Jackson S.D., Hargreaves J.S.J. Metal Oxide Catalysis

234 5 Solid-State NMR of Oxidation Catalysts

n - butylamine adsorption, four distinct resonances, at ∼ 49, 40, 33 and 30 ppm, were

identiﬁ ed in the region expected for the two α and β carbons of the butyl group.

By comparison with spectra of solid HCl and BCl

3

adducts of n - butylamine, a Lewis

acid adsorption site (where the alkylamine is bonded directly to a surface Al) is

clearly identiﬁ ed. The fact that the chemical shift of these peaks is higher than the

corresponding peaks for the BCl

3

adduct shows that the γ - Al

2

O

3

surface Lewis acid

site is stronger than BCl

3

.

This ﬁ eld, including the shift of focus to

15

N MAS and CP - MAS NMR of

15

N - enriched adsorbates, was subsequently developed by a number studies on

materials such as γ - alumina and amorphous silica – aluminas [211 – 213, 219 – 222] .

Similarly, solid - state

15

N NMR studies employing N

2

O as the adsorbate have also

yielded success [83, 85, 223] .

The use of

15

N spectroscopy fell out of favor as a means of characterizing acid

sites, as probe molecules such as pyridine can undergo fast chemical exchange on

some catalysts at room temperature [224] . However, Haw and coworkers [225]

addressed this problem by conducting experiments at a sufﬁ ciently low tempera-

ture to ensure slow - exchange spectra. This approach also resulted in higher sen-

sitivity through improved CP efﬁ ciency, the Boltzmann factor and reduced coil

noise. Figure 5.32 shows a pyridine -

15

N NMR titration of sulfated zirconia. Peaks

Figure 5.32

15

N CP - MAS spectra of pyridine -

15

N titrating

sulfated zirconia (4.57 wt% S): (a) 0.04 mmol/g,

(b) 0.08 mmol/g, (c) 0.12 mmol/g, (d) 0.20 mmol/g, and

(e) 0.47 mmol/g. Adapted from ref. [225] ; reprinted with

permission from the American Chemical Society.

at − 180 ppm and − 106 ppm, are assigned to Br ø nsted and Lewis acid sites respec-

tively. The peak at − 65 ppm corresponds to excess titrant.

Shimizu and coworkers have also studied pyridine adsorption over zirconia -

based catalysts – in this case tungstated zirconia [226] . In this work

15

N MAS NMR

experiments (spinning speed 5 – 7 kHz) were carried out at 140 K, providing the

advantages of low - temperature studies described above. Reduced zirconia, with no

tungsten, yields a

15

N NMR spectrum with only one peak at − 96 ppm. This can be

assigned to pyridine bound to Lewis acid sites. Upon the addition of tungsten three

peaks were observed, at − 72 ppm, − 108 ppm and − 181 to − 173 ppm. These were

assigned to physisorbed pyridine, Lewis complexes and Br ø nsted complexes

respectively. Br ø nsted acid sites were stronger after reduction of the tungstated

catalyst, an effect which was deemed to result in enhanced activity of the catalysts

for o - xylene isomerization.

5.5

Outlook

The development of new and improved NMR techniques is continual and fast -

paced, with the range of systems that are suitable for study and the information

that can be elucidated from them increasing all the time. Recent years have seen

a shift away from one - dimensional NMR techniques towards two - dimensional

techniques, such as MQMAS, which are often capable of providing higher resolu-

tion. In particular, the recent development of the SATRAS technique opens up

new possibilities. In addition to the applications outlined above, Antonijevic and

coworkers [28] have reported on the use of SATRAS to study host – guest interac-

tions and guest dynamics in framework solids. Nuclei that could be studied by

this method include

17

O,

23

Na,

27

Al and

71

Ga.

Existing techniques are also likely to be applied to a wider range of nuclei as

they become increasingly established. For instance, MQMAS has, to date, been

applied to a relatively small number of nuclei but recent studies have begun to

expand this number, for example to

51

V [27] . Advances in technical capabilities

may also prove signiﬁ cant, as higher ﬁ eld strengths and, in the case of MAS,

spinning rates become accessible. This will lead to increased information being

extracted from existing techniques as spectral resolution improves.

NMR is a valuable tool for acquiring important information that provides real

insights into catalyst structure and catalytic behavior. In the coming years, however,

improvements in hardware are likely to result in NMR becoming even more sig-

niﬁ cant as experiments reveal ever more information and developments within

other ﬁ elds become adopted for the study of catalysts.

Acknowledgments

The ATHENA project, supported by EPSRC of the UK and Johnson Matthey plc.

is gratefully acknowledged for funding aspects of the research reported herein.

5.5 Outlook 235

236 5 Solid-State NMR of Oxidation Catalysts

Additionally, Drs Melinda J. Duer and Robin Stein of the University of Cambridge,

Department of Chemistry, are thanked for conducting the experiment described

in Figure 5.23 . Finally, Prof. Lynn F. Gladden of the University of Cambridge,

Department of Chemical Engineering, is thanked for her valuable input and guid-

ance in the preparation of this chapter.

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Photoelectron Spectroscopy of Catalytic Oxide Materials

Detre Teschner , Elaine M. Vass , and Robert Schl ö gl

243

6

6.1

Introduction

Heterogeneous catalysis is one of the most important tools for industrial chemical

processes, making them economically feasible and also environmentally friend-

lier. Although heterogeneous catalysis has long been established in the chemical

industry, and our understanding of how catalysts function has greatly improved

since the 1980s, the lack of a widely accepted, universal theory of heterogeneous

catalytic reactions makes this ﬁ eld of physical chemistry still an “ undiscovered

land ” . Since most of the catalysts are solid materials, their surface geometric and

electronic structure should hold the key to the desired understanding of their

working principles. Among the various experimental techniques employed to

study surface properties, Photoelectron Spectroscopy ( PES ) plays an important

role. Owing to the short mean free path of photoelectrons in the solid, PES is

strongly biased towards the top few atomic layers of the solid, depending on the

kinetic energy of the detected electrons. The technique thus probes surface and

near - surface electronic properties of the solid sample, starting from the chemical

(oxidation) state of its constituents to the more complex valence - band electronic

structure. The latter, in combination with quantum chemical calculations, proved

to be essential in understanding the main bulk electronic structure of solid materi-

als between 1970 and 1990, and the combination is expected to experience a

revival, thus rejuvenating surface chemistry. Furthermore, X - ray Photoelectron

Spectroscopy ( XPS ) can provide information regarding the elemental stoichiome-

try of the near - surface region, which is often different from the bulk composition.

The catalytic function is acknowledged to be essentially dependent on the surface

composition and electronic properties, which make PES (and especially XPS) a

popular surface analytical tool.

Metal oxides currently ﬁ nd widespread application in many ﬁ elds of industry

from IT to chemical technologies, as in catalysis. In this chapter, after brieﬂ y

reviewing the basic principles and elements of PES and introducing how in situ

experimentation can provide an additional playing ﬁ eld to catalysis, we will

Metal Oxide Catalysis. Edited by S. David Jackson and Justin S. J. Hargreaves

ISBN: 978-3-527-31815-5

Jackson S.D., Hargreaves J.S.J. Metal Oxide Catalysis

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