Sustainable catalysis, Without metals or other endangered elements. Part 1

392 Pages·2015·13.33 MB·English

by  Clark

Sustainable Catalysis
Without Metals or Other Endangered Elements
Part 1
RSC Green Chemistry
Editor-in-Chief:
Professor James Clark, Department of Chemistry, University of York, UK
Series Editors:
Professor George A. Kraus, Department of Chemistry, Iowa State University,
Ames, Iowa, USA
Professor Andrzej Stankiewicz, Delft University of Technology,
The Netherlands
Professor Peter Siedl, Federal University of Rio de Janeiro, Brazil
Titles in the Series:
1: The Future of Glycerol: New Uses of a Versatile Raw Material
2: Alternative Solvents for Green Chemistry
3: Eco-Friendly Synthesis of Fine Chemicals
4: Sustainable Solutions for Modern Economies
5: Chemical Reactions and Processes under Flow Conditions
6: Radical Reactions in Aqueous Media
7: Aqueous Microwave Chemistry
8: The Future of Glycerol: 2nd Edition
9: Transportation Biofuels: Novel Pathways for the Production of Ethanol,
Biogas and Biodiesel
10: Alternatives to Conventional Food Processing
11: Green Trends in Insect Control
12: A Handbook of Applied Biopolymer Technology: Synthesis,
Degradation and Applications
13: Challenges in Green Analytical Chemistry
14: Advanced Oil Crop Biorefineries
15: Enantioselective Homogeneous Supported Catalysis
16: Natural Polymers Volume 1: Composites
17: Natural Polymers Volume 2: Nanocomposites
18: Integrated Forest Biorefineries
19: Sustainable Preparation of Metal Nanoparticles: Methods and
Applications
20: Alternative Solvents for Green Chemistry: 2nd Edition
21: Natural Product Extraction: Principles and Applications
22: Element Recovery and Sustainability
23: Green Materials for Sustainable Water Remediation and Treatment
24: The Economic Utilisation of Food Co-Products
25:BiomassforSustainableApplications:PollutionRemediationandEnergy
26: From C–H to C–C Bonds: Cross-Dehydrogenative-Coupling
27: Renewable Resources for Biorefineries
28: Transition Metal Catalysis in Aerobic Alcohol Oxidation
29: Green Materials from Plant Oils
30: Polyhydroxyalkanoates (PHAs) Based Blends, Composites and
Nanocomposites
31: Ball Milling Towards Green Synthesis: Applications, Projects,
Challenges
32: Porous Carbon Materials from Sustainable Precursors
33: Heterogeneous Catalysis for Today’s Challenges: Synthesis,
Characterization and Applications
34: Chemical Biotechnology and Bioengineering
35: Microwave-Assisted Polymerization
36: Ionic Liquids in the Biorefinery Concept: Challenges and Perspectives
37: Starch-based Blends, Composites and Nanocomposites
38: Sustainable Catalysis: With Non-endangered Metals, Part 1
39: Sustainable Catalysis: With Non-endangered Metals, Part 2
40: Sustainable Catalysis: Without Metals or Other Endangered
Elements, Part 1
41: Sustainable Catalysis: Without Metals or Other Endangered
Elements, Part 2
How to obtain future titles on publication:
Astandingorderplanisavailableforthisseries.Astandingorderwillbring
delivery of each new volume immediately on publication.
For further information please contact:
BookSalesDepartment,RoyalSocietyofChemistry,ThomasGrahamHouse,
Science Park, Milton Road, Cambridge, CB4 0WF, UK
Telephone: þ44 (0)1223 420066, Fax: þ44 (0)1223 420247
Email: [email protected]
Visit our website at www.rsc.org/books

Sustainable Catalysis
Without Metals or Other Endangered
Elements
Part 1
Edited by
Michael North
Green Chemistry Centre of Excellence, University of York, York, UK
Email: [email protected]
RSCGreenChemistryNo.40
PrintISBN:978-1-78262-640-4
PDFeISBN:978-1-78262-209-3
ISSN:1757-7039
AcataloguerecordforthisbookisavailablefromtheBritishLibrary
rTheRoyalSocietyofChemistry2016
Allrightsreserved
Apartfromfairdealingforthepurposesofresearchfornon-commercialpurposesorfor
privatestudy,criticismorreview,aspermittedundertheCopyright,DesignsandPatents
Act1988andtheCopyrightandRelatedRightsRegulations2003,thispublicationmaynot
bereproduced,storedortransmitted,inanyformorbyanymeans,withouttheprior
permissioninwritingofTheRoyalSocietyofChemistryorthecopyrightowner,orinthe
caseofreproductioninaccordancewiththetermsoflicencesissuedbytheCopyright
LicensingAgencyintheUK,orinaccordancewiththetermsofthelicencesissuedby
theappropriateReproductionRightsOrganizationoutsidetheUK.Enquiriesconcerning
reproductionoutsidethetermsstatedhereshouldbesenttoTheRoyalSocietyof
Chemistryattheaddressprintedonthispage.
TheRSCisnotresponsibleforindividualopinionsexpressedinthiswork.
Theauthorshavesoughttolocateownersofallreproducedmaterialnotintheirown
possessionandtrustthatnocopyrightshavebeeninadvertentlyinfringed.
PublishedbyTheRoyalSocietyofChemistry,
ThomasGrahamHouse,SciencePark,MiltonRoad,
CambridgeCB40WF,UK
RegisteredCharityNumber207890
Forfurtherinformationseeourwebsiteatwww.rsc.org
PrintedintheUnitedKingdombyCPIGroup(UK)Ltd,Croydon,CR04YY,UK
Preface
The12principlesofgreenchemistrywereoriginallyreportedbyAnastas1
intheformshowninBox1andlaterasthemnemonicshowninBox2by
Poliakoff.2 A feature of these principles is the use of catalytic reagents to
accomplish chemical transformations. The development of catalysts for
important chemical transformations certainly predates any notion of
green chemistry and has been a major feature of research in all areas of
chemistry for almost 150 years. Thus, physical chemists and material
scientists have dominated the development of heterogeneous catalysis;
physical and physical organic chemists have developed tools to allow
catalytic cycles to be determined. Inorganic and organic chemists have
developed new ligands and catalysts for homogeneous metal-based
catalysts and organic chemists have shown that metal-free asymmetric
catalysis can be achieved. Finally, biological chemists have studied the
mechanisms of enzyme-catalysed reactions and developed new
biochemical tools that allow the structure of enzymes to be modified to
enhance their catalytic activity for a particular substrate, or even allow
them to catalyse a different reaction.
There have been some remarkable achievements in catalyst development
recognisedbynumerousNobelprizesforworkdoneinthisarea(Box3)and
catalysis has progressed to the stage where it is now difficult to imagine a
reaction that cannot be achieved catalytically. However, examination of the
catalyticliteratureshowsthatthemajorityofcatalystsdeveloped,andmany
that are in commercial use rely upon the use of metals or other elements
whose abundance in the Earth’s crust is very limited and that are being
rapidly consumed. This is illustrated in Figure 1 for papers on asymmetric
catalysis published between 1999 and 2005.3
RSCGreenChemistryNo.40
SustainableCatalysis:WithoutMetalsorOtherEndangeredElements,Part1
EditedbyMichaelNorth
rTheRoyalSocietyofChemistry2016
PublishedbytheRoyalSocietyofChemistry,www.rsc.org
vii
viii Preface
Box 1 The 12 principles of green chemistry
according to Anastas
1. Itisbettertopreventwastethantotreatorcleanupwasteafteritis
formed.
2. Synthetic methods should be designed to maximise the in-
corporation of all materials used in the process into the final
product.
3. Whereverpracticable,syntheticmethodologiesshouldbedesigned
to use and generate substances that possess little or no toxicity to
human health and the environment.
4. Chemical products should be designed to preserve efficacy of
function while reducing toxicity.
5. The use of auxiliary substances (e.g. solvents, separation agents
etc.) should be made unnecessary wherever possible and innocu-
ous when used.
6. Energy requirements should be recognized for their environ-
mentalandeconomicimpactandshouldbeminimized.Synthetic
methods should be conducted at ambient temperature and
pressure.
7. A raw material or feedstock should be renewable rather than de-
pleting wherever technically and economically practicable.
8. Unnecessary derivatization (blocking group, protection/deprotec-
tion, temporary modification of physical/chemical processes)
should be avoided whenever possible.
9. Catalytic reagents (as selective as possible) are superior to stoi-
chiometric reagents.
10. Chemical products should be designed so that at the end of their
function they do not persist in the environment and break down
into innocuous degradation products.
11. Analyticalmethodologiesneedtobefurtherdevelopedtoallowfor
real-time,in-processmonitoringandcontrolpriortotheformation
of hazardous substances.
12. Substancesandtheformofasubstanceusedinachemicalprocess
should be chosen so as to minimise the potential for chemical
accidents, including releases, explosions and fires.
The availability of chemical elements depends on many factors as
discussed in Chapter 1 of Sustainable Catalysis: With Non-endangered
Metals,Part1.Withtheexceptionofhelium,whichistoolighttobeheldby
the Earth’s gravity and so is lost to space, chemical elements are not
actually being lost to planet Earth, rather they are being transferred from
relatively rich ores to much more diluted waste sites from where, in most
Preface ix
Box 2 The green chemistry mnemonic developed
by Poliakoff
P – Prevent wastes
R – Renewable materials
O – Omit derivatization steps
D – Degradable chemical products
U – Use safe synthetic methods
C – Catalytic reagents
T – Temperature, pressure ambient
I – In process monitoring
V – Very few auxiliary substances
E – E-factor, maximise feed in product
L – Low toxicity of chemical products
Y – Yes, it is safe
cases, it is not currently economically viable to recover them. This,
combined with growing demand for many elements, often low recycling
ratesandgeographicalandpoliticalrestrictionsonoreavailabilityleadsto
the concept of elemental sustainability. One pictorial representation of
elemental sustainability is shown in Figure 24 and this, along the British
GeologicalSurvey2012Risklist(BGS2012)5whichrankedthesupplyriskof
elements from10(high)to 1(low) forms thebasisof therestofthis book.
Thus, catalysts that contain only elements coloured green or orange in
Figure 2 and that have a relative supply risk index of 7.6 or lower in the
BGS2012areincludedinthisbookwiththreeexceptions.Palladiumwould
have been borderline to include (orange in Figure 2 and supply risk index
of7.6inBGS2012),buthasbeenexcludedasitissowidelyusedincatalysis
that it would have required a separate volume to cover its use in catalysis.
Achapteronscandiumandyttriumbasedcatalystswasplannedbutcould
not be delivered due to the author’s ill health.
After an introductory chapter on elemental sustainability, the first two
volumes of this work, Sustainable Catalysis: With Non-endangered Metals,
Parts 1 and 2, deal with sustainable metal based catalysts. Within each
subsequentchapter,theauthorshavebeenaskedtoexcludeanycatalystthat
contains ligands containing endangered elements (e.g. phosphorus) and to
highlight any examples that have other sustainable features (use of green
solvent, high atom economy, etc.). Where appropriate, elements have been
grouped together (e.g. thealkali metals inChapter 2) and those metals that
are most commonly used in catalysis have been given multiple chapters:
Chapters 4–7 for titanium, 12–13 for iron and 18–19 for aluminium. The
finalthreechaptersofPart2dealwiththallium,tinandleadbasedcatalysts.
Theseareincludedforcompletenessastheymeettherequirementsoutlined
x Preface
Box 3 Nobel prizes for catalysis (up to 2014)
2010:RichardF.Heck,Ei-ichiNegishiandAkiraSuzukiforpalladium-
catalysed cross couplings in organic synthesis.
2007: Gerhard Ertl for studies of chemical processes on solid
surfaces
2005: Yves Chauvin, Robert H. Grubbs and Richard R. Schrock
for the development of the metathesis method in organic syn-
thesis.
2001: William S. Knowles, Ryoji Noyori and K. Barry Sharpless
for work on chirally catalysed hydrogenation and oxidation
reactions.
1997: Paul D. Boyer, John E. Walker and Jens C. Skou for the eluci-
dation of the enzymatic mechanism underlying the synthesis of
adenosine triphosphate (ATP) and the first discovery of an ion-
transporting enzyme, Na1, K1 -ATPase.
1989: Sidney Altman and Thomas R. Cech for the discovery of the
catalytic properties of RNA.
1975: John Warcup Cornforth and Vladimir Prelog for work on the
stereochemistryofenzyme-catalyzed reactionsandresearch into the
stereochemistry of organic molecules and reactions.
1972: Christian B. Anfinsen, Stanford Moore and William H. Stein for
workonribonuclease,especiallyconcerningtheconnectionbetween
the amino acid sequence and the biologically active conformation
andforcontributiontotheunderstandingoftheconnectionbetween
chemical structure and catalytic activity of the active centre of the
ribonuclease molecule.
1963: Karl Ziegler and Giulio Natta for their discoveries in the field of
the chemistry and technology of high polymers.
1929: Arthur Harden and Hans Karl August Simon von Euler-Chelpin
for their investigations on the fermentation of sugar and fermen-
tative enzymes.
1918: Fritz Haber for the synthesis of ammonia from its elements.
1912: Victor Grignard and Paul Sabatier for the discovery of the so-
called Grignard reagent, which in recent years has greatly advanced
the progress of organic chemistry and for the method of hydrogen-
ating organic compounds in the presence of finely disintegrated
metals whereby the progress of organic chemistry has been greatly
advanced in recent years.
1909: Wilhelm Ostwald in recognition of his work on catalysis and for
his investigations into the fundamental principles governing chem-
ical equilibria and rates of reaction.