Nanomaterial-based catalyst

Nanomaterial-based catalysts are usually heterogeneous catalysts broken up into metal nanoparticles in order to speed up the catalytic process. Metal nanoparticles have a higher surface area so there is increased catalytic activity because more catalytic reactions can occur at the same time. Nanoparticle catalysts can also be easily separated and recycled with more retention of catalytic activity than their bulk counterparts.[1] These catalysts can play two different roles in catalytic processes: they can be the site of catalysis or they can act as a support for catalytic processes.[2] They are typically used under mild conditions to prevent decomposition of the nanoparticles at extreme conditions.[3]

Functionalized nanoparticles

Functionalized metal nanoparticles are more stable in solution compared to non-functionalized metal nanoparticles.[4] In liquid solutions, the metal nanoparticles are close enough together to be affected by van der Waals force. If there isn’t anything to oppose these forces, then the nanoparticles will aggregate, which will lead to a decrease in catalytic activity by lowering the surface area.[4] For organometallic functionalized nanoparticles, ligands are coordinated to the metal center to prevent aggregation. Using different ligands alters the properties and sizes of the nanoparticle catalysts. Nanoparticles can also be functionalized with polymers or oligomers to sterically stabilize the nanoparticles by providing a protective layer that prevents the nanoparticles from interacting with each other.[5] Alloys of two metals, called bimetallic nanoparticles, are used to create synergistic effects on catalysis between the two metals.[5]

Applications

Dehalogenation and hydrogenation

Nanoparticle catalysts can be used in the hydrogenolysis of C-Cl bonds such as polychlorinated biphenyls.[4][5] Hydrogenation of halogenated aromatic amines is also important for the synthesis of herbicides and pesticides as well as diesel fuel.[4] In organic chemistry, hydrogenation of a C-Cl bond with deuterium is used to selectively label the aromatic ring for use in experiments dealing with the kinetic isotope effect. Buil et al. created rhodium complexes that generated rhodium nanoparticles. These nanoparticles catalyzed the dehalogenation of aromatic compounds as well as the hydrogenation of benzene to cyclohexane.[5] Polymer-stabilized nanoparticles can also be used for the hydrogenation of cinnamaldehyde and citronellal.[4][6][7][8] Yu et al. found that the ruthenium nanocatalysts are more selective in the hydrogenation of citronellal compared to the traditional catalysts used.[8]

Hydrosilylation reactions

Hydrosilylation reaction

The Reduction of gold, cobalt, nickel, palladium, or platinum organometallic complexes with silanes creates a catalytically active metal nanoparticle that catalyzes the hydrosilylation reaction, which is important for the synthesis of optically active alcohols.[9] BINAP functionalized palladium nanoparticles and gold nanoparticles have been used for the hydrosilylaytion of styrene under mild conditions; they were found to be more catalytically active and more stable than non-nanoparticle Pd-BINAP complexes.[9][10] The reaction may also be catalyzed by a nanoparticle that consists of two metals.[4][11]

Organic redox reactions

Oxidation reaction of cyclohexane to synthesize adiapic acid

An oxidation reaction to form adipic acid is shown in figure 3 and it can be catalyzed by cobalt nanoparticles.[4] This is used in an industrial scale to produce the nylon 6,6 polymer. Other examples of oxidation reactions that are catalyzed by metallic nanoparticles include the oxidation of cyclooctane, the oxidation of ethene, and glucose oxidation.[4]

C-C coupling reactions

Heck coupling reaction

Metallic nanoparticles can catalyze C–C coupling reactions such as the hydroformylation of olefins,[4] the synthesis of vitamin E and the Heck coupling and Suzuki coupling reactions.[4]

Palladium nanoparticles were found to efficiently catalyze heck coupling reactions. It was found that increased electronegativity of the ligands on the palladium nanoparticles increased their catalytic activity.[4][12]

The compound Pd2(dba)3 is a source of Pd(0), which is the catalytically active source of palladium used for many reactions, including cross coupling reactions.[3] Pd2(dba)3 was thought to be a homogeneous catalytic precursor, but recent articles suggest that palladium nanoparticles are formed, making it a heterogeneous catalytic precursor.[3]

Alternative fuels

Much research on nanomaterial-based catalysts has to do with maximizing the effectiveness of the catalyst coating in fuel cells. Platinum is currently the most common catalyst for this application, however, it is expensive and rare, so a lot of research has been going into maximizing the catalytic properties of other metals by shrinking them to nanoparticles in the hope that someday they will be an efficient and economic alternative to platinum. Gold nanoparticles also exhibit catalytic properties, despite the fact that bulk gold is unreactive.

Fuel cells take advantage of the reaction between hydrogen and oxygen but catalysts are needed to facilitate this reaction. Nanomaterial catalysts can be used to improve energy production. In one experiment, yttrium stabilized zirconium nanoparticles were found to increase the efficiency and reliability of a solid oxide fuel cell.[13][14] Nanomaterial ruthenium/platinum catalysts could potentially be used to catalyze the purification of hydrogen for hydrogen storage.[15] Palladium nanoparticles can be functionalized with organometallic ligands to catalyze the oxidation of CO and NO to control air pollution in the environment.[13] Carbon nanotube supported catalysts can be used as a cathode catalytic support for fuel cells and metal nanoparticles have been used to catalyze the growth of carbon nanotubes.[13] Platinum-cobalt bimetallic nanoparticles combined with carbon nanotubes are promising candidates for direct methanol fuel cells since they produce a higher stable current electrode.[13]

Medicine

In magnetic chemistry, nanoparticles can be used for catalyst support for medicinal use.

Characterization of nanoparticles

Some techniques that can be used to characterize functionalized nanomaterial catalysts include X-ray photoelectron spectroscopy, transmission electron microscopy, circular dichroism spectroscopy, nuclear magnetic resonance spectroscopy, UV-visible spectroscopy and related experiments.

See also

References

  1. ↑ Fukui, Takehisa; Murata, Kenji, Ohara, Satoshi, Abe, Hiroya, Naito, Makio, Nogi, Kiyoshi (2004). "Morphology control of Ni–YSZ cermet anode for lower temperature operation of SOFCs". Journal of Power Sources 125 (1): 17–21. doi:10.1016/S0378-7753(03)00817-6.
  2. ↑ Pierluigi Barbaro, Francesca Liguori, ed. (2010). Heterogenized homogeneous catalysts for fine chemicals production : materials and processes. Dordrecht: Springer. ISBN 978-90-481-3695-7.
  3. ↑ 3.0 3.1 3.2 Zalesskiy, Sergey; Ananikov Valentine (March 2012). "Pd2(dba)3 as a Precursor of Soluble Metal Complexes and Nanoparticles: Determination of Palladium Active Species for Catalysis and Synthesis". Organometallics 31 (6): 2302–2309. doi:10.1021/om201217r.
  4. ↑ 4.0 4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9 4.10 Roucoux, Alain; Schulz, Jürgen, Patin, Henri (2002). "Reduced Transition Metal Colloids: A Novel Family of Reusable Catalysts?". Chemical Reviews 102 (10): 3757–3778. doi:10.1021/cr010350j. PMID 12371901.
  5. ↑ 5.0 5.1 5.2 5.3 Buil, María L.; Esteruelas, Miguel A.; Niembro, Sandra; Oliván, Montserrat; Orzechowski, Lars; Pelayo, Cristina; Vallribera, Adelina (2010). "Dehalogenation and Hydrogenation of Aromatic Compounds Catalyzed by Nanoparticles Generated from Rhodium Bis(imino)pyridine Complexes". Organometallics 29 (19): 4375–4383. doi:10.1021/om1003072.
  6. ↑ Yu, Weiyong; Liu, Hanfan, Liu, Manhong, Liu, Zhijie (2000). "Selective hydrogenation of citronellal to citronellol over polymer-stabilized noble metal colloids". Reactive and Functional Polymers 44 (1): 21–29. doi:10.1016/S1381-5148(99)00073-5.
  7. ↑ Yu, Weiyong; Liu, Manhong, Liu, Hanfan, An, Xiaohua, Liu, Zhijie, Ma, Xiaoming (1999). "Immobilization of polymer-stabilized metal colloids by a modified coordination capture: preparation of supported metal colloids with singular catalytic properties". Journal of Molecular Catalysis A: Chemical 142 (2): 201–211. doi:10.1016/S1381-1169(98)00282-9.
  8. ↑ 8.0 8.1 Yu, W; Liu, M; Liu, H; Ma, X; Liu, Z (1998). "Preparation, Characterization, and Catalytic Properties of Polymer-Stabilized Ruthenium Colloids". Journal of Colloid and Interface Science 208 (2): 439–444. doi:10.1006/jcis.1998.5829. PMID 9845688.
  9. ↑ 9.0 9.1 Tamura, Masaru; Fujihara, Hisashi (2003). "Chiral Bisphosphine BINAP-Stabilized Gold and Palladium Nanoparticles with Small Size and Their Palladium Nanoparticle-Catalyzed Asymmetric Reaction". Journal of the American Chemical Society 125 (51): 15742–15743. doi:10.1021/ja0369055. PMID 14677954.
  10. ↑ Leeuwen, Piet W.N.M. van; Chadwick, John C. Homogeneous catalysts : activity, stability, deactivation. Weinheim, Germany: Wiley -VCH. ISBN 978-3-527-32329-6.
  11. ↑ Lewis, Larry N.; Lewis, Nathan. (1986). "Platinum-catalyzed hydrosilylation – colloid formation as the essential step". Journal of the American Chemical Society 108 (23): 7228–7231. doi:10.1021/ja00283a016.
  12. ↑ Beller, Matthias; Fischer, Hartmut, Kühlein, Klaus, Reisinger, C.-P., Herrmann, W.A. (1996). "First palladium-catalyzed Heck reactions with efficient colloidal catalyst systems". Journal of Organometallic Chemistry 520 (1–2): 257–259. doi:10.1016/0022-328X(96)06398-X.
  13. ↑ 13.0 13.1 13.2 13.3 Moshfegh, A Z (2009). "Nanoparticle catalysts". Journal of Physics D: Applied Physics 42 (23): 233001. Bibcode:2009JPhD...42w3001M. doi:10.1088/0022-3727/42/23/233001.
  14. ↑ Ananikov, Valentine P.; Orlov, Nikolay V.; Beletskaya, Irina P. (2007). "Highly Efficient Nickel-Based Heterogeneous Catalytic System with Nanosized Structural Organization for Selective Se−H Bond Addition to Terminal and Internal Alkynes". Organometallics 26 (3): 740–750. doi:10.1021/om061033b.
  15. ↑ Beal, James. "New nanoparticle catalyst brings fuel-cell cars closer to showroom". University of Wisconsin at Madison. Retrieved 20 March 2012.

Further reading