Synthesis, characterisation and in situ colorimetry of electrochromic Ruthenium purple thin films

Mortimer, Roger J.; Varley, Thomas S.

doi:10.1016/j.dyepig.2010.10.009

Cited by 17 publications

(11 citation statements)

References 20 publications

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“…In the present article, a RP film was electrochemically deposited from a precursor solution containing an inorganic salt: potassium hexacyanoruthenate(II) which served as the source for Ru 2 þ color centers, and an organometallic compound, ferrocenecarboxaldehyde which furnished the Fe 3 þ species. Herein, the precursor solution is unlike the previously reported RP colloids [30]; it formed a pale yellow transparent homogeneous formulation in aqueous/non-aqueous solvents and yielded a colored deposit in the form of a thin film on conducting glass substrates under potentiodynamic conditions. This new deposition solution yielded purple colored (RP) films of high uniformity.…”

Section: Introductionmentioning

confidence: 95%

“…Prussian blue analogues involving the use of 3d and 4d group elements have been reported in the past [27][28][29]. Ruthenium purple (RP), a Prussian blue analogue, is relatively less investigated; it is also a dye, which strongly absorbs in the visible region with an absorption maximum positioned at 550 nm and appears purple in color [30]. The origin of color in RP is attributed to charge transfer between Ru 2 þ and Fe 3 þ centers.…”

Section: Introductionmentioning

confidence: 98%

“…RP can be synthesized in two different forms, soluble and insoluble forms, namely KFe[Ru(CN) 6 ] and Fe 4 [Ru (CN) 6 ] 3 [31,32]. In the past, RP thin films were electrodeposited from a solution containing a soluble RP colloid, prepared by dissolving FeCl 3 and potassium hexacyanoruthenium(II) in water [30]. Linear polyethylene imine (LPEI)-RP multilayered nanocomposites were also fabricated in the past using LbL technique and a transmittance change of 84% at 560 nm and a coloration efficiency of 205 cm 2 C À 1 were reported [33].…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

A WO3–poly(butyl viologen) layer-by-layer film/ruthenium purple film based electrochromic device switching by 1 volt application

Sydam

Deepa

Shivaprasad

et al. 2015

Solar Energy Materials and Solar Cells

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Section: Introductionmentioning

confidence: 95%

Section: Introductionmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

A WO3–poly(butyl viologen) layer-by-layer film/ruthenium purple film based electrochromic device switching by 1 volt application

Sydam

Deepa

Shivaprasad

et al. 2015

Solar Energy Materials and Solar Cells

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“…We have observed that the Prussian blue analogue, Ruthenium purple (RP) in its colored state and reduced methyl viologen ( N , N ′-dimethyl-4,4′-bipyridylium) in water have closely matching visible-region absorption spectra, and their colors appear identical to the eye. This provided motivation to explore their use as color-reinforcing electrochromic materials in an ECD; the color-forming reactions being shown in the Scheme above.…”

Section: Introductionmentioning

confidence: 99%

Novel Color-Reinforcing Electrochromic Device Based on Surface-Confined Ruthenium Purple and Solution-Phase Methyl Viologen

Mortimer

Varley

2011

Chem. Mater.

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A novel color-reinforcing electrochromic device (ECD) is described in which the anode and cathode reactions simultaneously exhibit reversible colorless to intense purple changes. Under coloration, the mixed-valence iron(III) hexacy anoruthenate(II) chromophore is formed on oxidation of iron(II) hexacyano ruthenate(II), with simultaneous reduction of the methyl viologen dication to form a mixture of the radical cation monomer/dimer. Using the CIE (Commission Internationale de l'Eclairage) system of colorimetry, the color stimulus of such ECDs and the changes that take place on reversibly switching between the colored and colorless states have been calculated from in situ visible spectra recorded under electrochemical control. On ECD color switching, with the excellent color-matching between the two purple states, sharp and reversible changes in the hue and saturation occur, as shown by the minimal hysteresis of the track of the CIE 1931 xy chromaticity coordinates. Extrapolation of the xy track to the color locus gave a complementary wavelength (λ c ) of 565 ((5) nm in close agreement with values obtained for the individual electrochromic materials. The concentration of the solution-phase methyl viologen and its diffusion to the cathode controlled both the proportion of surfaceconfined Ruthenium purple (RP) that is switched to the intense purple form and the overall ECD changes. For the ECDs' "on" states, the CIELAB 1976 color space coordinates were L* = 86, a* = 9, and b* = À15, and L* = 79, a* = 15, and b* = À22, respectively, for 5 and 10 mmol dm À3 methyl viologen solution concentrations. CIELAB 1976 color space coordinates showed that the ECDs were fully transparent and colorless in the "off" states, with L* = 100, a* = 0, and b* = 0. Switching times, as estimated for 95% of the total absorbance change, were 4 and 10 s respectively, for coloration and bleaching for the 5 mmol dm À3 methyl viologen ECD, and 8 and 16 s for the 10 mmol dm À3 methyl viologen ECD.

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“…Quando os máximos de variação de cor se sobrepõem aos picos redox, o filme pode ser considerado contendo uma rápida compensação de cargas. Podem ser citados ainda outros estudos com azul da Prússia eletrodepositados sobre substratos de ITO flexíveis, 23,24 estudos colorimétricos in situ 25 e com metalocianinas. 26 Entre os óxidos inorgânicos, o material eletrocrômico com maior destaque é o óxido de tungstênio (WO 3 ) devido à sua importância histórica e aos altos valores de contrastes obtidos.…”

Section: Materiais Eletrocrômicosunclassified

Electrochromism: Basis and Application of Nanomaterials in Development of High Performance Electrodes

Quintanilha¹,

Rocha²,

Vichessi³

et al. 2014

Química Nova

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, describing the basic aspects and methodologies employed for the construction and analyses of different modified electrodes. The work presents the classic materials used for the construction of electrochromic electrodes, such as WO 3 and a view on the basic concepts of chromaticity as a useful approach for analyzing colorimetric results. The report also addresses how the incorporation of nanomaterials and the consequent novel modification of electrodes have furthered this area of science, producing electrochromic electrodes with high performance, high efficiency and low response times.Keywords: electrochromism; nanomaterials; modified electrodes. FUNDAMENTOS DE ELETROCROMISMOAs tecnologias desenvolvidas para o entretenimento visual têm grande impacto na sociedade e vem recebendo enormes investimentos. Como principais exemplos, existem as telas de LED (do inglês, light emission diode), LCD (do inglês, liquid crystal display) ou baseadas na emissão de radiação excitada por plasma. Neste contexto, os dispositivos baseados em eletrocromismo surgem como uma alternativa às tecnologias já empregadas, embora sua utilização em telas com grandes áreas, que requerem altas velocidades e grande variedade de cores ainda seja um desafio a ser superado. Podem ser encontrados muitos dispositivos simples que empregam esta tecnologia, como janelas inteligentes, espelhos retrovisores automotivos, displays, entre outros. 1 Neste cenário, surge em conjunto o interesse industrial em relação ao desenvolvimento e à produção em escalas comerciais de dispositivos eletrocrômicos poliméricos. Entre as principais empresas envolvidas na pesquisa e aplicação destes dispositivos estão a Isoclima, Saint Gobain e Pilkington na Europa, 2 Gentex, Apogee e Sage na América do Norte 3 e Asahi Glass, Nikon e Toyota na Ásia. 4O eletrocromismo consiste na mudança das propriedades ópticas de um determinado material após a aplicação de um estímulo elétrico na forma de corrente ou potencial. A mudança de coloração neste tipo de material ocorre devido à presença de grupos ou moléculas cromógenas, que absorvem a perturbação elétrica e como resposta, alteram suas propriedades ópticas. Materiais podem ser considerados eletrocrômicos se apresentam distintas mudanças de coloração reversíveis quando submetidos a uma reação de oxidação ou redução, sejam estas mudanças de transparente para colorido, ou mesmo a mudança entre cores. Novas classes de materiais têm sido foco de características espectrais passíveis de serem controladas. 5Quando um material possui dois ou mais estados redox e respectivas colorações diferentes, ele é denominado polieletrocrômico. Abaixo, na Equação 1, é representada uma reação eletrocrômica catódica reversível, na qual o material eletrocrômico é denominado como "E". Nesta reação, íons presentes no eletrólito (M + ) são inseridos na matriz do composto para que ocorra a compensação de cargas.Uma das primeiras observações de características eletrocrômicas ocorreu no ano de 1876, no trabalho de eletrooxidação da anilina, no qual o autor obser...

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Synthesis, characterisation and in situ colorimetry of electrochromic Ruthenium purple thin films

Cited by 17 publications

References 20 publications

A WO3–poly(butyl viologen) layer-by-layer film/ruthenium purple film based electrochromic device switching by 1 volt application

A WO3–poly(butyl viologen) layer-by-layer film/ruthenium purple film based electrochromic device switching by 1 volt application

Novel Color-Reinforcing Electrochromic Device Based on Surface-Confined Ruthenium Purple and Solution-Phase Methyl Viologen

Electrochromism: Basis and Application of Nanomaterials in Development of High Performance Electrodes

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