Homogeneous, Heterogeneous, and Enzymatic Catalysis
S. Ted Oyamal and Gabor A. Somorjai
Catalvsis Prosram of the Center for Advanced Materials, Lawrence Berkeley Laboratory, University of California, Berkeley. CA
Catalysts have been employed by mankind since antiquity
in such activities as wine-, bread-, and cheesemaking. In
many cases i t was found that the addition of a small portion
from a orevious batch. a "starter". was'necessarv to begin
the next production. 1d 1835~ e r z e l i u published
s an a c c o k t
that tied together earlier observations hv chemists such as
ThBnard, D&, and Diihereiner by suggesting that minute
amounts of a foreign substance were able to affect greatly
the course of chemical reactions, both inorganic and biologi-
cal. Berzelius attributed a mysterious force to the substance
that he called catalytic (1-3). In 1894 Ostwald proposed that
catalysts are substances that accelerate the rate of chemical
reactions without themselves heine consumed durine the
reactions ( 4 , 5 ) .This definition is sell applicable today.
The scooe of catalvsis is enormous (6). . . Catalvsts are wide-
ly used i n the com&ercial production of fueis, chemicals,
foods, and medicines. They also play an essential role in
processes in nature, like nitrogen fixation, metabolism, and
photosynthesis.
Classlflcatlon
Catalysts can be protons (7,8), ions ( 9 - l l ) , atoms (12,13),
molecules (12), or larger assemblages. Traditionally, cata-
lysts have been classified as homogeneous, heterogeneous,
and enzymatic, reflecting this increasing hierachy of com-
olexitv.
Protons, ions, atoms, and molecules may be considered
examples of homogeneous catalysts (14).In addition, metal
complexes and organometallic compounds are important
members of this class of catalysts (15-17). As the name
implies, these catalysts are part of agas phase or dissolved in
a liquid
. phase
. together with the reactant of the reaction.
In contrast to homogeneous catalysts, heterogen~ouscat-
nlystsare usually solid surfaces,attarhed tosolid surfaceli,or
of insoluble matrices such as polymers, and are, thus,
phase-separated from the fluid medium surrounding them.
Reeardless of their form. the active catalvtic comnonent is
locked a t the interface between the solidUandthekuid and
mav consist of a wide diversitv of soecies. Examoles are one
or two atoms of the total surface (?8),a larger ensemble of
such surface atoms (19-23), an organometallic compound
attached to the surface by covalent bonds (241, or a molecu-
lar cluster lying on the surface (25,26).
Enzymatic catalysts are like liquid-phase homogeneous
catalysts in being dissolved in a liquid media, but enzymatic
catalysts are of biologicalorigin and possess the highest level
of complexity among the three types (27-33). Ironically, as
mentioned in the opening sentence, they were probably the
first catalysts utilized by man. Enzymatic catalysts are pro-
teins composed of repeating units of amino acids, often
twisted into helices, and in turn folded into three-dimen-
sional structures. The protein structures often surround a
central organometallic structure.
Fundamentals
The action of catalysts will be illustrated by an example,
the water gas shift reaction catalyzed by iron and chromium
oxides.
H,O + CO- H, + CO,
This reaction is used in the production of hydrogen in sever-
al commercial processes. I t is an example of a heterogeneous
catalytic reaction, hut the principles derived from it are also
applicable to homogeneous and enzymatic catalytic reac-
tions. A simplified scheme for the reaction is presented be-
low.
In the first step, one of the reactants, HzO, reacts with an
empty catalytic site, denoted by *, to produce a product, Hz,
and a reactive intermediate consisting of an oxygen atom
associated with the site, denoted by O*. In the second step,
the other reactant, CO, reacts with the intermediate to pro-
duce the product, CO,, and regenerates the catalytic site, *.
The energetics associated with this process are given in the
figure. A key aspect of this scheme is that i t represents a
cycle that occurs many times as the reaction proceeds. Each
repetition of the cycle is called a turnouer. A good catalyst
will have millions of turnovers. In contrast, a stoichiometric
reactant will have only one. Several important points are to
be made concerning the energetics and scheme presented
above.
1. The energy level diagram shows that the catalyzed reaction has a
lower octiuation barrier (34)than the uncatalyzed thermal reac-
tion. This is the origin of the enhancement in the rate, and it
applies both in the forward and reverse directions of the reaction.
2. Regardless of the details of the mechanism and the energetics of
the transformationof reactants into products, their relative ener-
gies, as shown by do not change (35).This means that
the thermodvnamic eouilibrium. ~ ~ ~ ~
Catalysts increase the rate of approach to equilibriwm but not
-~
between them does not chanee.
the thermodynamic equilibrium value itself.
3. As shown by the overall reaction stoichiometry, there is no net
consumption or production of the catalytic site, *. The reaction
proceeds by repetition of the catalytic cycle or chain, with the
catalytic species remaining unchanged at the end. This explains
the observation noted earlier that miniscule amounts of catalyst
can aive rise to large amounts of product.
I. The intermediate, O', must be neither loo stab/<,nor roo unslo-
ble. I f i t is toostable, it will not decompose to form theprodurt:if
it is too unstahk, it will nor form in the first plare.
Economic Impact of Catalysis
Catalysts have a substantial economic role in modern soci-
ety. US. sales of process catalysts (those involving refining
and chemical nrocesses) amounted to 4.86 billion ih in 1985
corresponding to a val"e of $955 million. These figures are
forecasted to rise to 5.4 billion lb in 1990 corresoondine to a
value of $1.12 billion (36). The inclusion of emission and
pollution control catalysts raises these numbers by $510
million in 1985 and by $620 million in 1990 (37). Table 1
'Present address: Department of Chemical Engineering, Ciarkson
University, Potsdam. NY 13676.
Volume 65 Number 9 Seotember 1968 765
 Table 1. Estlmated U.S. Catalyst Volume and Sales Table 2. EItlmated Worldwide Enzyme Volume and Sales

1985 1990 1980 1990

Volume Value Volume Value Volumea Valueb Volume ValveC
(lo6lb) (loB$) (lOelb) (loE$) Enzyme (loe ib) (lo6$) (1061b) (loe$)

P e t r o I m Refining. 4870 545 5180 620 Alkaline protease l.Ob 80 N/Ad 220
Catslytic cracking 370 250 405 275 Glucose isomerase 0.1 45 N/A 40
Reforming 4.5 23 4.7 24 Leather bating NIA 30 NIA NIA
Hydrocracking 1.8 36 2.0 40 Papain 1.P 30 NIA N/A
Hydroheating 28 77 38 104 Rennets 0.02 30 NIA 75
Alkyiation 4265 160 4710 177 GIucoamyla6~ 0.7 25 NIA 50
Other amylases 0.7 21 NIA 25
Chemical RoductiorP 190 410 230 500 Pectinase 0.02 6 NIA NIA
Polymerization 50 175 60 220 Bromelaln 0.063 3 NIA NIA
Alkylation 90 50 110 60 All others NIA 20 NIA N/A
Hydrogenation 9.6 35 11 40
Dehydrogenation 3.7 10 4.6 12 Total 3.82 290 NIA 499.
Oxidation. ammoxidation. 11 85 14 105
and owchlorination Lewis. C.: KrisllaMMI. 6. Chem. M. 1985,Sepl. 2. 574.
Ammonia, hydrogen, and 26 55 31 60 'Sant, D. "Enzyme. I~rtrlal": In Kirk-OmmerEncyclwedlsofChemical TBchmL
methanol production ogy, 3rd ed.: Wlley: New Ywk, 1980: Val. 9, p 173.
oO~I~lo. D. Eu. C h m . Newsi984.Ootober. 23.
dNIA. available.
~rrumor1980 figurer tor unavailable 1990 figures.

Stinson.S. c. Chem. Em Nowi9116. Februar, 17.27. Fromamahnrtvhl by Fmsl

&Sullivan. New Yo*. Thermal
awimon.~.M.:Hunter.D.:Ssvaga.P.;Mio.S.:Sohw~,J.;Ualt.Q.:Csnnon,D.R.
C h W& 1988, June 25, 20.
(DO nn lnclvae emiaalon and pollutim mmol figures. NIA, not available.

I
breaks down these fieures amoune the various catalyst cate-
gories. The additionof sales from'the fermentation industry
adds several hundred millionsof dollars to these fiaures (38). Reactants
The figures above are for the U S . market. 1&usion of
sales for western Eurooe and Japan raises the total world-
wide sales value to $2.6 billion in 1985, predicted to rise to
$4-5 billion in 1990 (37).
Acid catalysts for alkylation in the liquid phase dominate ,\ catalytic reaction
the oroduction of commodity fuels and chemicals. These
hombgeneous catalysts, in the form of aluminum chloride,
sulfuric, phosphoric, and hydrofluoricacids, account for 90%
of
~ the
- total
~ ~- volume of ~rocesscatalvsts
~~~~ (Table 1 ) . In terms of
value, however, heteiogeneous catalysts amount to 80% of Reaction Path
total sales.
In comparison to fuel and chemical process catalysts, en- E m level dianam for Wm hMoUletlcal catatviic and thermal water gas shin
-.
zvmes have smaller markets in volume and sales (Table 2). reaction The overall heal of react on is g ven oy AHo,,,, me aclivatlon
1; 1980 the estimated value of worldwide enzyme sales was barriers in the forwardand backwarn dlrenlan by E,.., and L,... .respec-
tively, and Ule actiuat on oanier far me lnermsl reaction by Em,
$290 million (39). In 198'3 another estimated value was S360-
400 million (40). These figures do not include the value of
enzymes used internally by food and pharmaceutical pro-
ducers. By 1990 total visible sales are predicted to rise to employed to treat naphtha, a fraction of crude oil somewhat
nearly $500 million (Table 2). liahter than gas oil that contains larae amounts of straight-
ccain paraffins. Reforming reactions reconstruct or "re-
lndustrlal Usage of Catalysts form" the hydrocarbons in the feed so as to increase the
The following section descrihes the most important cata- octane level: The catalysts differ from cracking catalysts
lvsts emoloved commerciallv in the world as listed in Tables
- A ~ ~ ~ ~
because they tend to conserve the carhon number of the
1and 2.'Thk section dealing with petroleum refining covers reactants and because thev oroduce a substantial amount of
the major operations used in the production of fuels. The hyproduct hydrogen gas. ~ y d r o c r a c k i ncatalysts
~ are used
section involving chemicals descrihes a few of the major to reduce the molecular weight of a feedstock. A tvoical use
orocesses used to ~ r o d u c eindustrial chemicals. The section is the conversion of light gasoil in the presence ofhydrogen
covering foods a i d medicines deals exclusively with en- to n a ~ h t h afor easoline oroduction through- reform in^.. HY-
-
zymes. drotreating comprises hydrogenolysis of nitrogen and sulfur
comoounds orior to catalvtic cracking. Finally, o1k)lalron
Petmleum Refining converts isoliutane and b"tylenes proauced i n t h e catalytic
There are five major processes in the refining of petro- cracking step into a mixture of dimers known as alkylate.
leum: catalytic cracking, reforming, hydrocracking, hydro- This product is a gasoline blending stock of high octane
treating, and alkylation (Table 3). Catalytic cracking is used value.
t o convert a moderately heavy crude oil fraction known as
eas oil to a liehter nroduct with a high content of hrauched- Chemical Production
:hain and aromatic h y d r o c a r b ~ n s . ~ ~ h eare
s e the species The catalytic processes involved here are of much lower
responsible for raising gasoline octane levels. Reforming is volume than those in the petroleum refining industry hut

766 Journal of Chemical Education

 Table 3. Catalvsts Used in Petroleum Retlnlno

Pmcess Typical Reactions Catalysts

CataWic cracking (41.4 a C-C bond breaking: Zeolnes embedded In silica-alumina mablces
C ~ a -CloHes
b + CaHm
Dealkylation:
Cdi-CHS CsHaf C4Hs

-
+

Hydmsen transfer:
C6Hl + 3C8Hq6 C.H6 3C8Ht8+
lmIz8tion:
RCIOHB -
Iswnerlration. Dehyhocyclizatlon: Pt, Ir. Rh on porous oxide suppwls

n-C7Hls +

Aromatlzation:
dcH' + Hz

CHa
I

NI. CO,Mo, W, Pt, W supported on Sl-alumhates or zeolites

Hydrobaatins (41.42,50-53)
+
R-SH HI -
De~~lturlzatlon:
RH H2S +
Sulfded CoMo, NlMo w NIW oxldes supported on alumina

rmnitrogenation:
+
R-NH2 HZ RH NHs - +
Alkylatim (4n Alkytatlon:
ffi.H,~ + CH
Ie - ikc-octane
Liquid H2S01of HF

Table 4. Catalysts Used In Chemlcal Production

Rocess Typical Reactions Catalysts

Polymerization (41.42,55. 57)

-
Linear lowdensity polyethylene:
RCH2=CH2 -(<H2<Hd-
Ti halides wW A1 and Mg alkyls

Alkylatim (41.55)
C& + CH+H2 -
Ethyl benzene production:
CeH4H2<H8
AICI:,

Hydrogenation(54.55.56.557
Vegetable oil -
Hydrogenationof vegetable oils:
Hardened oil
Ni, noble metals suppwted

Butadlene production:
CH3<H2<H2<H3 - CH2==Cn--CH=CH*
Chromium oxide-aluminum oxide

Partial oxidetion (61.62.64.66.67)

C4H10 0s + -
Maleic anhydride productim:
C1H209

-
Awylonitriie production:
+ +
Cans o2 NHP CH2==Cn--CN
BI-Md, + o m r oxide additives
Ammonia synmesis (68-70)
-
Ammonia productlon:
+
N2 3H2 2NH3
Fe promoted with A1A. K20, MgO

Memane reforming (71-73.75)

-
Hydrogen production:
OH, + H20 GO + 3H2
Supported NI

Metham1synmsls (55,72,7 4
+
CO ZH2 CHJOH -
Methanol production: ZnO-Cr203, Cu0"-ZnO-Cr203

produce an extremely important and varied selection of

products. These are outlined in Table 4.
Foods, Medicines, and Other P r w ~ c (39,4
t ~ 1)
This section will cover the industrial uses of enzymes with
-NH-C-CH-NH-C-CH-NH-
II
0
II
0
I
-
somewhat greater detail than the preceding two sections.
Proteases (76).The function of these enzymes is to hydro- R R
lyze the peptide bond in proteins. Considerable variety ex- I I
ists in source, specificity, and reaction conditions for these
-NH-C-CH-NH1 + HO-C-CH-NH-
1I II
enzymes. 0 0

Volume 65 Number 9 September 1988 767

 1. Alkaline proteases are derived from bacteria. They find wide
application in detergents, leather tanning, protein hydrolysis, hrew-
ing, and sllver rwovery from film.
2. Pa'npoln (7:) is a plant procease derived frum the papaya fruit
It isemployed mdgestive aids. wound debridemenr, tooth cleaning.
and, mist importantly,as a meat tenderizer.
3. B~omeloinis another plant protease with uses similar to that of
. . It is obtained from the s t u m ~ sleft over from nineannle
~aoain.
harvests.
. ..
4. Rennet (78) or rennin is an animal protease derived from the
stomachs of calves as well as from microorganisms.It is employed in
the manufacture of cheese to clot milk.
Glucose isomerase (79). This enzyme is found in many
organisms and in practice is used in the form of entrapped
cells or bound to ion-exchange resins. It converts glucose t o
fructose, one of the principal components of table sugar.
HOCH
I
I
- HO~H
I
Leather Bating Enzymes. These enzymes are employed in
leather manufacture to remove flesh from hides. They are
generally derived from hog and beef pancreas and consist of
mixtures of enzymes that attack both proteins and lipids.
Amylases (76,80).These enzymes hydrolyze the D-glyco-
sidic linkage in starch.
1. Glucoamylase is found in blood, molds, and bacteria. It pra-
d u e s glucose by removing the endglucose unit in long-chain carbo-
hydrates such as starch, glycogen, dextrins, and maltoses. Its main
commercial use is in the production of glucose syrup, glucose paste,
and crystalline glucose.
2. Otheramyloses,constituting a large family of enzymes that act
on different substrates, are found in saliva, animal tissues, plants,
yeasts, and other microorganisms.They find wide use in the manu-
facture of glue, starchy syrups, and in various steps in the produc-
tion of brewery and bakery products.
Pectinases (76).These enzymes carry out the hydrolytic
-.
deeradation of the D-alvcosidic linkage in pectins. The latter
s u h a n c e s , also known as pectic substances, are polymeric
components of plant cell walls and, like starch, are composed
of sugar residues linked by glycosidic bonds. The chemistry
is the same as shown for the amylases above. The main
application of pectinases is in the production of fruit juices,
wines, and other food products.
Perspectives on Catalysis
Although homogeneous liquid-phase acids in the form of
H2S04 and H F are the industrial catalysts used in the high-
768 Journal of Chemical Education
est volume (Table I), they have low specificity and, thus,
limited use in new reactions requiring high product selectiv-
ity. As new catalysts, organometallic compounds are partic-
ularly attractive hecause of the possibility of systematically
varying their organic ligands so as to obtain desired catalytic
properties (15-17). Advances in precise inorganic and or-
ganometallic synthesis are making possible the design of
engineered catalvsts (81). From an industrial standpoint
homogeneous caialysts are difficult to use because they are
not readilv . senarable
. from the products that are formed in
the same phase. However, advantages in activity, selectivity,
or severity of reaction conditions override these consider-
ations. New technologies involving immobilization (82)and
phase transfer catalysis (83-89) will he used to overcome the
separations problems.
From an engineering standpoint heterogeneous catalysts
are the easiest catalvsts to handle because thev are stable a t
high temperature and are phase-separated from the reac-
tants and nroductu. Thes thus iind widespread use in indus-
t e impokmce they have been difficult to
try. ~ e s ~ itheir
understand from a fundamental standpoint. New advances
are rapidly changing this. The techniq"es of surface science
(90-92), which allow the use of surface-sensitive spectrosco-
pies such as low-energy electron spectroscopy (LEED), X-
ray photoelectron spectroscopy ( X P S ) ,and Auger electron
spectroscopy ( A E S ) ,allow the examination of model cata-
lysts in the form of single crystals (93, 94). Spectroscopic
&hniques such as Four~ertransform Infrared spectroscopy
FTIHI,extended X-ray absorpt~onh e structure rEX.4FS)
and laser Raman spectroscopy and the use of dynamic tech-
niques (95)allow the examination of the catalyst surface a t
reaction conditions.
The active surface on heterogeneous catalysts provides a
different environment from the active sites on homogeneous
or enzvmaticratalysts. On a surface the presenceof adjacent
sites and the possibility of surface diffusion 1%) a1lou.s nu-
merous reacti\.e species t o come together or a single reactive
~ntermediateto migrate from site to site. On homogeneous
metal complexes or in enzymes the need for coordinat~wly
open sites creaces much more strlnyent requiremt:ntr on the
-~~~~~~ ~ ~ ~
.
number of snecies that can react a t an active site. Further-
~~
more, because surfaces can have a wide range of energetical-
ly different sites (97,98)and because variations in coverage
can change the energetics of the entire surface (99),surfaces
have a built-in adaptability to reaction conditions (100).
Enzymes possess extremely high specificity and activity.
Their com~lexitvmakes them very difficult to understand.
In many cases they are able to react with only one particular
group in a substrate, even in the presence of other very
similar groups. They show very high activity, being able to
carrv out reactions a t physiological temperatures, that het-
erogeneous catalysts can only carry out a t elevated tempera-
tures. From an industrial standpoint, because like homoge-
neous catalysts enzymes are dispersed in solution, their sep-
aration from the reaction products is difficult. Techniques
such as immobilization are beine developed to solve this
problem (101-103). However, i n m a n y cases enzymes are
used to break bonds in massive or insoluble substrates, and
for this purpose immobilization is detrimental. Other limita-
tions are that enzymes are difficult to obtain in pure form,
tend to work in a narrow temperature and pH range, and are
sensitive to strong chemicals. A possible solution to these
problems may bd designed synthetic enzymes produced
through such techniques as genetic engineering (104).Syn-
thetic enzymes could offer ease of purification, increased
stability to heat or denaturizing agents, use in nonaqueous
solvents, and even catalysis of new reactions (105-107).
Literature Clted
I. Bene1ius.J. J. Ar~berilrtelseorn/ramsiepen i / w B och komi: Stockholm. 18L:p239.
?. d o r ~ e s J. His Life and Work Sfeele. B.. Transl.;Almqvirf & Viksell:
. E. Bmeliua,
Siakholm. 1970.