GENERAL ARTICLE

Molecular Mechanism of Heterogeneous Catalysis

The 2007 Nobel Prize in Chemistry
R S Swathi and K L Sebastian

(left) R S Swathi is a Senior Research Fellow at the Department of Inorganic and Physical Chemistry, working with Prof. K L Sebastian. Her research interests include theoretical study of resonance energy transfer involving various donor-acceptor systems. (right) K L Sebastian is a Professor at the Department of Inorganic and Physical Chemistry, Indian Institute of Science. His area of interest is theoretical chemistry.

G e rh a r d E rtl, th e G e r m a n p h y sic a l ch e m ist, w a s a w a r d e d th e N o b e l P riz e in ch e m istr y fo r th e y e a r 2 0 0 7 , fo r h is c o n trib u tio n s in th e a re a o f su r fa c e sc ie n c e . H is p a in sta k in g w o r k le d to a m ic r o sc o p ic u n d e r sta n d in g o f h e te ro g e n e o u s c a ta ly sis in in d u stria lly im p o rta n t c h e m ic a l r e a c tio n s . T h e se in c lu d e th e H a b e r{ B o sc h p r o c e ss fo r th e p ro d u c tio n o f a m m o n ia , a n d th e c a ta ly tic o x id a tio n o f c a rb o n m o n o x id e . 1 . In tr o d u c tio n A m m o n ia is a n im p o rta n t ch em ica l a s it is u sed in th e p ro d u ctio n o f fertilizers a n d o th er ch em ica ls. It is m a n u fa ctu red b y th e rea ctio n o f n itro g en w ith h y d ro g en . T h is h a s th e a d va n ta g e th a t n itro g en is v ery rea d ily ava ila b le, a s it co n stitu tes 7 8 .1 % o f a ir. F u rth er, th e rea ctio n b etw een n itro g en a n d h y d ro g en , N 2 (g ) + 3 H 2 (g ) $ 2 N H 3 (g ) H = 9 2 :4 k J = m o l (a t2 9 8 K ) (1 ) is ex o th erm ic, a n d h en ce o n e m ig h t h av e ex p ected it to o ccu r ea sily, o n ce y o u m ix th e tw o g a ses a t ro o m tem p era tu re. H ow ev er, o n m ix in g , th e rea ctio n d o es n o t o ccu r a t a ll, a s th e a ctiva tio n en erg y fo r th e rea ctio n is v ery la rg e. T h e rea so n fo r th e h ig h a ctiva tio n en erg y is th a t th e rst step o f th e rea ctio n is th e b rea k in g o f th e b o n d b etw een th e tw o n itro g en a to m s. A s it is a trip le b o n d , th is step n eed s a lo t o f en erg y, a s a resu lt o f w h ich th e a ctiva tio n en erg y fo r th e rst step in th e rea ctio n is v ery la rg e. T h u s, ev en a t th e h ig h tem p era tu re o f 5 0 0 o C , th e rea ctio n o ccu rs w ith v ery lo w y ield . A s th ere is n et red u ctio n in v o lu m e w h en a m m o n ia is fo rm ed (see

Keywords 2007 Chemistry Nobel Prize, heterogeneous catalysis, surface science experiments.

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(1 )), o n e ex p ects h ig h p ressu re to fav o r th e fo rm a tio n o f a m m o n ia . In sp ite o f th is, a t a tem p era tu re o f 5 0 0 C a n d a p ressu re o f 2 5 0 a tm o sp h eres, th e y ield is still low . A b rea k th ro u g h in th e sy n th esis w a s m a d e in 1 9 0 9 , w h en F ritz H a b er, a G erm a n ch em ist, sy n th esized a m m o n ia u sin g th e rea ctio n rep resen ted b y eq u a tio n (1 ). H e rea lized th a t th e rea ctio n o ccu rs at a p p recia b le ra tes, u n d er co n d itio n s m en tio n ed a b ov e, if a p o ro u s iro n ca ta ly st, p rep a red b y red u cin g th e iro n ox id e m a g n etite (F e 3 O 4 ) is u sed . In 1 9 1 0 C a rl B o sch , u sed th is fo r th e in d u stria l p ro d u ctio n o f a m m o n ia . U sin g th is p ro cess, a m m o n ia w a s m a n u fa ctu red in G erm a n y d u rin g th e rst W o rld W a r, w h ich w a s th en u sed to p ro d u ce th e m u ch n eed ed a m m o n iu m n itra te, fo r u se in ex p lo siv es. A t th a t tim e, a ll th e n a tu ra l so u rces o f n itra te w ere u n d er B ritish co n tro l a n d if H a b er h a d n o t d ev elo p ed th e p ro cess, th e co u rse o f h isto ry w o u ld h av e b een v ery d i eren t! H a b er a n d B o sch w ere aw a rd ed th e N o b el P rize, fo r th eir w o rk , in th e y ea rs 1 9 1 8 a n d 1 9 3 1 , resp ectiv ely. T h e iro n ca ta ly st is in th e so lid sta te, a n d th e rea ctio n o ccu rs o n its su rfa ce, w h ere th e tw o g a ses, n itro g en a n d h y d ro g en g et a d so rb ed a n d th en rea ct. T h is rea ctio n is a n ex a m p le o f h etero g en eo u s ca ta ly sis, a p ro cess o f ca ta ly sis w h erein th e rea cta n ts a n d th e ca ta ly st a re in d i eren t p h a ses o f m a tter. T h e rea ctio n , ev en th o u g h co m m ercia lized , req u ires ra th er h ig h tem p era tu re a n d p ressu re a n d it still rem a in s a d rea m to h av e a ca ta ly st w h ich w o u ld w o rk a t low er tem p era tu res a n d p ressu res. O sm iu m is a b etter ca ta ly st, b u t h a s th e d isa d va n ta g e o f b ein g m o re ex p en siv e, a n d h en ce is n o t u sed fo r in d u stria l p ro d u ctio n . It is in terestin g th a t b a cteria ca lled rh izo b ia ca n co n v ert n itro g en in to a m m o n ia a n d th en o th er co m p o u n d s. T h e m ech an ism o f th is is n o t u n d ersto o d a n d is a v ery a ctiv e a rea o f resea rch [1 ]. In o rd er to d ev elo p a b etter ca ta ly st fo r in d u stria l p ro d u ctio n , it is n ecessa ry to h av e a clea r u n d ersta n d in g o f th e m ech a n ism o f th e rea ctio n , v iz., th e va rio u s step s in v o lv ed in

Fritz Haber, who was responsible for demonstrating that ammonia can be produced using an iron catalyst, and later together with Bosch, pioneered its industrial production. He was awarded the Nobel Prize in chemistry for the year 1918.

Carl Bosch, who was awarded the Nobel Prize in chemistry for the year 1931 for pioneering the industrial production of ammonia.

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Processes occurring on surfaces are very difficult to study both experimentally and theoretically, which led Fermi to exclaim: God made the bulk but the Devil created the surface.

th e p ro cess, a n d h ow th e ca ta ly st w o rk s. In sp ite o f th e o b v io u s im p o rta n ce o f th is rea ctio n , su ch m icro sco p ic d eta ils rem a in ed u n k n ow n fo r a v ery lo n g tim e. T h e rea so n w a s th a t p ro cesses o ccu rrin g o n su rfa ces w ere v ery d i cu lt to stu d y b o th ex p erim en ta lly a n d th eo retica lly. In fa ct, th e N o b el P rize w in n in g p h y sicist, E n rico F erm i, is rep u ted to h av e sa id : \G od m ade the bu lk bu t the D evil created the su rface". 2 . A B ir d 's E y e V ie w o f E rtl's C o n trib u tio n s T h e 2 0 0 7 C h em istry N o b el P rize w a s aw a rd ed to G erh a rd E rtl w o rk in g a t th e F ritz H a b er In stitu te in B erlin , fo r h is stu d ies w h ich led to a n u n d ersta n d in g o f th e m icro sco p ic step s in th e ca ta ly tic fo rm a tio n o f a m m o n ia a s w ell a s o th er im p o rta n t su rfa ce ca ta ly zed p ro cesses [2 ]. H e u tilized v ery p ow erfu l ex p erim en ta l tech n iq u es to o b ta in a co m p lete p ictu re o f th e m o lecu la r p ro cesses in v o lv ed in su ch ca ta ly tic rea ctio n s. S u rfa ces a re ca p a b le o f ca ta ly zin g m a n y ch em ica l rea ctio n s. A n u n d ersta n d in g o f a n y su ch ca ta ly tic p ro cess o n a su rfa ce h a s fa r-rea ch in g im p lica tio n s in b o th a ca d em ic resea rch a n d in th e in d u stria l d ev elo p m en t o f ch em ica l p ro cesses. F o r in sta n ce, th e ex h a u st o f m o to r v eh icles co n ta in s h ig h ly tox ic g a ses. P a rticu la rly u n d esira b le is ca rb o n m o n ox id e (C O ), w h ich h a s to b e rem ov ed fro m th e ex h a u st b efo re it is relea sed in to th e a tm o sp h ere. T h e o b v io u s p ro ced u re w o u ld b e to ox id ize it to ca rb o n d iox id e C O 2 a n d P t w a s k n ow n to ca ta ly ze th e ox id a tio n . E rtl stu d ied th is rea ctio n in d eta il a n d fo u n d th e elem en ta ry step s in v o lv ed in th e p ro cess [3 ]. H is w o rk a lso fo cu ssed o n th e g en era tio n o f a rti cia l fertilizers a n d th e stu d y o f rea ctio n s in fu el cells w h ich o ccu r o n electro d e su rfa ces. H is o th er sig n i ca n t co n trib u tio n s in clu d e a n u n d ersta n d in g o f th e m ech a n ism o f fo rm a tio n o f ru st o n a n iro n su rfa ce, th e rea so n s fo r th e d ep letio n o f o zo n e lay er a n d h ow o n e co u ld d ev ise m eth o d s to p rev en t th e d ep letio n .

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3 . S u rfa c e S c ie n c e E x p e r im e n ts S u rfa ce scien ce ex p erim en ts a re v ery d i cu lt to p erfo rm . T h e rea so n is th a t su rfa ces ea sily g et co n ta m in a ted b y th e a tm o sp h eric g a ses. F o r ex a m p le, ea ch a to m o n a su rfa ce ex p o sed to a p ressu re o f 1 a tm is stru ck a b o u t 1 0 8 tim es in o n e seco n d . E v en w h en th e p ressu re is red u ced to 1 0 4 P a , ea ch su rfa ce a to m is h it 1 0 tim es in o n e seco n d , w h ich a g a in g ets co n ta m in a ted v ery ra p id ly. T h erefo re, to stu d y a ch em ica l rea ctio n h a p p en in g o n a su rfa ce, o n e h a s to k eep th e su rfa ce in a lm o st n ea r va cu u m co n d itio n s. T h e co n d itio n s u sed in v o lv e p ressu res low er th a n a b o u t 1 0 7 P a o r 1 0 0 n P a ( 1 0 9 T o rr) a n d a re k n ow n a s u ltra h ig h va cu u m (U H V ) [4 ]. T h e tech n iq u es fo r g en era tio n o f U H V b eca m e ava ila b le o n ly in th e 1 9 5 0 s a n d 6 0 s. U H V req u ires th e u se o f sp ecia l m a teria ls in crea tin g th e va cu u m sy stem , ex trem e clea n lin ess to m a in ta in th e va cu u m sy stem , a n d b a k in g th e en tire sy stem to rem ov e w a ter a n d o th er tra ce g a ses th a t a re a ccu m u la ted . A t su ch low p ressu res th e m ea n free p a th o f a g a s m o lecu le is a p p rox im a tely 4 0 k m . S o th e g a s m o lecu les w ill co llid e w ith th e ch a m b er w a lls m a n y tim es b efo re co llid in g w ith ea ch o th er. A lm o st a ll th e in tera ctio n s th erefo re ta k e p la ce o n va rio u s su rfa ces in th e ch a m b er. T h e ex p erim en ta l sig n a tu res o f lay ers o f a d so rb ed a to m s a n d m o lecu les a re ra th er w ea k . T h erefo re, in v estig a tio n o f a p a rticu la r ch em ica l rea ctio n o n a su rfa ce n eed s a ca refu l ch o ice o f ex p erim en ta l tech n iq u es. E rtl w a s a m o n g th e p io n eers in p ro b in g m o n o lay ers o f a to m s a n d m o lecu les o n p u re su rfa ces. H e m a d e u se o f a va riety o f eleg a n t tech n iq u es fo r th is p u rp o se. T h is in clu d ed L ow E n erg y E lectro n D i ra ctio n (L E E D ), p h o to electro n sp ectro sco p y, In fra red sp ectro sco p y, w o rk fu n ctio n m ea su rem en ts, a n d a va riety o f o th er tech n iq u es [5 ]. L E E D g iv es u s in fo rm a tio n o n th e p a ttern s th a t a d so rb a tes fo rm o n th e su rfa ces. A d so rb a te-su rfa ce in tera ctio n s a re p ro b ed b y F o u rier T ra n sfo rm In fra red S p ectro sco p y (F T IR ). A d so rb a te cov era g e ca n b e q u a n ti-

Surface science experiments are very difficult to perform.

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ed b y w o rk fu n ctio n m ea su rem en ts. A n o th er eleg a n t tech n iq u e is th e S ca n n in g T u n n elin g M icro sco p y (S T M ), w h ich ca n b e u sed to p ro b e th e a to m ic lo ca tio n s a n d th e lo ca l electro n ic stru ctu re o n a su rfa ce, a n d to m a n ip u la te a to m s o n su rfa ces. E rtl is v ery u n iq u e, in th a t h e clev erly u sed a ll th ese tech n iq u es to g et a co m p lete p ictu re o f in d u stria lly releva n t p ro cesses o ccu rrin g o n su rfa ces [6 ]. A s a resu lt o f th e sy stem a tic in v estig a tio n s h e w a s a b le to g iv e a n sw ers to certa in fu n d a m en ta l q u estio n s in su rfa ce scien ce th a t w ere u n a n sw ered fo r d eca d es. 4 . C a ta ly tic P ro d u c tio n o f A m m o n ia W h en a m o lecu la r sp ecies a p p ro a ch es a su rfa ce, it ca n u n d erg o sev era l p ro cesses n ea r th e su rfa ce. It m ay ju st b in d to th e su rfa ce b y va n d er W a a ls in tera ctio n s, a p ro cess th a t is k n ow n a s p h y siso rp tio n . A ltern a tiv ely, it m ay fo rm ch em ica l b o n d s w ith th e su rfa ce a to m s, lea d in g to ch em iso rp tio n . S o m etim es a m o lecu le m ay u n d erg o d isso cia tio n a t th e su rfa ce a n d th e co n stitu en t fra g m en ts fo rm ch em ica l b o n d s w ith th e su rfa ce. If o n e o f th e fra g m en ts n d s a su ita b le a d so rb ed sp ecies n ea rb y, it m ay th en rea ct w ith su ch a sp ecies o n th e su rfa ce a n d fo rm n ew p ro d u cts, w h ich leav e th e su rfa ce in a p ro cess k n ow n a s d eso rp tio n . T h ese p o ssib ilities a re sch em a tica lly sh ow n in F igu re 1 .
Figure 1. Possible processes that atoms/molecules can undergo near a surface: a. An atom is adsorbed onto a surface. b. A moleculegets dissociatively chemisorbed onto the surface. c. Two chemisorbed atoms on the surface undergo a reaction, form a new product which finally desorbs from the surface.

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In th e p ro d u ctio n o f a m m o n ia , n itro g en a n d h y d ro g en m o lecu les g et a d so rb ed o n th e su rfa ce o f th e iro n ca ta ly st th a t is u sed . T h en th ey rea ct ea sily a s a resu lt o f stay in g in p rox im ity w ith ea ch o th er. T h e rea ctio n o ccu rs in sev era l step s. T h e b o ttlen eck in su ch a p ro cess is th e slow est step . It d eterm in es th e ov era ll sp eed o f th e p ro cess a n d h en ce is k n ow n a s th e ra te d eterm in in g step . If o n e ca n d ev ise a m eth o d o lo g y fo r sp eed in g u p th e slow est step o f th e rea ctio n , th e ra te o f th e rea ctio n ca n b e in crea sed . E rtl u sed a clea n iro n su rfa ce in a va cu u m ch a m b er a n d in tro d u ced n itro g en a n d h y d ro g en g a ses in to th e ch a m b er. It w a s a lrea d y k n ow n th a t th e h y d ro g en m o lecu le im m ed ia tely d isso cia tes in to its co n stitu en t a to m s o n a tta ch in g to th e su rfa ce. B u t, it w a s u n lik ely th a t th e n itro g en m o lecu le w ith v ery stro n g trip le b o n d w o u ld d isso cia te in to n itro g en a to m s a n d fo rm b o n d s w ith iro n . S o , a n in terestin g q u estio n th a t E rtl a sk ed w a s w h eth er h y d ro g en rea cts w ith th e a to m ic fo rm o f n itro g en o r its m o lecu la r fo rm lea d in g to th e fo rm a tio n o f a m m o n ia . S o , th e rst ta sk a t h a n d w as to d istin g u ish b etw een th e a to m ic a n d m o lecu la r n itro g en o n th e iro n su rfa ce. W h en a su rfa ce is b o m b a rd ed w ith p h o to n s o f a p p ro p ria te en erg y, th ey ca n k n o ck o th e electro n s in th e a to m s w h ich a re p resen t o n th e su rfa ce. T h e k in etic en erg ies o f th e electro n s th a t a re k n o ck ed o ca n b e m ea su red , a n d th e tech n iq u e is k n ow n a s p h o to electro n sp ectro sco p y [7 ]. F ro m th e ex p erim en ta l d a ta , it is p o ssib le to u n d ersta n d th e ch em ica l en v iro n m en t o f th e a to m to w h ich th e electro n b elo n g s. It is p o ssib le to d istin g u ish if th e a to m ex ists o n its ow n o n th e su rfa ce o r is p a rt o f a n o th er m o lecu le th a t is a d so rb ed o n to th e su rfa ce. T h u s o n e ca n n d th e co n cen tra tio n o f n itro g en a to m s o n th e iro n su rfa ce. In a n ex p erim en t, d u rin g th e p ro cess o f a d d in g th e h y d ro g en to th e sy stem , th e co n cen tra tio n o f n itro g en a to m s w a s m o n ito red . If th e rea ctio n w a s w ith m o lecu la r n itro g en , th e co n cen tra tio n o f n itro g en a to m s

Photoelectron spectroscopy can be used to investigate whether nitrogen exists on the surface as atoms or as molecules.

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Ertl then concluded that the three hydrogens actually add up one by one to the nitrogen to generate ammonia.

sh o u ld n o t ch a n g e a s o n e a d d s h y d ro g en g a s. B u t, a d ecrea se in th e co n cen tra tio n o f th e n itro g en a to m s w a s o b serv ed co n rm in g th a t th e rea ctio n is a ctu a lly b etw een d isso cia ted h y d ro g en a to m s a n d n itro g en a to m s. S o , th e slow est step o f th e rea ctio n is th e d isso cia tio n o f n itro g en m o lecu le in to its co n stitu en t a to m s. A fter co n rm in g th a t th e rea ctio n is b etw een th e h y d ro g en a n d n itro g en a to m s a d so rb ed o n th e su rfa ce, th e n ex t step w a s to u n d ersta n d th e rea ctio n s lea d in g to th e fo rm a tio n o f a m m o n ia fro m th ese a to m s. B u t, o n ce th e slow est step (d isso cia tio n o f n itro g en m o lecu le in to its a to m s) o ccu rred , th e o th er step s w ere v ery fa st. H en ce it w a s n o t p o ssib le to stu d y th e o th er step s, w ith th e tim e reso lu tio n o f th e tech n iq u es ava ila b le. H ere a g a in , E rtl rea so n ed th a t a s th e rea ctio n is rev ersib le, o n e co u ld sta rt w ith a m m o n ia a n d try to lo o k a t its d isso cia tio n o n th e su rfa ce. T h e id ea w o rk ed q u ite w ell a n d h e co u ld stu d y th e d isso cia tio n p ro cess a n d h e m ea su red th e ra tes a t w h ich th e a m m o n ia m o lecu le relea ses its h y d ro g en a to m s. N H 2 a s su ch co u ld n o t b e id en ti ed sp ectro sco p ica lly. B u t, b y lettin g N H 3 a n d D 2 o n th e iro n su rfa ce, h e co u ld o b serv e h y d ro g en a to m s o n th e su rfa ce in d ica tin g th e d isso cia tio n o f N H 3 . T h e p resen ce o f N H w a s co n rm ed b y sev era l sp ectro sco p ic tech n iq u es lik e u ltra v io let p h o to electro n sp ectro sco p y (U P S ), seco n d a ry io n m a ss sp ectro m etry (S IM S ), h ig h reso lu tio n electro n en erg y lo ss sp ectro sco p y (H R E E L S ). H e th en co n clu d ed th a t th e th ree h y d ro g en s a ctu a lly a d d u p o n e b y o n e to th e n itro g en to g en era te a m m o n ia . T h u s, th e H a b er-B o sch p ro cess o ccu rs in sev era l step s, g iv en b elow : N 2 * N 2 ;a d * 2 N a d (2 ) ) ) H N NH
ad+ ad+ 2

* 2H )
ad ad

ad ad 2 ;a d

(3 ) (4 ) (5 )

H H

* NH ) * NH )

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NH

2 ;a d +

ad

* NH )

3 ;a d

* NH )

(6 )

T h e rst step is th e a d so rp tio n o f n itro g en a n d h y d ro g en m o lecu les o n to th e iro n su rfa ce. N itro g en a t rst p h y siso rb s a s a m o lecu le, a n d th en d isso cia tes in to a to m s, w h ich rem a in ch em iso rb ed o n th e su rfa ce. O n th e o th er h a n d , h y d ro g en m o lecu le ch em iso rb s d isso cia tiv ely, to g iv e h y d ro g en a to m s o n th e su rfa ce. T h e ch em iso rb ed n itro g en a to m th en im m ed ia tely p ick s u p th ree h y d ro g en a to m s, on e by on e lea d in g to th e fo rm a tio n o f a m m o n ia . F in a lly th e a m m o n ia m o lecu le d eso rb s fro m th e su rfa ce. T h e w h o le p ro cess is sh ow n in F igu re 2 a n d th e co rresp o n d in g en erg etics o f th e p ro cess is sh ow n in F igu re 3 . T h u s, h e d ev elo p ed a co m p lete p ictu re o f th e ca ta ly tic fo rm a tio n o f a m m o n ia , o n e o f th e m o st im p o rta n t in d u stria l ch em ica l p ro cesses. A ttem p ts w ere m a d e to sp eed u p th e slow est step , v iz., th e d isso cia tio n o f N 2 in to a to m ic n itro g en . It w a s fo u n d th a t th e a d d itio n o f p o ta ssiu m to th e ca ta ly st a ctu a lly

Figure 2. Steps involved in the HaberBosch process (the red balls denote the nitrogen atoms and the blue ones, the hydrogen atoms): a. N2 and H2 approach the iron surface. b. H2 undergoes dissociative chemisorption leading to hydrogen atoms on the surface. c. N2 gets physisorbed onto the surface. d. N2 undergoes dissociation on the surface and the nitrogen atoms bind to the iron atoms. e. Atomic nitrogen picks up a hydrogen atom on the surface forming NH. f. NH combines with another H atom forming NH2. g. NH2 picks up another hydrogen atom to form NH3. h. Ammonia desorbs from the iron surface.

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Figure 3. Energetics of the steps involved in the HaberBosch process. The energies are given in kJ/mol. Note that the first step is the physisorption of nitrogen, and that this is not activated. The next step is the dissociation of nitrogen into two nitrogen atoms, which are chemisorbed on the surface. E* is the activation energy for this step. Overall value of H under the conditions of the synthesis is 46 kJ/mol.
The figure is reproduced with permission from www.nobelprize.org

in crea ses th e ra te o f th is p ro cess. B u t, th e m ech a n ism w a s n o t u n d ersto o d . E rtl ca m e u p w ith a n ex p la n a tio n a s to w h y p o ta ssiu m sp eed s u p th e rea ctio n . T h e a d so rp tio n en erg ies o f n itro g en o n a n iro n su rfa ce w ith a n d w ith o u t th e p o ta ssiu m w ere m ea su red a n d th e a d so rp tio n en erg y w a s fo u n d to in crea se b y 1 0 1 5 k J / m o l o n a d d in g p o ta ssiu m [8 ]. T h erefo re, th e rea ctio n o ccu rred fa ster in th e p resen ce o f p o ta ssiu m . F u rth er, p o ta ssiu m d o n a tes electro n s to th e n eig h b o rin g iro n a to m s th ereb y lea d in g to th e fa cile d isso cia tio n o f th e n itro g en m o lecu le. T h u s p o ta ssiu m a cts a s a p ro m o ter fo r th e ca ta ly tic rea ctio n . 5 . C a ta ly tic O x id a tio n o f C O to C O
2

Ertl demonstrated unambiguously that the reaction involves atomic nitrogen adsorbed on the surface of iron and the slowest step in the process is the formation of chemisorbed atomic nitrogen by the dissociation of molecular nitrogen.

E rtl's resea rch w a s a lw ay s co n cern ed w ith th e u n d ersta n d in g o f fu n d a m en ta l scien ce. A ro u n d 1 9 8 0 , E rtl b eca m e in terested in th e ox id a tio n o f C O to C O 2 . T h e rea ctio n is ca ta ly zed b y p la tin u m . T h e ox id a tio n o f ca rb o n m o n ox id e to ca rb o n d iox id e o ccu rs in p resen ce o f a p la tin u m ca ta ly st v ia th e fo llow in g elem en ta ry step s [3 ]: ) CO * CO O O
2 ad ad 2

(7 ) (8 ) (9 )

* O )

2ad ad

! 2O ! CO

ad+

CO

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T h e C O m o lecu le rst ch em iso rb s o n to th e m eta l su rfa ce. O x y g en m o lecu le u n d erg o es d isso cia tiv e ch em iso rp tio n o n th e su rfa ce. T h e ch em iso rb ed ox y g en a to m s co m b in e w ith C O m o lecu le o n th e su rfa ce, lea d in g to th e fo rm a tio n o f ca rb o n d iox id e, w h ich th en d eso rb s. A sch em a tic o f th e p ro cess is sh ow n in F igu re 4 . W h en E rtl sta rted w o rk in g o n it, it w a s a lrea d y k n ow n th a t th e ra te o f ca ta ly tic ox id atio n o f C O o n a p la tin u m su rfa ce w a s n o t co n sta n t, b u t o scilla ted a s a fu n ctio n o f tim e. E rtl p la ced th e rea cta n ts in U H V w ith a sin g le cry sta l o f p la tin u m . H e o b serv ed th a t th e a rra n g em en t o f a to m s o n th e su rfa ce ch a n g es to a cco m m o d a te th e C O m o lecu les th a t a re a d so rb ed o n it. T h is reco n stru ctio n o f th e su rfa ce in tu rn in crea ses th e a m o u n t o f ox y g en th a t ca n b e a d so rb ed o n th e su rfa ce, a s a resu lt o f w h ich th e ra te o f th e rea ctio n in crea ses. A s C O is co n su m ed in th e rea ctio n , th e cov era g e o f C O ev en tu a lly d ro p s, a n d th e su rfa ce g o es b a ck to its orig in a l stru ctu re, a n d th e ra te o f ox id a tio n d ecrea ses. T h is cy cle rep ea ts, lea d in g to th e o scilla to ry b eh a v io r o f th e ra te. T h e a n a ly sis o f E rtl led to th e co n clu sio n th a t certa in reg io n s o f th e su rfa ce w o u ld b e cov ered m a in ly b y C O w h ile o th er reg io n s w o u ld b e cov ered b y ox y g en . T o v erify th is, E rtl red esig n ed a p h o to em issio n electro n m icro sco p e so a s to o b ta in im ag es o f th e su rfa ce, w ith su b -m icro n reso lu tio n . T h e im a g es sh ow ed d a rk a n d lig h t reg io n s, co rresp o n d in g to C O a n d ox y g en rich a rea s. F u rth er, th ese reg io n s w ere q u ite o rg a n ized a n d fo rm ed trav elin g w av es o n th e tw o d im en sio n a l su rfa ces. A lth o u g h su ch n o n -lin ea r w av es w ere w ell k n ow n in so lu tio n , it w a s th e rst tim e th a t th ey w ere o b serv ed o n

Figure 4. The process of catalytic conversion of carbon monoxide to carbon dioxide. a. Carbon monoxide and oxygen molecules approach the metal surface. b. Both the molecules chemisorb onto the surface. c. Oxygen molecule undergoes dissociation and the chemisorbed oxygen atoms interact with carbon monoxide. d. Carbon dioxide is formed and then gets desorbed from the metal surface.
The figure is reproduced with permission from Prof. Ertls home page.

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a su rfa ce. S ev era l n o n -lin ea r p h en o m en a lik e [9 ] ro ta tin g sp ira ls a n d ch a o tic p a ttern s, w h ich w ere k n ow n in o th er co n tex ts, in a rea s lik e b eh a v io r o f w ea th er, fo rm a tio n o f g a la x ies, a n d th e d y n a m ics o f th e h ea rt w ere o b serv ed o n th e su rfa ce, a s a resu lt o f th is rea ctio n . (A b ea u tifu l v id eo o f th ese p a ttern s a cco m p a n ied b y m u sic co m p o sed b y P h ilip M ay ers is ava ila b le fo r d ow n lo a d [1 0 ]) T h e w o rk o f E rtl led to a v ery d eta iled u n d ersta n d in g o f th e m ech a n ism o f o scilla tio n s, a lo n g sta n d in g p u zzle in th e a rea .
Gerhard Ertl, Professor at the Fritz Haber Institute in Berlin.

6 . B r ie f B io g ra p h ic a l S k e tc h o f E rtl E rtl w a s b o rn in 1 9 3 6 , a t B a d C a n n sta d t, a p a rt o f th e G erm a n city S tu ttg a rt. A s a b oy h e h a d a k een in terest in scien ce, a n d g rew u p ta k in g ra d io s a p a rt, p erfo rm in g ch em ica l rea ctio n s in h is b ed ro o m , a n d p lay in g th e p ia n o , h is g rea t lov e. H e sw itch ed ov er to p h y sics, w h en h is m o th er o b jected to th e sm ells th a t a lw ay s w ere co m in g o u t o f th e b ed ro o m ! A t th e U n iv ersity h e w a s a stu d en t o f p h y sics a n d a t th a t tim e su p p o rted h im self b y jo in in g a b a n d th a t p lay ed a t w ed d in g s a n d d a n ce h a lls. H e jo in ed th e T ech n ica l U n iv ersity o f M u n ich a s a d o cto ra l stu d en t in 1 9 6 2 . H is a d v iser w a s H ein z G erish er, a w ell k n ow n p h y sica l ch em ist. E rtl a p p a ren tly a sk ed h im in w h ich eld h e sh o u ld w o rk a n d G erish er to ld h im th a t th e w h o le eld o f a ir-so lid in terfa ce h a s n o t y et b een stu d ied a n d th a t a n y th in g th a t o n e co u ld d o in th e a rea w o u ld b e fa scin a tin g . E rtl sta rted w o rk in g in th e a rea , a n d w a s so o n h o o k ed . In 1 9 6 8 , a t th e y o u n g a g e o f 3 2 , E rtl b eca m e a p ro fesso r a t th e U n iv ersity o f H a n n ov er. H e a ttra cted a la rg e n u m b er o f ex cellen t stu d en ts - th e stu d en ts, o n th eir p a rt w ere v ery d ed ica ted to h im , so th a t w h en h e m ov ed to L u d w ig M a x im ilia n s U n iv ersity in M u n ich in 1 9 7 3 , a ll th e ten m em b ers o f h is g ro u p m ov ed w ith h im . In 1 9 8 6 , E rtl m ov ed to th e F ritz H a b er In stitu te a s th e D irecto r o f th e D ep a rtm en t o f P h y sica l C h em istry, a n d a g a in h is

Ertl thoroughly investigated the complex kinetics involved in the catalytic oxidation of CO on the surface of Pt, and showed that it leads to a variety of non-linear phenomena, like oscillations, spiral waves, and chaotic patterns.

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g ro u p o f 3 0 m ov ed w ith h im ! H e retired fro m th is p o sitio n in 2 0 0 4 , a n d is p resen tly a n E m eritu s P ro fesso r a t th e sa m e In stitu te. In 1 9 7 4 , E rtl listen ed to a talk b y P a u l E m m ett, o n e o f th e g rea t m en o f ca ta ly sis, an d in th a t ta lk , E m m ett p o in ted o u t th a t th e m ech a n ism o f a m m o n ia sy n th esis w a s n o t k n ow n . In sp ired b y th e ta lk , E rtl d ecid ed to w o rk o n th e p ro b lem , a n d so on it b eca m e h is life lo n g p a ssio n . H e esta b lish ed th e m ech a n ism a fter lo n g y ea rs o f h a rd w o rk . It w a s a tim e at w h ich n ew er a n d n ew er tech n iq u es w ere b ein g in tro d u ced in th e eld o f su rfa ce scien ce, a n d w h en ev er h e w a s ab le to set u p a n ew to o l, E rtl w o u ld ta k e a n ew lo o k a t th e p ro b lem s th a t h e h a d stu d ied ea rlier, p a rticu la rly, a m m o n ia sy n th esis. T h is is ty p ica l o f E rtl, w h o a lw ay s w an ted to h av e p erfect u n d ersta n d in g o f a ll th e p h en o m en a , a n d h is in v estig a tio n s a lw ay s sto o d th e test o f tim e. T h e N o b el C o m m ittee fo cu sed o n E rtl's co n trib u tio n s to u n cov erin g th e m ech a n ism of ca ta ly tic rea ctio n s. A n o th er scien tist, w h o h a s m a d e im p o rta n t co n trib u tio n s to th e a rea o f su rfa ce scien ce is G a b o r S o m o rja i o f th e U n iv ersity o f C a lifo rn ia , B erk eley. It w a s ex p ected th a t E rtl a n d S o m o rja i to g eth er w o u ld w in th e N o b el P rize in th e a rea o f su rfa ce scien ce. In fa ct, th e 1 9 9 8 W o lf p rize in ch em istry w a s aw a rd ed jo in tly to E rtl a n d S o m o rja i. O n O cto b er 1 0 , 2 0 0 7 , w h ich w a s E rtl's 7 5 th b irth d ay, h e w a s in fo rm ed b y th e N o b el C o m m ittee th a t h e h a d w o n th e p rize. T h e la st tim e th a t th e p rize w a s g iv en in th e a rea o f su rfa ce scien ce w as in th e y ea r 1 9 3 2 , w h en it w a s w o n b y th e A m erica n p h y sica l ch em ist, Irv in g L a n g m u ir. 7 . F in a l R e m a rk s T h e w in n in g o f th e N o b el P rize b y E rtl w a s n o t b eca u se o f a ch a n ce d iscov ery o r lu ck . H e sta rted w o rk in g o n a n a rea , w h ich w a s to ta lly u n ex p lo red a t th e tim e

The problems that Ertl worked on were the most important in the field, unsolved for a long time, of great industrial importance, and he worked very hard to understand the fundamental scientific aspects of the problem.

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h e g o t in to it. T h e p ro b lem s th a t h e w o rk ed o n w ere th e m o st im p o rta n t in th e eld , u n so lv ed fo r a lo n g tim e, o f g rea t in d u stria l im p o rta n ce, a n d h e w o rk ed v ery h a rd to u n d ersta n d th e fu n d a m en ta l scien ti c a sp ects o f th e p ro b lem . H e p u rsu ed th em w ith th e ch a ra cteristic G erm a n th o ro u g h n ess a n d ten a city, u sin g th e b est tech n iq u es, ev en red esig n in g h is eq u ip m en t so a s to lo o k a t o n e p a rticu la r a sp ect o f th e p ro b lem . It is fo r th is p a in sta k in g e o rt to u n d ersta n d th e scien ce b eh in d in d u stria lly im p o rta n t su rfa ce ch em ica l p ro cesses th a t E rtl w a s aw a rd ed th e N o b el P rize fo r ch em istry in 2 0 0 7 .
Suggested Reading
[1] [2] [3] [4] [5] Address for Correspondence R S Swathi and K L Sebastian Department of Inorganic and Physical Chemistry Indian Institute of Science, Bangalore 560012, India Email: kls@ipc.iisc.ernet.in swathi@ipc.iisc.ernet.in [10] [6] [7] [8] [9] J R Postgate, Nitrogen Fixation, Cambridge University Press, 1998. For more information on the prize announcement and related information, log on to www.nobelprize.org. G Ertl, Journal of Molecular Catalysis A: Chemical, Vol.5, p.182, 2002. P Atkins and J D Paula, Physical Chemistry, Oxford University Press, 2006. G Ertl and H J Freund, Physics Today, p.32, 1999. http://w3.rz-berlin.mpg.de/pc/ERTL/Ertl.html. G Ertl and J Kuppers, Low Energy Electrons and Surface Chemistry, VCH, Weiheim, 1985. G Ertl, S B Lee and M Weiss, Surf. Sci., Vol.113, p.527, 1982. For an introduction to such non-linear phenomena, see the article: B M Deb, Mainak Sadhukhan, Sudarson Sekhar Sinha, Suchita Sengupta and Ranjit Biswas, Resonance, Vol.13, No.1, pp.5480, 2008. http://www.fhhi-berlin.mpg.de/surfimag/arts.htm A video named On Platinum, composed by P Mayers showing the variety of patterns that are formed on the Pt surface may be downloaded from here.

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