XPS analysis of Fe2O3-TiO2-Au nanocomposites prepared by a plasma-assisted route

Fe2O3 nanodeposits have been grown on fluorine-doped tin oxide (FTO) substrates by plasma enhanced-chemical vapor deposition (PE-CVD). Subsequently, the obtained systems have been functionalized through the sequential introduction of TiO2 and Au nanoparticles (NPs) by means of radio frequency (RF)-sputtering. The target nanocomposites have been specifically optimized in view of their ultimate functional application in solar-driven H2 generation. In the present study, our attention is focused on a detailed X-ray photoelectron spectroscopy (XPS) characterization of the surface composition for a representative Fe2O3-TiO2-Au specimen. In particular, this report provides a detailed discussion of the analyzed C 1s, O 1s, Fe 2p, Ti 2p, and Au 4f regions. The obtained results point to the formation of pure Fe2O3-TiO2-Au composites, with gold present only in its metallic state and each of the constituents maintaining its chemical identity

A study of Pt-/alpha-Fe2O3 nanocomposites by XPS

alpha-Fe2O3 matrices were deposited on Fluorine-doped Tin Oxide (FTO) substrates by Plasma Enhanced- Chemical Vapor Deposition (PE-CVD) from Fe(hfa)_2TMEDA (hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate; TMEDA = N,N,N’,N’-tetramethylethylenediamine). The obtained nanosystems were subsequently functionalized by platinum nanoparticles (NPs) via Radio Frequency (RF)-sputtering, exposing samples either to a pre- or post-sputtering thermal treatment at 650°C for one hour in air. Interestingly, Pt oxidation state in the final composite systems strongly depended on the adopted processing conditions. In this work, a detailed X-ray Photoelectron Spectroscopy (XPS) analysis was carried out in order to investigate the material chemical composition, with particular regard to the relative Pt(0)/Pt(II)/Pt(IV) content. The obtained results evidenced that, when annealing is performed prior to sputtering, only PtO and PtO2 are revealed in the final Pt/alpha-Fe2O3 nanocomposite. In a different way, annealing after sputtering results in the co-presence of Pt(0), Pt(II) and Pt(IV) species, the former arising from the thermal decomposition of PtO2 to metallic platinum

The Early Steps of Molecule-to-Material Conversion in Chemical Vapor Deposition (CVD): A Case Study

Transition metal complexes with \u3b2-diketonate and diamine ligands are valuable precursors for chemical vapor deposition (CVD) of metal oxide nanomaterials, but the metal-ligand bond dissociation mechanism on the growth surface is not yet clarified in detail. We address this question by density functional theory (DFT) and ab initio molecular dynamics (AIMD) in combination with the Blue Moon (BM) statistical sampling approach. AIMD simulations of the Zn \u3b2-diketonate-diamine complex Zn(hfa)2TMEDA (hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate; TMEDA = N,N,N\u2032,N\u2032-tetramethylethylenediamine), an amenable precursor for the CVD of ZnO nanosystems, show that rolling diffusion of this precursor at 500 K on a hydroxylated silica slab leads to an octahedral-to-square pyramidal rearrangement of its molecular geometry. The free energy profile of the octahedral-to-square pyramidal conversion indicates that the process barrier (5.8 kcal/mol) is of the order of magnitude of the thermal energy at the operating temperature. The formation of hydrogen bonds with surface hydroxyl groups plays a key role in aiding the dissociation of a Zn-O bond. In the square-pyramidal complex, the Zn center has a free coordination position, which might promote the interaction with incoming reagents on the deposition surface. These results provide a valuable atomistic insight on the molecule-to-material conversion process which, in perspective, might help to tailor by design the first nucleation stages of the target ZnO-based nanostructures

WO3-decorated ZnO nanostructures for light-activated applications

In the present work, a two-step vapor-phase route was implemented for the tailored design of ZnO\u2013WO3 nanoheterostructures supported on fluorine-doped tin oxide (FTO) substrates. Under optimized conditions, the sequential use of chemical vapor deposition (CVD) and radio frequency (RF)-sputtering for the deposition of zinc and tungsten oxides respectively, resulted in the growth of calyx-like ZnO nanostructures uniformly decorated by a conformal dispersion of low-sized WO3 nanoparticles. The target materials were characterized by means of a multi-technique approach, with particular regard to their structural, compositional, morphological and optical properties. Finally, their photocatalytic performances were preliminarily tested in the abatement of NOX gases (NO and NO2). Due to the unique porous morphology of the ZnO nanodeposit and the high density of ZnO\u2013WO3 heterojunctions, WO3-decorated ZnO revealed appealing De-NOX characteristics in terms of both degradation efficiency and selectivity. Such features, along with the photoinduced superhydrophilicity and self-cleaning properties of the present nanomaterials, candidate them as promising functional platforms for applications in smart windows and building materials for environmental remediation

Dual Improvement of β‐MnO2 Oxygen Evolution Electrocatalysts via Combined Substrate Control and Surface Engineering

The development of catalysts with high intrinsic activity towards the oxygen evolution reaction (OER) plays a critical role in sustainable energy conversion and storage. Herein, we report on the development of efficient (photo)electrocatalysts based on functionalized MnO2 systems. Specifically, β-MnO2 nanostructures grown by plasma enhanced-chemical vapor deposition on fluorine-doped tin oxide (FTO) or Ni foams were decorated with Co3O4 or Fe2O3 nanoparticles by radio frequency sputtering. Upon functionalization, FTO-supported materials yielded a performance increase with respect to bare MnO2, with current densities at 1.65 V vs. the reversible hydrogen electrode (RHE) up to 3.0 and 3.5 mA/cm2 in the dark and under simulated sunlight, respectively. On the other hand, the use of highly porous and conductive Ni foam substrates enabled to maximize cooperative interfacial effects between catalyst components. The best performing Fe2O3/MnO2 system provided a current density of 17.9 mA/cm2 at 1.65 V vs. RHE, an overpotential as low as 390 mV, and a Tafel slope of 69 mV/decade under dark conditions, comparing favorably with IrO2 and RuO2 benchmarks. Overall, the control of β-MnO2/substrate interactions and the simultaneous surface property engineering pave the way to an efficient energy generation from abundant natural resources

Soft Loans as an Instrument of Development Finance: A Comparative Assessment and Options for the Future

Within the framework of the Post-2015 Development Agenda, discussions on Financing for Development and the future of Official Development Assistance (ODA) have intensified. Amongst the instruments under review are soft loans. Though originally conceived as export promotion tools, development objectives have recently become more prominent in soft loan policies. Albeit regulated through the Arrangement on Officially Supported Export Credits, soft loans claim a place amongst the instruments of development policy. By means of comparative case study analysis, this paper examines the relevance of soft loans as an instrument of development policy. We discuss three characteristics of soft loan financing: (i) the institutional heterogeneity of programmes between countries, (ii) the hybrid nature of the instruments between export promotion and development objectives, and (iii) the underlying notions of development. Upon that basis, scenarios for the future use of soft loans as an instrument of development finance are presented

Controllable Anchoring of Graphitic Carbon Nitride on MnO₂ Nanoarchitectures for Oxygen Evolution Electrocatalysis

International audienc

Manganese(II) Molecular Sources for Plasma-Assisted CVD of Mn Oxides and Fluorides: From Precursors to Growth Process

A viable route to manganese-based materials of high technological interest is plasma-assisted chemical vapor deposition (PA-CVD), offering various degrees of freedom for the growth of high-purity nanostructures from suitable precursors. In this regard, fluorinated \u3b2-diketonate diamine Mn(II) complexes of general formula Mn(dik)2\ub7TMEDA [TMEDA = N,N,N\u2032,N\u2032-tetramethylethylenediamine; Hdik = 1,1,1,5,5,5-hexafluoro-2,4-pentanedione (Hhfa), or 1,1,1-trifluoro-2,4-pentanedione (Htfa)] represent a valuable option in the quest of candidate molecular sources for PA-CVD environments. In this work, we investigate and highlight the chemico-physical properties of these compounds of importance for their use in PA-CVD processes, through the use of a comprehensive experimental\u2013theoretical investigation. Preliminary PA-CVD validation shows the possibility of varying the Mn oxidation state, as well as the system chemical composition from MnF2 to MnO2, by simple modulations of the reaction atmosphere, paving the way to a successful utilization of the target compounds in the growth of manganese-containing nanomaterials for different technological applications

Surface Functionalization of Grown-on-Tip ZnO Nanopyramids: From Fabrication to Light-Triggered Applications

We report on a combined chemical vapor deposition (CVD)/radio frequency (RF) sputtering synthetic strategy for the controlled surface modification of ZnO nanostructures by Ti-containing species. Specifically, the proposed approach consists in the CVD of grown-on-tip ZnO nanopyramids, followed by titanium RF sputtering under mild conditions. The results obtained by a thorough characterization demonstrate the successful ZnO surface functionalization with dispersed Ti-containing species in low amounts. This phenomenon, in turn, yields a remarkable enhancement of photoactivated superhydrophilic behavior, self-cleaning ability, and photocatalytic performances in comparison to bare ZnO. The reasons accounting for such an improvement are unravelled by a multitechnique analysis, elucidating the interplay between material chemico-physical properties and the corresponding functional behavior. Overall, the proposed strategy stands as an amenable tool for the mastering of semiconductor-based functional nanoarchitectures through <i>ad hoc</i> engineering of the system surface