Valence shell electronically excited states of norbornadiene and quadricyclane.

The absolute photoabsorption cross sections of norbornadiene (NBD) and quadricyclane (QC), two isomers with chemical formula C7H8 that are attracting much interest for solar energy storage applications, have been measured from threshold up to 10.8 eV using the Fourier transform spectrometer at the SOLEIL synchrotron radiation facility. The absorption spectrum of NBD exhibits some sharp structure associated with transitions into Rydberg states, superimposed on several broad bands attributable to valence excitations. Sharp structure, although less pronounced, also appears in the absorption spectrum of QC. Assignments have been proposed for some of the absorption bands using calculated vertical transition energies and oscillator strengths for the electronically excited states of NBD and QC. Natural transition orbitals indicate that some of the electronically excited states in NBD have a mixed Rydberg/valence character, whereas the first ten excited singlet states in QC are all predominantly Rydberg in the vertical region. In NBD, a comparison between the vibrational structure observed in the experimental 11B1-11A1 (3sa1 ← 5b1) band and that predicted by Franck-Condon and Herzberg-Teller modeling has necessitated a revision of the band origin and of the vibrational assignments proposed previously. Similar comparisons have encouraged a revision of the adiabatic first ionization energy of NBD. Simulations of the vibrational structure due to excitation from the 5b2 orbital in QC into 3p and 3d Rydberg states have allowed tentative assignments to be proposed for the complex structure observed in the absorption bands between ∼5.4 and 7.0 eV.

Direct-Patterning ZnO Deposition by Atomic-Layer Additive Manufacturing Using a Safe and Economical Precursor.

Area-selective atomic layer deposition (AS-ALD) is a bottom-up nanofabrication method delivering single atoms from a molecular precursor. AS-ALD enables self-aligned fabrication and outperforms lithography in terms of cost, resistance, and equipment prerequisites, but it requires pre-patterned substrates and is limited by insufficient selectivity and finite choice of substrates. These challenges are circumvented by direct patterning with atomic-layer additive manufacturing (ALAM) - a transfer of 3D-printing principles to atomic-layer manufacturing where a precursor supply nozzle enables direct patterning instead of blanket coating. The reduced precursor vapor consumption in ALAM as compared with ALD calls for the use of less volatile precursors by replacing diethylzinc used traditionally in ALD with bis(dimethylaminopropyl)zinc, Zn(DMP)2 . The behavior of this novel ZnO ALAM process follows that of the corresponding ALD in terms of deposit quality and growth characteristics. The temperature window for self-limiting growth of stoichiometric, crystalline material is 200-250 °C. The growth rates are 0.9 Å per cycle in ALD (determined by spectroscopic ellipsometry) and 1.1 Å per pass in ALAM (imaging ellipsometry). The preferential crystal orientation increases with temperature, while energy-dispersive X-ray spectroscopic and XPS show that only intermediate temperatures deliver stoichiometric ZnO. A functional thin-film transistor is created from an ALAM-deposited ZnO line and characterized.

Synergistic Combination of Reductive Covalent Functionalization and Atomic Layer Deposition-Towards Spatially Defined Graphene-Organic-Inorganic Heterostructures.

Three-dimensionally (3D) well-ordered and highly integrated graphene hybrid architectures are considered to be next-generation multifunctional graphene materials but still remain elusive. Here, we report the first realization of unprecedented 3D-patterned graphene nano-ensembles composed of a graphene monolayer, a tailor-made structured organophenyl layer, and three metal oxide films, providing the first example of such a hybrid nano-architecture. These spatially resolved and hierarchically structured quinary hybrids are generated via a two-dimensional (2D)-functionalization-mediated atomic layer deposition growth process, involving an initial lateral molecular programming of the graphene lattice via lithography-assisted 2D functionalization and a subsequent stepwise molecular assembly in these regions in the z-direction. Our breakthrough lays the foundation for the construction of emerging 3D-patterned graphene heterostructures.

Uranium-mediated electrocatalytic dihydrogen production from water.

Depleted uranium is a mildly radioactive waste product that is stockpiled worldwide. The chemical reactivity of uranium complexes is well documented, including the stoichiometric activation of small molecules of biological and industrial interest such as H2O, CO2, CO, or N2 (refs 1 - 11), but catalytic transformations with actinides remain underexplored in comparison to transition-metal catalysis. For reduction of water to H2, complexes of low-valent uranium show the highest potential, but are known to react violently and uncontrollably forming stable bridging oxo or uranyl species. As a result, only a few oxidations of uranium with water have been reported so far; all stoichiometric. Catalytic H2 production, however, requires the reductive recovery of the catalyst via a challenging cleavage of the uranium-bound oxygen-containing ligand. Here we report the electrocatalytic water reduction observed with a trisaryloxide U(III) complex [(((Ad,Me)ArO)3mes)U] (refs 18 and 19)--the first homogeneous uranium catalyst for H2 production from H2O. The catalytic cycle involves rare terminal U(IV)-OH and U(V)=O complexes, which have been isolated, characterized, and proven to be integral parts of the catalytic mechanism. The recognition of uranium compounds as potentially useful catalysts suggests new applications for such light actinides. The development of uranium-based catalysts provides new perspectives on nuclear waste management strategies, by suggesting that mildly radioactive depleted uranium--an abundant waste product of the nuclear power industry--could be a valuable resource.

Molecular Stacking on Graphene.

The sequential vertical polyfunctionalization of 2D addend-patterned graphene is still elusive. Here, we report a practical realization of this goal via a "molecular building blocks" approach, which is based on a combination of a lithography-assisted reductive functionalization approach and a post-functionalization step to sequentially and controllably link the molecular building blocks ethylpyridine, cis-dichlorobis(2,2'-bipyridyl)ruthenium, and triphenylphosphine (4-methylbenzenethiol, respectively) on selected lattice regions of a graphene matrix. The assembled 2D hetero-architectures are unambiguously characterized by various spectroscopic and microscopic measurements, revealing the stepwise stacking of the molecular building blocks on the graphene surface. Our method overcomes the current limitation of a one-layer-only binding to the graphene surface and opens the door for a vertical growth in the z-direction.

A Self-Ordered Nanostructured Transparent Electrode of High Structural Quality and Corresponding Functional Performance.

The preparation of a highly ordered nanostructured transparent electrode based on a combination of nanosphere lithography and anodization is presented. The size of perfectly ordered pore domains is improved by an order of magnitude with respect to the state of the art. The concomitantly reduced density of defect pores increases the fraction of pores that are in good electrical contact with the underlying transparent conductive substrate. This improvement in structural quality translates directly and linearly into an improved performance of energy conversion devices built from such electrodes in a linear manner.

Catalytically Triggered Energy Release from Strained Organic Molecules: The Surface Chemistry of Quadricyclane and Norbornadiene on Pt(111).

We have investigated the surface chemistry of the polycyclic valence-isomer pair norbornadiene (NBD) and quadricyclane (QC) on Pt(111). The NBD/QC system is considered to be a prototype for energy storage in strained organic compounds. By using a multimethod approach, including UV photoelectron, high-resolution X-ray photoelectron, and IR reflection-absorption spectroscopic analysis and DFT calculations, we could unambiguously identify and differentiate between the two molecules in the multilayer phase, which implies that the energy-loaded QC molecule is stable in this state. Upon adsorption in the (sub)monolayer regime, the different spectroscopies yielded identical spectra for NBD and QC at 125 and 160 K, when multilayer desorption takes place. This behavior is explained by a rapid cycloreversion of QC to NBD upon contact with the Pt surface. The NBD adsorbs in a η2 :η1 geometry with an agostic Pt-H interaction of the bridgehead CH2 subunit and the surface. Strong spectral changes are observed between 190 and 220 K because the hydrogen atom that forms the agostic bond is broke. This reaction yields a norbornadienyl intermediate species that is stable up to approximately 380 K. At higher temperatures, the molecule dehydrogenates and decomposes into smaller carbonaceous fragments.

Stimulus-Responsive Nanoporous System Based on a Redox-Active Molecular Self-Assembled Monolayer.

Ordered arrays of electrically conducting cylindrical nanotubes are created by atomic layer deposition of a thin titanium dioxide layer onto the pore walls of an anodic alumina matrix. All geometric parameters (pore length and diameter and TiO2 layer thickness) are defined and tunable experimentally. The titanium dioxide surface is subsequently functionalized with ferrocenylacetic acid. The chemisorbed ferrocene moieties are oxidized chemically and electrochemically. Monitoring the redox chemistry by UV-visible absorption spectroscopy allows for the quantification of the total density of redox-active units grafted to the surface, as well as the fraction of them oxidized at a given applied potential. The capillary properties of the surface can be adjusted by the applied potential, as quantified by contact angle measurements.

Synthesis, Characterization, and Properties of Iron(II) Spin-Crossover Molecular Photoswitches Functioning at Room Temperature.

Spin-crossover molecular switches [FeII(H2B(pz)2)2L] (L = novel phenanthroline-based ligands featuring photochromic diarylethene units; pz = 1-pyrazolyl) were synthesized and thoroughly characterized by variable-temperature X-ray crystallography, Mössbauer spectroscopy, and magnetic measurements. The effect of substituents introduced into the phenanthroline backbone (L2) and into the photochromic diarylethene unit (L3) on photophysical properties of metal-free ligands and spin-crossover iron(II) complexes 2 and 3, respectively, were investigated in detail. Both ligands and complexes could be switched with light in solution at room temperature. The photocyclization of 2 was accompanied by a high-spin to low-spin photoconversion determined at 19%. The closed-ring isomers of L3 and 3 reveal the lifetimes in the range of minutes, whereas those of L2 and 2 are thermally stable for days in solutions at room temperature. The reversibility of the photoswitching can be improved by avoiding the photostationary states. Prospective introduction of anchoring groups to the phenanthroline backbone might allow the construction of chemisorbed self-assembled monolayers of spin-crossover species switchable with light at room temperature.

A model electrode of well-defined geometry prepared by direct laser-induced decoration of nanoporous templates with Au-Ag@C nanoparticles.

We present an original type of model electrode system consisting of bimetallic Au-Ag nanoparticles embedded in an amorphous carbon matrix with an extremely well-defined geometry of parallel, straight, cylindrical macropores. The samples are prepared in one step by direct laser deposition of the metal/carbon composite onto the inner walls of a porous 'anodic' alumina matrix serving as a template. The coating is homogeneous from top to bottom of the pores, and the amount of material deposited can be tuned by the duration of the deposition procedure. As a test system, we demonstrate that a bimetallic Ag-Au@C system is catalytically active for the electrochemical oxidation of glucose in alkaline solution, the anodic reaction of a direct glucose fuel cell. Furthermore, the electrocatalytic current density increases with the amount of Ag-Au@C NPs deposited, up to a point at which the pores are clogged with it. This type of model system allows for the systematic study of geometric effects in fuel cell electrodes. It can be generalized to a number of different nanoparticle compositions, and thereby, to various electrocatalytic reactions.

Atomic Layer Deposition from Dissolved Precursors.

We establish a novel thin film deposition technique by transferring the principles of atomic layer deposition (ALD) known with gaseous precursors toward precursors dissolved in a liquid. An established ALD reaction behaves similarly when performed from solutions. "Solution ALD" (sALD) can coat deep pores in a conformal manner. sALD offers novel opportunities by overcoming the need for volatile and thermally robust precursors. We establish a MgO sALD procedure based on the hydrolysis of a Grignard reagent.

Understanding the light induced hydrophilicity of metal-oxide thin films.

Photocatalytic effects resulting in water splitting, reduction of carbon dioxide to fuels using solar energy, decomposition of organic compounds, and light-induced hydrophilicity observed on surfaces of various metal oxides (MOx), all rely on the same basic physical mechanisms, and have attracted considerable interest over the past decades. TiO2 and ZnO, two natively n-type doped wide bandgap semiconductors exhibit the effects mentioned above. In this study we propose a model for the photo-induced hydrophilicity in MOx films, and we test the model for TiO2/Si and ZnO/Si heterojunctions. Experimentally, we employ a wet exposure technique whereby the MOx surface is exposed to UV light while a water droplet is sitting on the surface, which allows for a continuous recording of contact angles during illumination. The proposed model and the experimental techniques allow a determination of minority carrier diffusion lengths by contact angle measurements and suggest design rules for materials exhibiting photocatalytic hydrophilicity. We expect that this methodology can be extended to improve our physical understanding of other photocatalytic surface effects.

Stability of Bimetallic PtxRuy - From Model Surfaces to Nanoparticulate Electrocatalysts.

Fundamental research campaigns in electrocatalysis often involve the use of model systems, such as single crystals or magnetron-sputtered thin films (single metals or metal alloys). The downsides of these approaches are that oftentimes only a limited number of compositions are picked and tested (guided by chemical intuition) and that the validity of trends is not verified under operating conditions typically present in real devices. These together can lead to deficient conclusions, hampering the direct application of newly discovered systems in real devices. In this contribution, the stability of magnetron-sputtered bimetallic PtxRuy thin film electrocatalysts (0 at. % to 100 at. % Ru content) along with three commercially available carbon-supported counterparts (50-67 at. % Ru content) was mapped under electrocatalytic conditions in acidic electrolytes using online ICP-MS. We found several differences between the two systems in the amount of metals dissolved along with the development of the morphology and composition. While the Pt-rich PtxRuy compositions remained unchanged, 30-50 nm diameter surface pits were detected in the case of the Ru-rich sputtered thin films. Contrastingly, the surface of the carbon-supported NPs enriched in Pt accompanied by the leaching of a significant amount of Ru from the alloy structure was observed. Change in morphology was accompanied by a mass loss reaching around 1-2 wt % in the case of the sputtered samples and almost 10 wt % for the NPs. Since PtxRuy has prime importance in driving alcohol oxidation reactions, the stability of all investigated alloys was screened in the presence of isopropanol. While Pt dissolution was marginally affected by the presence of isopropanol, several times higher Ru dissolution was detected, especially in the case of the Ru-rich compositions. Our results underline that trends in terms of electrocatalytic activity and stability cannot always be transferred from model samples to systems that are closer to the ones applied in real devices.

A Mild Method for the Activation of Cation Exchange Membranes Used in Tubular PEM Electrolyzers.

Co-extrusion of both half-cells in tubular PEM water electrolyzers can lower the costs for hydrogen production, since the number of components is reduced and the production process is simplified. However, after co-extrusion of the inner half-cell and the ion exchange membrane, the membrane is in its fluoride sulfonyl form and must be hydrolyzed to achieve the proton conductive sulfonic acid to be ready for use. Common practice is the hydrolysis using concentrated alkaline solutions, which causes a corrosion of the laminated anode electrode. We developed a less corrosive method using triethylsilanol as reactant. Tubular membranes hydrolyzed with this new procedure were characterized and tested in an electrolyzer laboratory test setup.

Monolithic Two-Terminal Tandem Solar Cells Using Sb2S3 and Solution-Processed PbS Quantum Dots Achieving an Open-Circuit Potential beyond 1.1 V.

Multijunction solar cells have the prospect of a greater theoretical efficiency limit than single-junction solar cells by minimizing the transmissive and thermalization losses a single absorber material has. In solar cell applications, Sb2S3 is considered an attractive absorber due to its elemental abundance, stability, and high absorption coefficient in the visible range of the solar spectrum, yet with a band gap of 1.7 eV, it is transmissive for near-IR and IR photons. Using it as the top cell (the cell where light is first incident) in a two-terminal tandem architecture in combination with a bottom cell (the cell where light arrives second) of PbS quantum dots (QDs), which have an adjustable band gap suitable for absorbing longer wavelengths, is a promising approach to harvest the solar spectrum more effectively. In this work, these two subcells are monolithically fabricated and connected in series by a poly(3,4-ethylene-dioxythiophene) polystyrene sulfonate (PEDOT:PSS)-ZnO tunnel junction as the recombination layer. We explore the surface morphology of ZnO QD films with different spin-coating conditions, which serve as the PbS QD cell's electron transport material. Furthermore, we examine the differences in photogenerated current upon varying the PbS QD absorber layer thickness and the electrical and optical characteristics of the tandem with respect to the stand-alone reference cells. This tandem architecture demonstrates an extended spectral response into the IR with an open-circuit potential exceeding 1.1 V and a power conversion efficiency of 5.6%, which is greater than that of each single-junction cell.

Ultrafast electronic relaxation pathways of the molecular photoswitch quadricyclane.

The light-induced ultrafast switching between molecular isomers norbornadiene and quadricyclane can reversibly store and release a substantial amount of chemical energy. Prior work observed signatures of ultrafast molecular dynamics in both isomers upon ultraviolet excitation but could not follow the electronic relaxation all the way back to the ground state experimentally. Here we study the electronic relaxation of quadricyclane after exciting in the ultraviolet (201 nanometres) using time-resolved gas-phase extreme ultraviolet photoelectron spectroscopy combined with non-adiabatic molecular dynamics simulations. We identify two competing pathways by which electronically excited quadricyclane molecules relax to the electronic ground state. The fast pathway (<100 femtoseconds) is distinguished by effective coupling to valence electronic states, while the slow pathway involves initial motions across Rydberg states and takes several hundred femtoseconds. Both pathways facilitate interconversion between the two isomers, albeit on different timescales, and we predict that the branching ratio of norbornadiene/quadricyclane products immediately after returning to the electronic ground state is approximately 3:2.

GD-OES Investigations of Lithium-Ion Battery Graphite Anodes: Impact of Plasma Parameters and Electrode Properties.

Due to the demand of lithium-ion battery investigations with glow discharge optical emission spectroscopy (GD-OES), a fundamental study of the influence of essential GD-OES parameters toward graphite anodes in an argon plasma was conducted and compared to previous investigations of massive materials. It is shown that increased applied voltage (500-700 V) enhances the sputtering rate by up to 100%/100 V while keeping the crater shape unaffected. In contrast to this, gas pressure variation seems to be the main tool for crater shape adjustment. Enhancement of the gas pressure (160-300 Pa) pushes the crater profile from a concave to flat shape and to concave again. Known plasma effects are discussed and correlated with the observations. A set of measuring parameters providing a good balance between the crater shape and the sputtering rate is proposed. Additionally, an increase of the duty cycle in the pulsed glow discharge mode leads to a linear increase of the sputtering rate, while a pulse duration rise enhances the sputtering rate in a nonlinear fashion. Thus, different pulsing conditions represent instruments for enhancement of the sputtering rate without affecting the crater shape significantly. Our investigation of different electrode densities shows that lower densities lead to a larger sputtered volume as well as a larger concavity of the released crater.

Current status of carbon monoxide dehydrogenases (CODH) and their potential for electrochemical applications.

Anthropogenic carbon dioxide (CO2) levels are rising to alarming concentrations in earth's atmosphere, causing adverse effects and global climate changes. In the last century, innovative research on CO2 reduction using chemical, photochemical, electrochemical and enzymatic approaches has been addressed. In particular, natural CO2 conversion serves as a model for many processes and extensive studies on microbes and enzymes regarding redox reactions involving CO2 have already been conducted. In this review we focus on the enzymatic conversion of CO2 to carbon monoxide (CO) as the chemical conversion downstream of CO production render CO particularly attractive as a key intermediate. We briefly discuss the different currently known natural autotrophic CO2 fixation pathways, focusing on the reversible reaction of CO2, two electrons and protons to CO and water, catalyzed by carbon monoxide dehydrogenases (CODHs). We then move on to classify the different type of CODHs, involved catalyzed chemical reactions and coupled metabolisms. Finally, we discuss applications of CODH enzymes in photochemical and electrochemical cells to harness CO2 from the environment transforming it into commodity chemicals.

Preparation of geometrically highly controlled Ga particle arrays on quasi-planar nanostructured surfaces as a SCALMS model system.

This study establishes a preparative route towards a model system for supported catalytically active liquid metal solutions (SCALMS) on nanostructured substrates. This model is characterized by a uniquely precise geometrical control of the gallium particle size distribution. In a SCALMS system, the Ga serves as a matrix material which can be decorated with a catalytically active material subsequently. The corresponding Ga containing precursor is spin-coated on aluminum based substrates, previously nanostructured by electrochemical anodization. The highly ordered substrates are functionalized with distinct oxide coatings by atomic layer deposition (ALD) independently from the morphology. After preparation of the metal particles on the oxide interface, the characterization of our model system in terms of its geometry parameters (droplet diameter, size distribution and population density) points to SiO2 as the best suited surface for a highly controlled geometry. This flexible model system can be functionalized with a dissolved noble metal catalyst for the application chosen.

Nature-inspired functional porous materials for low-concentration biomarker detection.

Nanostructuration is a promising tool for enhancing the performance of sensors based on electrochemical transduction. Nanostructured materials allow for increasing the surface area of the electrode and improving the limit of detection (LOD). In this regard, inverse opals possess ideal features to be used as substrates for developing sensors, thanks to their homogeneous, interconnected pore structure and the possibility to functionalize their surface. However, overcoming the insulating nature of conventional silica inverse opals fabricated via sol-gel processes is a key challenge for their application as electrode materials. In this work, colloidal assembly, atomic layer deposition and selective surface functionalization are combined to design conductive inverse opals as an electrode material for novel glucose sensing platforms. An insulating inverse opal scaffold is coated with uniform layers of conducting aluminum zinc oxide and platinum, and subsequently functionalized with glucose oxidase embedded in a polypyrrole layer. The final device can sense glucose at concentrations in the nanomolar range and is not affected by the presence of common interferents gluconolactone and pyruvate. This method may also be applied to different conductive materials and enzymes to generate a new class of highly efficient biosensors.