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Effects of surfactant head group modification on vertically oriented mesoporous silica produced by the electrochemically assisted surfactant assembly method.

ABSTRACT: Production of mesoporous silica films with vertically oriented pores has been a challenge since interest in such systems developed in the 1990s. Vertical orientation can be achieved by the electrochemically assisted surfactant assembly (EASA) method using cationic surfactants such as cetyltrimethylammonium bromide (C₁₆TAB). The synthesis of porous silicas using a series of surfactants with increasing head sizes is described, from octadecyltrimethylammonium bromide (C₁₈TAB) to octadecyltriethylammonium bromide (C₁₈TEAB). These increase pore size, but the degree of hexagonal order in the vertically aligned pores reduces as the number of ethyl groups increases. Pore accessibility is also reduced with the larger head groups.

SUBMITTER: Mohamed NAN

PROVIDER: S-EPMC10263000 | biostudies-literature | 2023 Jun

REPOSITORIES: biostudies-literature

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Effects of surfactant head group modification on vertically oriented mesoporous silica produced by the electrochemically assisted surfactant assembly method.

Mohamed Nabil A N NAN Han Yisong Y Harcourt-Vernon Sarah S Hector Andrew L AL Houghton Anthony R AR Reid Gillian G Williams Daryl R DR Zhang Wenjian W

Nanoscale advances 20230517 12

Production of mesoporous silica films with vertically oriented pores has been a challenge since interest in such systems developed in the 1990s. Vertical orientation can be achieved by the electrochemically assisted surfactant assembly (EASA) method using cationic surfactants such as cetyltrimethylammonium bromide (C<sub>16</sub>TAB). The synthesis of porous silicas using a series of surfactants with increasing head sizes is described, from octadecyltrimethylammonium bromide (C<sub>18</sub>TAB) ...[more]

PMID: 37325528

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Project description:Recent and potential applications of electrochromic materials include smart windows, optoelectronic devices, and energy conversion. In this study, we have incorporated bis(terpyridine) iron (II) complexes into vertically-oriented silica thin films deposited on indium-tin oxide (ITO) and their electrochromic behavior has been investigated. If 2,2':6',2″-terpyridine is commonly used as a ligand for forming metallo-supramolecular assemblies, with the objective to get metal-terpyridine complexes with multiple stable redox states, their simple and reliable arrangement into linear structures enabling effective electronic communication is however more challenging. We propose to overcome this difficulty by generating such complexes within vertical nanochannels on electrode. Terpyridine ligands were firstly immobilized by combining a click chemistry azide/alkyne approach with an electrochemically-assisted self-assembly (EASA) method used to grow an oriented mesoporous silica membrane bearing azide groups which were further derivatized with 4'-ethynyl-terpyridine ligands. The resulting terpyridine-functionalized films were consecutively dipped in an aqueous solution of Fe(BF4)2 and then in a solution of terpyridine in acetonitrile to form the bis(terpyridine) iron (II) complexes in situ. The electrochromic properties of the films functionalized at various levels were examined by monitoring the changes in their UV/Vis spectra upon electrochemical oxidation at controlled potential of +1.2 V vs. Ag/AgCl. Due to facile charge delocalization during the Fe2+ to Fe3+ redox process, the bis(terpyridine) iron (II) functionalized silica films exhibited electrochromic properties by changing from violet to non-colored using TBABF4 in acetonitrile as an electrolyte. The bis(terpyridine) iron(II) film experienced reversible electrochromic switching by applying +0.5 V in a reverse reduction electrochemical process. The Fe(tpy)2-functionalized silica thin films displayed a good contrast ratio (ΔT%) of 47% and relatively high coloration efficiency (CE) of about 245 cm2/C with a response time of coloring and bleaching of a few seconds (< 4 s).

Dataset Information

Effects of surfactant head group modification on vertically oriented mesoporous silica produced by the electrochemically assisted surfactant assembly method.

Publications

Effects of surfactant head group modification on vertically oriented mesoporous silica produced by the electrochemically assisted surfactant assembly method.

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