ammonia.

The number of ammonia molecules

to be twice that of copper atoms held on the support, by XPS. When the catalyst to N Is of ammonia

confirming

results obtained

was heated above 3OO"C, the XPS peak as expected from the observations

which was ascribed by gas analysis

vanished

and TG analysis. by chemical analysis and it was found This corresponds between we

The amount of copper held was determined

that IO wt % of copper was held on the silica surface to half the number of hydroxyls ethyl magnesium conclude copper

at saturation.

on silica as determined hydroxyl groups.

by the reaction

bromide and surface

Based on these results,

that a pair of surface ion and diammine

hydroxyl

protons

is exchanged

with one tetrammine holding at 265 -

(II)

copper

(II) is formed on the surface without It decomposes

any appreciable 300C.

amount of counter anion from the solution.

Table 1 shows the results obtained were calcined in air at various

by means of the XRD method When the catalysts

after the catalysts with higher copper due to bulk CuO were

temperatures.

loading were calcined were observed obtained together

at 800C or 900C in air, the XRD patterns with those of cristobalite, with lower copper of isolated loading

while no bulk CuO patterns even calcined

for the catalyst The presence

at these high

temperatures. electronic

cupric

ion was suggested loading.

later by the

spectra of the catalysts

with lower copper

383

4 lo+e/"c

FIGURE 3

Temperature

programmed

reduction

spectra

of Cu/Si02 catalyst.

a, 10 wt%

Cu;

b, 1 wt % Cu. The catalysts experiments.

were calcined

in air at 500C for 3 h prior to the

TABLE Change

1 in XRD patterns /wt % 110 of Cu/SiO2 catalyst calcination 500 a a a a a temperature 700 a a a a b 800 a a (CUO) (CUO) b /"C 900 a (CUO) cuoc cuoc cuoc

catalyst

Cu/Si02 CulSi02 Cu/Si02 Cu/Si02 Cu/SiO,

(0.5) (1.0) (8.0) (10.4) (11.1)

a a a a a

ano CuO patterns b not determined 'cristobalite

were observed

was formed

Figure calcined with

3 illustrates

typical

TPR spectra obtained

from the catalysts

which were

at 500C in air. A strong peak appeared The peak temperature

around 280 - 300C for the catalyst with that obtained on bulkCu0.

10 % copper.

almost coincides

384 The number of hydrogen molecules atoms loaded on the silica. was predominantly at 500C. However, which was calcined consumed was practically the same as that of copper that cupric oxide in air

From these results, with

it was concluded

formed when the catalyst

10 wt % copper was calcined in XRD patterns

since no bulk CuO was observed at 5OO"C,

of the catalyst

the cupric oxide formed was very likely to exist as state. In conjunction with the results

small clusters of CuO in highly dispersed obtained by DTA, it was concluded copper(I1)

that these clusters

were formed by the decomposition DTA peak was observed. exothermic peak

of diammine

at 260 - 300C where

the exothermic

They would further crystallize was observed. In contrast

into bulk CuO at 720C where another

to these results,

two TPR peaks are seen at 280 - 300C The latter TPR peak is located at on bulk CuO or small clusters of

and 650C on the catalyst with much higher temperature CuO, suggesting

1 wt % copper.

compared

to that observed

that the cupric

ions held are, at least in part, strongly is decreased. catalysts

interacted

with silica when the amount of its loading Figure 4 illustrates dried or calcined UV/VIS/NIR

spectra of copper/silica

which were

in air at various temperatures.

1

When 10 wt % copper was loaded on

I

Ref. = A1203 (D)

lO%R

(A)
temperature -air-drying _______-,,(yJc

---

500C 900C .i _/'-~iL,

--._z
O-H 200 400 600 Wave length 800 /nm 1000 1400 1600

FIGURE 4

UV/VIS/NIR

spectra of Cu/Si02 catalysts.

385 silica, the absorptions at 1400 and 1500 nm which are ascribed groups [11] greatly decrease to the overtone intensities of amninia and

absorptions

of the hydroxyl which

in their

the absorption

is ascribed

to the N-H stretching

vibration

appears

at 1530 nm. This was also confirmed by the infrared spectra of the catalysts. The -1 absorption at 960 cm , which is ascribed to the Si-0 stretching vibration of the SiOH group on the surface protons with tetrammine Figures absorptions surface [12], decreases ions. the spectra obtained below 1000 nm. The transfer between The absorption in an due to the exchange of surface hydroxyl

copper(I1)

4 (C) and (D) illustrate observed

at 270 and 350 nm are ascribed and clustered

to charge

oxygen

and the isolated

ions [13], respectively. of cupric

band at 700 - 900 nm is assigned octahedral environment

to d-d transitions

ions situated

[I3 - 151. The latter absorption or calcined cations.

is seen with all catalysts that copper be noted

which were dried at room temperature is present predominantly as divalent

at llO"C, indicating it should

In particular,

that the absorption the catalyst absorption evidently diammine

appears

at 680 nm on the catalyst or calcined

with 0.5 wt % copper when at 110C although the This since cisat 670 -

was dried at room temperature structureless copper

is somewhat

on the catalyst

with 10 wt % copper. by the ion exchange absorption

shows that diammine copper

(II)

was formed

(II)

complex

in solution

gave a characteristic

680 nm according

to Bjerrum et al Cl63 and Grant and Kollrack

c171.

l
0 4 8

clustered, 12

wt.%,
FIGURE 5 Relation between reflectivity

cu
= (1-R_)2/2R_ and wt % copper.

F(R,)

Figure 5 shows the plots of the reflectivities estimated catalyst by the Kubelka-Munk equation

at 270 and 350 nm which were the weight % of copper species in the

[18] against

dried at room temperature. with

It is seen that the isolated

predominate increase

on catalysts with increase absorption

less than 2 - 3 wt % copper, loading.

while the clustered

species

in copper

When the catalysts region became

were dried at llO"C, the 350 nm suggesting change

in the charge transfer particularly species were

broader and that around

became discernible, that the isolated

on the catalysts in part clustered.

with 1 - 3 wt % copper, However, no appreciable

386 occurred in the charge transfer bands of other catalysts having copper lower or

higher than this amount. copper

When the catalyst decomposed

was heated above 260 - 3OO"C, the diammine as described with above. The spectra greatly The clustered

(II) held on the surface

changed and became structureless diammine transformed

for the catalyst

10 wt % copper.

into highly dispersed with lower copper

cupric oxide as discussed loading, the isolated

above. On the still

other hand, for catalysts kept their structure

species

even after heating

at 500C. This was illustrated

by retention

of the sharp absorption heated at 9OO"C, indicates

band around 270 nm together bands in the region

with that near 750 nm. When 270 - 350 nm became However, broader. It

the absorption

that the isolated species had in part clustered. 2+ transition of Cu still remained.

the d-d

10 -

8-

CuO(crvsta1)

+ (d)

- m-----m_ , 2 N
# z

--N ..
(d) Cu++(iso) + (e) CuO (highly dispersed)

6(d)

*. '.

4-

2 _ ,(a')diamnine-Cu(II)(iso.dehydrated) f '.+(b')diammine-Cu(II)(clus.dehydrate!i) (a'), (a) 0

(a') + (b') + (c')

I I I i (a)diammine-Cu(II)(iso)+(b)(clusi) (a)+(b)+(c)tetrammine-Cu(I1)
2 4 6 '8 10 12 14 16

wt.%,
FIGURE 6 Structure of the CulSi02 catalyst.

cu
(iso) = isolated, (clus) = clustered.

When copper was impregnated ion exchange method,

on silica

in an amount

exceeding

saturation

by the

a strong absorption

which was ascribed

to nitrate

occurred

at 1385 cm -' [19]. The excess amount nitrate.

is probably

held as tetrammine it decomposed.

copper

(II)

When this species was heated above 3OO"C,

By calcination This was CuO

at 500C in air, the XRD patterns in marked contrast

due to bulk CuO were readily observed. on the ion exchanged catalysts

to the observations 720C. obtained

on which

was only formed above

Based on the results held on the silica of copper loading

by various

analytical

methods,

the states of copper as a function

gel surface are tentatively and calcination temperature

summarized

in a diagram

as shown in Figure 6. It is evident

381 that the states are strongly lOO"C, the isolated dependent upon these parameters. are present. At temperatures below

and clustered

diammines exists

The ammine

corresponding (II) nitrate. All

to more than 10 wt % copper, After the dehydration copper ammine remain ammines present around

however,

as free tetrammine species

copper

lOO"C, isolated

are in part clustered.

on the surface

decompose cupric

around

265 - 300C. The clustered while isolated species

transforms

into highly dispersed cupric

ion clusters,

partly as isolated CuO clusters tetrammine

ions, even after decomposition.

When highly into bulk CuO.

dispersed However,

are heated above 72O"C, they transform (II) nitrate rapidly decomposes

again

copper

into bulk CuO even at 500C.

CONCLUSION Copper-silica a variety catalysts prepared by an ion exchange method were characterized held on the support temperature of the by

of methods. affected

It was shown that the states of copper by the amount of copper

were greatly

loaded and the calcination obtained, a surface involved diagram

of the catalyst. catalyst

On the basis of the results as a function

was presented

of the parameters

in the preparation

of the catalyst.

ACKNOWLEDGEMENT We would like to thank Professor M. Nagayama and Dr. H. Konno, Hokkaido University,

for their help in the XPS measurements

and discussion.

REFERENCES J.R. Anderson, "Structure of Metallic Catalysts", Academic Press, New York, 1975 A. Sugier and 0. Bloch, Proc. Fourth Intern. Cong. Catalysis, Akademiai, Tiado, Budapest, 1971, p. 238. H. Kobayashi, N. Takezawa and C. Minochi, Chem. Lett., (1976) 1347. C. Minochi, H. Kobayashi and N. Takezawa, Chem. Lett., (1976) 507. K. Takahashi, N. Takezawa and H. Kobayashi, Applied Catal., 2 (1982) 363. H. Kobayashi, N. Takezawa, C, Minochi and K. Takahashi, Chem. Lett., (1980) 1197 H. Kobayashi, N. Takezawa and C. Minochi, Bull. Fat. of Eng., Hokkaido Univ., 102 (1981) 13. H. Kobayashi, N. Takezawa and C. Minochi, J. Catal., 69 (1981) 487. 98 M. Sato, T. Kanabayashi, N. Kobayashi and Y. Shima, J. Catal., 7 (1967) 342. 10 D.C. Frost, A. Ishitani and C.A. McDowell, Mol. Phys., 24 (1878) 861. 11 L.H. Little, "Infrared Spectra of Adsorbed Species", Academic Press, New York, 1966. R. Soga, Bull. Chem. Sot. Japan, 34 (1961) 1461. G.K. Boreskov, Proc. Sixth Intern. Cong. Catal., London, The Chemical Society, London, 1976, p. 204. R.M. Frieman, J.J. Freeman and K.W. Lytle, J. Catal., 55 (1978) 10. 1': F.N. Khasnov, V.N. Vorb'ev and G. Sh. Talipov, Kinet. i Katal., 19 (1978) 577. 16 J. Bjerrum, J. Ballhausen and C.K. Jorgenson, Acta Chem. Stand., 8 (1954) 1275. D.M. Grant and R. Kollrack, J. Inorg. Nucl. Chem., 23 (1961) 25. 1; P. Kubelka and F. Munk, 2. Tech. Phys., 12 (1931) 593. 19 F.A. Miller and C. Wilkins, Anal. Chem., 24 (1952) 1253. 1 2