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In-situ characterization of heterogeneous

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catalysts themed issue

Guest editor Bert M. Weckhuysen

Please take a look at the issue 12 2010 table of contents to

access other reviews in this themed issue
 EDITORIAL www.rsc.org/csr | Chemical Society Reviews

Preface: recent advances in the in-situ

characterization of heterogeneous catalystsw
Bert M. Weckhuysen
DOI: 10.1039/c0cs90031a

Heterogeneous catalysis is a fascinating, the last decade a tremendous increase in-situ characterization techniques for
but complex multidisciplinary science, in the number of manuscripts dealing elucidating the genesis and working
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which is core business to our energy,
automotive, chemical and pharmaceutical
industries as most chemical reactions
are catalyzed by at least one material
containing a multitude of often distinct
catalytic functionalities. Although progress
has been made in our understanding of
the working principles and dynamics
of catalytic solids, their genesis and
mechanistic functioning under realistic
reaction conditions—as schematically
visualized in Fig. 1—represent still very
important scientific challenges to both
academia and industrial scientists. The
prospect of rational design of materials
with specific active sites to selectively
catalyze a chemical reaction in high
yield is very attractive. First of all, it
represents the most economical and
sustainable way of producing our daily
life transportation fuels, materials and
chemicals, but maybe as crucial—from
a pure fundamental point of view—it
is important to have insight into the
interfacial chemistry taking place between
the gas or liquid phase and the catalytic
surface at e.g. elevated temperatures and
pressures. Such knowledge may also be
very valuable to other research areas, e.g.
sensor technology and geochemistry.
Deep mechanistic insight into the
fundamentals of heterogeneous catalysis
can only be acquired by using advanced
characterization methods as well as
proper in-situ reaction cells and related
measurement protocols. This is the field
of in-situ or operando characterization.
Interestingly, we have seen especially in
with the use of in-situ and operando
catalyst characterization, including the
introduction of novel methods and
related measurement approaches. Fig. 2
outlines the three research areas, which
have received the most attention in
recent years; i.e., (a) the realization of
time-resolved combined spectroscopy
under more realistic reaction conditions;
(b) the development of in-situ tools to
characterize catalytic transformations in
the liquid phase; and (c) the development
of space-resolved and tomographic
characterization approaches, ultimately
allowing to perform single molecule-
single active site/catalyst particle in-situ
studies.
In view of all these aspects, I felt it was
the right time to put together a dedicated
issue for Chemical Society Reviews on
this very important scientific subject.
With the view of trying to represent as
much as possible of a wide variety of
in-situ characterization methods as applied
on a range of catalytic materials, I have
collected a series of 28 review articles
covering the advantages, limitations,
challenges and future possibilities of
principles of heterogeneous catalysts.
Special emphasis will be on recent
advances as many of the authors of this
collection of articles also present their
latest results. In this respect, this themed
issue of Chemical Society Reviews can be
seen as a valuable addition to two edited
books on in-situ characterization of
catalytic solids (J. F. Haw, In-situ
Spectroscopy of Heterogeneous Catalysis,
Wiley-VCH, 2002, and B. M. Weckhuysen,
In-situ Spectroscopy of Catalysts, American
Scientific Publishers, 2004) and a
compilation of general review articles,
which appeared in the period 2006–2009
in the book series Advances in Catalysis
(vol. 50–52).
In this dedicated issue, reviews on
general aspects of in-situ catalyst
characterization are included, which
may help researchers entering this field
to familiarize themselves with some
important aspects and recent trends.
Bentrup (DOI: 10.1039/b919711g) nicely
illustrates the potential of combining
in-situ characterization methods in one
experimental set-up. In this manner,
complementary information can be directly

Inorganic Chemistry and Catalysis Group,

Debye Institute for Nanomaterials Science,
Utrecht University, Sorbonnelaan 16,
3584 CA Utrecht, The Netherlands.
E-mail: b.m.weckhuysen@uu.nl;
Fax: +31 30 251 1027
w Part of the themed issue covering recent
advances in the in-situ characterization of Fig. 1 In-situ characterization approach to elucidate the intricate chemistry taking place during
heterogeneous catalysts. (a) catalyst synthesis and/or assembly; (b) catalytic reaction and (c) molecular diffusion.

This journal is c The Royal Society of Chemistry 2010 Chem. Soc. Rev., 2010, 39, 4557–4559 4557

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Fig. 2 Three research areas which have received the most attention in recent years in the area of
in-situ or operando catalyst characterization: (a) combined time-resolved spectroscopy under
more realistic reaction conditions; (b) spectroscopy in the liquid phase, including water and
(c) single molecule-single active site/catalyst particle spectroscopy.
compared leading to a more unified
picture of the phenomena taking place
during a catalytic process. Meunier
(DOI: 10.1039/b919705m) focuses on
the importance of verifying if an in-situ
spectroscopic measurement has sufficient
validity to make conclusions about a
potential reaction mechanism and high-
lights the potential pitfalls in performing
in-situ characterization experiments and
makes recommendations for designing
proper operando spectroscopic cells.
Foster and Lobo (DOI: 10.1039/
c0cs00016g) build further on these ideas
and show with some case studies how
one can identify reaction intermediates
and catalytic active sites by using the
in-situ catalyst characterization approach.
In the arena of catalyst synthesis, three
review articles focus on the in-situ
characterization methods for elucidating
the intricate chemistry of the synthesis of
porous crystalline materials, including
zeolites and metal organic frameworks
(MOFs). O’Brien, Beale and Weckhuysen
(DOI: 10.1039/c0cs00088d) in their
review focus on the use of synchrotron-
based characterization methods for
understanding the principles of porous
catalytic solids synthesis, while Fan,
Feng and Li (DOI: 10.1039/c0cs00012d)
convincingly illustrate the power of
in-situ UV Raman spectroscopy for
4558 Chem. Soc. Rev., 2010, 39, 4557–4559
studying the synthesis mechanism and
assembly processes of molecular sieves.
In a third review, Aerts, Kirschhock
and Martens (DOI: 10.1039/b919704b)
present a comprehensive review article
on the spectroscopic methods currently
available to probe zeolite synthesis
processes.
Magnetic resonance methods, including
NMR, MRI and EPR, are nowadays
more and more used to elucidate the
organic transformations taking place
within catalytic solids as well as the
dynamics of transport phenomena and
catalyst preparation processes in e.g. a
reactor or catalyst pellet. Four review
articles are focusing on these aspects of
heterogeneous catalysis research. Blasco
(DOI: 10.1039/c0cs00033g) and Ivanova
and Kolyagin (DOI: 10.1039/c0cs00011f)
highlight the use of in-situ NMR for
elucidating the reaction mechanisms of
heterogeneous catalysts with special
emphasis on zeolite materials. Brückner
(DOI: 10.1039/b919541f) nicely illustrates
the power of in-situ EPR for developing
structure–activity relationships for
various catalytic solids. Finally, Lysova
and Koptyug (DOI: 10.1039/b919540h)
summarize the intriguing space-resolved
findings one can obtain by using
MRI for investigating heterogeneous
catalysts.
This journal is
One of the most used methods for
in-situ catalyst characterization is
vibrational spectroscopy, including both
IR and Raman methods. This themed
issue contains eight review articles
which highlight the power of vibrational
techniques and related methods.
Whereas Wachs and Roberts (DOI:
10.1039/c0cs00145g) highlight in-situ
and operando Raman characterization
studies of supported metal oxide and
bulk metal oxide catalysts, Kim,
Kosuda, Van Duyne and Stair (DOI:
10.1039/c0cs00044b) emphasize in their
review the potential of resonance
Raman, and surface- and tip-enhanced
Raman spectroscopy for studying catalytic
solids and heterogeneous catalytic
reactions. Two reviews by Lamberti,
Zecchina, Groppo and Bordiga (DOI:
10.1039/c0cs00117a) and by Vimont,
Thibault-Starzyk and Daturi (DOI:
10.1039/b919543m) discuss the advances
in the use of IR spectroscopy to give
insight into the active sites, reaction
intermediates and plausible reaction
mechanisms of catalytic solids. As many
catalytic reactions are taking place at the
liquid–solid interface, attenuated total
reflection (ATR)-IR spectroscopy offers
many new opportunities for elucidating
reaction mechanisms and surface inter-
mediates in a wide variety of catalytic
processes. This emerging topic has
been reviewed by Mojet, Ebbesen and
Lefferts (DOI: 10.1039/c0cs00014k) and
Andanson and Baiker (DOI: 10.1039/
b919544k). Another vibrational spectro-
scopy review article focuses on the
catalyst chemical imaging capabilities of
Raman and IR spectroscopy and is
authored by Stavitski and Weckhuysen
(DOI: 10.1039/c0cs00064g). Finally,
Chmelik and Karger (DOI: 10.1039/
c0cs00100g) present a review article
in which amongst other methods
interference and IR microscopies are
used to investigate molecular diffusion
phenomena in porous catalytic solids,
including zeolites and MOFs.
Other important in-situ methods are
based on electronic spectroscopy and
include UV-Vis and fluorescence spectro-
scopy. In recent years we have seen
important steps forward in developing
micro- and nano-spectroscopy approaches
for investigating catalytic solids at work.
This has led to in-situ single particle
and single molecule studies revealing
c The Royal Society of Chemistry 2010
 fascinating new insights in molecular
diffusion processes and the functioning
of heterogeneous catalysts. Three review
articles focus on the use of fluorescence
microscopy for elucidating catalytic
reactivity. De Cremer, Sels, De Vos,
Hofkens and Roeffaers (DOI: 10.1039/
c0cs00047g) present a comprehensive
review article on the latest developments
in this field of research, while Tachikawa
and Majima (DOI: 10.1039/b919698f)
focus on single molecule-single particle
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fluorescence imaging of photocatalytic
processes. A third fluorescence micro-
scopy review article on catalyst reactivity
is by Peng Chen, Zhou, Shen, Andoy,
Choudhary, Han, Liu and Meng (DOI:
10.1039/b909052p). These authors have
summarized the recent progress in single
molecule-single particle fluorescence
nanoscopy. Another fluorescence micro-
scopy review features the visualization of
diffusion processes at the nanoscale and
is authored by Michaelis and Bräuchle
(DOI: 10.1039/c0cs00107d). Schoonheydt
(DOI: 10.1039/c0cs00080a) has reviewed
the use of UV-Vis spectroscopy and
microscopy. The latter in-situ method is
fully complementary with fluorescence
This journal is c The Royal Society of Chemistry 2010
microscopy and is now more and more
used in a combined fashion.
Finally, there are five review articles,
which are mainly focused on the use of
X-ray spectroscopy of heterogeneous
catalysts. It nicely illustrates the
increasing importance and availability
of suitable synchrotron beamlines for
doing in-situ catalyst characterization
work. Singh, Lamberti and van
Bokhoven (DOI: 10.1039/c0cs00054j)
summarize the recent advances in X-ray
absorption and emission spectroscopy
for elucidating the catalytic chemistry
of supported metal catalyst materials,
while Bordiga, Bonino, Lillerud and
Lamberti (DOI: 10.1039/c0cs00082e)
show the potential of X-ray absorption
spectroscopy to understand the structure
and reactivity of MOF materials. Hard
and soft X-ray microscopy and tomo-
graphy and their use in characterizing
catalytic solids are reviewed by
Grunwaldt and Schroer (DOI: 10.1039/
c0cs00036a) and by Beale, Jacques and
Weckhuysen (DOI: 10.1039/c0cs00089b).
Special emphasis is placed in these review
articles on the developments of in-situ
X-ray nanoscopy of catalytic solids as a
Chem. Soc. Rev., 2010, 39, 4557–4559
powerful tool, fully complementary to
the above mentioned in-situ fluorescence
nanoscopy techniques. Newton and
van Beek (DOI: 10.1039/b919689g)
present a state-of-the-art overview
of what is currently possible when
combining synchrotron-based X-ray
methods with vibrational spectroscopy
techniques and can be seen as a more
particular view of combining in-situ
characterization methods as discussed
in the Bentrup review article (DOI:
10.1039/b919711g).
I would like to take the opportunity to
thank all the authors and referees for
their valuable time in composing and
reviewing the excellent review articles
giving the reader different perspectives
on this important scientific discipline
within heterogeneous catalysis research.
Finally, I would like to thank the Editor,
Dr Robert Eagling, and staff of Chemical
Society Reviews for giving me the
opportunity to assemble this themed
issue on in-situ characterization of
catalytic solids. It was a real pleasure
working together with them on reading
and selecting the 28 review articles
assembled in this themed issue.
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