Catalysis: Volume 27

256 Pages·2015·7.866 MB·English

by  James Spivey, Yi-Fan Han, K Dooley, Cynthia Lo, Angelika Brueckner, Vadim Guliant, Hui Li, Shaobin Wang, Sven Jaras

Catalysis
Volume 27
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A Specialist Periodical Report
Catalysis
Volume 27
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6 A Review of Recent Literature
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8 Editors
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8 James J. Spivey, Louisiana State University, USA
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9/ Yi-FanHan,EastChinaUniversityofScienceandTechnology,Shanghai,
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10 China
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1 K. M. Dooley, Louisiana State University, USA
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org | Authors
sc. Javier Barrientos, KTH - Royal Institute of Technology, Sweden
bs.r Magali Boutonnet, KTH - Royal Institute of Technology, Sweden
u
p://p Angelika Bru¨ckner, Leibniz-Institut fu¨r Katalyse e. V. an der Universita¨t
htt Rostock, Germany
on Zhuo Cheng, Washington University, USA
n . 015 Vadim V. Guliants, University of Cincinnati, USA
o2
d y Dirk Hollmann, Leibniz-Institut fu¨r Katalyse e. V. an der Universita¨t
adeuar Rostock, Germany
wnloFebr Sven Ja¨rås, KTH - Royal Institute of Technology, Sweden
Do05 Eunmin Lee, Washington University, USA
n
o Hexing Li, Shanghai Normal University, China
d
he Hui Li, Shanghai Normal University, China
s
bli Cynthia S. Lo, Washington University, USA
u
P Luis Lo´pez, KTH - Royal Institute of Technology, Sweden and
Universidad Mayor de San Andre´s, Boliva
Fa´tima Pardo, KTH - Royal Institute of Technology, Sweden and
Universidad Mayor de San Andre´s, Boliva
Thomas Risse, Freie Universita¨t Berlin, Germany
Rodrigo Sua´rez Par´ıs, KTH - Royal Institute of Technology, Sweden
Hongqi Sun, Curtin University, Australia
Shaobin Wang, Curtin University, Australia
Wei Wei, Shanghai Normal University, China
Yu Zhao, Shanghai Normal University, China
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sc. ISBN: 978-1-78262-054-9
bs.r eISBN: 978-1-78262-269-7
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p://p DOI: 10.1039/9781782622697
htt ISSN: 0140-0568
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n . 015 A catalogue record for this book is available from the British Library
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adeuar & The Royal Society of Chemistry 2015
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Do05 All rights reserved
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he Apart from any fair dealing for the purpose of research or private study for
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bli non-commercialpurposes,orcriticismorreview,aspermittedundertheterms
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of the UK Copyright, Designs and Patents Act, 1988 and the Copyright and
Related Rights Regulations 2003, this publication may not be reproduced,
stored or transmitted, in any form or by any means, without the prior
permission in writing of The Royal Society of Chemistry, or in the case of
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Organization outside the UK. Enquiries concerning reproduction outside the
terms stated here should be sent to The Royal Society of Chemistry at the
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Published by The Royal Society of Chemistry,
Thomas Graham House, Science Park, Milton Road,
Cambridge CB4 0WF, UK
Registered Charity Number 207890
For further information see our web site at www.rsc.org
Preface
DOI: 10.1039/9781782622697-FP005
Chapter 1: Preparation and catalytic applications of amorphous alloys
In this chapter, preparation and catalytic applications of amorphous
5 alloys is reviewed by Hui Li, Wei Wei, Yu Zhao, and Hexing Li from
0
0
P ShanghaiNormalUniversity,Shanghai,China.Amorphousalloysareone
F
7- of the most important catalytic materials and considered as a new gen-
9
6
2 eration of metallic catalysts. Mastery over the composition and/or
2
6
2 morphology of amorphous alloy enables control of its properties and
8
7
1 enhancementofitsapplicationsascatalyst.Theaimofthischapteristo
8
7
9 present the recent developments in the design- and fabrication of
9/
03 amorphous alloys through a chemical reduction method with an em-
1
0. phasis on composition- and morphology control. The examples dis-
1
oi: cussed in this review highlight the need to design and synthesis of
d
g | amorphous alloy with controllable composition or morphology in order
c.or to promote catalytic performances. Perhaps more importantly, they also
s
s.r are of value for researchers in the area of heterogeneous catalysis to
b
pu develop highly-efficient metallic catalysts.
p://
htt Chapter2:Insituelectronparamagneticresonance(EPR)–auniquetool
n
o for analysing structure and reaction behaviour of paramagnetic sites in
n . 015 model and real catalysts
o2
d y Inthenextreview,Insituelectronparamagneticresonanceisreviewedby
dear
au ThomasRisse,DirkHollmannandAngelikaBru¨cknerfromUniversityof
wnloFebr Rostock,Rostock,Mecklenburg-Vorpommern, Germany.The majority of
o5
D0 catalytic reactions involves reduction and/or reoxidation steps in which
n
d o electrons are transferred between catalysts and substrates. EPR spec-
e
h troscopy can sensitively probe the local environment of paramagnetic
s
bli catalyticsitesaswellastheirbehaviorincatalyticredoxprocessessinceit
u
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can beappliedunder awide range of conditions.After ashortsummary
of the most important application examples of in situ EPR in redox
catalysis, the main features of EPR spectra such g and A matrices and
approaches of their evaluation are presented using model systems that
containAuatomsdepositedonMgOsinglecrystalsurfaces.Toillustrate
theversatilityofinsituEPRforderivingstructure–reactivityrelationships
in catalysis, two application examples are presented in more detail: (1)
AnalysisofheterogeneoussupportedVO /TiO catalystsduringoxidative
x 2
dehydrogenation of propane in the gas phase and (2) Study of photo-
catalyticwatersplittingoverahomogeneouscatalyticsystemcomprising
an iridium photosensitizer complex and an iron carbonyl catalyst.
Chapter3:PresentandfutureprospectsinheterogeneouscatalystsforC
1
chemistry
Eunmin Lee, Zhuo Cheng, and Cynthia S. Lo (Washington University,
St.Louis,USA)examinetherecentresearchanddevelopmentincatalysis
of C reactants, including significant reactions involving CO and CH .
1 2 4
The conversion of these thermodynamically stable reactants into higher
Catalysis,2015,27,v–vi | v
(cid:2)c TheRoyalSocietyofChemistry2015
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volume and higher value products is a key challenge. There is particular
interest in converting these C reactants into higher carbon-number
1
products,suchashigheroxygenatesandliquidfuels.Studiestoexamine
various bond-breaking and bond-forming reactions are in the heart of
catalytic research. Examples of recent advances include synthesis and
catalyticunderstandingofreactionsonmetalnanoparticles,redox-active
metaloxidesupports,zeolitecatalysts,andtheuseofionicliquids.These
5
0 are the result of characterization tools that we anticipate will drive C
0 1
P
F development over the next decade.
7-
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26 Chapter 4: Catalytic oxidation of organic pollutants in aqueous solution
2
26 using sulfate radicals
8
17 An area of increasing importance in catalysis is its application to water
8
97 purification. In this review, Hongqi Sun and Shaobin Wang of Curtin
9/
3 University, Australia, review recent progress in advanced oxidation pro-
0
1
0. cessesasappliedtoorganiccontaminantsinaqueousmedia.Thefocusis
1
oi: on the interaction of catalyst with persulfate and peroxymonosulfate
d
g | ions. However, purely photolytic processes, and those which are light-
c.or assisted, are considered as well. Keys to more effective utilization of the
s
s.r sulfates are explored.
b
u
p://p Chapter5:Catalyticconversionofbiomass-derivedsynthesisgastofuels
htt This topic is timely, but its breadth requires a substantial joint effort,
on here from groups at both the Royal Institute of Technology (KTH) in
n . 015 SwedenandUniversidadMayordeSanAndr´esinBolivia.Theeffortisled
o2
d y by Rodrigo Su´arez Par´ıs of KTH. The authors first introduce the subject
adeuar by exploring the nature (compositions, physical properties) of typical
nloebr biomassgasifier effluents, then consider in turn the Fischer-Tropsch,
wF
Do05 substitute natural gas, ethanol/mixed alcohols, and methanol/dimethyl
n
o etherupgradingprocesses.Theyalsoexplorefurthercatalyticupgradesto
d
he certain Fischer-Tropsch products. In each case, they cover not only the
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bli descriptive catalysis, but also consider mechanism, thermodynaics, and
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process details.
Chapter 6: Theoretical studies of selective propane oxidation and
ammoxidation over vanadium-based multi-metal oxides
Oneofthemoststudiedcatalyticprocessesisherere-examinedbyVadim
Guliants of the University of Cincinnati. But in the present review the
focus is on recent insights provided by theoretical studies, in particular
density functional theory simulations of the surface of the important
Mo–V–Te–Nb–O M1 phase catalyst. These studies have led to new
mechanistic insights into the initial propane activation steps. Recent
studies are now beginning to shed light on the entire multielectron re-
action pathway for propane ammoxidation on multicomponent bulk
metaloxides,usingacombinationofCI-NEBanddimermethods.Forthe
M1 surface, it was found that V51¼O is the preferred surface site for all
three H abstraction steps, and that H abstraction from propane is the
rate-determining step for propane ammoxidation.
vi | Catalysis,2015,27,v–vi
CONTENTS
Cover
Imageprovidedcourtesyof
computationalsciencecompany
Accelrys(www.accelrys.com).An
7
0 electrondensityisosurfacemapped
0
FP withtheelectrostaticpotentialforan
7- organometallicmolecule.
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26 Thisshowsthechargedistribution
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6 acrossthesurfaceofthemolecule
2
78 withtheredareashowingthe
1
8 positivechargeassociatedwiththe
7
9/9 centralmetalatom.Researchcarried
03 outusingAccelrysMaterials
0.1 Studioss.
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p://p Preface v
htt
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n . 015 Insituelectronparamagneticresonance(EPR)–auniquetoolfor 1
o2
ded ary analysing structure and reaction behaviour of paramagnetic sites
nloaebru in model and real catalysts
wF
o5 Thomas Risse, Dirk Hollmann and Angelika Bru¨ckner
D0
on 1 Introduction 1
d
e 2 Basic experimental considerations 3
h
s
bli 3 Cw EPR spectroscopy of spin 1/2 systems 5
u
P 4 Pulse spectroscopic techniques: hyperfine interactions as 14
an introductory example
5 Case studies 16
6 Conclusions 29
References 30
Theoretical studies of selective propane oxidation and 33
ammoxidation over vanadium-based multi-metal oxides
Vadim V. Guliants
1 Introduction 33
2 Experimental studies of the M1 and M2 phases 34
3 Propane oxidation over vanadia-based catalysts 37
4 Theoretical studies of propane oxidation over V-based 42
bulk mixed oxides
5 Conclusions 57
References 58
Catalysis,2015,27,vii–viii | vii
(cid:2)c TheRoyalSocietyofChemistry2015
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Catalytic conversion of biomass-derived synthesis gas to fuels 62
Rodrigo Sua´rez Par´ıs, Luis Lo´pez, Javier Barrientos, Fa´tima Pardo,
Magali Boutonnet and Sven Ja¨rås
1 Introduction 62
2 Fischer–Tropsch fuels 65
3 Synthetic natural gas 95
7 4 Ethanol and mixed alcohols 106
0
P0 5 Other fuels: methanol and DME 118
F
7- 6 Conclusions and future perspectives 124
9
26 Acknowledgements 125
2
26 References 125
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8
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03 Preparation and catalytic applications of amorphous alloys 144
1
10. Hui Li, Wei Wei, Yu Zhao and Hexing Li
oi:
d 1 General introduction 144
org | 2 Composition control 146
sc. 3 Morphology control 163
bs.r 4 Conclusions and prospects 182
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p:// Acknowledgement 182
htt References 182
n
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n . 015
o2
d y Present and future prospects in heterogeneous catalysts for C 187
dear 1
nloaebru chemistry
ow5 F Eunmin Lee, Zhuo Cheng and Cynthia S. Lo
D0
n 1 Introduction 187
o
ed 2 State of the field 188
h
blis 3 Future outlook 198
u
P 4 Conclusions 202
References 202
Catalytic oxidation of organic pollutants in aqueous solution 209
using sulfate radicals
Hongqi Sun and Shaobin Wang
1 Introduction 209
2 Activation of persulfate (PS) 211
3 Homogeneous activation of peroxymonosulfate (PMS) 223
4 Heterogeneous activation of peroxymonosulfate (PMS) 230
5 Conclusions and perspective 242
References 243
viii | Catalysis,2015,27,vii–viii
In situ electron paramagnetic resonance
(EPR) – a unique tool for analysing
structure and reaction behaviour of
paramagnetic sites in model and real
catalysts
1
0
0
0
7-0 Thomas Risse,a Dirk Hollmannb and Angelika Bru¨ckner*b
9
6
2 DOI: 10.1039/9781782622697-00001
2
6
2
8
7
1
8
7 Themajorityofcatalyticreactionsinvolvesreductionand/orreoxidationstepsinwhich
9
9/ electronsaretransferredbetweencatalystsandsubstrates.EPRspectroscopycansensi-
3
0 tivelyprobethelocalenvironmentofparamagneticcatalyticsitesaswellastheirbehavior
1
0. incatalyticredoxprocessessinceitcanbeappliedunderawiderangeofconditions.After
1
oi: a short summary of the most important application examples of in situ EPR in redox
d
g | catalysis,themainfeaturesofEPRspectrasuchgandAmatricesandapproachesoftheir
or evaluationarepresentedusingmodelsystemsthatcontainAuatomsdepositedonMgO
sc. single crystal surfaces. To illustrate the versatility of in situ EPR for deriving structure–
bs.r reactivityrelationshipsincatalysis,twoapplicationexamplesarepresentedinmoredetail:
u
p://p d(1e)hyAdnroaglyesnisatioonf ohfepteroropgaenneeoinusthesugpapsoprtheadseVaOndx/T(i2O)2Stucdaytaolyfstpshodtourciantgalytoicxidwaatitveer
htt splitting over a homogeneous catalytic system comprising an iridium photosensitizer
n
o complexandanironcarbonylcatalyst.
n . 015
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dear
nloaebru 1 Introduction
wF
Do05 EPRspectroscopyhasbeenusedtocharacterizecatalystssinceveryearly
n
o on,becauseofitsabilitytoprovidedetailedinformationonparamagnetic
d
he speciessuchastheirgeometricandelectronicstructureortheirchemical
s
bli environment. In terms of the systems being investigated, EPR covers a
u
P wide range of applications from heterogeneous, via homogeneous cata-
lysts all the way to enzymatic systems. Paramagnetic species in catalytic
systemsrangefromsitesconsideredcrucialforcatalyticturnover,suchas
transitionmetalions,toparamagneticreactionintermediates.Analyzing
theirbehaviorinsitu,i.e.underconditionsascloseaspossibletothoseof
a catalytic reaction, can be most helpful for deriving structure–reactivity
relationships and reaction mechanisms. Nevertheless, applications of
in situ EPR spectroscopy for monitoring catalytic reactions are not as
numerous compared to other common methods such as vibrational
spectroscopy or X-ray techniques, due to the fact that it is restricted to
systems containing unpaired electrons. However, for catalytic redox
processes in which electrons are transferred between catalyst and
aInstitutfu¨rChemieundBiochemie,FreieUniversita¨tBerlin,Takustr.3,
14195Berlin,Germany
bLeibniz-Institutfu¨rKatalysee.V.anderUniversita¨tRostock,Albert-Einstein-Str.29a,
18059Rostock,Germany.E-mail:[email protected]
Catalysis,2015,27,1–32 | 1
(cid:2)c TheRoyalSocietyofChemistry2015
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reactants,insituEPR(oroperandoEPR,asitiscalledwhentogetherwith
theEPRspectrumcatalyticconversion/selectivitydataaremeasured)isa
uniquetool,sinceitcanvisualizethiselectrontransferdirectlyaslongas
paramagnetic species are involved. This has been illustrated in the past
for a variety of hydrocarbon conversion reactions. Thus, mixed oxide
and oxynitride bulk phases such as vanadium–phosphorus oxides,1
vanadium–molybdenum oxides,2 mixed VTiSbSi oxides,3 VAlON and
01 VZrON oxynitrides4 or heteropolyacids of defined structure5 have been
0
0
0 used for selective oxidation of alkanes and aromatics. Such reactions
7-
9 have also been monitored by in situ EPR over supported vanadia and
6
22 bismuth molybdate catalysts1 while supported chromia1 and nickel
6
82 catalysts6,7 were studied during non-oxidative aromatization of alkanes
7
1
8 as well as during interaction with butenes. Another important class of
7
9
9/ heterogeneous catalytic systems analysed by in situ EPR comprises
3
10 zeolites containing transition metal ions either incorporated in the
0.
1 frameworkorlocatedinporepositions.Manyofsuchcatalystshavebeen
oi:
d used to remove nitrogen oxides (NO ) from exhaust gases. Relevant
org | examples comprise the use of Co–BExA8 and Fe–ZSM-59 for selective
bs.rsc. cthaetaslyatmicerepduurpctoiosenboyfKNuOcxh,ebruotvaeltsoalC.,uw–hZoSsMe-5wohrakshbaesenbeweinderleyviuesweeddfoinr
u
p://p ref. 1. The interaction of benzene with oxygen has been recently studied
htt on the same type of catalysts to understand the gas-phase oxidation of
on benzenetophenol.10For amorecomprehensive selectionofapplication
n . 015 examplesforinsituEPRinheterogeneouscatalysisthereaderisreferred
d oy 2 to a number of reviews.1,2,11–13 Surprisingly, the use of in situ EPR spec-
adeuar troscopy for elucidating structure–reactivity relationships in homo-
wnloFebr geneous redox catalysis is even more limited than in heterogeneous
Do05 catalysis.
n
o In EPR spectroscopy the sample is placed in an external magnetic
d
he field to lift the degeneracy of the electron spin states and microwave
s
bli radiation is used to induce magnetic dipole transitions between these
u
P
states. Historically, most of the information has been obtained using
continuous wave EPR spectroscopy operating at a microwave frequency
of E10 GHz in the so-called X-band. Spectrometers of this kind are still
by far the most abundant ones, however, the last decades have seen a
significant diversification of experimental capabilities, namely, the
commercial availability of spectrometers operating at different micro-
wavefrequenciesaswellaspulsespectrometers,whichenablestheuseof
these techniques also outside of laboratories dedicated to instrumental
developments in EPR spectroscopy.14,15
The aim of this chapter is to acquaint the reader with the basic
principlesandapplicationopportunitiesofinsituEPRinredoxcatalysis.
The introductory part starts with a presentation of instrumental aspects
andexperimentalprocedures(Section2),followedbyadiscussionofthe
mostimportantparameters,thegandAmatrixcomponents,thatcanbe
derivedfromEPRspectra(Section3).Herewewillfocusontheexamples
of Au atoms and O (cid:3)(cid:4) radicals deposited on a MgO(001) surface, which
2
both represent the simplest case of paramagnetic species with a single
unpaired electron and a spin of S¼1/2. We will restrict ourselves to the
2 | Catalysis,2015,27,1–32