journal article·2016-03Open access

Optimized reduction conditions for the microfluidic synthesis of 1.3 ± 0.3 nm Pt clusters

M. Jakir Hossain, Md. Saidur Rahman, M. S. Rahman, M. A. Ali, N. C. Nandi, P. Noor, K. N. Ahmed, S. Akhter

Abstract

Recently, small (<2 nm) and monodispersed Pt clusters has gained much attention due to their high catalytic activity in the aerobic oxidations. However, the chemical synthesis of small Pt clusters is not trivial; high temperature is often required to completely reduce the Pt 4+/2+ ions to Pt 0 , which accelerates the growth of the Pt clusters. Here, we discussed a very simple microfluidic reduction of Pt 4+ to Pt 0 by NaBH 4 in the presence of PVP that produces <2 nm Pt clusters in any variable reduction conditions. The microfluidic reduction conditions were optimized for the synthesis of possible smallest Pt clusters in terms of five reaction parameters: (1) temperature, (2) concentration of H 2 PtCl 6 , (3) molar ratio of NaBH 4 to Pt 4+ ions, (4) molar ratio of PVP-monomer to Pt 4+ ions, and (5) molecular weight/chain length of PVP. We found that possible smallest particles with average diameter 1.3 ± 0.3 nm were produced when aqueous solutions of H 2 PtCl 6 (4 mM) and NaBH 4 (40 mM) containing PVP (160 mM) were injected into the micromixer placed in an icebath at a flow rate of 200 mL/h. The produced particles were characterized by UV–visible absorption spectrophotometry, powder X-ray diffractometry and transmission electron microscopy.
Source: openalex_inverted_index · Quality: baseline

Research context

OpenAlex topics: Electrocatalysts for Energy Conversion · Catalytic Processes in Materials Science · Advanced Photocatalysis Techniques

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

References (49)

Show source-provided references
1. Hirai, H., Toshima, N.: In: Tailored Metal Catalysts. Iwasawa Y., (Ed) Reidel Publishing, Dordrecht (1986)
2. Tsunoyama, H., Ichikuni, N., Sakurai, H., Tsukuda, T.: Effect of electronic structures of Au clusters stabilized by poly (N-vinyl-2-pyrrolidone) on aerobic oxidation catalysis. J. Am. Chem. Soc. 131, 7086–7093 (2009)10.1021/ja810045y ↗
3. Xiao, C.X., Cai, Z.P., Wang, T., Kou, Y., Yan, N.: Aqueous-phase Fischer–Tropsch synthesis with a ruthenium nanocluster catalyst. Angew. Chem. 120, 758–761 (2008)10.1002/ange.200703481 ↗
4. Xiao, C.X., Wang, H.Z., Mu, X.D., Kou, Y.: Ionic-liquid-like copolymer stabilized nanocatalysts in ionic liquids I. Platinum catalyzed selective hydrogenation of o-chloronitrobenzene. J. Catal. 250, 25–32 (2007)10.1016/j.jcat.2007.05.009 ↗
5. Song, S., Liu, R., Zhang, Y., Feng, J., Liu, D., Xing, Y., Zhao, F., Zhang, H.: Colloidal noble-metal and bimetallic alloy nanocrystals: a general synthetic method and their catalytic hydrogenation properties. Chem. A Eur. J. 16, 6251–6256 (2010)10.1002/chem.200903279 ↗
6. Yan, N., Zhao, C., Luo, C., Dyson, P.J., Liu, H., Kou, Y.: One-step conversion of cellobiose to C6-alcohols using a ruthenium nanocluster catalyst. J. Am. Chem. Soc. 128, 8714–8715 (2006)10.1021/ja062468t ↗
7. Mu, X.D., Meng, J.Q., Li, Z.C., Kou, Y.: Rhodium nanoparticles stabilized by ionic copolymers in ionic liquids: long lifetime nanocluster catalysts for benzene hydrogenation. J. Am. Chem. Soc. 127, 9694–9695 (2005)10.1021/ja051803v ↗
8. Zhao, C., Wang, H.Z., Yan, N., Xiao, C.X., Mu, X.D., Dyson, P.J., Kou, Y.: Ionic-liquid-like copolymer stabilized nanocatalysts in ionic liquids: II. Rhodium Catal. Hydrog. Arenes J. Catal. 250, 33–40 (2007)
9. Zhao, C., Gan, W., Fan, X., Cai, Z., Dyson, P.J., Kou, Y.: Aqueous-phase biphasic dehydroaromatization of bio-derived limonene into p-cymene by soluble Pd nanocluster catalysts. J. Catal. 254, 244–250 (2008)10.1016/j.jcat.2008.01.003 ↗
10. He, L., Liu, H., Xiao, C.X., Kou, Y.: Liquid-phase synthesis of methyl formate via heterogeneous carbonylation of methanol over a soluble copper nanocluster catalyst. Green Chem. 10, 619–622 (2008)10.1039/b804459g ↗
11. Somorjai, G.A.: Introduction to Surface Chemistry and Catalysis. Wiley, New York (1994)
12. White, R.J., Luque, R., Budarin, V.L., Clark, J.H., Macquarrie, D.J.: Supported metal nanoparticles on porous materials. Methods and applications. Chem. Soc. Rev. 38, 481–494 (2009)10.1039/B802654H ↗
13. Astruc, D., Lu, F., Aranzaes, J.R.: Nanoparticles as recyclable catalysts: the frontier between homogeneous and heterogeneous catalysis. Angew. Chem. Int. Ed. 44, 7852–7872 (2005)10.1002/anie.200500766 ↗
14. Rioux, R.M., Song, H., Grass, M., Habas, S., Niesz, K., Hoefelmeyer, J.D., Yang, P., Somorjai, G.A.: Monodisperse platinum nanoparticles of well-defined shape: synthesis, characterization, catalytic properties and future prospects. Top. Catal. 39, 167–174 (2006)10.1007/s11244-006-0053-2 ↗
15. Chen, A., Holt-Hindle, P.: Platinum-based nanostructured materials: synthesis, properties, and applications. Chem. Rev. 110, 3767–3804 (2010)10.1021/cr9003902 ↗
16. Xu, S., Yang, Q.: Well-dispersed water-soluble Pd nanocrystals: Facile reducing synthesis and application in catalyzing organic reactions in aqueous media. J. Phys. Chem. C 112, 13419–13425 (2008)10.1021/jp800539x ↗
17. Zhang, Q., Xie, J., Yang, J., Lee, J.Y.: Monodisperse icosahedral Ag, Au, and Pd nanoparticles: size control strategy and superlattice formation. ACS Nano 3, 139–148 (2008)10.1021/nn800531q ↗
18. Wiley, B., Sun, Y., Xia, Y.: Synthesis of silver nanostructures with controlled shapes and properties. Acc. Chem. Res. 40, 1067–1076 (2007)10.1021/ar7000974 ↗
19. Van Rheenen, P.R., McKelvy, M.J., Glaunsinger, W.S.: Synthesis and characterization of small platinum particles formed by the chemical reduction of chloroplatinic acid. J. Solid State Chem. 67, 151–169 (1987)10.1016/0022-4596(87)90350-1 ↗
20. Knecht, M.R., Weir, M.G., Myers, V.S., Pyrz, W.D., Ye, H., Petkov, V., Buttrey, D.J., Frenkel, A.I., Crooks, R.M.: Synthesis and characterization of Pt dendrimer-encapsulated nanoparticles: effect of the template on nanoparticle formation. Chem. Mater. 20, 5218–5228 (2008)10.1021/cm8004198 ↗
21. Borodko, Y., Thompson, C.M., Huang, W., Yildiz, H.B., Frei, H., Somorjai, G.A.: Spectroscopic study of platinum and rhodium dendrimer (PAMAM G4OH) compounds: structure and stability. J. Phys. Chem. C 115, 4757–4767 (2011)10.1021/jp1116454 ↗
22. Hossain, M.J., Tsunoyama, H., Yamauchi, M., Ichikuni, N., Tsukuda, T.: High-yield synthesis of PVP-stabilized small Pt clusters by microfluidic method. Catal. Today 183, 101–107 (2012)10.1016/j.cattod.2011.10.008 ↗
23. Gobby, D., Angeli, P., Gavriilidis, A.: Mixing characteristics of T-type microfluidic mixers. J. Micromech. Microeng. 11, 126 (2001)10.1088/0960-1317/11/2/307 ↗
24. Soleymani, A., Kolehmainen, E., Turunen, I.: Numerical and experimental investigations of liquid mixing in T-type micromixers. Chem. Eng. J. 135, S219–S228 (2008)10.1016/j.cej.2007.07.048 ↗
25. Schwesinger, N., Frank, T., Wurmus, H.: A modular microfluid system with an integrated micromixer. J. Micromech. Microeng. 6, 99 (1996)10.1088/0960-1317/6/1/023 ↗
26. Munson, M.S., Yager, P.: Simple quantitative optical method for monitoring the extent of mixing applied to a novel microfluidic mixer. Anal. Chim. Acta 507, 63–71 (2004)10.1016/j.aca.2003.11.064 ↗
27. Hessel, V., Hardt, S., Löwe, H., Schönfeld, F.: Laminar mixing in different interdigital micromixers: I. Experimental characterization. AIChE J. 49, 566–577 (2003)10.1002/aic.690490304 ↗
28. Hardt, S., Schönfeld, F.: Laminar mixing in different interdigital micromixers: II. Numerical simulations. AIChE J. 49, 578–584 (2003)10.1002/aic.690490305 ↗
29. Rioux, R.M., Song, H., Hoefelmeyer, J.D., Yang, P., Somorjai, G.A.: High-surface-area catalyst design: synthesis, characterization, and reaction studies of platinum nanoparticles in mesoporous SBA-15 silica. J. Phys. Chem. B 109, 2192–2202 (2005)10.1021/jp048867x ↗
30. Teranishi, T., Hosoe, M., Tanaka, T., Miyake, M.: Size control of monodispersed Pt nanoparticles and their 2D organization by electrophoretic deposition. J. Phys. Chem. B 103, 3818–3827 (1999)10.1021/jp983478m ↗
31. Campelo, J.M., Luna, D., Luque, R., Marinas, J.M., Romero, A.A.: Sustainable preparation of supported metal nanoparticles and their applications in catalysis. Chem. Sus. Chem. 2, 18–45 (2009)10.1002/cssc.200800227 ↗
32. Toshima, N., Harada, M., Yonezawa, T., Kushihashi, K., Asakura, K.: Structural analysis of polymer-protected palladium/platinum bimetallic clusters as dispersed catalysts by using extended X-ray absorption fine structure spectroscopy. J. Phys. Chem. 95, 7448–7453 (1991)10.1021/j100172a061 ↗
33. Borodko, Y., Humphrey, S.M., Tilley, T.D., Frei, H., Somorjai, G.A.: Charge-transfer interaction of poly(vinylpyrrolidone) with platinum and rhodium nanoparticles. J. Phys. Chem. C 111, 6288–6295 (2007)10.1021/jp068742n ↗
34. Elechiguerra, J.L., Reyes-Gasga, J., Yacaman, M.J.: The role of twinning in shape evolution of anisotropic noble metal nanostructures. J. Mater. Chem. 16, 3906–3919 (2006)10.1039/b607128g ↗
35. Teranishi, T., Miyake, M.: Size control of palladium nanoparticles and their crystal structures. Chem. Mater. 10, 594–600 (1998)10.1021/cm9705808 ↗
36. Lim, B., Jiang, M., Tao, J., Camargo, P.H., Zhu, Y., Xia, Y.: Shape-controlled synthesis of Pd nanocrystals in aqueous solutions. Adv. Funct. Mater. 19, 189–200 (2009)10.1002/adfm.200801439 ↗
37. Leszczyńska, A., Njuguna, J., Pielichowski, K., Banerjee, J.R.: Polymer/montmorillonitenanocomposites with improved thermal properties: part I. Factors influencing thermal stability and mechanisms of thermal stability improvement. Thermochim. Acta 453, 75–96 (2007)10.1016/j.tca.2006.11.002 ↗
38. Shao-Horn, Y., Sheng, W.C., Chen, S., Ferreira, P.J., Holby, E.F., Morgan, D.: Instability of supported platinum nanoparticles in low-temperature fuel cells. Top. Catal. 46, 285–305 (2007)10.1007/s11244-007-9000-0 ↗
39. Chen, Z., Waje, M., Li, W., Yan, Y.: Supportless Pt and PtPd nanotubes as electrocatalysts for oxygen-reduction reactions. Angew. Chem. Int. Ed. 46, 4060–4063 (2007)10.1002/anie.200700894 ↗
40. Garron, A., Świerczyński, D., Bennici, S., Auroux, A.: New insights into the mechanism of H2 generation through NaBH4 hydrolysis on Co-based nanocatalysts studied by differential reaction calorimetry. Int. J. Hydrog. Energy 34, 1185–1199 (2009)10.1016/j.ijhydene.2008.11.027 ↗
41. Gonçalves, A., Castro, P., Novais, A., Fernandes, V.R., Rangel, C.M., Matos, H.: Dynamic modeling of hydrogen generation via hydrolysis of sodium borohydride. Reactions 1, 2 (2007)
42. Duff, D.G., Edwards, P.P., Johnson, B.F.: Formation of a polymer-protected platinum sol: a new understanding of the parameters controlling morphology. J. Phys. Chem. 99, 15934–15944 (1995)10.1021/j100043a036 ↗
43. Ingelsten, H.H., Bagwe, R., Palmqvist, A., Skoglundh, M., Svanberg, C., Holmberg, K., Shah, D.O.: Kinetics of the formation of nano-sized platinum particles in water-in-oil microemulsions. J. Colloid Interface Sci. 241, 104–111 (2001)10.1006/jcis.2001.7747 ↗
44. Leontyev, I.N., Kuriganova, A.B., Leontyev, N.G., Hennet, L., Rakhmatullin, A., Smirnova, N.V., Dmitriev, V.: Size dependence of the lattice parameters of carbon supported platinum nanoparticles: X-ray diffraction analysis and theoretical considerations. RSC Adv. 4, 35959–35965 (2014)10.1039/C4RA04809A ↗
45. Kuhrt, C., Anton, R.: On the origin of a lattice expansion in palladium and Pd@Au vapour deposits on various substrates. Thin Solid Films 198, 301–315 (1991)10.1016/0040-6090(91)90348-2 ↗
46. Onodera, S.: Lattice parameters of fine copper and silver particles. J. Phys. Soc. Jpn. 61, 2190–2193 (1992)10.1143/JPSJ.61.2190 ↗
47. Qiu, L., Liu, F., Zhao, L., Yang, W., Yao, J.: Evidence of a unique electron donor-acceptor property for platinum nanoparticles as studied by XPS. Langmuir 22, 4480–4482 (2006)10.1021/la053071q ↗
48. Alayoglu, S., Nilekar, A.U., Mavrikakis, M., Eichhorn, B.: Ru–Pt core–shell nanoparticles for preferential oxidation of carbon monoxide in hydrogen. Nat. Mater. 7, 333–338 (2008)10.1038/nmat2156 ↗
49. Suo, Y., Zhuang, L., Lu, J.: First-principles considerations in the design of Pd-alloy catalysts for oxygen reduction. Angew. Chem. Int. Ed. 46, 2862–2864 (2007)10.1002/anie.200604332 ↗