Temperature jump in electric double-layer study

Benderskiĭ, V. A.; Velichko, G.I.

doi:10.1016/0368-1874(82)85295-7

Cited by 81 publications

(81 citation statements)

References 20 publications

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“…The picture is complicated by the existence of a chemical interaction between the water and the metal surface that tends to orientate the water molecules even in the absence of any electric field. This natural orientation is with the oxygen closer to the metal surface in the case of gold and mercury electrodes, as reflected in the fact that the PME is located slightly negative to the PZC [Benderskii and Velichko, 1982;Climent et al, 2002c]. The decrease in the work function upon water dosage supports the same picture for Pt [Villegas and Weaver, 1996].…”

Section: Double-layer Effects Of Adatom Modificationsupporting

confidence: 67%

Clues for the Molecular‐Level Understanding of Electrocatalysis on Single‐Crystal Platinum Surfaces Modified byp‐Block Adatoms

Climent

Garcı́a-Aráez

Feliu

2008

Fuel Cell Catalysis

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Section: Double-layer Effects Of Adatom Modificationsupporting

confidence: 67%

Clues for the Molecular‐Level Understanding of Electrocatalysis on Single‐Crystal Platinum Surfaces Modified byp‐Block Adatoms

Climent

Garcı́a-Aráez

Feliu

2008

Fuel Cell Catalysis

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“…[34] Temperature jump measurements of the open-cell potential provided information on the change of the entropy of formation of the double layer with the electrode charge. [35,36] This method was applied, for example, to the Pt(111)-electrolyte interface where implications for the orientation of water molecules were recently derived. [37] Both methods may be partly applicable also for the electrochemical processes investigated herein and could provide complementary information on the entropy of the surface processes.…”

Section: Discussionmentioning

confidence: 99%

Heat Effects upon Electrochemical Copper Deposition on Polycrystalline Gold

2010

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Heat effects upon Cu deposition on polycrystalline Au surfaces from sulphuric acid electrolytes were calorimetrically measured. By combination of pyroelectric temperature detection at the backside of a thin electrode foil with pulsed electrochemistry, sensitivities to electrochemical conversions of a few percent of a Cu monolayer (ML), corresponding to about 1 microJ cm(-2) were achieved. We compared the heat evolution upon Cu under potential deposition (UPD), Cu deposition onto a fully developed Cu UPD layer and bulk Cu deposition onto a 300 ML thick Cu layer on Au. The heat effects were measured dependent on the amplitudes of the applied potential steps, that is, the driving forces of the respective reactions. From the differences of the heat effects among the Cu deposition processes, we deduced implications on the reaction mechanisms. For Cu UPD, the heat effects were explicable by the deposition of 1.3 Cu atoms per two electrons flowing to the electrode accompanied by sulphate coadsorption, similar to Cu UPD from sulphuric acid solutions on Au(111). Upon Cu deposition on a Cu UPD layer the heat effects signal considerable anion coadsorption up to the deposition of about 0.5 ML of Cu. At higher conversions the deposition mechanism gradually changes towards bulk Cu deposition, accompanied by reduction of the sulphate coverage.

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“…In addition to the previous description, thermodynamic considerations demonstrate that the thermal coefficient of the potential drop is linked with the entropy of double layer formation through [32,33,35,36]:…”

Section: E V Vs Shementioning

confidence: 92%

Investigating interfacial parameters with platinum single crystal electrodes

et al. 2017

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The concepts of total and free charge of platinum single crystal electrodes are revised in this paper, together with the associated concepts of potential of zero total and free charge. Total charges can be measured from CO displacement method. Results on solution of different pH are described. A novel buffer composition is used to attain pH values close to neutrality while avoiding interferences from anion adsorption processes. Stress is made on the fact that free charges are not accessible through electrochemical measurement for systems at equilibrium since adsorption processes (hydrogen and hydroxyl) interfere with free charge determination. Still, a model is described that allows, under some assumptions, extract free charge values and the corresponding potential of zero free charge for Pt (111) electrodes. On the other hand, fast measurement outside equilibrium can separate free charges from adsorption processes based on their different time constant. In this way, the laser induced temperature jump experiment allows determination of the potential of maximum entropy, a magnitude that is intimately related with the potential of zero free charge. Values of the potential of maximum entropy as a function of pH are given for the different basal planes of platinum.

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Temperature jump in electric double-layer study

Cited by 81 publications

References 20 publications

Clues for the Molecular‐Level Understanding of Electrocatalysis on Single‐Crystal Platinum Surfaces Modified byp‐Block Adatoms

Clues for the Molecular‐Level Understanding of Electrocatalysis on Single‐Crystal Platinum Surfaces Modified byp‐Block Adatoms

Heat Effects upon Electrochemical Copper Deposition on Polycrystalline Gold

Investigating interfacial parameters with platinum single crystal electrodes

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