Self-assembly of alkanols on Au(111) surfaces

Self-assembled monolayers (SAMs) of alkanols (1-C(N)H(2N+1)OH) with varying carbon-chain lengths (N = 10-30) have been systematically studied by means of scanning tunneling microscopy (STM) at the interfaces between alkanol solutions (or liquids) and Au(111) surfaces. The carbon skeletons were found to lie flat on the surfaces. This orientation is consistent with SAMs of alkanols on highly oriented pyrolytic graphite (HOPG) and MoS2 surfaces, and also with alkanes on reconstructed Au(111) surfaces. This result differs from a prior report, which claimed that 1-decanol molecules (N = 10) stood on their ends with the OH polar groups facing the gold substrate. Compared to alkanes, the replacement of one terminal CH3 group with an OH group introduces new bonding features for alkanols owing to the feasibility of forming hydrogen bonds. While SAMs of long-chain alkanols (N > 18) resemble those of alkanes, in which the aliphatic chains make a greater contribution, hydrogen bonding plays a more important role in the formation of SAMs of short-chain alkanols. Thus, in addition to the titled lamellar structure, a herringbone-like structure, seldom seen in SAMs of alkanes, is dominant in alkanol SAMs for values of N < 18. The odd-even effect present in alkane SAMs is also present in alkanol SAMs. Thus, the odd N alkanols (alkanols with an odd number of carbon atoms) adopt perpendicular lamellar structures owing to the favorable interactions of the CH3 terminal groups, similar to the result observed for odd alkanes. In contrast to alkanes on Au(111) surfaces, for which no SAMs on an unreconstructed gold substrate were observed, alkanols are capable of forming SAMs on either the reconstructed or the unreconstructed gold surfaces. Structural models for the packing of alkanol molecules on Au(111) surfaces have been proposed, which successfully explain these experimental observations.     

Unimolecular rectification of monolayers of CH3C(O)S-C14H28Q(+)-3CNQ(-) and CH3C(O)S-C16H32Q(+)-3CNQ(-) organized by self-assembly, Langmuir-Blodgett, and Langmuir-Schaefer techniques

The advantage of "self-assembly" (strong covalent binding to substrates) was combined with the advantage of Langmuir-Blodgett (LB) or Langmuir-Schaefer (LS) transfer to a solid substrate (quantitative transfer of monolayers to the substrate). The electrical rectification (asymmetric conduction) by a monolayer of thioacetylalkylquinolinium tricyanoquinodimethanide was critically compared when these molecules had been transferred, by such competing techniques, onto gold electrodes, and then covered by a "cold gold" pad electrode. Unimolecular rectification was observed in the expected directions in the LB and LS monolayers. The Self-Assembled Monolayers (SAMs) were disordered; macroscopic measurements of rectification were unsuccessful for the SAMs, but successful for the down-stroke LB and LS monolayers, whose orientation and potential bonding to the Au surface should be identical to that of an ideal SAM.     

一种新型C60-硫醚衍生物分子在金表面上的自组装

报导了一种新型C60 硫醚分子在金表面上自组装膜的形成,并通过接触角、扫描隧道显微术（STM）、X射线光电子能谱（XPS）、电化学和光电化学手段对其进行表征.高分辩STM形貌图证明,在Au(111)基底上C60基团存在并直观显示出特殊的单层膜结构. XPS分析表明,这一新型C60 硫醚分子是通过金硫键固定在金表面上的,并且在组装过程中存在分子内碳硫键断裂步骤.     

Self-assembly of C(60) pi-extended tetrathiafulvalene (exTTF) dyads on gold surfaces

The first self-assembly of a C60 pi-extended tetrathiafulvalene (exTTF) dyad on a gold surface is reported. Four fullerene derivatives, two of them containing p-quinonoid pi-extended tetrathiafulvalenes (exTTFs), have been synthesized, and their solution electrochemistry has been investigated by means of cyclic voltammetry. Fullerene-containing SAMs of thioctic acid derivatives 3 and 6 have also been investigated by cyclic voltammetry. The cyclic voltammograms of both compounds exhibit three reversible reduction waves, and for compound 6, one irreversible oxidation process corresponding to the oxidation of the exTTF subunit is observed. Stable self-assembled monolayers (SAMs) of fullerene derivative 3 were formed on gold surfaces, whereas dyad 6 does not present a very clear electrochemical response, most probably as a result of structural rearrangements on the monolayer or charge transfer between the C60 and exTTF moieties.     

硒杂环化合物(4,5-苯并苤硒脑)在金表面上的自组装

为了寻求新的自组装单分子膜体系,构建新的功能膜,研究了具备平面型的大环共轭硒杂环化合物-- 4,5-苯并苤硒脑(苯并[c]硒二唑,简称苤硒脑)在金表面的自组装单分子膜.通过X射线光电子能谱(XPS)和电化学手段对其进行表征.XPS研究结果表明,自组装形成单分子膜后,苤硒脑分子中Se3d结合能从57.4 eV下降到57.1 eV;表明硒杂环化合物是通过金硒键固定在金表面上的;电化学循环伏安法实验表明,金电极表面上自组装该有机硒后, Fe(CN)63-/4-的氧化还原峰几乎完全消失;以四硼酸钠为底液,测得该化合物自组装在金表面上时,其还原电位在-0.66 V,与在溶液中用裸金电极测得的还原峰电位基本一致.     

Formation of highly ordered and orientated gold islands: effect of immersion time on the molecular adlayer structure of pentafluorobenzenethiols (PFBT) SAMs on Au(111)

Self-assembled monolayers (SAMs) of pentafluorobenzenethiol (PFBT) on Au(111) substrates, prepared with different immersion times (ITs) at room temperature, were studied using scanning tunneling microscopy (STM) and infrared reflection-absorption spectroscopy (IRRAS). In the present study, the focus was on several important points of interest in the field of SAMs. First, the gold islands formed upon adsorption of PFBT molecules on the gold surface were monitored at different ITs in terms of their size, density, and shape. After short ITs (5 to 30 min), small gold islands with rounded shape were formed. These gold islands were arranged in a rather regular fashion and found to be quite mobile under the influence of the STM-tip during the scanning. When the IT was increased to 16 h, the results revealed the formation of highly ordered and orientated gold islands with very unusual shapes with straight edges meeting at 60° or 120° running preferentially along the [11(-)0] substrate directions. The density of the gold islands was found to decrease with increasing IT until they almost disappeared from the SAMs prepared after 190 h of IT. On top of the gold islands, the PFBT molecules were found to adopt the closely packed (10√3 × 2) structure. Second, a number of structural defects such as disordered regions at the domain boundaries and dark row(s) of molecules within the ordered domains of the PFBT SAMs were observed at different ITs. The SAMs prepared after 190 h of IT were found to be free of these defects. Third, at low and moderate ITs, a variation in the PFBT molecular contrast was observed. This contrast variation was found to depend mainly on the tunneling parameters. Finally, our results revealed that the organization process of PFBT SAMs is IT-dependent. Consequently, a series of structural phases, namely, α, β, γ, δ, and ε were found. The α-, β-, γ-, and δ-phases were typically accompanied by the ε-phase that appeared on top of gold islands. With increasing IT, the α→β→ γ→δ→ε phase transitions took place. The resulting ε-phase, which covered the entire gold surface after 190 h of IT, yielded well-ordered self-assembled monolayers with large domains having a (10√3 × 2) superlattice structure.     

Globotriose- and oligo(ethylene glycol)-terminated self-assembled monolayers: surface forces, wetting, and surfactant adsorption

A set of oligo(ethylene glycol)-terminated and globotriose-terminated self-assembled monolayers (SAMs) has been prepared on gold substrates. Such model surfaces are well defined and have good stability due to the strong binding of thiols and disulfides to the gold substrate. They are thus very suitable for addressing questions related to effects of surface composition on wetting properties, surface interactions, and surfactant adsorption. These issues are addressed in this report. Accurate wetting tension measurements have been performed as a function of temperature using the Wilhelmy plate technique. The results show that the nonpolar character of oligo(ethylene glycol)-terminated SAMs increases slightly but significantly with temperature in the range 20-55 degrees C. On the other hand, globotriose-terminated SAMs are fully wetted by water at room temperature. Surface forces measurements have been performed and demonstrated that the interactions between oligo(ethylene glycol)-terminated SAMs are purely repulsive and similar to those determined between adsorbed surfactant layers with the same terminal headgroup. On the other hand, the interactions between globotriose-terminated SAMs include a short-range attractive force component that is strongly affected by the packing density in the layer. In some cases it is found that the attractive force component increases with contact time. Both these observations are rationalized by an orientation- and conformation-dependent interaction between globotriose headgroups, and it is suggested that hydrogen-bond formation, directly or via bridging water molecules, is the molecular origin of these effects.     

Supramolecular incorporation of fullerenes on gold surfaces: comparison of C60 incorporation by self-assembled monolayers of different calix[n]arene (n = 4, 6, 8) derivatives

[reaction: see text] Two new calix[6]arene derivatives 3 and 4 in a 1,4-anti conformation and one calix[8]arene derivative 5 were synthesized. SAMs of calix[n]arene (n = 4, 6, 8) derivatives 1-5 were formed on gold bead electrodes. Cyclic voltammetry with Ru(NH3)6(3+/2+) as a redox probe, together with impedance spectroscopy and reductive desorption, indicates that SAMs of 5 have a higher coverage than those of 3 and 4 due to the presence of hydrogen bonding and possibly its conformation. Noncovalent immobilization of C60 on gold surfaces was achieved with SAMs of calix[8]arene derivative 5 but not with those of 1-4.     

Synthesis and structural characterization of glucopyranosylamide films on gold

Self-assembled monolayers (SAMs) of glucose derivatives on gold have been prepared from alpha- and beta-glucopyranosylamide derivatives. The glucosyl conjugates were synthesized stereoselectively via the in situ generation of glucosyl isoxazolines followed by treatment with thiopyridyl esters. The resulting film structures were characterized by atomic force microscopy, reflection Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The experimental data indicated that alpha- or beta-linked glucopyranosylamide derivatives with free hydroxyl groups attach to gold via the thiol linker. Both derivatives form monolayer films with high packing densities--comparable to those typically observed for alkanethiol monolayers on gold. Acetate analogues of these conjugates do not form SAMs on gold; they form multilayered films under identical deposition conditions.     

Interfacial supramolecular self-assembled monolayers of C(60) by thiolated beta-cyclodextrin on gold surfaces via monoanionic C(60)

The supramolecular self-assembled monolayers (SAMs) of C(60) by thiolated beta-cyclodextrin (CD) on gold surfaces were constructed for the first time using C(60) monoanion. The results indicate that monoanionic C(60) plays a crucial role in the formation of the C(60)-containing self-assembled monolayers. The generation of C(60) monoanion and the formation process of C(60) SAMs were monitored in-situ by UV-visible and near-IR spectroscopy. The resulting C(60) SAMs were fully characterized by spectroscopic ellipsometry (SE), cyclic voltammetry, X-ray photoelectron spectroscopy (XPS), and water contact angle measurements. After the immobilization of C(60) by the SAMs of thiolated beta-CD, the film thickness increased by approximately 1 nm from 0.8 to 1.8 nm as determined by SE, demonstrating the formation of the supramolecular self-assembled monolayers of thiolated beta-CD/C(60). The new C(60) SAMs exhibited one quasi-reversible redox couple at half wave potential of -0.57 V vs SCE in aqueous solution containing 0.1 M KCl. The surface coverage of C(60) on the gold surfaces was estimated to be 1.1 x 10(-10) mol cm(-2). The XPS showed the assembly of C(60) over the thiolated beta-CD SAMs. The surface hydrophobicity increased greatly upon the formation of the C(60)-containing SAMs as analyzed by water contact angle measurements. The results are in agreement with the formation of 1:1 complex of C(60) and cyclodextrin on gold surfaces, though it also reveals some non-homogeneous features of the monolayers.     

Self-assembled monolayers of electroactive polychlorotriphenylmethyl radicals on Au(111)

Two new polychlorotriphenylmethyl (PTM) derivatives bearing a thioacetate and a disulfide group have been synthesized to anchor on gold substrate. On the basis of these molecules, three strategies were followed to prepare self-assembled monolayers (SAMs) of electroactive PTMs. The resulting SAMs were fully characterized by contact angle, atomic force microscopy (AFM), and time-of-flight secondary ion mass spectroscopy (ToF-SIMS). The high coverage surface and stability of the SAMs were demonstrated by cyclic voltammetry. In addition, the electrochemical experiments proved that these SAMs are bistable since it is possible to reversibly switch between the PTM radical state to the corresponding anion. The magnetic response was investigated by electron paramagnetic resonance. We observed that when the PTM SAMs are in their radical form they confer magnetic functionality to the surface, whereas when they are in the anionic state, the surface is diamagnetic. Thus, the PTM-modified substrates are multifunctional surfaces since they combine magnetic and electroactive properties. The reported results show the high potential of these materials for the fabrication of surface molecular devices.     

Poly(ethylene glycol) monolayer formation and stability on gold and silicon nitride substrates

Poly(ethylene glycol) (PEG) self-assembled monolayers (SAMs) are extensively used to modify substrates to prevent nonspecific protein adsorption and to increase hydrophilicity. X-ray photoelectron spectroscopy analysis, complemented by water contact angle measurements, is employed to investigate the formation and stability upon aging and heating of PEG monolayers formed on gold and silicon nitride substrates. In particular, thiolated PEG monolayers on gold, with and without the addition of an undecylic spacer chain, and PEG monolayers formed with oxysilane precursors on silicon nitride have been probed. It is found that PEG-thiol SAMs are degraded after less than two weeks of exposure to air and when heated at temperatures as low as 120 degrees C. On the contrary, PEG-silane SAMs are stable for more than two weeks, and fewer molecules are desorbed even after two months of aging, compared to those desorbed in two weeks from the PEG-thiol SAMs. A strongly bound hydration layer is found on PEG-silane SAMs aged for two months. Heating PEG-silane SAMs to temperatures as high as 160 degrees C improves the quality of the monolayer, desorbing weakly bound contaminants. The differences in stability between PEG-thiol SAMs and PEG-silane SAMs are ascribed to the different types of bonding to the surface and to the fact that the thiol-Au bond can be easily oxidized, thus causing desorption of PEG molecules from the surface.     

New dialkyldithiophosphinic acid self-assembled monolayers (SAMs): influence of gold substrate morphology on adsorbate binding and SAM structure

We report the fabrication and characterization of new self-assembled monolayers (SAMs) formed from dihexadecyldithiophosphinic acid [(C(16))(2)DTPA] molecules on gold substrates. In these SAMs, the ability of the (C(16))(2)DTPA headgroup to chelate to the gold surface depends on the morphology of the gold substrate. Gold substrates fabricated by electron-beam evaporation (As-Dep gold) consist of ～50-nm grains separated by deep grain boundaries (～10 nm). These grain boundaries inhibit the chelation of (C(16))(2)DTPA adsorbates to the surface, producing SAMs in which there is a mixture of monodentate and bidentate adsorbates. In contrast, gold substrates produced by template stripping (TS gold) consist of larger grains (～200-500 nm) with shallower grain boundaries (<2 nm). On these substrates, the low density of shallow grain boundaries allows (C(16))(2)DTPA molecules to chelate to the surface, producing SAMs in which all molecules are bidentate. The content of bidentate adsorbates in (C(16))(2)DTPA SAMs formed on As-Dep and TS gold substrates strongly affects the SAM properties: Alkyl chain organization, wettability, frictional response, barrier properties, thickness, and thermal stability all depend on whether a SAM has been formed on As-Dep or TS gold. This study demonstrates that substrate morphology has an important influence on the structure of SAMs formed from these chelating adsorbates.     

Structure-dependent charge transport and storage in self-assembled monolayers of compounds of interest in molecular electronics: effects of tip material, headgroup, and surface concentration

The electrical properties of self-assembled monolayers (SAMs) on a gold surface have been explored to address the relation between the conductance of a molecule and its electronic structure. We probe interfacial electron transfer processes, particularly those involving electroactive groups, of SAMs of thiolates on Au by using shear force-based scanning probe microscopy (SPM) combined with current-voltage (i-V) and current-distance (i-d) measurements. Peak-shaped i-V curves were obtained for the nitro- and amino-based SAMs studied here. Peak-shaped cathodic i-V curves for nitro-based SAMs were observed at negative potentials in both forward and reverse scans and were used to define the threshold tip bias, V(TH), for electric conduction. For a SAM of 2',5'-dinitro-4,4'-bis(phenylethynyl)-1-benzenethiolate, VII, V(TH) was nearly independent of the tip material [Ir, Pt, Ir-Pt (20-80%), Pd, Ni, Au, Ag, In]. For all of the SAMs studied, the current decreased exponentially with increasing distance, d, between tip and substrate. The exponential attenuation factors (beta values) were lower for the nitro-based SAMs studied here, as compared with alkylthiol-based SAMs. Both V(TH) and beta of the nitro-based SAMs also depended strongly on the molecular headgroup on the end benzene ring addressed by the tip. Finally, we confirmed the "memory" effect observed for nitro-based SAMs. For mixed SAMs of VII and hexadecanethiol, I, the fraction of the charge collected in the negative tip bias region that can be read out at a positive tip bias on reverse scan (up to 38%) depended on the film composition and decreased with an increasing fraction of I, suggesting that lateral electron hopping among molecules of VII occurs in the vicinity of the tip.     

Isostructural self-assembled monolayers. 2. Methyl 1-(3-mercaptopropyl)-oligo(ethylene oxide)s

The structural order and ordering conditions of the self-assembled monolayers (SAMs) of HSCH2CH2CH2O(EO)xCH3, where EO = CH2CH2O and x = 3-9, on polycrystalline gold (Au) were determined by reflection-absorption infrared spectroscopy (RAIRS), spectroscopic ellipsometry (SE), and electrochemical impedance spectroscopy. For x = 5-7, RAIRS and SE data show that the oligo(ethylene oxide) [OEO] segments adopt the near single phase, 7/2 helical conformation of the folded-chain crystal polymorph of crystalline poly(ethylene oxide), oriented normal to the substrate. These SAMs exhibit OEO segment structure and orientation identical to that found in a previous isostructural series [HS(CH2CH2O)6-8C18H37 SAMs. Vanderah, D. J., et al. Langmuir 2003, 19, 3752] and are anisotropic films for surface science metrology where structure is constant and thickness increases in 0.30 nm increments. In addition, this is the first example of OEO SAMs to attain this highly ordered, helical conformation where the (EO)x segment is separated from the Au-sulfur headgroup by a polymethylene chain. For x = 4, 8, and 9, the SAMs are largely helical but show evidence of nonhelical conformations and establish the upper and lower limits of the isostructural set. For x = 3, the SAMs are largely disordered containing some all-trans conformation. SAM order as a function of immersion time from 100% water and 95% ethanol indicates that the HSCH2CH2CH2O(EO)5-7CH3 SAMs order faster and under a wider range of conditions than omega-alkyl 1-thiaolio(ethylene oxide) [HS(EO)xCH3] SAMs, reported earlier (Vanderah, D. J., et al. Langmuir 2002, 18, 4674 and Vanderah, D. J., et al. Langmuir 2003, 19, 2612).     

Odd-even effects in self-assembled monolayers of omega-(biphenyl-4-yl)alkanethiols: a first-principles study

Conjugated molecules with a saturated alkyl linker between a thiol docking group and the pi-conjugated core have been shown to form self-assembled monolayers (SAMs) with a high degree of long-range order and uniformity. Additionally, pronounced odd-even effects have been observed in a number of properties characterizing these SAMs. We focus on omega-(biphenyl-4-yl)alkanethiols with n = 0-6 -(CH2)n- units deposited on Au(111) and investigate the microscopic origin of these odd-even effects in terms of the local sulfur-gold bonding geometry by employing first-principles calculations. An additional structural parameter, the torsion angle between the two phenyl rings in the biphenyl moiety, is identified and its relation to the experimentally observed odd-even effects is discussed. More importantly, we address relevant quantities for the application of these SAMs in molecular electronic devices, in particular, the modification of the work function of the underlying metal substrate and the energetic alignment of the molecular orbitals in the SAM with the Fermi level. While no clear trend emerges for the former, we find pronounced odd-even effects for the latter. Furthermore, the insertion of a single methylene unit between the biphenyl core and the thiol appears to largely decouple the valence electronic systems of the pi-conjugated segment and the gold substrate. Our results thus provide a solid theoretical basis for the interface energetics in this important class of systems.     

Synthesis and surface structure of thymine-functionalized, self-assembled monolayer-protected gold nanoparticles

Thymine-functionalized SAM-protected gold nanoparticles with diameters of 2.2 +/- 0.3 nm and 7.0 +/- 1.0 nm were prepared via a modified two-phase transfer method. UV-vis spectra showed that particle size and solvent type, as well as surface charge, influenced the gold surface plasmon band absorption, along with the interaction between thymine terminal groups in the solution. Although the bulky thymine end groups interacted strongly on the particle surface, a well-ordered monolayer of thyminethiol derivatives with a long hydrocarbon chain was formed on the particle surface, exhibiting an ordered, all-trans conformation of the methylene backbone, similar to those of corresponding self-assembled monolayers (SAMs) generated from normal alkanethiols. A larger particle size and a longer reaction time facilitated the formation of more ordered thymine-terminated thiol SAMs. Thermal analysis indicated that reorientation of the SAMs during heat treatment occurred by two processes, caused possibly by the separate recrystallization of the hydrocarbon long chains and thymine units. More ordered SAMs with a higher thermal stability were formed on the larger particle surfaces when compared with those on the smaller ones. A greater density of molecular packing was found on the smaller particle surfaces. However, SAMs formed on the larger gold particles resembled 2D SAMs on the smooth, flat gold surfaces. XPS results confirmed the thymine structure as well as the chemical bond between gold and sulfur. One type of adsorbed sulfur species was observed for the smaller particles and two for the larger ones, but a slightly higher binding energy of thiolate was found for the smaller ones.     

GaAs基底上金纳米粒子的二维组装及其表面增强喇曼散射活性

利用巯基苯胺作耦联分子,成功地将Au纳米粒子组装到GaAs(100)表面上,并且用TM-AFM观察了纳米粒子在表面上的分布情况.Raman研究表明,该基底显示出表面增强喇曼散射活性.     

4,5-Bis(diphenylthiophosphinoyl)-1,2,3-triazolate interaction with gold nanoparticles and flat surfaces to form self-assembled monolayers

The interaction of the 4,5-bis(diphenylthiophosphinoyl)-1,2,3-triazolate (SPTz⁻) with different gold surfaces was investigated (nanoparticles, an electrode, and flat sheets). Studies on binding affinity of this dithiophosphin-triazolate on a gold electrode were performed by cyclic voltammetry (CV). Voltammograms exhibit two reductive desorption and only one oxidative readsorption, indicating that once reabsorbed, the molecule achieves a unique conformation. The morphology and average size of modified gold nanoparticles were studied by transmission electron microscopy (TEM) (av. diameter of 5.9 ± 1.8 nm). Further characterization was made by UV-visible (UV-vis) spectroscopy showing surface plasmon resonance (SPR) at about 580 nm. The bonding configurations of SPTz⁻ on gold have also been investigated by comparing the FT-IR and FT-Raman spectra. The ³¹P{¹H} NMR spectrum of capped nanoparticles exhibited two sharp signals at 30.3 and 29.6 ppm and a very broad signal at 72.7 ppm. X-ray photoelectron spectroscopy (XPS) showed SPTz⁻ can accomplish a strong interaction with gold nanoparticles through bonds involving a sulfur atom and a nitrogen from the triazole ring with a free terminal PS group, forming self-assembled monolayers (SAM). This may allow subsequent functionalization through free S/N atoms of the formed SAMs. The SPTz⁻ packing led to a reduction in packing density that permits large spaces between adsorbed headgroups and the inclusion of carbon and oxygen impurities from small molecules; nevertheless, oxidized sulfur or nitrogen species were not detected, indicating the chemical stability of the obtained SAMs.     

Enhanced catalytic activity of Fe phthalocyanines linked to Au(111) via conjugated self-assembled monolayers of aromatic thiols for O2 reduction

We have obtained and characterized self assembled monolayers (SAMs) of 4-aminothiophenol (4-ATP) and 1-(4-mercaptophenyl)-2,6-diphenyl-4-(4-pyridyl)pyridinium tetrafluoroborate (MDPP) functionalized with iron phthalocyanine (FePc) adsorbed on gold (111) electrodes. The catalytic activity of these SAMs/FePc was examined for the reduction of O₂ in aqueous media (pH = 4) and compared with that of bare gold and of gold coated directly with FePc molecules. Scanning tunneling microscopy (STM) studies confirm the functionalization of the 4-ATP by FePc. The electrocatalytic studies carried out with Au/FePc, Au/4-ATP/FePc and Au/MDPP/FePc electrodes show that the O₂ reduction takes place by a 4-electron transfer to give water in contrast to a 2-electron-transfer process observed on the bare gold. The activity of the electrodes increases as follows: Au < Au/FePc < Au/4-ATP/FePc < Au/MDPP/FePc.