Browsing by Author "Li C."
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Item Open Access Continuous mesoporous pd films by electrochemical deposition in nonionic micellar solution(American Chemical Society, 2017) Iqbal, M.; Li C.; Wood, K.; Jiang B.; Takei, T.; Dag, Ö.; Baba, D.; Nugraha, A. S.; Asahi, T.; Whitten, A. E.; Hossain, M. S. A.; Malgras, V.; Yamauchi, Y.Mesoporous metals that combine catalytic activity and high surface area can provide more opportunities for electrochemical applications. Various synthetic methods, including hard and soft templating, have been developed to prepare mesoporous/nanoporous metals. Micelle assembly, typically involved in soft-templates, is flexible and convenient for such purposes. It is, however, difficult to control, and the ordering is significantly destroyed during the metal deposition process, which is detrimental when it comes to designing precisely mesostructured materials. In the present work, mesoporous Pd films were uniformly electrodeposited using a nonionic surfactant, triblock copolymer poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide), as a pore-directing agent. The interaction between micelles and metal precursors greatly influences the metal growth and determines the final structure. The water-coordinated species interact with the ethylene oxide moiety of the micelles to effectively drive the Pd(II) species toward the working electrode surface. From small-angle neutron scattering data, it is found that spherical P123 micelles, with an average diameter of ∼14 nm, are formed in the electrolyte, and the addition of Pd ions does not significantly modify their structure, which is the essence of the micelle assembly approach. The uniformly sized mesopores are formed over the entire mesoporous Pd film and have an average pore diameter of 10.9 nm. Cross-sectional observation of the film also shows mesopores spanning continuously from the bottom to the top of the film. The crystallinity, crystal phase, and electronic coordination state of the Pd film are also confirmed. Through this study, it is found that the optimized surfactant concentration and applied deposition potential are the key factors to govern the formation of homogeneous and well-distributed pores over the entire film. Interestingly, the as-prepared mesoporous Pd films exhibit superior electrocatalytic activity toward the ethanol oxidation reaction by fully utilizing the accessible active surface area. Our approach combines electrochemistry with colloidal and coordination chemistry and is widely applicable to other promising metals and alloy electrocatalysts.Item Open Access Electrochemical synthesis of mesoporous gold films toward mesospace-stimulated optical properties(Nature Publishing Group, 2015) Li C.; Dag Ö.; Dao, T.D.; Nagao, T.; Sakamoto, Y.; Kimura, T.; Terasaki O.; Yamauchi, Y.Mesoporous gold (Au) films with tunable pores are expected to provide fascinating optical properties stimulated by the mesospaces, but they have not been realized yet because of the difficulty of controlling the Au crystal growth. Here, we report a reliable soft-templating method to fabricate mesoporous Au films using stable micelles of diblock copolymers, with electrochemical deposition advantageous for precise control of Au crystal growth. Strong field enhancement takes place around the center of the uniform mesopores as well as on the walls between the pores, leading to the enhanced light scattering as well as surface-enhanced Raman scattering (SERS), which is understandable, for example, from Babinet principles applied for the reverse system of nanoparticle ensembles. © 2015 Macmillan Publishers Limited. All rights reserved.Item Open Access First synthesis of continuous mesoporous copper films with uniformly sized pores by electrochemical soft templating(Wiley-VCH Verlag, 2016) Li C.; Jiang B.; Wang, Z.; Li Y.; Hossain, M. S. A.; Kim, J. H.; Takei, T.; Henzie, J.; Dag, Ö.; Bando, Y.; Yamauchi, Y.Although mesoporous metals have been synthesized by electrochemical methods, the possible compositions have been limited to noble metals (e.g., palladium, platinum, gold) and their alloys. Herein we describe the first fabrication of continuously mesoporous Cu films using polymeric micelles as soft templates to control the growth of Cu under sophisticated electrochemical conditions. Uniformly sized mesopores are evenly distributed over the entire film, and the pore walls are composed of highly crystalized Cu.Item Open Access Mesoporous metallic rhodium nanoparticles(Nature Publishing Group, 2017) Jiang B.; Li C.; Dag, Ö.; Abe, H.; Takei, T.; Imai, T.; Hossain, M. S. A.; Islam, M. T.; Wood, K.; Henzie, J.; Yamauchi, Y.Mesoporous noble metals are an emerging class of cutting-edge nanostructured catalysts due to their abundant exposed active sites and highly accessible surfaces. Although various noble metal (e.g. Pt, Pd and Au) structures have been synthesized by hard- and soft-templating methods, mesoporous rhodium (Rh) nanoparticles have never been generated via chemical reduction, in part due to the relatively high surface energy of rhodium (Rh) metal. Here we describe a simple, scalable route to generate mesoporous Rh by chemical reduction on polymeric micelle templates [poly(ethylene oxide)-b-poly(methyl methacrylate) (PEO-b-PMMA)]. The mesoporous Rh nanoparticles exhibited a ∼1/42.6 times enhancement for the electrocatalytic oxidation of methanol compared to commercially available Rh catalyst. Surprisingly, the high surface area mesoporous structure of the Rh catalyst was thermally stable up to 400 °C. The combination of high surface area and thermal stability also enables superior catalytic activity for the remediation of nitric oxide (NO) in lean-burn exhaust containing high concentrations of O 2.Item Open Access Molecular catalysts for artificial photosynthesis: general discussion(Royal Society of Chemistry, 2017) Wang, M.; Artero, V.; Hammarström, L.; Martinez, J.; Karlsson, J.; Gust, D.; Summers, P.; Machan, C.; Brueggeller, P.; Windle, C. D.; Kageshima, Y.; Cogdell, R.; Tolod, K. R.; Kibler, A.; Apaydin, D. H.; Fujita, E.; Ehrmaier, J.; Shima, S.; Gibson, E.; Karadas, F.; Harriman, A.; Inoue, H.; Kudo, A.; Takayama, T.; Wasielewski, M.; Cassiola, F.; Yagi, M.; Ishida, H.; Franco, F.; Kang, S. O.; Nocera, D.; Li C.; Fonzo, F. D.; Park, H.; Sun, L.; Setoyama, T.; Kang, Y. S.; Ishitani, O.; Shen, J. R.; Son, H. J.; Masaoka, S.Item Open Access Standing mesochannels: mesoporous PdCu films with vertically aligned mesochannels from nonionic micellar solutions(American Chemical Society, 2018) Iqbal, M.; Kim, J.; Yuliarto, B.; Jiang B.; Li C.; Dağ, Ömer; Malgras, V.; Yamauchi, Y.Mesoporous bimetallic palladium (Pd) alloy films with mesochannels perpendicularly aligned to the substrate are expected to show superior electrocatalytic activity and stability. The perpendicular mesochannels allow small molecules to efficiently access the active sites located not only at the surface but also within the film because of low diffusion resistance. When compared to pure Pd films, alloying with a secondary metal such as copper (Cu) is cost-effective and promotes resistance against adventitious poisoning through intermediate reactions known to impair the electrocatalytic performance. Here, we report the synthesis of mesoporous PdCu films by electrochemical deposition in nonionic micellar solutions. The mesoporous structures are vertically aligned on the substrate, and the final content of Pd and Cu can be adjusted by tuning the initial precursor molar ratio in the electrolyte solution.