The past, present and future of heterogeneous catalysis

Quá khứ, hiện tại và tương lai của xúc tác dị thể. Xúc tác dị thể là xúc tác trong đó chất xúc tác ở khác pha với chất phản ứng.Chất xúc tác dị thể thường là chất rắn và phản ứng xảy ra trên bề mặt chất xúc tác. Thường gặp nhất là những hệ xúc tác dị thể gồm pha rắn và pha khí (các chất tham gia phản ứng và sản phẩm phản ứng). Ðặc điểm của phản ứng xúc tác dị thể là phản ứng diễn ra nhiều giai đoạn, có hai đặc trưng: Quá trình xảy ra ở lớp đơn phân tử trên bề mặt chất xúc tác. Ðặc trưng này thể hiện ở chỗ trong xúc tác dị thể thì khuếch tán và hấp phụ đóng vai trò quan trọng. Chất xúc tác không phải là những phân tử, ion riêng rẽ mà là một tổ hợp những nguyên tử, ion

Ioana Fechetea, Ye Wangb, Jacques C Védrinec,∗

a Laboratoire des Matériaux, Surfaces et Procédés pour la Catalyse, CNRS UMR 7515, Université de Strasbourg, 25 rue Becquerel, F-67087 Strasbourg, France

b State Key Laboratory of Physical Chemistry of Solid Surfaces and National Engineering Laboratory for Green Chemical Productions of Alcohols, Ethers and Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, PR China

c Laboratoire de Réactivité de Surface, CNRS UMR 7197, Université Pierre et Marie Curie, 4 Place Jussieu, F- 75252 Paris, France

Thisreviewhighlightskeycatalyticdiscoveriesandthemainindustrialcatalyticprocessesoverthelast

300yearsthatinvolvedcommodities,finechemicals,petrochemicals,petroleumtransformationforfuelsandenergysupply,emissioncontrol,andsoforth.Inthepast,discoverieshaveoftenfollowedeventssuch

aswarsorembargos,whereasthecurrentdrivingforcesofstudies,researchesandthendiscoveriesaim

atabetterunderstandingofcatalyticprocesses,atreducingthecostsofrawmaterialsandprocesses,atdevelopingnewcatalyticmaterialsandataddressingenvironmentalissues.Thisreviewfocusesonthehistoryofmanycatalyticindustrialprocesses,environmentalissues,catalyticmaterials,especiallytheirexpectedcatalyticproperties,oncatalystcharacterisationbyphysicalmethodsanddevelopmentofinsituconditions,i.e.,characterisationunderactualworkingconditionswithreactantsandproductsanalyzedon-line.Emphasisisalsoplacedonhighselectivityincatalyticreactionsandthemajorchallengesforthefuture,suchasenvironmentalissues,energysupply,pollutioncontrolforvehiclesandindustrialplants,air/VOCs/waterpurification,hydrogensourcesandcarbondioxidestorage/upgrading,transformationofbiomassasapromisingsourceofrawmaterials,andcatalyticwatersplittingperspectives

Thisreviewisasurveyofheterogeneouscatalysisandisnotcomprehensivebutleadstotheconclusionthat,althoughmanycatalystsandcatalyticprocesseshavealreadybeendiscoveredanddevelopedoverthepastcentury,manyopportunitiesneverthelessexistfornewdevelopments,newprocessesandnewcatalyticmaterials.Itfollowsthatsubstantialchallengesexistfortheyoungergenerationofresearchersandengineers,asemphasizedattheendofthemanuscript

© 2012 Elsevier B.V All rights reserved

1 Introduction

∗ Corresponding author Tel.: +33 144275514.

E-mail address: jacques.vedrine@upmc.fr (J.C Védrine).

[7–13]

0920-5861/$ – see front matter © 2012 Elsevier B.V All rights reserved.

Table 1

Historical aspects in heterogeneous catalysis [7–13]

2 The catalysts

fine particles Moreover, one of the most important

state

MeAPOs

process)

Fig 2.Illustration of a molecule in a pore and shape selectivity in dealuminated mordenite zeolite.

Fig 4. Variations of van der Waals energy W and the force between a

spheri-cal molecule (radius d) and a spherical micropore (radius a) vs curvature (s = d/a)

[47–49]

Fig.3

Fig 5.Adipic acid processes using the old process (left) and the new process (right).

[51–58]hasbeendiscoveredattheBoreskovInstituteofCatalysis

Fig 6. Scheme of the effect of the adsorption rate of reactants on the reactivity,

depending on the polarity of the reactants versus that of the zeolite [63,64]

[65–68].However,aconvenientwaytoincreasep-xylene

MCM-22 [100–102],discovered byMobil, which hasa uniquecrystal

Fig 7. Historical view of functions of coordination polymers reported from 1990 to 2005 Structures of 3-D porous coordination polymers, [Cu(SiF 6 )(4,4  -bpy) 2 ] n(1,left), [Zn O(BDC) ] (2,right), and the 1-D oxygen array are listed [124]

Fig 8. Self-assembly of polymetallic cluster nodes (left; top: m4-oxo{M4 O(-CO 2 ) 6};bottom:{M2 (-CO 2 ) 4}paddlewheel) and organic linkers (right) yielding metal–organic frameworks (center) [125,126]

etal.[104,105]describedthemicroporousaluminophosphates

Fig 9. MOFs structures: Left: MIL-53, metal terephtalate (with Al, Cr, Fe ou V), which captures hydrogen into the framework formed of tunnels Centre and right: MIL-100, whose octahedra, constituted by chromates (CrO ), organise in tetrahedra and form cavities of diameter 2–3 nm as observed by electron microscopy from [127]

thestructure type.AccordingtoMartens[112],eventhehighly

Fig 10.MOF: MIL-101 metal terphthalate with cages of 3.2 nm [128]

[127]

Fig 11. Schematic behavior observed upon adsorption, desorption of guest molecules (a) induced pores (b) breathing pore; (c) pores exchanging guest with

Table 2

Comparison of MOFs with zeolites for some properties relevant to catalysis [131]

Brønsted acidity Bridging Si(OH)Al hydroxyl groups Introduced by post synthesis

Diffusion High for small molecules in gas phase, slow in liquid phase High but strongly influenced by linkers

Basicity Arises from framework oxygens Introduced post synthesis or through linkers

Framework defects Important role in many reactions Expected to play a minor role

Active site environment Mostly hydrophilic, but may also be hydrophobic Considerably hydrophobic

Poisoning of active sites Reactivation by thermal treatment Thermal treatment not valid

Chirality Not possible or difficult Homochiral solid from chiral linkers or post synthesis modifications

[137],etc

enzymes

Fig 13.World energy consumption in 2005 (∼13 TW or 87 Gbarrels oil) [245]

[141],bettermultifunctionalitytoprocessalargevarietyof

in1991 [154].CNTs have highlyunique electronic,mechanical,

FSM-16[171].Atthemicroscopicscale,thesematerialsareessentially

[200–210],moleculardesigneddispersionapproach[211–213]and

[237]andsynergyeffects[238–240].Heterogeneousbifunctional

[242]havealsoshownthatafterabifuntionalcatalyst,9-thiourea

3 Energy resources

Fig 14. Some perspectives of oil demand in a near future from WEO 2006 Note that

billions tonnes should read giga tonnes.

Fig.14

Fig.15

Table 3

Main chemical products from natural gas.

Source: IFP Energies Nouvelles.

fuel

inTable4.Woodisanimportantsourceforlignin.Theproduction

Table 4

Crops mobilised for energy pruposes versus total production in 2007.

Total harvest (Mt) % for bioenergies

From FAOSTA, FAPRI.

4 Hydrogen as a future energy source

product

[260,261],Ni[262,263],Cu[264,265],Ru[266,267],Au[268,269],

Pt[270]

production

Table 5

Commercial uses of wood (in Mm 3 ) and breakdown of conventional energy uses in 2007.

Wood harvest Sawn wood Wood for paper Wood for board Wood for fuel Fuel wood %

system

candidates

infancy

RuO [282]

5 Challenges for refineries

[290].TheconfinementofironoxideparticlesinsidetheCNTsor

(FCC)

[300,301] A two-stage hydrogenation process is usually used

[330–332]andnoblemetalcatalysts[300,324,333–349].Excellent

6 CO 2 emissions as a prospective source for fuels and chemicals [353–358]

changes inthe climate Theenergy sector,which is thelargest

7 Activation and upgrading of light alkanes

8 Waste air, water and VOCs treatments

compounds

[390,391]

[388,389,392–402].Themostactivecatalystsarethenoblemetal

9 Photocatalysis

[282,420–423]

TiO2[423].ThreecommonTiO2polymorphsexistinnature,which,

carriers

10 Solar photon conversion [433]

Fig 16.Major factors influencing selectivity in catalytic reactions [455]

11 Green chemistry – selectivity in catalysis

[436].Theprincipleofgreenchemistryisthatratherthanusing

[293,442–447].Highselectivityisthemostimportantaspectofa

12 Major challenges for the future

field

Table 6

Major problems and challenges in automotive car industry.

Lean burn gasoline engine Efficiency higher by ca 25% NO x trapping; SOx tolerant traps Dry particulate emissions from diesel engines DOC reduces SOF, HC, and CO; no

current catalyst/system to treat dry soot

Catalyst to lower lightoff T of soot; addition of Cu and Ce-organometallics

to fuel Diesel engine lean NO x Direct decomposition or reduction of

NO x in O 2 -rich atmosphere

Larger operating window for PM or BM-catalysts, NH 3 or urea SCR.

resources

13 Conclusions

[455].Sunlightandwaterareinfiniteresourcesandcanprovidethe

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