Extended Brewer hypo-hyper--interionic bonding theory II. Strong metal-support interaction grafting of composite electrocatalysts

Neophytides, Stylianos G.; Zafeiratos, Spyridon; Παπακωνσταντίνου, Γεώργιος; Jakšić, Jelena M.; Paloukis, Fotios; Jakšić, Milan M.

doi:10.1016/j.ijhydene.2004.07.005

Cited by 39 publications

(70 citation statements)

References 93 publications

(179 reference statements)

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“…[6] It is known that energy band gap has a great impact on the catalytic activity of semi-conductive materials, which implies that the analysis of the anatase-rutile relationship should be one of the most important properties of synthesized TiO2 and Pt/TiO2 as advance catalytic materials. In addition, but most important for the bifunctional electrocatalysis, Pt/TiO2 combination fits well to interactive interionic bonding theory [7] for the hyper-d metallic electrocatalysts supported on hypo-d oxide.…”

Section: Introductionsupporting

confidence: 66%

TiO2 From Colloidal Dispersion as Support in Pt/TiO2 Nanocomposite for Electrochemical Applications

Košević¹,

Šekularac²,

Živković³

et al. 2017

Croat. Chem. Acta

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TiO2 powder was synthesized by a forced hydrolysis process and used for the synthesis of Pt/TiO2 composite that is to be foreseen as an advanced electrode material. Pt was incorporated into the synthesized TiO2 from a Pt colloidal dispersion as a precursor prepared by a microwave-assisted polyol process. Physicochemical properties of TiO2 and TiO2-supported Pt were investigated by scanning electron microscopy, dynamic light scattering and X-ray spectroscopy and diffraction techniques. The properties of Pt/TiO2 composite are correlated to the basic voltammetric response of its thin-layer form. It was found that subsequent thermal treatment of synthesized TiO2, which caused crystallization into mainly rutile phase, is required for appropriate Pt incorporation. Although being appropriately loaded by Pt, and the voltammetric response is typical for Pt-based material, the voltammetry of Pt/TiO2 corresponded to much lower loadings. The possibility for Pt particles to be trapped inside TiO2 agglomerates is indicated. The catalyst usage from the synthesized Pt/TiO2 was found quite moderate due to this trapping.

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Section: Introductionsupporting

confidence: 66%

TiO2 From Colloidal Dispersion as Support in Pt/TiO2 Nanocomposite for Electrochemical Applications

Košević¹,

Šekularac²,

Živković³

et al. 2017

Croat. Chem. Acta

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“…The same Brewer- [53] type d-d intermetallic bonding model has been the already anticipated basis for Livage and Guzman [19], Neophytides et al [20,21], and Tauster and Fung [22] promotional strong metalsupport interaction (SMSI) effect, with the far-reaching consequences in heterogeneous catalysis, electrocatalysis. The latter systematically predetermined interactive grafting [55,56] and the homogeneous, even uniform distribution of prevailing hyper-d-metallic catalysts upon hypo-d-oxide supports [1-4, 20, 21]. The same type of hypo-hyper-d-dinteractive bonding between nanostructured metal particles of such composite catalysts and their hypo-d-oxide supports additionally reinforces the entire electrocatalytic activity effect [55,56].…”

Section: Hypo-hyper-d-d-interbonding Nature Of Electrocatalysis For Hmentioning

confidence: 99%

“…The latter systematically predetermined interactive grafting [55,56] and the homogeneous, even uniform distribution of prevailing hyper-d-metallic catalysts upon hypo-d-oxide supports [1-4, 20, 21]. The same type of hypo-hyper-d-dinteractive bonding between nanostructured metal particles of such composite catalysts and their hypo-d-oxide supports additionally reinforces the entire electrocatalytic activity effect [55,56]. The pronounced cathodic and anodic interactive spillover (effusion) contributions within the SMSI have been significant for the present theory and its embodiment in electrocatalysis of hydrogen and oxygen electrode reactions for low-and medium-temperature (L&MT) PEMFC and water electrolysis (WE) [1-4, 20, 21].…”

Section: Hypo-hyper-d-d-interbonding Nature Of Electrocatalysis For Hmentioning

confidence: 99%

“…As a consequence, the d band of transition elements has been confirmed to play a crucial role in the bonding, adsorptive, catalytic, and electrocatalytic properties, and, consequently, any search for advances and synergism should be based on the d-d interelectronic correlations and modifications [52,55,56]. Such a state of theoretical knowledge and experimental evidence leads to the conclusion that every hypo-hyperd-d interelectronic phase diagram behaves as the part of the periodic table between the two initial periods of the interacting ingredients.…”

Section: Hypo-hyper-d-d-interbonding Nature Of Electrocatalysis For Hmentioning

confidence: 99%

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Spillover Phenomena and Its Striking Impacts in Electrocatalysis for Hydrogen and Oxygen Electrode Reactions

Παπακωνσταντίνου

Jakšić

Labou

et al. 2011

Advances in Physical Chemistry

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The core subject of the present paper represents the interrelated spillover (effusion) phenomena both of the primary oxide and the H-adatoms, their theory and practice, causes, appearances and consequences, and evidences of existence, their specific properties, and their alterpolar equilibria and kinetic behavior, structural, and resulting catalytic, and double layer charging features. The aim is to introduce electron conductive and d-d interactive individual and composite (mixed valence) hypo-doxide compounds, of increased altervalent capacity, or their suboxides (Magnéli phases), as the interactive catalytic supports and therefrom provide (i) the strong metal-support interaction (SMSI) catalytic effect and (ii) dynamic spillover interactive transfer of primary oxides (M-OH) and free effusional H-adatoms for further electrode reactions and thereby advance the overall electrocatalytic activity. Since hypo-d-oxides feature the exchange membrane properties, the higher the altervalent capacity, the higher the spillover effect. In fact, altervalent hypo-d-oxides impose spontaneous dissociative adsorption of water molecules and then spontaneously pronounced membrane spillover transferring properties instantaneously resulting with corresponding bronze type (Pt/H x WO 3 ) under cathodic and/or its hydrated state (Pt/W(OH) 6 ), responsible for Pt-OH effusion, under anodic polarization, this way establishing instantaneous reversibly revertible alterpolar bronze features (Pt/H 0.35 WO 3 ⇔ Pt/W(OH) 6 ) and substantially advanced electrocatalytic properties of these composite interactive electrocatalysts. Such nanostructured-type electrocatalysts, even of mixed-valence hypo-d-oxide structures (Pt/H 0.35 WO 3 /TiO 2 /C, Pt/H x NbO 3 /TiO 2 /C), have for the first time been synthesized by the sol-gel methods and shown rather high stability, electron conductivity, and nonexchanged initial pure monobronze spillover and catalytic properties. Such a unique electrocatalytic system, as the striking target issue of the present paper, has been shown to be the superior for substantiation of the revertible cell assembly for spontaneous reversible alterpolar interchanges between PEMFC and WE. The main target of the present thorough review study has been to throw some specific insight light on the overall spillover phenomena and their effects in electrocatalysis of oxygen and hydrogen electrode reactions from diverse angles of view and broad contemporary experimental methods and approaches (XPS, FTIR, DRIFT, XRD, potentiodynamic spectra, UHRTEM).

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“…In-situ activation does not require a separate surface activation step which adds considerably to the cost of the cathode. According, to Brewer hypo-hyper-d-interionic bonding theory, suitable compounds for in-situ activation are systems that combine early transition with late transition d-electronic metals, since their bimetallic surfaces are expected to exhibit modified chemical properties compared to pure metal surfaces [8,9]. The increase of electrocatalytic activity has been explained by the synergetic electronic effect [10].…”

Section: Introductionmentioning

confidence: 99%

Kinetics of hydrogen evolution reaction in alkaline electrolysis on a Ni cathode in the presence of Ni–Co–Mo based ionic activators

Nikolić

Maslovara

Tasić

et al. 2015

Applied Catalysis B: Environmental

119

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Extended Brewer hypo-hyper--interionic bonding theory II. Strong metal-support interaction grafting of composite electrocatalysts

Cited by 39 publications

References 93 publications

TiO2 From Colloidal Dispersion as Support in Pt/TiO2 Nanocomposite for Electrochemical Applications

TiO2 From Colloidal Dispersion as Support in Pt/TiO2 Nanocomposite for Electrochemical Applications

Spillover Phenomena and Its Striking Impacts in Electrocatalysis for Hydrogen and Oxygen Electrode Reactions

Kinetics of hydrogen evolution reaction in alkaline electrolysis on a Ni cathode in the presence of Ni–Co–Mo based ionic activators

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