Catalytic hydrogen adsorption of nano-crystalline hydrotalcite derived mixed oxides

Nano-crytalline hydrotalcite derived reduced mixed oxides containing magnesium, nickel and aluminium (MNAM) have been synthesized using coprecipitation and showed successfully nickel catalysed reversible hydrogen adsorption using the temperature programmed technique under near ambient conditions. ICP-MS and XRD analysis ensured the adsorbent homogeneity and different crystalline phases of mixed oxides. Morphology and textural properties of mixed oxides have been explored using the FESEM, BET and HRTEM analysis techniques. Nano-crystalline and mesporous reduced mixed oxides exhibited a 3.9 wt% H₂ adsorption capacity in where desorption capacity was 1.9 wt% H₂. Hydrogen adsorbed surface and different phases were analysed by XPS, Raman and FTIR analysis techniques. The hydrogen adsorption enthalpy (ΔH) and entropy (ΔS) changes of reduced mixed oxides were −47.58 kJ/mol and −120.98 J/mol K, respectively, and the promising desorption activation energy of 65 kJ/mol correspond its reversibility as potential energy storage material.     

In situ inelastic neutron scattering studies of the rotational and translational dynamics of molecular hydrogen adsorbed in single-wall carbon nanotubes (SWNTs)

Inelastic neutron scattering (INS) spectra were measured in situ from progressively increased amounts of para-hydrogen physisorbed in bundles of single-walled carbon nanotubes at temperatures in the vicinity of 20 K. INS from the bound H₂ molecules consists of two distinct parts carrying complementary information. In the low energy and momentum transfer region, at about 14.5 meV we observe a sharp line corresponding to rotational transitions between the ground para-J = 0 state and the ground ortho-J = 1 state without change of the translational state of the molecular centre of mass (CoM). This we call the “bound” spectrum. At higher energy transfers, a series of broad peaks are observed, corresponding to rotational transitions between the para-J = 0 state and different ortho-states (J = 1, 3, 5, … ,) shifted out in energy transfer by an amount equal to the CoM recoil energy. This we call the “recoil” spectrum. Both parts of each spectrum are analysed using the Young and Koppel model. From the “bound” spectrum we estimate the mean height of the barrier to rotation and the mean square displacements of the molecules accommodated at different adsorption sites. The “recoil” spectrum allows us to derive the mean translational kinetic energy of the adsorbed hydrogen as a function of the surface concentration.     

A study of adsorption kinetics and thermodynamics of ω-mercaptoalkylhydroquinone self-assembled monolayer on a gold electrode

The adsorption kinetics and thermodynamics for the formation of redox active self-assembled monolayer (SAM) of 2-(n-mercaptoalkyl)hydroquinone (abbreviated as H₂Q(CH₂)_nSH, where n = 4, 6, 8, 10, and 12) on gold electrode has been investigated by cyclic voltammetry to study the effects of concentration and alkyl chain length. The time dependence of surface coverage, differential capacitance, and formal potential of electroactive hydroquinone(H₂Q) moiety supports that the adsorption of H₂Q(CH₂)_nSH molecules typically processes with a two-step adsorption consisted of a fast initial adsorption and a slowly following reorganization. The adsorption processes can be satisfactorily described by simple Langmuir adsorption kinetics, irrespective of concentration and alkyl chain length of adsorbate molecule. Based on Langmuir kinetics, the adsorption rate constant was determined at the initial step for the formation of all H₂Q(CH₂)_nSH-SAMs studied in this work. The rate constant value was found to be decreased with increasing alkyl chain length and decreasing bulk solution concentration (≤10 μM). The dependence of a surface coverage (Γ_e) at adsorption equilibrium on the bulk concentration is accurately described by the Langmuir isotherm at several concentrations ranging from 8 × 10⁻⁶ to 1 × 10⁻⁵ M for all H₂Q(CH₂)_nSH molecules. Parameters characterizing the adsorption thermodynamics, such as Γ_s, adsorption coefficient (β), and adsorption free energy (ΔG_ads) were determined from this isotherm.     

XPS and flow-cell EQCM study of albumin adsorption on passivated chromium surfaces: Influence of potential and pH

The adsorption of albumin (BSA: bovine serum albumin) on passivated chromium surfaces was studied in deaerated sulphate solutions as a function of potential (in the passive state) and pH (from 4 to 10). In situ switch-flow cell EQCM measurements were coupled to ex situ XPS analyses. EQCM results showed that (i) the initial adsorption rate is about 3.3 ng cm⁻² s⁻¹ which corresponds to 3 × 10¹⁰ molecules cm⁻² s⁻¹, irrespective of the passive potential and pH, and (ii) the passive potential as well as the pH have no influence on the amount of adsorbed BSA (Δm = 440 ± 70 ng cm⁻² on the adsorption plateau). From the XPS N 1s and C 1s signals, which provide a fingerprint for the protein, it can be concluded that BSA is adsorbed on the Cr surface and is chemically intact. The XPS results show that (i) when increasing the passive potential, the oxide layer thickness increases (mean value: d_ox = 2.2 ± 0.2 nm), and (ii) the passive film is not modified by the adsorption of protein. From combined EQCM and XPS data, a full coverage of the Cr surface by the adsorbed proteins (γ = 1) is demonstrated at pH 4 (whatever the passive potential). The thickness of the continuous BSA layer (h_BSA) is 3.3 ± 0.3 nm, which corresponds to one monolayer “side-on”, i.e. oriented parallel to the surface. At pH 5.5 and 10, the adsorbed proteins form islands. The surface coverage is much lower (γ ∼ 0.5), and the height of the protein islands is significantly higher (h_BSA ∼ 6.5 nm). The results suggest a strong interaction (partially covalent) between the protein and the passivated chromium surface.     

Potential-pH diagrams for hydroxyl and hydrogen adsorbed on a copper surface

The principle of equilibrium potential-pH diagrams for two-dimensional layers adsorbed on metal surfaces in aqueous solution is applied to the case of hydrogen and oxygen species electroadsorbed on copper. The conditions of adsorption of species on copper surfaces in water may be predicted from thermodynamic calculations of the equilibrium potentials of the dissolved species/adsorbed species couples and drawing of potential-pH diagrams. Standard chemical potentials for hydroxyl chemisorbed on Cu(1 1 1) are derived from recent electrochemical data, while those for hydrogen chemisorbed on Cu(1 1 1) are derived from gas phase adsorption data. The E-pH relations associated with the equilibria between water and adsorbed hydroxyl, and between solvated protons and adsorbed hydrogen are given. The possible diagrams showing the E-pH domains of thermodynamic stability of the species adsorbed on a copper (1 1 1) surface (H₂O_ads, OH_ads and H_ads) in water are calculated at 25 °C and superimposed to the usual Pourbaix diagram for the Cu-H₂O system.     

Numerical estimation of hydrogen storage limits in carbon-based nanospaces

Theoretical limits of the hydrogen adsorption in carbon nanospaces are modeled using Monte Carlo simulations. A detailed analysis of storage capacity of slit pores has been performed as a function of the pore size, gas pressure (up to 100 bars) and temperature of adsorption (77 and 298 K). The H₂-slit wall interaction has been modeled assuming energies of adsorption ranging from 4.5 kJ/mol (pure graphene surface) to 15 kJ/mol (hypothetical chemically modified graphene). The quantum nature of H₂ has been incorporated in the calculations using the Feynman-Hibbs approach. It has been shown that in a hypothetical chemically modified porous carbon, with energy of adsorption of 15 kJ/mol or higher and pore size between 0.8 and 1.1 nm, the gravimetric and volumetric storage capacity can achieve targets required for practical applications. The relation between the energy of adsorption and the effective delivery has been discussed.     

The adsorption of Sn on Pt(1 1 1) and its influence on CO adsorption as studied by XPS and FTIR

The coverage of Sn on Pt(1 1 1) which is obtained by electrochemical deposition from 5×10⁻⁵ M Sn²⁺ in 0.5 M H₂SO₄ has been determined by XPS for different deposition times. Complete suppression of hydrogen adsorption corresponds to a coverage of ?_max=0.35 (Sn to surface Pt atoms).Co-adsorption of CO with Sn on Pt(1 1 1) has been studied by FTIR spectroscopy. The IR spectra of the stretching vibration of CO can be interpreted in terms of the vibrational signature of the Pt(1 1 1)/CO system and no vibrational bands associated with CO on Sn are detected. At high Sn coverages, the 1840 cm⁻¹ band associated with bridge-bonded CO and the 2070 cm⁻¹ band assigned to on-top CO are present, however, no hollow site adsorption which is characterized by the 1780 cm⁻¹ band is revealed within the resolution of the experiment. This vibrational signature corresponds to a less compressed adlayer compared to the (2×2)-3CO saturation structure on Pt(1 1 1). At lower Sn coverages, signatures from both the compressed and the less compressed CO adlayer structures are seen in the spectra. From earlier structural and electrochemical studies it is known that Sn is adsorbed in 2D islands and influences CO molecules in its neighbourhood electronically. This leads to a disappearance of the IR band from CO adsorbed in the hollow site at high Sn coverages and to higher population of the weakly adsorbed state of CO for all Sn-modified surfaces, i.e. a relative increase of the amount of CO oxidised at low potentials. In addition to this electronic effect, Sn also exerts a co-catalytic effect at low Sn coverages on that part of CO which is adsorbed at a larger distance from Sn due to a bi-functional mechanism. The IR spectra shows for the Sn-modified Pt(1 1 1) surface that the transition from the compressed CO adlayer which is characterized by the hollow site adsorption of CO to the less compressed one which exhibits a characteristic band associated with bridge-bonded CO occurs already at 250 mV instead of 400 mV.     

Activation, characterization and hydrogen storage properties of the mesoporous carbon CMK-3

Activation of mesoporous carbon CMK-3 with CO₂ for hydrogen storage was studied. Huge structure and texture changes emerged for the activated CMK-3 based on the characterization by using XRD, TEM and nitrogen adsorption at 77 K. The ordered mesoporous structure of CMK-3 gradually became disorder and its specific surface area and volume of pores especially micropores were enhanced remarkably. Hydrogen sorption measurement showed that the activation led to an obvious increase of the H₂ sorption capacity of CMK-3. The maximum H₂ uptake of 2.27 wt% at 77 K and 1 bar was obtained for the sample activated at 1223 K for 8 h. The small pores with the diameter smaller than 1 nm contributed greatly to the H₂ uptake, and were confirmed more effective than other pores for hydrogen storage.     

A perovskite-type KNbO3 nanoneedles based biosensor for direct electrochemistry of hydrogen peroxide

A KNbO₃ nanoneedles (KNs) based hydrogen peroxide (H₂O₂) biosensor was first proposed. Perovskite-type KNs can directly catalyze H₂O₂. The mechanism can be explained by Molecular Orbital Principles, with the formation of σ-bonding between the e_g orbital of surface niobium ions and surface adsorbed oxygen-related intermediate species. Direct electron transfer between the Horseradish peroxidase (HRP) and electrode surface was achieved. Co-catalyst system of both HRP and KNbO₃ was introduced to the oxidation of H₂O₂, thus the as-prepared biosensor exhibited high sensitivity (750 μA mM⁻¹ cm⁻²) and ultrafast response (1–2 s) to H₂O₂. Therefore, KNs provide a promising material for enzymes assembly and sensing application.     

Properties of electrolytes in the micropores of activated carbon

The dependence of the composition of aqueous electrolytes in the pore system of activated carbon on the potential has been determined by monitoring the amount of ions exchanged with the external electrolyte upon immersion and upon changing the electrode potential. From the investigation with KF solutions, a quantity δ/√? = 4 × 10⁻¹⁰ m is evaluated where δ is half the width of the micropores, and ? the (relative) permittivity. This is in accordance with δ ≈ 1 nm and ? ≈ 7 applying to essentially immobilized water and fits into the results with the other electrolytes. Anions are adsorbed in the cases of sodium perchlorate and potassium hydroxide, while protons are adsorbed in the case of acids (HCl, H₂SO₄). The adsorption of ClO₄⁻ seems to result from electrostatic interaction with the solid, while H⁺ and OH⁻ are strongly chemisorbed, probably at surface groups like >CO. Ionic mobilities of ions in the micropores have been determined from conductance measurements concerning the pore electrolyte of a single spherical particle of activated carbon. Mobilities are more than one order of magnitude lower than those in bulk electrolyte, probably due to an increased viscosity of the liquid in the narrow pores and/or to the coulombic interaction with charged domains of the solid. The rate of charging of the capacitor (solid/micropore electrolyte) is assisted by macropores distributing ions throughout the carbon material.     

Effect of chemisorbed carbon monoxide on Pt/C electrode on the mechanism of the hydrogen oxidation reaction

The influence of poisoning of Pt catalyst by CO on the kinetics and mechanism of H₂ oxidation reaction (HOR) at Pt/C electrode in 0.5 mol dm⁻³ HClO₄, saturated with H₂ containing 100 ppm CO, was examined with rotating disc electrode (RDE) at 22 °C. Commercial carbon black, Vulcan XC-72 was used as support, while Pt/C catalyst was prepared by modified polyol synthesis method in an ethylene glycol (EG) solution. The kinetically controlled current (I_k) for the HOR at Pt/C decreases significantly at CO coverage (Θ_CO) > 0.6. For Θ_CO < 0.6 the HOR takes place through Tafel-Volmer mechanism with Tafel reaction as rate-determining step at the low CO coverage, while Volmer step controls the overall reaction rate at the medium CO coverage. When CO coverage is higher then 0.6, Heyrovsky-Volmer mechanism is operative for the HOR with Heyrovsky as the rate-determining step (rds).     

Electrochemical quartz crystal nanobalance and chronocoulometry studies of phenylalanine adsorption on Au

The interfacial adsorption behaviour of the amino acid, phenylalanine (Phe), was studied at a polycrystalline Au surface in 0.05 M KClO₄ using cyclic voltammetry, chronocoulometry (CC) and electrochemical quartz crystal nanobalance (EQCN) frequency measurements. The frequency was observed to decrease with increasing concentration of Phe, indicating that the frequency measurements were following analyte adsorption directly. Both CC and EQCN frequency measurements showed a two-stage adsorption process, consistent with the molecule being adsorbed in the horizontal position at negative potentials, but rearranged to the more upright position at potentials more positive to the potential of zero charge. From the slopes at the onset of each of these two regions in plots of change in mass from the EQCN frequency measurements versus the surface charge density from CC measurements, the calculated molar mass corresponded to that of Phe displacing adsorbed water molecules for EQCN measurements made with small bulk concentrations of Phe (i.e., <1 × 10⁻⁴ mol L⁻¹).The adsorption process from CC measurements for Phe, described using the Henry adsorption isotherm, gave Gibbs energies of adsorption (ΔG_ADS) ranging from −18 to −35 kJ mol⁻¹ over the potential range of −0.6 to 0.6 V. The observed decrease in frequency of the EQCN measurements with additions of aliquots of amino acid and the substantial ΔG_ADS values suggests that Phe adsorbs onto the surface via chemisorption. Surface concentrations (1.2 × 10⁻¹⁰ mol cm⁻²) were in excellent agreement between the EQCN and CC measurements for small bulk concentrations of Phe (4.0 × 10⁻⁵ mol L⁻¹), in very good agreement with previously published results at the Au(1 1 1) surface. Thus, for small bulk concentrations of analyte, these electrochemical techniques complement one another to enhance our knowledge of the behaviour of thin organic films at electrode surfaces.     

Adsorption of asparagine on the gold electrode and air/solution interface

The adsorption of asparagine (Asn) on a gold electrode from 0.1 M LiClO₄ aqueous solutions was investigated. The experimental data obtained from ac impedance measurements were analyzed to determine the dependence of adsorption parameters, i.e. the standard Gibbs energy of adsorption (ΔG⁰), maximal value of surface excess concentration (Γ_max) of Asn and parameter of interactions in the adsorbed layer (A) on the electrode potential. The relatively large value of Gibbs energy of adsorption (∼ −47 kJ mol⁻¹) gives the evidence of a very strong adsorption of Asn at the polycrystalline Au electrode. The comparison of the adsorption behavior of Asn at the air/solution and the Au/solution interfaces points out to the significant electronic interactions of adsorbate molecules with the Au electrode, since the adsorption of Asn on a free surface (from the same solutions) is very week. The analysis of the electrochemical data as well as the infrared reflection absorption spectroscopy (IRAS) results reveal that Asn molecules are anchored to the Au surface through oxygen atoms of the carboxylate group COO⁻ and through the amide carbonyl group.     

Study of the hydrogen absorption in Pd in alkaline solution

Hydrogen adsorption/absorption in palladium thin deposits on gold electrode, in 0.1 M NaOH solution, was studied. The contributions of adsorption and absorption to the total charge of hydrogen are separated from the total isotherms at different deposit thicknesses. The adsorbed hydrogen charge increases to a plateau of ∼73.5 μC cm⁻², which corresponds to the surface coverage ratio by adsorbed hydrogen of 0.36. The absorbed hydrogen charge agreed with that obtained from the permeation experiments at 50 μm Pd foil, at potentials between +100 and +300 mV vs. RHE. EIS was carried out at thin Pd deposits. The kinetics of hydrogen sorption is slower in alkaline solutions than in acids and the isotherms are shifted towards more negative potentials.     

Adsorption of phosphate species on poly-oriented Pt and Pt(1 1 1) electrodes over a wide range of pH

The adsorption of phosphate anions from phosphate solutions at poly-oriented and single-crystal platinum electrodes, primarily Pt(1 1 1), was studied over a wide range of pH by cyclic voltammetry. The features observed at the poly-oriented Pt electrode in phosphate solution may be related to the different crystalline facets, the (1 1 1) orientation presenting the most significant behavior in terms of phosphate adsorption. On the reversible hydrogen electrode (RHE) scale, the phosphate adsorption strength decreases with increasing alkalinity of the solution. Qualitatively, three different pH regions can be distinguished. At pH < 6 only a broad reversible peak is observed, corresponding to the adsorption of H₂PO₄⁻ and further deprotonation to adsorbed HPO₄⁻. For 6 < pH < 11 a butterfly feature followed by one or two anodic peaks (depending on scan rate) is observed, ascribed to the adsorption of HPO₄⁻ followed by its subsequent deprotonation to adsorbed PO₄³⁻. The splitting into two or three voltammetric features, and the irreversibility of the two features at more positive potential, is ascribed to the deprotonation reaction leading to a surface species (i.e. phosphate) which needs to change its surface coordination. At pH > 11 a reversible pre-wave and a sharp spike are observed, ascribed to the co-adsorption of phosphate and hydroxide.     

Combination rate of hydrogen atoms adsorbed on a polycrystalline platinum electrode at hydrogen underpotentials in sulphuric acid solution

Steady-state cathodic currents i_c passing through a polycrystalline, smooth Pt electrode in 0.5 M H₂SO₄ were measured at constant potentials in the range from 0.45 to 0.05 V, at which the coverage by adsorbed hydrogen on the electrode surface is less than unity. It was found that current i_c, which results from the combination of adsorbed hydrogen atoms, depends on both the adsorption state and the coverage on the electrode surface. The characteristic variation of i_c with hydrogen coverage was explained in terms of the geometric arrangement of the adsorption sites. The combination rate constant and the mobility of the adsorbed hydrogen atoms estimated from the steady-state current measurement were in agreement with those obtained using the open-circuit decay method.     

Investigation of adsorption and inhibitive effect of 2-mercaptothiazoline on corrosion of mild steel in hydrochloric acid media

The inhibition effect of 2-mercaptothiazoline (2MT) on the corrosion behavior of mild steel (MS) in 0.5 M HCl solution was studied in both short and long immersion times (120 h) using potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and linear polarization resistance (LPR) techniques. For long-term tests, hydrogen gas evolution (VH₂−t) and the change of the open circuit potential with immersion time (E_ocp − t) were also measured in addition to the former three techniques. The surface morphology of the MS after its exposure to 0.5 M HCl solution with and without 1.0 × 10⁻² M 2MT with the different immersion times was examined by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The thermal stability of the inhibitor film was investigated by thermogravimetric analysis (TGA). The value of activation energy (E_a) for the MS corrosion and the thermodynamic parameters such as adsorption equilibrium constant (K_ads), free energy of adsorption (ΔG_ads), adsorption heat (ΔH_ads) and adsorption entropy (ΔS_ads) values were calculated and discussed. The potential of zero charge (PZC) of the MS in inhibited solution was studied by the EIS method, and a mechanism for the adsorption process was proposed. The results showed that 2MT performed excellent inhibiting effect for the corrosion of the MS. Finally, the high inhibition efficiency was discussed in terms of adsorption of inhibitor molecules and protective film formation on the metal surface. TGA results also indicated that the inhibitor film on the surface had a relatively good thermal stability.     

Electroreduction of nitrate ions on Pt(1 1 1) electrodes modified by copper adatoms

Kinetics and mechanism of nitrate ion reduction on Pt(1 1 1) and Cu-modified Pt(1 1 1) electrodes have been studied by means of cyclic voltammetry, potentiostatic current transient technique and in situ FTIRS in solutions of perchloric and sulphuric acids to elucidate the role of the background anion. Modification of platinum surface with copper adatoms or small amount of 3D-Cu crystallites was performed using potential cycling between 0.05 and 0.3 V in solutions with low concentration of copper ions, this allowed us to vary coverage θ_Cu smoothly. Following desorption of copper during the potential sweep from 0.3 to 1.0 V allowed us to estimate actual coverage of Pt surface with Cu adatoms. Another manner of the modification was also applied: copper was electrochemically deposited at several constant potentials in solutions containing 10⁻⁵ or 10⁻⁴ M Cu²⁺ and 5 mM NaNO₃ with registration of current transients of copper deposition and nitrate reduction.It has been found that nitrate reduction at the Pt(1 1 1) surface modified by copper adatoms in sulphuric acid solutions is hindered as compared to pure platinum due to induced sulphate adsorption at E < 0.3 V. Sulphate blocks the adsorption sites on the platinum surface and/or islands of epitaxial Cu(1 × 1) monolayer thus hindering the adsorption of nitrate anions and their reduction. The extent of inhibition weakly depends on the copper adatom coverage. Deposition of a small amount of bulk copper does not affect noticeably the rate of nitrate reduction.Nitrate reduction on copper-modified Pt(1 1 1) electrodes in perchloric acid solutions occurs much faster as compared to pure platinum. The steady-state currents are higher by 4 and 2 orders of magnitude at the potentials of 0.12 and 0.3 V, respectively. The catalytic effect of copper adatoms is largely caused by the facilitation of nitrate adsorption on the platinum surface near Cu_ad and/or on the islands of the Cu(1 × 1) monolayer (induced nitrate adsorption).Hydrogen adatoms block the adsorption sites on platinum for NO₃⁻ anion adsorption and inhibit reactions of nitrate reduction even at moderate surface coverage.The products of nitrate reduction in sulphuric and perchloric acids are essentially the same (NO and ammonia) irrespective of the presence or absence of Cu on the platinum surface.     

Electrochemical formation of nanometric layers of tin selenides on Ti surface

Photoelectrically active tin selenide coatings of nanometric thickness were manufactured by electrodeposition from separate solutions of Sn and Se precursors. Sn was deposited from acidic SnSO₄ electrolytes and Se was deposited from H₂SeO₃ solutions. Fine-grained Sn coatings were deposited at potential φ = −0.3 V with 100% current efficiency. Se coatings were formed at two potentials: φ = −0.5 V, forming Se⁰, and φ = −0.85 V, forming Se²⁻ ions. After the Sn coating was immersed into H₂SeO₃ solution, small quantities (∼2 at.%) of SnSe were formed and SeO₃²⁻ was adsorbed on the surface. A short-time deposition of Se at φ = −0.5 V passivated the surface, so no Sn dissolution is observed upon anodic polarization. XPS and Auger data indicated that under those conditions 20 at.% of Se⁰ and only 2 at.% of SnSe were formed. Thickening of Sn and Se layers led to formation of larger quantities of Se⁰ (75 at.%) and SnSe (4-5 at.%) on the surface, whereas deeper layers contained up to 10 times more of SnSe phase. Upon deposition of Se at φ = −0.85 V, new SnSe₂ phase was formed and the quantity of SnSe phase is increased and that of Se⁰ was reduced. All coatings formed exhibited photoelectric properties.     

Investigation of the surface properties and the hydrogen evolution reaction, HER, at thermal rhodium oxide electrodes

A systematic investigation was conducted of the surface properties and the HER at electrodes of nominal composition Ti/Rh_xTi_(1−x)O_y prepared by thermal decomposition (T_cal: 500 °C; t_cal: 2 h; O₂ flux: 5 dm³ min⁻¹) from salt precursor solutions dissolved in 6.0 mol dm⁻³ HNO₃. Films were characterized ex situ by SEM, EDX, XPS and XRD and in situ by open circuit potential measurements and CV. The electrochemical behaviour was investigated by CV as function of the anodic, E_λ,a, and cathodic, E_λ,c, switching potentials showing the Rh surface oxidation states strongly depend on these experimental variables. Surface Rh-sites are reduced to metallic rhodium in the cathodic potential region while higher oxidation states (I-III) are formed at more positive potentials (E ≥ 0.5 V/RHE). Hydrogen adsorption and desorption peaks as well as a short double layer charging region are observed at intermediate potential values. The HER was investigated by Tafel coefficients and reaction order with respect to H⁺ as function of nominal Rh-content.