Nanomaterial-

based catalyst

Nanomaterial-based catalysts are usually het erogeneous cat alyst s broken up int o met al
nanopart icles in order t o enhance t he cat alyt ic process. Met al nanopart icles have high
surface area, which can increase cat alyt ic act ivit y. Nanopart icle cat alyst s can be easily
separat ed and recycled.[1][2][3] They are t ypically used under mild condit ions t o prevent
decomposit ion of t he nanopart icles.[4]

Functionalized
nanoparticles
Funct ionalized met al nanopart icles are more st able t oward solvent s compared t o non-
funct ionalized met al nanopart icles.[5][6] In liquids, t he met al nanopart icles can be affect ed by
van der Waals force. Part icle aggregat ion can somet imes decrease cat alyt ic act ivit y by
lowering t he surface area.[7] Nanopart icles can also be funct ionalized wit h polymers or
oligomers t o st erically st abilize t he nanopart icles by providing a prot ect ive layer t hat
prevent s t he nanopart icles from int eract ing wit h each ot her.[8] Alloys of t wo met als, called
bimet allic nanopart icles, are used t o creat e synergist ic effect s on cat alysis bet ween t he t wo
met als.[9]
Potential applications

Dehalogenation and hydrogenation

Nanopart icle cat alyst s are act ive for t he hydrogenolysis of C-Cl bonds such as
polychlorinat ed biphenyls.[5][6] Anot her react ion is hydrogenat ion of halogenat ed aromat ic
amines is also import ant for t he synt hesis of herbicides and pest icides as well as diesel
fuel.[5] In organic chemist ry, hydrogenat ion of a C-Cl bond wit h deut erium is used t o
select ively label t he aromat ic ring for use in experiment s dealing wit h t he kinet ic isot ope
effect . Buil et al. creat ed rhodium complexes t hat generat ed rhodium nanopart icles. These
nanopart icles cat alyzed t he dehalogenat ion of aromat ic compounds as well as t he
hydrogenat ion of benzene t o cyclohexane.[6] Polymer-st abilized nanopart icles can also be
used for t he hydrogenat ion of cinnamaldehyde and cit ronellal.[5][7][10][9] Yu et al. found t hat t he
rut henium nanocat alyst s are more select ive in t he hydrogenat ion of cit ronellal compared t o
t he t radit ional cat alyst s used.[9]

Hydrosilylation reactions

Hydrosilylation reaction

The Reduct ion of gold, cobalt , nickel, palladium, or plat inum organomet allic complexes wit h
silanes produces met al nanopart icle t hat cat alyze t he hydrosilylat ion react ion.[11] BINAP-
funct ionalized palladium nanopart icles and gold nanopart icles have been used for t he
hydrosilylayt ion of st yrene under mild condit ions; t hey were found t o be more cat alyt ically
act ive and more st able t han non-nanopart icle Pd-BINAP complexes.[11][12] The react ion may
also be cat alyzed by a nanopart icle t hat consist s of t wo met als.[5][13]
Organic redox reactions

Oxidation reaction of cyclohexane to synthesize adiapic acid

An oxidat ion react ion t o form adipic acid is shown in figure 3 and it can be cat alyzed by cobalt
nanopart icles.[5] This is used in an indust rial scale t o produce t he nylon 6,6 polymer. Ot her
examples of oxidat ion react ions t hat are cat alyzed by met allic nanopart icles include t he
oxidat ion of cyclooct ane, t he oxidat ion of et hene, and glucose oxidat ion.[5]

C-C coupling reactions

Heck coupling reaction

Met allic nanopart icles can cat alyze C–C coupling react ions such as t he hydroformylat ion of
olefins,[5] t he synt hesis of vit amin E and t he Heck coupling and Suzuki coupling react ions.[5]

Palladium nanopart icles were found t o efficient ly cat alyze Heck coupling react ions. It was
found t hat increased elect ronegat ivit y of t he ligands on t he palladium nanopart icles
increased t heir cat alyt ic act ivit y.[5][14]

The compound Pd2(dba)3 is a source of Pd(0), which is t he cat alyt ically act ive source of
palladium used for many react ions, including cross coupling react ions.[4] Pd2(dba)3 was
t hought t o be a homogeneous cat alyt ic precursor, but recent art icles suggest t hat palladium
nanopart icles are formed, making it a het erogeneous cat alyt ic precursor.[4]
Alternative fuels
Iron oxide and cobalt nanopart icles can be loaded ont o various surface act ive mat erials like
alumina t o convert gases such as carbon monoxide and hydrogen int o liquid hydrocarbon fuels
using t he Fischer-Tropsch process.[15][16]

Much research on nanomat erial-based cat alyst s has t o do wit h maximizing t he effect iveness
of t he cat alyst coat ing in fuel cells. Plat inum is current ly t he most common cat alyst for t his
applicat ion, however, it is expensive and rare, so a lot of research has been going int o
maximizing t he cat alyt ic propert ies of ot her met als by shrinking t hem t o nanopart icles in t he
hope t hat someday t hey will be an efficient and economic alt ernat ive t o plat inum. Gold
nanopart icles also exhibit cat alyt ic propert ies, despit e t he fact t hat bulk gold is unreact ive.

Yt t rium st abilized zirconium nanopart icles were found t o increase t he efficiency and reliabilit y
of a solid oxide fuel cell.[17][18] Nanomat erial rut henium/plat inum cat alyst s could pot ent ially
be used t o cat alyze t he purificat ion of hydrogen for hydrogen st orage.[19] Palladium
nanopart icles can be funct ionalized wit h organomet allic ligands t o cat alyze t he oxidat ion of
CO and NO t o cont rol air pollut ion in t he environment .[17] Carbon nanot ube support ed
cat alyst s can be used as a cat hode cat alyt ic support for fuel cells and met al nanopart icles
have been used t o cat alyze t he growt h of carbon nanot ubes.[17] Plat inum-cobalt bimet allic
nanopart icles combined wit h carbon nanot ubes are promising candidat es for direct met hanol
fuel cells since t hey produce a higher st able current elect rode.[17]

Medicine
In magnet ic chemist ry, nanopart icles can be used for cat alyst support for medicinal use.
Nanozymes
Besides convent ional cat alysis, nanomat erials have been explored for mimicking nat ural
enzymes. The nanomat erials wit h enzyme mimicking act ivit ies are t ermed as nanozymes.[20]
Many nanomat erials have been used t o mimic variet ies of nat ural enzymes, such as oxidase,
peroxidase, cat alase, SOD, nuclease, et c. The nanozymes have found wide applicat ions in
many areas, from biosensing and bioimaging t o t herapeut ics and wat er t reat ment .

Nanostructures for
electrocatalysis
Nanocat alyst s are of wide int erest in fuel cells and elect rolyzers, where t he cat alyst st rongly
affect s efficiency.

Nanoporous surfaces
In fuel cells, nanoporous mat erials are widely used t o make cat hodes. Porous nanopart icles of
plat inum have good act ivit y in nanocat alysis but are less st able and t heir lifet ime is short .[21]

Nanoparticles
One drawback t o t he use of nanopart icles is t heir t endency t o agglomerat e. The problem can
be mit igat ed wit h t he correct cat alyst support . Nanopart icles are opt imal st ruct ures t o be
used as nanosensors because t hey can be t uned t o det ect specific molecules. Examples of
Pd nanopart icles elect rodeposit ed on mult i-walled carbon nanot ubes have shown good
act ivit y t owards cat alysis of cross-coupling react ions.[22]

Nanowires
Nanowires are very int erest ing for elect rocat alyt ic purpose because t hey are easier t o
produce and t he cont rol over t heir charact erist ics in t he product ion process is quit e precise.
Also, nanowires can increase faradaic efficiency due t o t heir spat ial ext ent and t hus t o great er
availabilit y of react ant s on t he act ive surface.[23]

Materials
The nanost ruct ures involved in elect rocat alysis processes can be made up of different
mat erials. Through t he use of nanost ruct ured mat erials, elect rocat alyst s can achieve good
physical-chemical st abilit y, high act ivit y, good conduct ivit y and low cost . Met allic
nanomat erials are commonly made up of t ransit ion met als (most ly iron, cobalt , nickel,
palladium, plat inum). Mult i-met al nanomat erials show new propert ies due t o t he
charact erist ics of each met al. The advant ages are t he increase in act ivit y, select ivit y and
st abilit y and t he cost reduct ion. Met als can be combined in different ways such as in t he
core-shell bimet allic st ruct ure: t he cheapest met al forms t he core and t he most act ive one
(t ypically a noble met al) const it ut es t he shell. By adopt ing t his design, t he use of rare and
expensive met als can be reduced down t o 20%.[24]

One of t he fut ure challenges is t o find new st able mat erials, wit h good act ivit y and especially
low cost . Met allic glasses, polymeric carbon nit ride (PCN) and mat erials derived from met al-
organic frameworks (MOF) are just a few examples of mat erials wit h elect rocat alyt ic
propert ies on which research is current ly invest ing.[25][26][27]
Photocatalysis
Many of t he phot ocat alyt ic syst ems can benefit from t he coupling wit h a noble met al; t he
first Fujishima-Honda cell made use of a co-cat alyst plat e as well. For inst ance, t he essent ial
design of a disperse phot ocat alyt ic react or for wat er split t ing is t hat of a wat er sol in which
t he dispersed phase is made up of semiconduct or quant um dot s each coupled t o a met allic
co-cat alyst : t he QD convert s t he incoming elect romagnet ic radiat ion int o an excit on whilst
t he co-cat alyst act s as an elect ron scavenger and lowers t he overpot ent ial of t he
elect rochemical react ion.[28]

Characterization of
nanoparticles
Some t echniques t hat can be used t o charact erize funct ionalized nanomat erial cat alyst s
include X-ray phot oelect ron spect roscopy, t ransmission elect ron microscopy, circular
dichroism spect roscopy, nuclear magnet ic resonance spect roscopy, UV-visible spect roscopy
and relat ed experiment s.

See also

Nanomaterials
Nanotechnology
Transition metal
 Quantum dot
Platinum nanoparticles
Icosahedral twins
Nanozymes

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Further reading

Santen, Rutger Anthony van; Neurock,

Matthew (2006). Molecular
heterogeneous catalysis : a conceptual
and computational approach ([Online-
 Ausg.] ed.). Weinheim: Wiley-VCH.
ISBN 978-3-527-29662-0.

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