The Effect of the 3D Nanoarchitecture and Ni-Promotion on the Hydrogen Evolution Reaction in MoS2 /Reduced GO Aerogel Hybrid Microspheres Produced by a Simple One-Pot Electrospraying Procedure.

The transition toward renewable energy sources requires low-cost, efficient, and durable electrocatalysts for green H2 production. Herein, an easy and highly scalable method to prepare MoS2 nanoparticles embedded in 3D partially reduced (pr) graphene oxide (GO) aerogel microspheres (MoS2 /prGOAMs) with controlled morphology and composition is described. Given their peculiar center-diverging mesoporous structure, which allows easy access to the active sites and optimal mass transport, and their efficient electron transfer facilitated by the intimate contact between the MoS2 and the 3D connected highly conductive pr-GO sheets, these materials exhibit a remarkable electrocatalytic activity in the hydrogen evolution reaction (HER). Ni atoms, either as single Ni atoms or NiO aggregates are then introduced in the MoS2 /prGOAMs hybrids, to facilitate water dissociation, which is the slowest step in alkaline HER, producing a bifunctional catalyst. After optimization, Ni-promoted MoS2 /prGOAMs obtained at 500 °C reach a remarkable η10 (overpotential at 10 mA cm-2 ) of 160 mV in 1 m KOH and 174 mV in 0.5 m H2 SO4 . Moreover, after chronopotentiometry tests (15 h) at a current density of 10 mA cm-2 , the η10 value improves to 147 mV in alkaline conditions, indicating an exceptional stability.

Hybridization of Molecular and Graphene Materials for CO2 Photocatalytic Reduction with Selectivity Control.

In the quest for designing efficient and stable photocatalytic materials for CO2 reduction, hybridizing a selective noble-metal-free molecular catalyst and carbon-based light-absorbing materials has recently emerged as a fruitful approach. In this work, we report about Co quaterpyridine complexes covalently linked to graphene surfaces functionalized by carboxylic acid groups. The nanostructured materials were characterized by X-ray photoemission spectroscopy, X-ray absorption spectroscopy, IR and Raman spectroscopies, high-resolution transmission electron microscopy and proved to be highly active in the visible-light-driven CO2 catalytic conversion in acetonitrile solutions. Exceptional stabilities (over 200 h of irradiation) were obtained without compromising the selective conversion of CO2 to products (>97%). Most importantly, complete selectivity control could be obtained upon adjusting the experimental conditions: production of CO as the only product was achieved when using a weak acid (phenol or trifluoroethanol) as a co-substrate, while formate was exclusively obtained in solutions of mixed acetonitrile and triethanolamine.

Carbon Dots from Citric Acid and its Intermediates Formed by Thermal Decomposition.

Thermal decomposition of citric acid is one of the most common synthesis methods for fluorescent carbon dots; the reaction pathway is, however, quite complex and the details are still far from being understood. For instance, several intermediates form during the process and they also give rise to fluorescent species. In the present work, the formation of fluorescent C-dots from citric acid has been studied as a function of reaction time by coupling infrared analysis, X-ray photoelectron spectroscopy, liquid chromatography/mass spectroscopy (LC/MS) with the change of the optical properties, absorption and emission. The reaction intermediates, which have been identified at different stages, produce two main emissive species, in the green and blue, as also indicated by the decay time analysis. C-dots formed from the intermediates have also been synthesised by thermal decomposition, which gave an emission maximum around 450 nm. The citric acid C-dots in water show short temporal stability, but their functionalisation with 3-aminopropyltriethoxysilane reduces the quenching. The understanding of the citric acid thermal decomposition reaction is expected to improve the control and reproducibility of C-dots synthesis.

Fabrication of Ti substrate grain dependent C/TiO2 composites through carbothermal treatment of anodic TiO2.

Composite materials of titania and graphitic carbon, and their optimized synthesis are highly interesting for application in sustainable energy conversion and storage. We report on planar C/TiO2 composite films that are prepared on a polycrystalline titanium substrate by carbothermal treatment of compact anodic TiO2 with acetylene. This thin film material allows for the study of functional properties of C/TiO2 as a function of chemical composition and structure. The chemical and structural properties of the composite on top of individual Ti substrate grains are examined by scanning photoelectron microscopy and micro-Raman spectroscopy. Through comparison of these data with electron backscatter diffraction, it is found that the amount of generated carbon and the grade of anodic film crystallinity correlate with the crystallographic orientation of the Ti substrate grains. On top of Ti grains with ∼(0001) orientations the anodic TiO2 exhibits the highest grade of crystallinity, and the composite contains the highest fraction of graphitic carbon compared to Ti grains with other orientations. This indirect effect of the Ti substrate grain orientation yields new insights into the activity of TiO2 towards the decomposition of carbon precursors.

Polyvinyl alcohol electrospun nanofibers containing Ag nanoparticles used as sensors for the detection of biogenic amines.

Polyvinyl alcohol (PVA) electrospun nanofibers containing Ag nanoparticles (NPs) have been deposited on glass substrates. The aim of the work was to test the feasibility of this approach for the detection of biogenic amines by using either the Ag localized surface plasmon resonance quenching caused by the adsorption of amines on Ag NPs or by detecting the amines by surface enhanced Raman spectroscopy (SERS) after adsorption, from the gas phase, on the metal NPs. Two different approaches have been adopted. In the first one an ethanol/water solution containing AgNO3 was used directly in the electrospinning apparatus. In this way, a simple heat treatment of the nanofibers mat was sufficient to obtain the formation of Ag NPs inside the nanofibers and a partial cross-link of PVA. In the second procedure, the Ag NPs were deposited on PVA nanofibers by using the supersonic cluster beam deposition method, so that a beam of pure Ag NPs of controlled size was obtained. Exposure of the PVA mat to the beam produced a uniform distribution of the NPs on the nanofibers surface. Ethylendiamine vapors and volatile amines released from fresh shrimp meat were chemisorbed on the nanofibers mats. A SERS spectrum characterized by a diagnostic Ag-N stretching vibration at 230 cm(-1) was obtained. The results allow to compare the two different approaches in the detection of ammines.

Yttrium oxide/gadolinium oxide-modified platinum nanoparticles as cathodes for the oxygen reduction reaction.

Rare-earth-element (Y, Gd) modified Pt nanoparticles (NPs) supported on a carbon substrate (Vulcan XC-72) are synthesized via a water-in-oil chemical route. In both cases, X-ray diffraction (XRD) measurements show the non-formation of an alloyed material. Photoemission spectroscopy (XPS) results reveal that Y and Gd are oxidized. Additionally, no evidence of an electronic modification of Pt can be brought to light. Transmission electron microscopy (TEM) studies indicate that Pt-Y(2)O(3) and Pt-Gd(2)O(3) particles are well dispersed on the substrate-and that their average particle sizes are smaller than the Pt-NP sizes. The catalytic activity of the Pt-Y(2)O(3)/C and Pt-Gd(2)O(3)/C catalysts towards the oxygen reduction reaction (ORR) is studied in a 0.5 M H(2)SO(4) electrolyte. The surface and mass specific activities of the Pt-Y(2)O(3)/C catalyst towards the ORR at 0.9 V (vs. the reversible hydrogen electrode, RHE) are (54.3±1.2) µA cm(-2)(Pt) and MA=(23.1±0.5) mA mg(-1)(Pt), respectively. These values are 1.3-, and 1.6-fold higher than the values obtained with a Pt/C catalyst. Although the as-prepared Pt-Gd(2)O(3)/C catalyst has a lower catalytic activity for the ORR compared to Pt/C, the heat-treated sample shows a surface specific activity of about (53.0±0.7) µA cm(-2) Pt , and a mass specific activity (MA) of about (18.2±0.5) mA mg(-1) Pt at 0.9 V (vs. RHE). The enhancement of the ORR kinetics on the Pt-Y(2)O(3)/C and heat-treated Pt-Gd(2)O(3)/C catalysts could be associated with the formation of platinum NPs presenting modified surface properties.

The Interaction of Amines with Gold Nanoparticles.

Understanding the interactions between amines and the surface of gold nanoparticles is important because of their role in the stabilization of the nanosystems, in the formation of the protein corona, and in the preparation of semisynthetic nanozymes. By using fluorescence spectroscopy, electrochemistry, X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy, and molecular simulation, a detailed picture of these interactions is obtained. Herein, it is shown that amines interact with surface Au(0) atoms of the nanoparticles with their lone electron pair with a strength linearly correlating with their basicity corrected for steric hindrance. The kinetics of binding depends on the position of the gold atoms (flat surfaces or edges) while the mode of binding involves a single Au(0) with nitrogen sitting on top of it. A small fraction of surface Au(I) atoms, still present, is reduced by the amines yielding a much stronger Au(0)-RN.+ (RN. , after the loss of a proton) interaction. In this case, the mode of binding involves two Au(0) atoms with a bridging nitrogen placed between them. Stable Au nanoparticles, as those required for robust semisynthetic nanozymes preparation, are better obtained when the protein is involved (at least in part) in the reduction of the gold ions.

Atomic structure and special reactivity toward methanol oxidation of vanadia nanoclusters on TiO2(110).

We have grown highly controlled VOx nanoclusters on rutile TiO2(110). The combination of photoemission and photoelectron diffraction techniques based on synchrotron radiation with DFT calculations has allowed identifying these nanostructures as exotic V4O6 nanoclusters, which hold vanadyl groups, even if vanadium oxidation state is formally +3. Our theoretical investigation also indicates that on the surface of titania, vanadia mononuclear species, with oxidation states ranging from +2 to +4, can be strongly stabilized by aggregation into tetramers that are characterized by a charge transfer to the titania substrate and a consequent decrease of the electron density in the vanadium 3d levels. We then performed temperature programmed desorption experiments using methanol as probe molecule to understand the impact of these unusual electronic and structural properties on the chemical reactivity, obtaining that the V4O6 nanoclusters can selectively convert methanol to formaldehyde at an unprecedented low temperature (300 K).

Palladium nanoparticles supported on nitrogen-doped HOPG: a surface science and electrochemical study.

We have investigated by photoemission spectroscopy and scanning tunnelling microscopy what are the chemical and structural changes induced by nitrogen ion implantation (500 eV) on highly oriented pyrolytic graphite and how the defects induced by this process modify the growth and thermal stability of palladium nanoparticles, deposited in situ by physical vapour deposition. Since nitrogen derived defects are mostly buried below the surface, they are not accessible for a chemical interaction with metal nanoparticles; however, the amorphization induced by the ion beam in the outermost layers of the substrate beneficially affects the metal morphology, limiting the size of the nanoparticles and improving their thermal stability. The supported nanoparticles have been tested towards the oxygen reduction reaction indicating that the electrochemical activity does not depend significantly on the ion implantation, but mostly on the amount of palladium.

Nanoneedles of Mixed Transition Metal Phosphides as Bifunctional Catalysts for Electrocatalytic Water Splitting in Alkaline Media.

In this work, mixed Ni/Co and Ni/Fe metal phosphides with different metal ratios were synthesized through the phosphidization of high-surface-area hydroxides grown hydrothermally on carbon cloth. The materials were characterized by means of X-ray photoemission spectroscopy, X-ray diffraction, energy dispersive X-ray analysis, and electron microscopies. The electrocatalytic performance in the electrochemical water splitting was tested in alkaline media. With the aim of determining the chemical stability of the mixed phosphides and the possible changes undergone under catalytic conditions, the materials were characterized before and after the electrochemical tests. The best performances in the hydrogen evolution reaction were achieved when synergic interactions are established among the metal centers, as suggested by the outstanding performances (50 mV to achieve 10 mA/cm2) of materials containing the highest amount of ternary compounds, i.e., NiCoP and NiFeP. The best performances in the oxygen evolution reaction were reached by the Ni-Fe materials. Under these conditions, it was demonstrated that a strong oxidation of the surface and the dissolution of the phosphide/phosphate component takes place, with the consequent formation of the corresponding metal oxides and hydroxides.

Catalytic Activity of Defect-Engineered Transition Me tal Dichalcogenides Mapped with Atomic-Scale Precision by Electrochemical Scanning Tunneling Microscopy.

Unraveling structure-activity relationships is a key objective of catalysis. Unfortunately, the intrinsic complexity and structural heterogeneity of materials stand in the way of this goal, mainly because the activity measurements are area-averaged and therefore contain information coming from different surface sites. This limitation can be surpassed by the analysis of the noise in the current of electrochemical scanning tunneling microscopy (EC-STM). Herein, we apply this strategy to investigate the catalytic activity toward the hydrogen evolution reaction of monolayer films of MoSe2. Thanks to atomically resolved potentiodynamic experiments, we can evaluate individually the catalytic activity of the MoSe2 basal plane, selenium vacancies, and different point defects produced by the intersections of metallic twin boundaries. The activity trend deduced by EC-STM is independently confirmed by density functional theory calculations, which also indicate that, on the metallic twin boundary crossings, the hydrogen adsorption energy is almost thermoneutral. The micro- and macroscopic measurements are combined to extract the turnover frequency of different sites, obtaining for the most active ones a value of 30 s-1 at -136 mV vs RHE.

Tracking thermally-activated transformations in a nanostructured metal/oxide/metal system.

We present experimental and theoretical evidence of sequential redox processes and structural transformations occurring by increasing temperature in a metal/oxide/metal system obtained via deposition of Fe atoms onto a z'-TiO(1.25)/Pt(111) ultrathin film in UHV. The initial reduction of the z'-TiO(x) phase by Fe at room temperature is followed by Fe diffusion and partial penetration into the substrate at intermediate temperatures. This triggers the formation of a bi-component material in which mixed FeO/TiO(2) nanoislands coexist on a h-TiO(1.14) ultrathin film, notably restructured (from rectangular to hexagonal) and reduced (from Ti : O = 1 : 1.25 to 1 : 1.14) with respect to the original TiO(1.25) phase. Further heating recovers the pristine z'-TiO(x) phase while Fe completely dissolves into the substrate.

How do H2 oxidation molecular catalysts assemble onto carbon nanotube electrodes? A crosstalk between electrochemical and multi-physical characterization techniques.

Molecular catalysts show powerful catalytic efficiency and unsurpassed selectivity in many reactions of interest. As their implementation in electrocatalytic devices requires their immobilization onto a conductive support, controlling the grafting chemistry and its impact on their distribution at the surface of this support within the catalytic layer is key to enhancing and stabilizing the current they produce. This study focuses on molecular bioinspired nickel catalysts for hydrogen oxidation, bound to carbon nanotubes, a conductive support with high specific area. We couple advanced analysis by transmission electron microscopy (TEM), for direct imaging of the catalyst layer on individual nanotubes, and small angle neutron scattering (SANS), for indirect observation of structural features in a relevant aqueous medium. Low-dose TEM imaging shows a homogeneous, mobile coverage of catalysts, likely as a monolayer coating the nanotubes, while SANS unveils a regular nanostructure in the catalyst distribution on the surface with agglomerates that could be imaged by TEM upon aging. Together, electrochemistry, TEM and SANS analyses allowed drawing an unprecedented and intriguing picture with molecular catalysts evenly distributed at the nanoscale in two different populations required for optimal catalytic performance.

Sulfur Doping versus Hierarchical Pore Structure: The Dominating Effect on the Fe-N-C Site Density, Activity, and Selectivity in Oxygen Reduction Reaction Electrocatalysis.

Nitrogen doping has been always regarded as one of the major factors responsible for the increased catalytic activity of Fe-N-C catalysts in the oxygen reduction reaction, and recently, sulfur has emerged as a co-doping element capable of increasing the catalytic activity even more because of electronic effects, which modify the d-band center of the Fe-N-C catalysts or because of its capability to increase the Fe-Nx site density (SD). Herein, we investigate in detail the effect of sulfur doping of carbon support on the Fe-Nx site formation and on the textural properties (micro- and mesopore surface area and volume) in the resulting Fe-N-C catalysts. The Fe-N-C catalysts were prepared from mesoporous carbon with tunable sulfur doping (0-16 wt %), which was achieved by the modulation of the relative amount of sucrose/dibenzothiophene precursors. The carbon with the highest sulfur content was also activated through steam treatment at 800 °C for different durations, which allowed us to modulate the carbon pore volume and surface area (1296-1726 m2 g-1). The resulting catalysts were tested in O2-saturated 0.5 M H2SO4 electrolyte, and the site density (SD) was determined using the NO-stripping technique. Here, we demonstrate that sulfur doping has a porogenic effect increasing the microporosity of the carbon support, and it also facilitates the nitrogen fixation on the carbon support as well as the formation of Fe-Nx sites. It was found that the Fe-N-C catalytic activity [E1/2 ranges between 0.609 and 0.731 V vs reversible hydrogen electrode (RHE)] does not directly depend on sulfur content, but rather on the microporous surface and therefore any electronic effect appears not to be determinant as confirmed by X-ray photoemission spectroscopy (XPS). The graph reporting Fe-Nx SD versus sulfur content assumes a volcano-like shape, where the maximum value is obtained for a sulfur/iron ratio close to 18, i.e., a too high or too low sulfur doping has a detrimental effect on Fe-Nx formation. However, it was highlighted that the increase of Fe-Nx SD is a necessary but not sufficient condition for increasing the catalytic activity of the material, unless the textural properties are also optimized, i.e., there must be an optimized hierarchical porosity that facilitates the mass transport to the active sites.

Stability of TiO2 polymorphs: exploring the extreme frontier of the nanoscale.

The structure of two ordered stoichiometric TiO(2) nanophases supported on Pt(111) and (1x2)-Pt(110) substrates, prepared by reactive evaporation of Ti in a high-oxygen background, is compared by discussing experimental data (i.e. low-energy electron diffraction, scanning tunneling microscopy) and density functional theory calculations. Two rectangular phases, called rect-TiO(2) and rect'-TiO(2) were obtained on both the hexagonal Pt(111) and the rectangular (1x2)-Pt(110) substrates, generally suggesting that they are weakly interacting with the substrates. The rect-TiO(2) phase is actually confined to a TiO(2) double layer, while the rect'-TiO(2) can extend up to a thickness of several layers and is obtained when higher Ti doses are evaporated. While the rect-TiO(2) is best described as a thickness-limited lepidocrocite-like nanosheet, growing as a single-domain-commensurate (14x4) phase on (1x2)-Pt(110) and as a six-domains-incommensurate phase on Pt(111), the thicker rect'-TiO(2) phase can be best described as a TiO(2)(B) supported nanolayer (NL). This represents the first example of the TiO(2)(B) phase in the form of a supported NL, whose properties are still largely unexplored. The important point is that, because of the weak interaction between the oxide NLs and the Pt surfaces, the substrate does not play a role in stabilizing the 2D nanostructures. Rather, it acts as a sort of lab bench where sub-nanosized titania crystallites self-assemble, so that the final NLs are representative of 2D confined titania at the bottom of the nanoscale.

Stability and chemisorption properties of ultrathin TiO(x)/Pt(111) films and Au/TiO(x)/Pt(111) model catalysts in reactive atmospheres.

The stability of three ultrathin TiO(x)/Pt(111) films with different stoichiometry and defectivity and the corresponding Au/TiO(x)/Pt(111) model catalysts in CO or a CO-O(2) (1 : 1) gas mixture up to a pressure of 100 mbar has been investigated. According to previous studies, the ultrathin films proved to be effective substrates to deposit in UHV Au nanoparticles with specific morphologies and lateral sizes ranging between 1 and 6 nm. The films have been characterized before and after the exposure using X-ray photoemission spectroscopy (XPS), low-energy electron diffraction (LEED) and scanning tunnelling microscopy (STM). Additional in situ measurements of the CO chemisorption behavior were performed using polarization-modulation infrared reflection-absorption spectroscopy (PM-IRAS). A fully oxidized film is stable in CO and CO-O(2) (1 : 1) ambient, while the reduced films undergo an oxidative dewetting process at RT in the latter atmosphere. This process ultimately produces a nano-composite surface, where very tiny (from 0.5 to 3 nm lateral sizes) titania nanograins are mixed with open, uncovered areas of the Pt substrate. IRAS measurements on the corresponding Au/TiO(x)/Pt(111) model catalysts demonstrated that the CO chemisorption strongly depends on the Au nanoparticle size and morphology, while the actual Ti oxidation state of the oxide support does not seem to play a significant role.

A DVD-MoS2/Ag2S/Ag Nanocomposite Thiol-Conjugated with Porphyrins for an Enhanced Light-Mediated Hydrogen Evolution Reaction.

We have recently demonstrated in a previous work an appreciable photoelectrocatalytic (PEC) behavior towards hydrogen evolution reaction (HER) of a MoS2/Ag2S/Ag nanocomposite electrochemically deposited on a commercial writable Digital Versatile Disc (DVD), consisting therefore on an interesting strategy to convert a common waster product in an added-value material. Herein, we present the conjugation of this MoS2/Ag2S/Ag-DVD nanocomposite with thiol-terminated tetraphenylporphyrins, taking advantage of the grafting of thiol groups through covalent S-S bridges, for integrating the well-known porphyrins photoactivity into the nanocomposite. Moreover, we employ two thiol-terminated porphyrins with different hydrophilicity, demonstrating that they either suppress or improve the PEC-HER performance of the overall hybrid, as a function of the molecule polarity, sustaining the concept of a local proton relay. Actually, the active polar porphyrin-MoS2/Ag2S/Ag-DVD hybrid material presented, when illuminated, a better HER performance, compared to the pristine nanocomposite, since the porphyrin may inject photoelectrons in the conduction band of the semiconductors at the formed heterojunction, presenting also a stable operational behavior during overnight chopped light chronoamperometric measurement, thanks to the robust bond created.

One-pot synthesis of MoS2(1-x)Se2x on N-doped reduced graphene oxide: tailoring chemical and structural properties for photoenhanced hydrogen evolution reaction.

In this work we designed a one-pot solvothermal synthesis of MoS2(1-x)Se2x nanosheets directly grown on N-doped reduced graphene oxide (hereafter N-rGO). We optimized the synthesis conditions to control the Se : S ratio, with the aim of tailoring the optoelectronic properties of the resulting nanocomposites for their use as electro- and photoelectro-catalysts in the hydrogen evolution reaction (HER). The synthesis protocol made use of ammonium tetrathiomolybdate (ATM) as MoS2 precursor and dimethyl diselenide (DMDSe) as selenizing agent. By optimizing growth conditions and post-annealing treatments, we produced either partially amorphous or highly crystalline chalcogen-defective electrocatalysts. All samples were tested for the HER in acidic environment, and the best performing among them, for the photoassisted HER. In low crystallinity samples, the introduction of Se is not beneficial for promoting the catalytic activity, and MoS2/N-rGO was the most active electrocatalyst. On the other hand, after the post-annealing treatment and the consequent crystallization of the materials, the best HER performance was obtained for the sample with x = 0.38, which also showed the highest enhancement upon light irradiation.

Hybrid Transition Metal Dichalcogenide/Graphene Microspheres for Hydrogen Evolution Reaction.

A peculiar 3D graphene-based architecture, i.e., partial reduced-Graphene Oxide Aerogel Microspheres (prGOAM), having a dandelion-like morphology with divergent microchannels to implement innovative electrocatalysts for the hydrogen evolution reaction (HER) is investigated in this paper. prGOAM was used as a scaffold to incorporate exfoliated transition metals dichalcogenide (TMDC) nanosheets, and the final hybrid materials have been tested for HER and photo-enhanced HER. The aim was to create a hybrid material where electronic contacts among the two pristine materials are established in a 3D architecture, which might increase the final HER activity while maintaining accessible the TMDC catalytic sites. The adopted bottom-up approach, based on combining electrospraying with freeze-casting techniques, successfully provides a route to prepare TMDC/prGOAM hybrid systems where the dandelion-like morphology is retained. Interestingly, the microspherical morphology is also maintained in the tested electrode and after the electrocatalytic experiments, as demonstrated by scanning electron microscopy images. Comparing the HER activity of the TMDC/prGOAM hybrid systems with that of TMDC/partially reduced-Graphene Oxide (prGO) and TMDC/Vulcan was evidenced in the role of the divergent microchannels present in the 3D architecture. HER photoelectron catalytic (PEC) tests have been carried out and demonstrated an interesting increase in HER performance.

Copper Vanadate Nanobelts as Anodes for Photoelectrochemical Water Splitting: Influence of CoOx Overlayers on Functional Performances.

The design and development of environmentally friendly and robust anodes for photoelectrochemical (PEC) water splitting plays a critical role for the efficient conversion of radiant energy into hydrogen fuel. In this regard, quasi-1D copper vanadates (CuV2O6) were grown on conductive substrates by a hydrothermal procedure and processed for use as anodes in PEC cells, with particular attention on the role exerted by cobalt oxide (CoOx) overlayers deposited by radio frequency (RF) sputtering. The target materials were characterized in detail by a multitechnique approach with the aim at elucidating the interplay between their structure, composition, morphology, and the resulting activity as photoanodes. Functional tests were performed by standard electrochemical techniques like linear sweep voltammetry, impedance spectroscopy, and by the less conventional intensity modulated photocurrent spectroscopy, yielding an important insight into the material PEC properties. The obtained results highlight that, despite the fact that the supposedly favorable band alignment between CuV2O6 and Co3O4 did not yield a net current density increase, cobalt oxide-functionalized anodes afforded a remarkable durability enhancement, an important prerequisite for their eventual real-world applications. The concurrent phenomena accounting for the observed behavior are presented and discussed in relation to material physico-chemical properties.