Sacrificial hydrogen generations from water mediated by a series of viologen-dye relays

Keller, Patrick; Moradpour, Alec; Amouyal, Edmond; Zidler, Bertrand

doi:10.1016/0304-5102(81)80013-2

Cited by 14 publications

(3 citation statements)

References 6 publications

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“…The three curves were calculated combining Eqs. (17) and (18) with Eq. (17), (18) (2) Study of the Back Reaction One of the most important considerations concerning photochemical systems for water dissociation is related to the back reaction (reaction (4» leading to the ground state reactants immediately following the primary electron transfer reaction (reaction (3».…”

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On the Effect of Electron Relay Redox Potential on Electron Transfer Reactions in a Water Photoreduction Model System

Amouyal

Zidler

1982

Israel Journal of Chemistry

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Abstract. The influence of electron relay redox potential (EI/') on the electrontransfer reactions occurring in the photo-induced hydrogen generation from water has been investigated using the Ru(bipy)~+ IMV'+ IEDTA/colloidal Pt model system. Quenching rate constants k q for electron transfer quenching of Ru(bipy)~+" by a series of 2,2'-and 4,4'-bipyridinium ions and by a series of phenanthroline ions having different redox potential EI/2 have been determined by laser flash spectroscopy in deaerated aqueous solutions at pH 5. The rate constants k h of the back electron transfer following the quenching reaction have been obtained for five bipyridinium ions under the same experimental conditions. Our results show that: (I) for the same EI/" the quencher molecular structure of the two homogeneous series does not affect k q significantly; (2) for the two series, k q increases with increasing E 1/' up to a value which is close to the diffusion-controlled limit. The same correlation between k q and E'I2 is obtained for the two series. Such a correlation is satisfactorily interpreted in the frame of existing theories describing electron-transfer reactions. particularly with the Rehm-Weller treatment, provided that an intrinsic barrier .:la"(O) = 5.2 kcal. M-I is used; (3) k h is close to the diffusion-controlled limit for E 112 comprised between -0.33 and -0.65 V (vs NHE); (4) a correlation between H, production rates and EI/, is suggested, and a maximum H, production is observed for EI/' = -0.45 V (vs. NHE) corresponding to compounds 1 and 14.

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On the Effect of Electron Relay Redox Potential on Electron Transfer Reactions in a Water Photoreduction Model System

Amouyal

Zidler

1982

Israel Journal of Chemistry

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“…We have previously shown that Stern−Volmer quenching constants correlate with association constants, determined by Benesi−Hildebrandt treatment of UV−vis absorbance data, and therefore provide a measure of the strength of the dye-receptor complex. 9b,e The degree of quenching is also an indication of the electron-accepting abilities of the viologens and should therefore correlate with their reduction potentials . To confirm this relationship, the reduction potentials of benzyl viologens (BV), 4,4 ‘ -BV , 3,4 ‘ -BV , and 3,3 ‘ -BV (Figure ), were determined by cyclic voltammetry (CV) and were compared to their quenching constants.…”

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Boronic Acid-Based Bipyridinium Salts as Tunable Receptors for Monosaccharides and α-Hydroxycarboxylates

et al. 2007

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Several novel diboronic acid-substituted bipyridinium salts were prepared and, using a fluorescent reporter dye, were tested for their ability to selectively bind various monosaccharides and alpha-hydroxycarboxylates in an aqueous medium. The fluorescence sensing mechanism relies on the formation of a ground-state charge-transfer complex between the dye and bipyridinium. An X-ray crystal structure of this complex is described herein. Glucose selectivity over fructose and galactose was achieved by designing the bipyridinium-based receptors to be capable of attaining a 1:1 receptor/substrate stoichiometry via cooperative diboronic acid binding.

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“…Σε προηγούμενες μελέτες[32,34], ο σχηματισμός in situ τέτοιων κολλοειδών επιτυγχανόταν μέσω αναγωγής αλάτων του Pt. Αυτό το σύστημα, παρήγαγε αποτελεσματικά Η2, οδηγούσε σε επαναλαμβανόμενα αποτελέσματα και έδινε λεπτομερή περιγραφή του μηχανισμού[18], όπως και την κβαντική απόδοση του σχηματισμού του υδρογόνου[42]. Αυτοί είναι οι λόγοι που αυτό το σύστημα μελετήθηκε από πολλές ομάδες[43][44][45][46][47] και ακόμη θεωρείται σύστημα αναφοράς για δοκιμές νέων PS, R, D και καταλυτών (Πίνακας 4.4.1), και για ηλιακούς φωτοχημικούς αντιδραστήρες σε πιλοτικό επίπεδο[48].Σχήμα 4.2.1.…”

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Φωτοκαταλυτική Παραγωγή Υδρογόνου Με Διθειολενικά Σύμπλοκα

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Η παρούσα εργασία διενεργήθηκε στα πλαίσια της διδακτορικής διατριβής στο Εργαστήριο Ανόργανης Χημείας του Τμήματος Χημείας του Εθνικού και Καποδιστριακού Πανεπιστημίου Αθηνών. Καλύπτει βιβλιογραφικά φωτοκαταλυτικά συστήματα παραγωγής υδρογόνου ομογενούς κατάλυσης. Παρουσιάζεται η σύνθεση και ο χαρακτηρισμός των συμπλόκων : [ReBr(CO)3(amphen)] (amphen = 5 – άμινο -1,10 – φαινανθρολίνη), [ReBr(CO)3(phendione)] (phendione = 1,10 – φαινανθρολίνη– 5,6 – διόνη), [ReCl(CO)3(amphen)], [Re(CO)3Cl{dppz-3,6-(COOEt)2}] (dppz-3,6-(COOEt)2 = διπυριδο[3,2-a:2΄,3΄-c] φαιναζίνη-3,6- δικαρβοξυλαιθυλ εστέρας]). Επίσης παρουσιάζεται η κρυσταλλική δομή του συμπλόκου [ReBr(CO)3(pq)]. Τα σύμπλοκα: [ReBr(CO)3amphen], [ReBr(CO)3(phendione)], [ReCl(CO)3(amphen)],[ReBr(CO)3pq], [Re(CO)3Cl{dppz-3,6-(COOEt)2}], [Ga(di-o-F-p-py)-1-Ga],[Ga(tpfc)-2-Ga] και σύμπλοκο του Cu (I) {[Cu(I) (dppzCOOEt)2]} διερευνήθηκαν ως προς την ικανότατα τους να δρουν ως φωτοευαισθητοποιητές για να ανάγουν πρωτόνια σε ομογενή φωτοκαταλυτικά συστήματα. Ως καταλύτες για την μεταφορά πρωτονίων στο νερό χρησιμοποιήθηκαν κοβαλοξίμες, διθειολενικά σύμπλοκα του Ni,σύμπλοκα του Co(II) {[K(NCMe)3(L6)CoII-NCMe]∙MeCN∙H2O,[K(NCMe)3(L13)CoII-NCMe]} και σύμπλοκο του Cu (I) {[Cu(I)(dppzCOOEt)2]}. Στα πλαίσια της ερευνητικής εργασίας για την περιγραφή των φωτοκαταλυτικών μηχανισμών που λαμβάνουν χώρα, πραγματοποιήθηκαν πειράματα αποδιέγερσης του φωτοευαισθητοποιητή με προσθήκη καταλύτη.

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Sacrificial hydrogen generations from water mediated by a series of viologen-dye relays

Cited by 14 publications

References 6 publications

On the Effect of Electron Relay Redox Potential on Electron Transfer Reactions in a Water Photoreduction Model System

On the Effect of Electron Relay Redox Potential on Electron Transfer Reactions in a Water Photoreduction Model System

Boronic Acid-Based Bipyridinium Salts as Tunable Receptors for Monosaccharides and α-Hydroxycarboxylates

Φωτοκαταλυτική Παραγωγή Υδρογόνου Με Διθειολενικά Σύμπλοκα

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