The interaction of size-selected Ru3 clusters with TiO2: depth-profiling of encapsulated clusters.

Ru is a metal of interest in catalysis. Monodisperse Ru3 clusters as catalytic sites are relevant for the development of catalysts because clusters use significantly lower amounts of precious materials for forming active sites due to the small size of the cluster. However, retaining the mono-dispersity of the cluster size after deposition is a challenge because surface energy could drive both agglomeration and encapsulation of the clusters. In the present work Ru3 clusters are deposited by chemical vapor deposition (CVD) of Ru3(CO)12 and cluster source depositions of bare Ru3 onto radio frequency sputter-deposited TiO2 (RF-TiO2) substrates, TiO2(100), and SiO2. When supported on RF-TiO2, bare Ru3 is encapsulated by a layer of titania substrate material during deposition with a cluster source. Ligated Ru3(CO)12 is also encapsulated by a layer of titania when deposited onto sputter-treated RF-TiO2, but only through heat treatment which is required to remove most of the ligands. The titania overlayer thickness was determined to be 1-2 monolayers for Ru3(CO)12 clusters on RF-TiO2, which is thin enough for catalytic or photocatalytic reactions to potentially occur even without clusters being part of the very outermost layer. The implication for catalysis of the encapsulation of Ru3 into the RF-TiO2 is discussed. Temperature-dependent X-ray photoelectron spectroscopy (XPS), angle-resolved XPS, and temperature-dependent low energy ion scattering (TD-LEIS) are used to probe how the cluster-surface interaction changes due to heat treatment and scanning transmission electron microscopy (STEM) was used to image the depth of the surface from side-on.

Printing and Coating Techniques for Scalable Organic Photovoltaic Fabrication.

Within recent years, there has been an increased interest towards organic photovoltaics (OPVs), especially with their significant device performance reaching beyond 19% since 2022. With these advances in the device performance of laboratory-scaled OPVs, there has also been more attention directed towards using printing and coating methods that are compatible with large-scale fabrication. Though large-area (>100 cm2) OPVs have reached an efficiency of 15%, this is still behind that of laboratory-scale OPVs. There also needs to be more focus on determining strategies for improving the lifetime of OPVs that are suitable for scalable manufacturing, as well as methods for reducing material and manufacturing costs. In this paper, we compare several printing and coating methods that are employed to fabricate OPVs, with the main focus towards the deposition of the active layer. This includes a comparison of performances at laboratory (<1 cm2), small (1-10 cm2), medium (10-100 cm2), and large (>100 cm2) active area fabrications, encompassing devices that use scalable printing and coating methods for only the active layer, as well as "fully printed/coated" devices. The article also compares the research focus of each of the printing and coating techniques and predicts the general direction that scalable and large-scale OPVs will head towards.

Au9 nanocluster adsorption and agglomeration control through sulfur modification of mesoporous TiO2.

In the present work phenyl phosphine-protected Au9 nanoclusters were deposited onto (3-mercaptopropyl) trimethoxysilane (MPTMS) modified and unmodified mesoporous screen printed TiO2. The removal of the cluster ligands by annealing was applied to enhance the interaction between Au cluster cores and semiconductor surfaces in the creation of efficient photocatalytic systems. The heat treatment could lead to undesired agglomeration of Au clusters, affecting their unique properties as size specific clusters. To address this challenge, the semiconductor surfaces were modified by MPTMS. Characterization techniques confirm the effectiveness of the modification processes, and XPS demonstrates that S functionalized MTiO2 is more efficient than MTiO2 in increasing Au9 NCs adsorption by a factor of 10 and preventing Au cluster agglomeration even after annealing. Overall, this work contributes valuable insights into photocatalytic systems through controlled modification of semiconductor surfaces and Au nanocluster deposition.

Interfacial Modification of Lithium Metal Anode by Boron Nitride Nanosheets.

Metallic lithium (Li) is the most attractive anode for Li batteries because it holds the highest theoretical specific capacity (3860 mA h g-1) and the lowest redox potential (-3.040 V vs SHE). However, the poor interface stability of the Li anode, which is caused by the high reactivity and dendrite formation of metallic Li upon cycling, leads to undesired electrochemical performance and safety issues. While two-dimensional boron nitride (BN) nanosheets have been utilized as an interfacial layer, the mechanism on how they stabilize the Li-electrolyte interface remains elusive. Here, we show how BN nanosheet interlayers suppress Li dendrite formation, enhance Li ion transport kinetics, facilitate Li deposition, and reduce electrolyte decomposition. We show through both simulation and experimental data that the desolvation process of a solvated Li ion within the interlayer nanochannels kinetically favors Li deposition. This process enables long cycling stability, reduced voltage polarization, improved interface stability, and negligible volume expansion. Their application as an interfacial layer in symmetric cells and full cells that display significantly improved electrochemical properties is also demonstrated. The knowledge gained in this study provides both critical insights and practical guidelines for designing a Li metal anode with significantly improved performance.

Specific Ion Effects at the Vapor-Formamide Interface: A Reverse Hofmeister Series in Ion Concentration Depth Profiles.

Employing neutral impact collision ion scattering spectroscopy (NICISS), we have directly measured the concentration depth profiles (CDPs) of various monovalent ions at the vapor-formamide interface. NICISS provides CDPs of individual ions by measuring the energy loss of neutral helium atoms backscattered from the solution interface. CDPs at the vapor-formamide interface of Cl-, Br-, I-, Na+, K+, and Cs+ are measured and compared to elucidate the interfacial specific ion trends. We report a reverse Hofmeister series in the presence of inorganic ions (anion and cation) at the vapor-formamide interface relative to the water-vapor interface, and the CDPs are found to be independent of the counterion for most ions studied. Thus, ions at the surface of formamide follow a "Hofmeister paradigm" where the counterion does not impact the ion series. These specific ion trends are complemented with surface tension and X-ray absorption near-edge structure (XANES) measurements on formamide electrolyte solutions.

Reduction and Diffusion of Cr-Oxide Layers into P25, BaLa4Ti4O15, and Al:SrTiO3 Particles upon High-Temperature Annealing.

Chromium oxide (Cr2O3) is a beneficial metal oxide used to prevent the backward reaction in photocatalytic water splitting. The present work investigates the stability, oxidation state, and the bulk and surface electronic structure of Cr-oxide photodeposited onto P25, BaLa4Ti4O15, and Al:SrTiO3 particles as a function of the annealing process. The oxidation state of the Cr-oxide layer as deposited is found to be Cr2O3 on the surface of P25 and Al:SrTiO3 particles and Cr(OH)3 on BaLa4Ti4O15. After annealing at 600 °C, for P25 (a mixture of rutile and anatase TiO2), the Cr2O3 layer diffuses into the anatase phase but remains at the surface of the rutile phase. For BaLa4Ti4O15, Cr(OH)3 converts to Cr2O3 upon annealing and diffuses slightly into the particles. However, for Al:SrTiO3, the Cr2O3 remains stable at the surface of the particles. The diffusion here is due to the strong metal-support interaction effect. In addition, some of the Cr2O3 on the P25, BaLa4Ti4O15, and Al:SrTiO3 particles is reduced to metallic Cr after annealing. The effect of Cr2O3 formation and diffusion into the bulk on the surface and bulk band gaps is investigated with electronic spectroscopy, electron diffraction, DRS, and high-resolution imaging. The implications of the stability and diffusion of Cr2O3 for photocatalytic water splitting are discussed.

Modification of the Surface Composition of PTB7-Th: ITIC Blend Using an Additive.

We investigated the effect of adding p-anisaldehyde (AA) solvent to the ink containing poly[[2,60-4,8-di(5-ethylhexylthienyl)benzo[1,2-b:3,3-b]dithiophene][3-fluoro-2[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl]](PTB7-Th) and 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:20,30-d0]-s-indaceno[1,2-b:5,6-b0]-dithiophene(ITIC) on the morphology of the active layer. The present study focuses on determining the effect of the additive on the compositions at the surface of the PTB7-Th: ITIC composite and its morphology, forming one side of the interface of the blend with the MoOX electrode, and the influence of the structural change on the performance of devices. Studies of device performance show that the addition of the additive AA leads to an improvement in device performance. Upon the addition of AA, the concentration of PTB7-Th at the surface of the bulk heterojunction (BHJ) increases, causing an increase in surface roughness of the surface of the BHJ. This finding contributes to an understanding of the interaction between the donor material and high work function electrode/interface material. The implications for the interface are discussed.

Effect of TiO2 Film Thickness on the Stability of Au9 Clusters with a CrOx Layer.

Radio frequency (RF) magnetron sputtering allows the fabrication of TiO2 films with high purity, reliable control of film thickness, and uniform morphology. In the present study, the change in surface roughness upon heating two different thicknesses of RF sputter-deposited TiO2 films was investigated. As a measure of the process of the change in surface morphology, chemically -synthesised phosphine-protected Au9 clusters covered by a photodeposited CrOx layer were used as a probe. Subsequent to the deposition of the Au9 clusters and the CrOx layer, samples were heated to 200 ℃ to remove the triphenylphosphine ligands from the Au9 cluster. After heating, the thick TiO2 film was found to be mobile, in contrast to the thin TiO2 film. The influence of the mobility of the TiO2 films on the Au9 clusters was investigated with X-ray photoelectron spectroscopy. It was found that the high mobility of the thick TiO2 film after heating leads to a significant agglomeration of the Au9 clusters, even when protected by the CrOx layer. The thin TiO2 film has a much lower mobility when being heated, resulting in only minor agglomeration of the Au9 clusters covered with the CrOx layer.

Ion specificity in the measured concentration depth profile of ions at the Vapor-Glycerol interface.

HYPOTHESIS: Specific ion effects are manifest universally across many systems and solvents. Whilst broad understanding of these effects is emerging particularly for bulk effects, the perturbation introduced by the interfaces are generally not understood. We hypothesise that through a careful investigation of the distribution of ions at the glycerol-vapor interface we can better understand specific ion effects in this system and at interfaces. EXPERIMENTS: Neutral impact collision ion scattering spectroscopy (NICISS) is used to obtain and compare individual ion concentration depth profiles (CDP) for a range of monovalent inorganic anions and cations at 12 glycerol electrolyte solutions surfaces. FINDINGS: The distribution of ions at the vapor - glycerol interface is non-monotonic. Broadly, anions are concentrated at the outermost region of the interface and cations are depleted from the interface. The distribution of Cl- and I- is mostly independent of the counterion. However, for Br- ions the distribution depends on the counterion where Cs+, K+, and Na+ ions lead to a desorption of Br- ions from the interface. This is favoured by the large solvation energy of Br- ions and consistent with the law of matching effective ion sizes.

Understanding specific ion effects and the Hofmeister series.

Specific ion effects (SIE), encompassing the Hofmeister Series, have been known for more than 130 years since Hofmeister and Lewith's foundational work. SIEs are ubiquitous and are observed across the medical, biological, chemical and industrial sciences. Nevertheless, no general predictive theory has yet been able to explain ion specificity across these fields; it remains impossible to predict when, how, and to what magnitude, a SIE will be observed. In part, this is due to the complexity of real systems in which ions, counterions, solvents and cosolutes all play varying roles, which give rise to anomalies and reversals in anticipated SIEs. Herein we review the historical explanations for SIE in water and the key ion properties that have been attributed to them. Systems where the Hofmeister series is perturbed or reversed are explored, as is the behaviour of ions at the liquid-vapour interface. We discuss SIEs in mixed electrolytes, nonaqueous solvents, and in highly concentrated electrolyte solutions - exciting frontiers in this field with particular relevance to biological and electrochemical applications. We conclude the perspective by summarising the challenges and opportunities facing this SIE research that highlight potential pathways towards a general predictive theory of SIE.

Surface Passivation of Sputtered NiO x Using a SAM Interface Layer to Enhance the Performance of Perovskite Solar Cells.

Sputtered NiO x (sp-NiO x ) is a preferred hole transporting material for perovskite solar cells because of its hole mobility, ease of manufacturability, good stability, and suitable Fermi level for hole extraction. However, uncontrolled defects in sp-NiO x can limit the efficiency of solar cells fabricated with this hole transporting layer. An interfacial layer has been proposed to modify the sp-NiO x /perovskite interface, which can contribute to improving the crystallinity of the perovskite film. Herein, a 2-(3,6-dimethoxy-9H-carbazol-9-yl)ethyl]phosphonic acid (MeO-2PACz) self-assembled monolayer was used to modify an sp-NiO x surface. We found that the MeO-2PACz interlayer improves the quality of the perovskite film due to an enlarged domain size, reduced charge recombination at the sp-NiO x /perovskite interface, and passivation of the defects in sp-NiO x surfaces. In addition, the band tail states are also reduced, as indicated by photothermal deflection spectroscopy, which thus indicates a reduction in defect levels. The overall outcome is an improvement in the device efficiency from 11.9% to 17.2% due to the modified sp-NiO x /perovskite interface, with an active area of 1 cm2 (certified efficiency of 16.25%). On the basis of these results, the interfacial engineering of the electronic properties of sp-NiO x /MeO-2PACz/perovskite is discussed in relation to the improved device performance.

A Review of State of the Art in Phosphine Ligated Gold Clusters and Application in Catalysis.

Atomically precise gold clusters are highly desirable due to their well-defined structure which allows the study of structure-property relationships. In addition, they have potential in technological applications such as nanoscale catalysis. The structural, chemical, electronic, and optical properties of ligated gold clusters are strongly defined by the metal-ligand interaction and type of ligands. This critical feature renders gold-phosphine clusters unique and distinct from other ligand-protected gold clusters. The use of multidentate phosphines enables preparation of varying core sizes and exotic structures beyond regular polyhedrons. Weak gold-phosphorous (Au-P) bonding is advantageous for ligand exchange and removal for specific applications, such as catalysis, without agglomeration. The aim of this review is to provide a unified view of gold-phosphine clusters and to present an in-depth discussion on recent advances and key developments for these clusters. This review features the unique chemistry, structural, electronic, and optical properties of gold-phosphine clusters. Advanced characterization techniques, including synchrotron-based spectroscopy, have unraveled substantial effects of Au-P interaction on the composition-, structure-, and size-dependent properties. State-of-the-art theoretical calculations that reveal insights into experimental findings are also discussed. Finally, a discussion of the application of gold-phosphine clusters in catalysis is presented.

Cr2O3 layer inhibits agglomeration of phosphine-protected Au9 clusters on TiO2 films.

The properties of semiconductor surfaces can be modified by the deposition of metal clusters consisting of a few atoms. The properties of metal clusters and of cluster-modified surfaces depend on the number of atoms forming the clusters. Deposition of clusters with a monodisperse size distribution thus allows tailoring of the surface properties for technical applications. However, it is a challenge to retain the size of the clusters after their deposition due to the tendency of the clusters to agglomerate. The agglomeration can be inhibited by covering the metal cluster modified surface with a thin metal oxide overlayer. In the present work, phosphine-protected Au clusters, Au9(PPh3)8(NO3)3, were deposited onto RF-sputter deposited TiO2 films and subsequently covered with a Cr2O3 film only a few monolayers thick. The samples were then heated to 200 °C to remove the phosphine ligands, which is a lower temperature than that required to remove thiolate ligands from Au clusters. It was found that the Cr2O3 covering layer inhibited cluster agglomeration at an Au cluster coverage of 0.6% of a monolayer. When no protecting Cr2O3 layer was present, the clusters were found to agglomerate to a large degree on the TiO2 surface.

Influence of TiO2 surface defects on the adsorption of N719 dye molecules.

Surface defects influence the dye adsorption on TiO2 used as a substrate in dye-sensitized solar cells (DSSCs). In this study, we have used different Ar+ sputtering doses to create a controlled density of defects on a TiO2 surface exposed to different pre-heating temperatures in order to analyse the influence of defects on the N719 dye adsorption. TiO2 was pre-treated using two different treatments. The first treatment involved heating to 200 °C with subsequent sputtering at different doses. The second treatment included heating only, but at four different temperatures starting at 200 °C. After the pre-treatments, the TiO2 samples were immersed into an N719 dye solution for 24 hours at room temperature to dye the TiO2 substrates. The amount of Ti3+ surface defects introduced by the different pre-treatments and their influence on dye adsorption onto the TiO2 surface were examined by X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS) and metastable induced electron spectroscopy (MIES). Neutral impact collision ion scattering spectroscopy (NICISS) was used to determine the coverage of the TiO2 surface by adsorbed dye molecules. It was found that Ti3+ surface defects were formed by Ar+ sputtering but not by pre-treatment through heating alone. MIES analysis of the outer-most layer and density of states calculations show that the thiocyanate ligand of the N719 dye becomes directed away from the TiO2 surface. Both XPS and NICISS results indicate that the amount of adsorbed N719 dye decreases with increasing density of Ti3+ surface defects. Thus, the generation of surface defects reduces the ability of the TiO2 surface to adsorb the dye molecules. Heating alone as pre-treatment of the TiO2 substrates instead increases the dye adsorption, without causing detectable defects on the TiO2 surface.

Carbonisation of a polymer made from sulfur and canola oil.

A polymer made from equal masses of sulfur and canola oil was carbonised at 600 °C for 30 minutes. The resulting material exhibited improved uptake of mercury from water compared to the polymer. The carbonisation could also be done after using the polymer to clean up oil spills, which suprisingly improved mercury uptake to levels rivaling commercial carbons.

Creation of High-Performance Heterogeneous Photocatalysts by Controlling Ligand Desorption and Particle Size of Gold Nanocluster.

Recently, the creation of new heterogeneous catalysts using the unique electronic/geometric structures of small metal nanoclusters (NCs) has received considerable attention. However, to achieve this, it is extremely important to establish methods to remove the ligands from ligand-protected metal NCs while preventing the aggregation of metal NCs. In this study, the ligand-desorption process during calcination was followed for metal-oxide-supported 2-phenylethanethiolate-protected gold (Au) 25-atom metal NCs using five experimental techniques. The results clearly demonstrate that the ligand-desorption process consists of ligand dissociation on the surface of the metal NCs, adsorption of the generated compounds on the support and desorption of the compounds from the support, and the temperatures at which these processes occurred were elucidated. Based on the obtained knowledge, we established a method to form a metal-oxide layer on the surface of Au NCs while preventing their aggregation, thereby succeeding in creating a water-splitting photocatalyst with high activity and stability.

Au101-rGO nanocomposite: immobilization of phosphine-protected gold nanoclusters on reduced graphene oxide without aggregation.

Graphene supported transition metal clusters are of great interest for potential applications, such as catalysis, due to their unique properties. In this work, a simple approach to deposit Au101(PPh3)21Cl5 (Au101NC) on reduced graphene oxide (rGO) via an ex situ method is presented. Reduction of graphene oxide at native pH (pH ≈ 2) to rGO was performed under aqueous hydrothermal conditions. Decoration of rGO sheets with controlled content of 5 wt% Au was accomplished using only pre-synthesised Au101NC and rGO as precursors and methanol as solvent. High resolution scanning transmission electron microscopy indicated that the cluster size did not change upon deposition with an average diameter of 1.4 ± 0.4 nm. It was determined that the rGO reduction method was crucial to avoid agglomeration, with rGO reduced at pH ≈ 11 resulting in agglomeration. X-ray photoelectron spectroscopy was used to confirm the deposition of Au101NCs and show the presence of triphenyl phosphine ligands, which together with attenuated total reflectance Fourier transform infrared spectroscopy, advocates that the deposition of Au101NCs onto the surface of rGO was facilitated via non-covalent interactions with the phenyl groups of the ligands. Inductively coupled plasma mass spectrometry and thermogravimetric analysis were used to determine the gold loading and both agree with a gold loading of ca. 4.8-5 wt%. The presented simple and mild strategy demonstrates that good compatibility between size-specific phosphine protected gold clusters and rGO can prevent aggregation of the metal clusters. This work contributes towards producing an agglomeration-free synthesis of size-specific ligated gold clusters on rGO that could have wide range of applications.

Composition and properties of RF-sputter deposited titanium dioxide thin films.

The photocatalytic properties of titania (TiO2) have prompted research utilising its useful ability to convert solar energy into electron-hole pairs to drive novel chemistry. The aim of the present work is to examine the properties required for a synthetic method capable of producing thin TiO2 films, with well defined, easily modifiable characteristics. Presented here is a method of synthesis of TiO2 nanoparticulate thin films generated using RF plasma capable of homogenous depositions with known elemental composition and modifiable properties at a far lower cost than single-crystal TiO2. Multiple depositions regimes were examined for their effect on overall chemical composition and to minimise the unwanted contaminant, carbon, from the final film. The resulting TiO2 films can be easily modified through heating to further induce defects and change the electronic structure, crystallinity, surface morphology and roughness of the deposited thin film.

The interaction of size-selected Ru3 clusters with RF-deposited TiO2: probing Ru-CO binding sites with CO-temperature programmed desorption.

Small Ru clusters are efficient catalysts for chemical reactions such as CO hydrogenation. In this study 3-atom Ru3 clusters were deposited onto radio frequency (RF)-deposited TiO2 which is an inexpensive, nanoparticulate form of TiO2. TiO2 substrates are notable in that they form strong metal-substrate interactions with clusters. Using temperature programmed desorption to probe Ru-CO binding sites, and X-ray photoelectron spectroscopy to provide chemical information on clusters, differences in cluster-support interactions were studied for Ru3 deposited using both an ultra-high vacuum cluster source and chemical vapour deposition of Ru3(CO)12. The TiO2 was treated with different Ar+ sputter doses prior to cluster depositions, and SiO2 was also used as a comparison substrate. For cluster source-deposited Ru3, heating to 800 K caused cluster agglomeration on SiO2 and oxidation on non-sputtered TiO2. For cluster source-deposited Ru3 on sputtered TiO2 substrates, all Ru-CO binding sites were blocked as-deposited and it was concluded that for the binding sites to be preserved for potential catalytic benefit, sputtering of TiO2 before cluster deposition cannot be applied. Conversely, for Ru3(CO)12 on sputtered TiO2 the clusters were protected by their ligands and Ru-CO binding sites were only blocked once the sample was heated to 723 K. The mechanism for complete blocking of CO sites on sputtered TiO2 could not be directly determined; however, comparisons to the literature indicate that the likely reasons for blocking of the CO adsorption sites are encapsulation into the TiO x layer reduced through sputtering and also partial oxidation of the Ru clusters.

Cyclic Copper Uptake and Release from Natural Seawater-A Fully Sustainable Antifouling Technique to Prevent Marine Growth.

Unwanted growth of fouling organisms on underwater surfaces is an omnipresent challenge for the marine industry, costing billions of dollars every year in the transportation sector alone. Copper, the most widely used biocide in antifouling paints, is at the brink of a total ban in being used in antifouling coatings, as it has become an existential threat to nontargeted species due to anthropogenic copper inputs into protected waters. In the current study, using a porous and cross-linked poly(ethylene imine) structure under marine and fouling environments, available copper from natural seawater was absorbed and electrochemically released back as a potent biocide at 1.3 V vs Ag|AgCl, reducing marine growth by 94% compared to the control electrode (coupon) at 0 V. The coating can also function as an electrochemical copper sensor enabling real-time monitoring of the electrochemical uptake and release of copper ions from natural seawater. This allows tailoring of the electrochemical program to the changing marine environments, i.e., when the vessels move from high-copper-contaminated waters to coastal regions with low concentrations of copper.