Hydrogen evolution catalyzed by electrodeposited nanoparticles at the liquid/liquid interface

Nieminen, Joonas J.; Hatay, İmren; Ge, Peiyu; Méndez, Manuel A.; Murtomäki, Lasse

doi:10.1039/c1cc10637f

Cited by 83 publications

(89 citation statements)

References 20 publications

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“…A burgeoning area of research is concerned with the biphasic electrocatalysis of redox reactions of interest for energy research, including the oxygen (O 2 ) reduction reaction (ORR) [9][10][11][12][13][14][15][16][17][18][19] and the hydrogen (H 2 ) evolution reaction (HER) [20][21][22][23][24][25][26][27][28], using soft interfaces functionalized with molecular species, metallic NPs or inorganic non-precious metal-based materials. The use of adsorbed solid particulate electrocatalysts at electrochemically polarisable soft interfaces has recently been reviewed by Dryfe and co-workers [29].…”

Section: Introductionmentioning

confidence: 99%

“…Whereas several reports have highlighted the catalysis of biphasic reactions by (i) facilitating the transfer of protons [12,30,31], or other ions [17], across the soft interface and (ii) the use of interfacial species, either molecular [12,32,33] or solid particulates [22,26], to coordinate reactants to enable electrocatalysis, far less common is (iii) the use of NPs as bipolar electrodes to facilitate catalysis via direct interfacial electron transfer (IET) between a lipophilic electron donor and a hydrophilic electron acceptor or vice versa [8]. Such a process is termed interfacial redox catalysis.…”

Section: Introductionmentioning

confidence: 99%

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Gold Nanofilm Redox Catalysis for Oxygen Reduction at Soft Interfaces

Smirnov

Peljo

Scanlon

et al. 2016

Electrochimica Acta

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A B S T R A C TFunctionalization of a soft or liquid-liquid interface by a one gold nanoparticle thick "nanofilm" provides a conductive pathway to facilitate interfacial electron transfer from a lipophilic electron donor to a hydrophilic electron acceptor in a process known as interfacial redox catalysis. The gold nanoparticles in the nanofilm are charged by Fermi level equilibration with the lipophilic electron donor and act as an interfacial reservoir of electrons. Additional thermodynamic driving force can be provided by electrochemically polarising the interface. Using these principles, the biphasic reduction of oxygen by a lipophilic electron donor, decamethylferrocene, dissolved in a,a,a-trifluorotoluene was catalysed at a gold nanoparticle nanofilm modified water-oil interface. A recently developed microinjection technique was utilised to modify the interface reproducibly with the mirror-like gold nanoparticle nanofilm, while the oxidised electron donor species and the reduction product, hydrogen peroxide, were detected by ion transfer voltammetry and UV/vis spectroscopy, respectively. Metallization of the soft interface allowed the biphasic oxygen reduction reaction to proceed via an alternative mechanism with enhanced kinetics and at a significantly lower overpotential in comparison to a bare soft interface. Weaker lipophilic reductants, such as ferrocene, were capable of charging the interfacial gold nanoparticle nanofilm but did not have sufficient thermodynamic driving force to significantly elicit biphasic oxygen reduction.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Gold Nanofilm Redox Catalysis for Oxygen Reduction at Soft Interfaces

Smirnov

Peljo

Scanlon

et al. 2016

Electrochimica Acta

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“…The current wave at positive potentials varies linearly with the square root of the scan rate (data not shown), indicating that this process is limited by the diffusion of DMFc to the interface, as all other species are in excess. On replacing DMFc (standard redox potential in DCE versus the aqueous standard hydrogen electrode (SHE), [17] with a weaker reductant such as Fc (½E 0 [2] the current wave associated with the PCET process is no longer evident, as it is shifted in a positive direction, that is, outside of the available potential window, because of the difference between the redox potentials of DMFc and Fc. Nonetheless, an enhanced production of ferrocenium ions (Fc + ) in the presence of GO was clearly observed by iontransfer voltammetry (see Figure SI tion of GO to RGO and, as shown vide infra, the subsequent PCET process).…”

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Oxygen Reduction at Soft Interfaces Catalyzed by In Situ‐Generated Reduced Graphene Oxide

et al. 2013

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Graphene oxide (GO) in water was reduced heterogeneously by decamethylferrocene (DMFc) or ferrocene (Fc) in 1,2-dichloroethane (DCE), which could then act as a catalyst for an interfacial oxygen reduction reaction (ORR) and production of hydrogen peroxide (H 2 O 2 ). The reduced graphene oxide (RGO) produced at the liquid/liquid interface was characterized by using electron microscopy, spectroscopy (Raman, infrared, and electron energy loss), and electrochemical techniques.The oxygenated functional groups at the edge/defects of the RGO surface activate O 2 adsorption, forming superoxidelike adducts that can be protonated at the liquid/liquid interface and reduced by DMFc or Fc. This process is facilitated by the higher electrical conductivity of the RGO sheets. The key feature of this catalytic reaction is the in situ partial-reduction of GO at the liquid/liquid interface, forming an efficient and inexpensive catalyst for the production of H 2 O 2 .Electrochemistry at polarized interfaces between two immiscible electrolyte solutions (ITIES) has developed over the past 30 years, in which charge-transfer (electron-and ion-transfer) reactions have found applications in areas such as phase-transfer catalysis, solvent-extraction processes, chemical sensing, solar-energy-conversion systems, drug release and delivery, and in mimicking the function of biological membranes. [1] Liquid/liquid interfaces provide a unique platform at which to study ORRs, at which aqueous protons react with organic solubilized electron donors in the absence or presence of adsorbed catalysts, usually through a proton-coupled electron-transfer (PCET) reaction. [2] The molecular catalysts studied include cobalt, [3] free-base porphyrins, [4] and in situ-deposited platinum particles. [5] The ORR proceeds either by a 4 e À /4 H + pathway to produce water or a 2 e À /2 H + route to yield H 2 O 2 , which is considered a green oxidant.H 2 O 2 is widely used in many industrial areas, particularly in the chemical industry or for environmental protection, and is currently produced on an industrial scale through the biphasic anthrahydroquinone oxidation (AO) process (representing ca. 95 % of the world's H 2 O 2 production). [6] Generally, anthrahydroquinone is oxidized by O 2 to produce H 2 O 2 and anthraquinone and, subsequently, the formed anthraquinone is reduced back to the anthrahydroquinone by using H 2 in the presence of a metal catalyst. Both reactions occur in the organic phase, and H 2 O 2 is recovered by extraction to the aqueous phase. [6] The advantage of the AO process is the very high yield of H 2 O 2 generated per cycle. Conversely, side reactions generating organic byproducts need to be dealt with by regenerating the solution and by using separation techniques to eliminate such impurities. Conceptually, following the AO process, the reduction of O 2 was investigated at quinone-modified carbon surfaces. O 2 reduction to H 2 O 2 was mediated by surface-bound quinone groups via superoxide anion intermediates, [7] and such modified elec...

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“…33 Adsorption of a suitable catalyst at the liquidÀliquid interface can significantly enhance the reaction rates, thereby achieving interfacial redox catalysis at functionalized soft interfaces. 34 It is important to note that soft interfaces are polarizable and therefore offer an additional parameter to control the position of equilibrium: the Galvani potential difference across the interface (Δ o w φ). 35 The flow of current across the interface to reach a new equilibrium can be manipulated or even reversed in direction by adjusting Δ o w φ, and such reactions may be catalyzed by NPs adsorbed at the soft interface.…”

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confidence: 99%

Interfacial Redox Catalysis on Gold Nanofilms at Soft Interfaces

et al. 2015

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Soft or “liquid–liquid” interfaces were functionalized by roughly half a monolayer of mirror-like nanofilms of gold nanoparticles using a precise interfacial microinjection method. The surface coverage of the nanofilm was characterized by ion transfer voltammetry. These gold nanoparticle films represent an ideal model system for studying both the thermodynamic and kinetic aspects of interfacial redox catalysis. The electric polarization of these soft interfaces is easily controllable, and thus the Fermi level of the electrons in the interfacial gold nanoparticle film can be easily manipulated. Here, we study interfacial redox catalysis between two redox couples located in adjacent immiscible phases and highlight the catalytic properties of a gold nanoparticle film toward heterogeneous electron transfer reactions.

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Hydrogen evolution catalyzed by electrodeposited nanoparticles at the liquid/liquid interface

Abstract: Hydrogen evolution by decamethylferrocene in 1,2-dichloroethane can be catalyzed efficiently by platinum and palladium nanoparticles electrogenerated in situ at the liquid–liquid interface.

Cited by 83 publications

References 20 publications

Gold Nanofilm Redox Catalysis for Oxygen Reduction at Soft Interfaces

Gold Nanofilm Redox Catalysis for Oxygen Reduction at Soft Interfaces

Oxygen Reduction at Soft Interfaces Catalyzed by In Situ‐Generated Reduced Graphene Oxide

Interfacial Redox Catalysis on Gold Nanofilms at Soft Interfaces

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