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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

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

Inorganic Chemistry and Catalysis Group,

Debye Institute for Nanomaterials Science,
Utrecht University, Sorbonnelaan 16,
3584 CA Utrecht, The Netherlands.
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
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,
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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:
Fig. 2 Three research areas which have received the most attention in recent years in the area of 10.1039/c0cs00117a) and by Vimont,
in-situ or operando catalyst characterization: (a) combined time-resolved spectroscopy under Thibault-Starzyk and Daturi (DOI:
more realistic reaction conditions; (b) spectroscopy in the liquid phase, including water and 10.1039/b919543m) discuss the advances
(c) single molecule-single active site/catalyst particle spectroscopy.
in the use of IR spectroscopy to give
insight into the active sites, reaction
intermediates and plausible reaction
compared leading to a more unified studying the synthesis mechanism and mechanisms of catalytic solids. As many
picture of the phenomena taking place assembly processes of molecular sieves. catalytic reactions are taking place at the
during a catalytic process. Meunier In a third review, Aerts, Kirschhock liquid–solid interface, attenuated total
(DOI: 10.1039/b919705m) focuses on and Martens (DOI: 10.1039/b919704b) reflection (ATR)-IR spectroscopy offers
the importance of verifying if an in-situ present a comprehensive review article many new opportunities for elucidating
spectroscopic measurement has sufficient on the spectroscopic methods currently reaction mechanisms and surface inter-
validity to make conclusions about a available to probe zeolite synthesis mediates in a wide variety of catalytic
potential reaction mechanism and high- processes. processes. This emerging topic has
lights the potential pitfalls in performing Magnetic resonance methods, including been reviewed by Mojet, Ebbesen and
in-situ characterization experiments and NMR, MRI and EPR, are nowadays Lefferts (DOI: 10.1039/c0cs00014k) and
makes recommendations for designing more and more used to elucidate the Andanson and Baiker (DOI: 10.1039/
proper operando spectroscopic cells. organic transformations taking place b919544k). Another vibrational spectro-
Foster and Lobo (DOI: 10.1039/ within catalytic solids as well as the scopy review article focuses on the
c0cs00016g) build further on these ideas dynamics of transport phenomena and catalyst chemical imaging capabilities of
and show with some case studies how catalyst preparation processes in e.g. a Raman and IR spectroscopy and is
one can identify reaction intermediates reactor or catalyst pellet. Four review authored by Stavitski and Weckhuysen
and catalytic active sites by using the articles are focusing on these aspects of (DOI: 10.1039/c0cs00064g). Finally,
in-situ catalyst characterization approach. heterogeneous catalysis research. Blasco Chmelik and Karger (DOI: 10.1039/
In the arena of catalyst synthesis, three (DOI: 10.1039/c0cs00033g) and Ivanova c0cs00100g) present a review article
review articles focus on the in-situ and Kolyagin (DOI: 10.1039/c0cs00011f) in which amongst other methods
characterization methods for elucidating highlight the use of in-situ NMR for interference and IR microscopies are
the intricate chemistry of the synthesis of elucidating the reaction mechanisms of used to investigate molecular diffusion
porous crystalline materials, including heterogeneous catalysts with special phenomena in porous catalytic solids,
zeolites and metal organic frameworks emphasis on zeolite materials. Brückner including zeolites and MOFs.
(MOFs). O’Brien, Beale and Weckhuysen (DOI: 10.1039/b919541f) nicely illustrates Other important in-situ methods are
(DOI: 10.1039/c0cs00088d) in their the power of in-situ EPR for developing based on electronic spectroscopy and
review focus on the use of synchrotron- structure–activity relationships for include UV-Vis and fluorescence spectro-
based characterization methods for various catalytic solids. Finally, Lysova scopy. In recent years we have seen
understanding the principles of porous and Koptyug (DOI: 10.1039/b919540h) important steps forward in developing
catalytic solids synthesis, while Fan, summarize the intriguing space-resolved micro- and nano-spectroscopy approaches
Feng and Li (DOI: 10.1039/c0cs00012d) findings one can obtain by using for investigating catalytic solids at work.
convincingly illustrate the power of MRI for investigating heterogeneous This has led to in-situ single particle
in-situ UV Raman spectroscopy for catalysts. and single molecule studies revealing

4558 Chem. Soc. Rev., 2010, 39, 4557–4559 This journal is c The Royal Society of Chemistry 2010
fascinating new insights in molecular microscopy and is now more and more powerful tool, fully complementary to
diffusion processes and the functioning used in a combined fashion. the above mentioned in-situ fluorescence
of heterogeneous catalysts. Three review Finally, there are five review articles, nanoscopy techniques. Newton and
articles focus on the use of fluorescence which are mainly focused on the use of van Beek (DOI: 10.1039/b919689g)
microscopy for elucidating catalytic X-ray spectroscopy of heterogeneous present a state-of-the-art overview
reactivity. De Cremer, Sels, De Vos, catalysts. It nicely illustrates the of what is currently possible when
Hofkens and Roeffaers (DOI: 10.1039/ increasing importance and availability combining synchrotron-based X-ray
c0cs00047g) present a comprehensive of suitable synchrotron beamlines for methods with vibrational spectroscopy
review article on the latest developments doing in-situ catalyst characterization techniques and can be seen as a more
in this field of research, while Tachikawa work. Singh, Lamberti and van particular view of combining in-situ
and Majima (DOI: 10.1039/b919698f) Bokhoven (DOI: 10.1039/c0cs00054j) characterization methods as discussed
focus on single molecule-single particle summarize the recent advances in X-ray in the Bentrup review article (DOI:
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fluorescence imaging of photocatalytic absorption and emission spectroscopy 10.1039/b919711g).

processes. A third fluorescence micro- for elucidating the catalytic chemistry I would like to take the opportunity to
scopy review article on catalyst reactivity of supported metal catalyst materials, thank all the authors and referees for
is by Peng Chen, Zhou, Shen, Andoy, while Bordiga, Bonino, Lillerud and their valuable time in composing and
Choudhary, Han, Liu and Meng (DOI: Lamberti (DOI: 10.1039/c0cs00082e) reviewing the excellent review articles
10.1039/b909052p). These authors have show the potential of X-ray absorption giving the reader different perspectives
summarized the recent progress in single spectroscopy to understand the structure on this important scientific discipline
molecule-single particle fluorescence and reactivity of MOF materials. Hard within heterogeneous catalysis research.
nanoscopy. Another fluorescence micro- and soft X-ray microscopy and tomo- Finally, I would like to thank the Editor,
scopy review features the visualization of graphy and their use in characterizing Dr Robert Eagling, and staff of Chemical
diffusion processes at the nanoscale and catalytic solids are reviewed by Society Reviews for giving me the
is authored by Michaelis and Bräuchle Grunwaldt and Schroer (DOI: 10.1039/ opportunity to assemble this themed
(DOI: 10.1039/c0cs00107d). Schoonheydt c0cs00036a) and by Beale, Jacques and issue on in-situ characterization of
(DOI: 10.1039/c0cs00080a) has reviewed Weckhuysen (DOI: 10.1039/c0cs00089b). catalytic solids. It was a real pleasure
the use of UV-Vis spectroscopy and Special emphasis is placed in these review working together with them on reading
microscopy. The latter in-situ method is articles on the developments of in-situ and selecting the 28 review articles
fully complementary with fluorescence X-ray nanoscopy of catalytic solids as a assembled in this themed issue.

This journal is c The Royal Society of Chemistry 2010 Chem. Soc. Rev., 2010, 39, 4557–4559 4559