Noise Tailoring in Memristive Filaments.

In this study, the possibilities of noise tailoring in filamentary resistive switching memory devices are investigated. To this end, the resistance and frequency scaling of the low-frequency 1/f-type noise properties are studied in representative mainstream material systems. It is shown that the overall noise floor is tailorable by the proper material choice, as demonstrated by the order-of-magnitude smaller noise levels in Ta2O5 and Nb2O5 transition-metal oxide memristors compared to Ag-based devices. Furthermore, the variation of the resistance states allows orders-of-magnitude tuning of the relative noise level in all of these material systems. This behavior is analyzed in the framework of a point-contact noise model highlighting the possibility for the disorder-induced suppression of the noise contribution arising from remote fluctuators. These findings promote the design of multipurpose resistive switching units, which can simultaneously serve as analog-tunable memory elements and tunable noise sources in probabilistic computing machines.

Carrier-Induced Modification of Palladium Nanoparticles on Porous Boron Nitride for Alkyne Semi-Hydrogenation.

Chemical modifiers enhance the efficiency of metal catalysts in numerous applications, but their introduction often involves toxic or expensive precursors and complicates the synthesis. Here, we show that a porous boron nitride carrier can directly modify supported palladium nanoparticles, originating unparalleled performance in the continuous semi-hydrogenation of alkynes. Analysis of the impact of various structural parameters reveals that using a defective high surface area boron nitride and ensuring a palladium particle size of 4-5 nm is critical for maximizing the specific rate. The combined experimental and theoretical analyses point towards boron incorporation from defects in the support to the palladium subsurface, creating the desired isolated ensembles determining the selectivity. This practical approach highlights the unexplored potential of using tailored carriers for catalyst design.

Nanostructuring unlocks high performance of platinum single-atom catalysts for stable vinyl chloride production.

A worldwide replacement of the toxic mercuric chloride catalyst in vinyl chloride manufacture via acetylene hydrochlorination is slowed down by the limited durability of alternative catalytic systems at high space velocities. Here, we demonstrate that platinum single atoms on carbon carriers are substantially more stable (up to 1073 K) than their gold counterparts (up to 473 K), enabling facile and scalable preparation and precise tuning of their coordination environment by simple temperature control. By combining kinetic analysis, advanced characterisation, and density functional theory, we assess how the Pt species determines the catalytic performance and thereby identify Pt(II)-Cl as the active site, being three times more active than Pt nanoparticles. Remarkably, we show that Pt single atoms exhibit outstanding stability in acetylene hydrochlorination and surpass the space-time-yields of their gold-based analogues after 25 h time-on-stream, qualifying as candidate for sustainable vinyl chloride production.

Atom-by-Atom Resolution of Structure-Function Relations over Low-Nuclearity Metal Catalysts.

Controlling the structure sensitivity of catalyzed reactions over metals is central to developing atom-efficient chemical processes. Approaching the minimum ensemble size, the properties enter a non-scalable regime in which each atom counts. Almost all trends in this ultra-small frontier derive from surface science approaches using model systems, because of both synthetic and analytical challenges. Exploiting the unique coordination chemistry of carbon nitride, we discriminate through experiments and simulations the interplay between the geometry, electronic structure, and reactivity of palladium atoms, dimers, and trimers. Catalytic tests evidence application-dependent requirements of the active ensemble. In the semi-hydrogenation of alkynes, the nuclearity primarily impacts activity, whereas the selectivity and stability are affected in Suzuki coupling. This powerful approach will provide practical insights into the design of heterogeneous catalysts comprising well-defined numbers of atoms.

Corrosion fatigue in DLC-coated articulating implants: an accelerated methodology to predict realistic interface lifetime.

We present a methodology to accelerate and estimate the lifetime of an interlayer under dynamic loading in body-like media. It is based on accelerating corrosion fatigue processes taking place at the buried interface of a Si-based adhesion-promoting interlayer in articulating implants on a CoCrMo biomedical alloy; the implants are coated with diamond-like carbon (DLC). The number of interface loading cycles to delamination is determined by reciprocal loading in corrosive fluid. Its dependence on the load is summarized in a Wöhler-like curve of a DLC/DLC-Si/CoCrMo system in body working conditions: cyclic stresses at 37 °C in phosphate buffered saline (PBS). The presence of oxygen as a contaminant strongly affects the lifetime of the interface under corrosion fatigue. The main parameters acting on the prediction, with a special emphasis on simulated in vivo conditions, are analyzed and discussed: the media (PBS, Milli-Q water, NaCl, Ringers' solution and bovine calf serum), the load, the frequency and the composition of the interface determined by X-ray photoelectron spectroscopy.

Controlling the speciation and reactivity of carbon-supported gold nanostructures for catalysed acetylene hydrochlorination.

Carbon-supported gold catalysts have the potential to replace the toxic mercuric chloride-based system applied industrially for acetylene hydrochlorination, a key technology for the manufacture of polyvinyl chloride. However, the design of an optimal catalyst is essentially hindered by the difficulties in assessing the nature of the active site. Herein, we present a platform of carbon supported gold nanostructures at a fixed metal loading, ranging from single atoms of tunable oxidation state and coordination to metallic nanoparticles, by varying the structure of functionalised carbons and use of thermal activation. While on activated carbon particle aggregation occurs progressively above 473 K, on nitrogen-doped carbon gold single atoms exhibit outstanding stability up to temperatures of 1073 K and under reaction conditions. By combining steady-state experiments, density functional theory, and transient mechanistic studies, we assess the relation between the metal speciation, electronic properties, and catalytic activity. The results indicate that the activity of gold-based catalysts correlates with the population of Au(i)Cl single atoms and the reaction follows a Langmuir-Hinshelwood mechanism. Strong interaction with HCl and thermodynamically favoured acetylene activation were identified as the key features of the Au(i)Cl sites that endow their superior catalytic performance in comparison to N-stabilised Au(iii) counterparts and gold nanoparticles. Finally, we show that the carrier (activated carbon versus nitrogen-doped carbon) does not affect the catalytic response, but determines the deactivation mechanism (gold particle aggregation and pore blockage, respectively), which opens up different options for the development of stable, high-performance hydrochlorination catalysts.

In situ impedance matching in Nb/Nb2O5/PtIr memristive nanojunctions for ultra-fast neuromorphic operation.

The dynamical aspects of bipolar resistive switchings have been investigated in Nb/Nb2O5/PtIr nanojunctions. We found that the widely tuneable ON and OFF state resistances are well separated at low bias. On the other hand, the high-bias regime of the resistive switchings coincides with the onset of a high nonlinearity in the current-voltage characteristics, where the impedance of both states rapidly decreases and becomes equivalent around 50 Ω. This phenomenon enables the overriding of the RC limitations of fast switchings between higher resistance ON and OFF states. Consequently, nanosecond switching times between multiple resistance states due to subnanosecond voltage pulses are demonstrated. Moreover, this finding provides the possibility of impedance engineering by the appropriate choice of voltage signals, which facilitates that both the set and reset transitions take place in an impedance matched manner to the surrounding circuit, demonstrating the merits of ultra-fast operation of Nb2O5 based neuromorphic networks.

Selective ensembles in supported palladium sulfide nanoparticles for alkyne semi-hydrogenation.

Ensemble control has been intensively pursued for decades to identify sustainable alternatives to the Lindlar catalyst (PdPb/CaCO3) applied for the partial hydrogenation of alkynes in industrial organic synthesis. Although the geometric and electronic requirements are known, a literature survey illustrates the difficulty of transferring this knowledge into an efficient and robust catalyst. Here, we report a simple treatment of palladium nanoparticles supported on graphitic carbon nitride with aqueous sodium sulfide, which directs the formation of a nanostructured Pd3S phase with controlled crystallographic orientation, exhibiting unparalleled performance in the semi-hydrogenation of alkynes in the liquid phase. The exceptional behavior is linked to the multifunctional role of sulfur. Apart from defining a structure integrating spatially-isolated palladium trimers, the active ensembles, the modifier imparts a bifunctional mechanism and weak binding of the organic intermediates. Similar metal trimers are also identified in Pd4S, evidencing the pervasiveness of these selective ensembles in supported palladium sulfides.

Elucidating the Distribution and Speciation of Boron and Cesium in BCsX Zeolite Catalysts for Styrene Production.

An improved understanding of the nature and distribution of boron and cesium species in BCsX zeolites is a prerequisite to guide future developments in the environmentally attractive, yet challenging, production of styrene through the side-chain alkylation of toluene with methanol. Herein, standard characterization and catalytic tests are complemented by integrated visualization through time-of-flight secondary-ion mass spectrometry and energy-dispersive X-ray spectroscopy and detailed assessment by 133 Cs and 11 B NMR spectroscopy, to correlate the properties and performance during successive ion-exchange and impregnation steps in the preparation of both powders and millimeter-sized granules. The results highlight a significant impact of catalyst scaleup on the effective introduction of boron species, which originates chemical heterogeneity that is linked to selectivity losses. They also illustrate the complexity of elucidating the role of this promotor, which interacts with cesium cations and exhibits different coordination states and chemical environments, depending on the pretreatment.

Europium Oxybromide Catalysts for Efficient Bromine Looping in Natural Gas Valorization.

The industrialization of bromine-mediated natural gas upgrading is contingent on the ability to fully recycle hydrogen bromide (HBr), which is the end form of the halogen after the activation and coupling of the alkanes. Europium oxybromide (EuOBr) is introduced as a unique catalytic material to close the bromine loop via HBr oxidation, permitting low-temperature operation and long lifetimes with a stoichiometric feed (O2 :HBr=0.25)-conditions at which any catalyst reported to date severely deactivates because of excessive bromination. Besides, EuOBr exhibits unparalleled selectivity to methyl bromide in methane oxybromination, which is an alternative route for bromine looping. This novel active phase is finely dispersed on appropriate carriers and scaled up to technical extrudates, enhancing the utilization of the europium phase while preserving the performance. This catalytic system paves the way for sustainable valorization of stranded natural gas via bromine chemistry.

Solvothermally-Prepared Cu2 O Electrocatalysts for CO2 Reduction with Tunable Selectivity by the Introduction of p-Block Elements.

The electroreduction of CO2 to fuels and chemicals is an attractive strategy for the valorization of CO2 emissions. In this study, a Cu2 O electrocatalyst prepared by a simple and potentially scalable solvothermal route effectively targeted CO evolution at low-to-moderate overpotentials [with a current efficiency for CO (CECO ) of ca. 60 % after 12 h at -0.6 V vs. reversible hydrogen electrode, RHE], and its selectivity was tuned by the introduction of p-block elements (In, Sn, Ga, Al) into the catalyst. SEM, HRTEM, and voltammetric analyses revealed that the Cu2 O catalyst undergoes extensive surface restructuring (favorable for CO evolution) under the reaction conditions. The modification of Cu2 O with Sn and In further enhanced the current efficiency (CE) for CO (ca. 75 % after 12 h at -0.6 V). In contrast, the introduction of Al altered the selectivity profile of the catalyst significantly, decreasing the selectivity toward CO but promoting the reduction of CO2 to ethylene (CE≈7 %), n-propanol, and ethanol (CE≈2 % each) at -0.8 V vs. RHE. This result is related to a decreased reducibility of Al-doped Cu2 O that might preserve Cu+ species (favorable for C2 H4 production) under the reaction conditions, which is supported by XRD, X-ray photoelectron spectroscopy, and H2 temperature-programmed reduction observations.

Exclusively Gas-Phase Passivation of Native Oxide-Free Silicon(100) and Silicon(111) Surfaces.

Reactions in the gas phase are of primary technological importance for applications in nano- and microfabrication technology and in the semiconductor industry. We present exclusively gas-phase protocols to chemically passivate oxide-free Si(111) and Si(100) surfaces with short-chain alkynes. The resulting surfaces showed equal or better oxidation resistance than most existing liquid-phase-derived surfaces and rivaled the outstanding stability of a full-coverage Si(111)-propenyl surface.1,2 The most stable surface (Si(111)-ethenyl) grew one-fifth of a monolayer of oxide (0.04 nm) after 1 month of air exposure. We monitored the regrowth of oxides on passivated Si(111) and Si(100) surfaces by X-ray photoelectron spectroscopy (XPS) and observed a significant crystal-orientation dependence of initial rates when total oxide thickness was below approximately one monolayer (0.2 nm). This difference was correlated with the desorption kinetics of residual surface Si-F bonds formed during HF treatment. We discuss applications of the technology and suggest future directions for process optimization.

Indium Oxide as a Superior Catalyst for Methanol Synthesis by CO2 Hydrogenation.

Methanol synthesis by CO2 hydrogenation is attractive in view of avoiding the environmental implications associated with the production of the traditional syngas feedstock and mitigating global warming. However, there still is a lack of efficient catalysts for such alternative processes. Herein, we unveil the high activity, 100 % selectivity, and remarkable stability for 1000 h on stream of In2 O3 supported on ZrO2 under industrially relevant conditions. This strongly contrasts to the benchmark Cu-ZnO-Al2 O3 catalyst, which is unselective and experiences rapid deactivation. In-depth characterization of the In2 O3 -based materials points towards a mechanism rooted in the creation and annihilation of oxygen vacancies as active sites, whose amount can be modulated in situ by co-feeding CO and boosted through electronic interactions with the zirconia carrier. These results constitute a promising basis for the design of a prospective technology for sustainable methanol production.

Differences between individual ZSM-5 crystals in forming hollow single crystals and mesopores during base leaching.

After base treatment of ZSM-5 crystals below 100 nm in size, TEM shows hollow single crystals with a 10 nm shell. SEM images confirm that the shell is well- preserved even after prolonged treatment. Determination of the Si/Al ratios with AAS and XPS in combination with argon sputtering reveals aluminum zoning of the parent zeolite, and the total pore volume increases in the first two hours of base treatment. In corresponding TEM images, the amount of hollow crystals are observed to increase during the first two hours of base treatment, and intact crystals are visible even after 10 h of leaching; these observations indicate different dissolution rates between individual crystals. TEM of large, commercially available ZSM-5 crystals shows inhomogeneous distribution of mesopores among different crystals, which points to the existence of structural differences between individual crystals. Only tetrahedrally coordinated aluminum is detected with (27) Al MAS NMR after the base leaching of nano-sized ZSM-5.

On interlayer stability and high-cycle simulator performance of diamond-like carbon layers for articulating joint replacements.

Diamond like carbon (DLC) coatings have been proven to be an excellent choice for wear reduction in many technical applications. However, for successful adaption to the orthopaedic field, layer performance, stability and adhesion in physiologically relevant setups are crucial and not consistently investigated. In vitro wear testing as well as adequate corrosion tests of interfaces and interlayers are of great importance to verify the long term stability of DLC coated load bearing implants in the human body. DLC coatings were deposited on articulating lumbar spinal disks made of CoCr28Mo6 biomedical implant alloy using a plasma-activated chemical vapor deposition (PACVD) process. As an adhesion promoting interlayer, tantalum films were deposited by magnetron sputtering. Wear tests of coated and uncoated implants were performed in physiological solution up to a maximum of 101 million articulation cycles with an amplitude of ±2° and -3/+6° in successive intervals at a preload of 1200 N. The implants were characterized by gravimetry, inductively coupled plasma optical emission spectrometry (ICP-OES) and cross section scanning electron microscopy (SEM) analysis. It is shown that DLC coated surfaces with uncontaminated tantalum interlayers perform very well and no corrosive or mechanical failure could be observed. This also holds true in tests featuring overload and third-body wear by cortical bone chips present in the bearing pairs. Regarding the interlayer tolerance towards interlayer contamination (oxygen), limits for initiation of potential failure modes were established. It was found that mechanical failure is the most critical aspect and this mode is hypothetically linked to the α-ß tantalum phase switch induced by increasing oxygen levels as observed by X-ray diffraction (XRD). It is concluded that DLC coatings are a feasible candidate for near zero wear articulations on implants, potentially even surpassing the performance of ceramic vs. ceramic.

Wear mechanisms in metal-on-metal bearings: the importance of tribochemical reaction layers.

Metal-on-metal (MoM) bearings are at the forefront in hip resurfacing arthroplasty. Because of their good wear characteristics and design flexibility, MoM bearings are gaining wider acceptance with market share reaching nearly 10% worldwide. However, concerns remain regarding potential detrimental effects of metal particulates and ion release. Growing evidence is emerging that the local cell response is related to the amount of debris generated by these bearing couples. Thus, an urgent clinical need exists to delineate the mechanisms of debris generation to further reduce wear and its adverse effects. In this study, we investigated the microstructural and chemical composition of the tribochemical reaction layers forming at the contacting surfaces of metallic bearings during sliding motion. Using X-ray photoelectron spectroscopy and transmission electron microscopy with coupled energy dispersive X-ray and electron energy loss spectroscopy, we found that the tribolayers are nanocrystalline in structure, and that they incorporate organic material stemming from the synovial fluid. This process, which has been termed "mechanical mixing," changes the bearing surface of the uppermost 50 to 200 nm from pure metallic to an organic composite material. It hinders direct metal contact (thus preventing adhesion) and limits wear. This novel finding of a mechanically mixed zone of nanocrystalline metal and organic constituents provides the basis for understanding particle release and may help in identifying new strategies to reduce MoM wear.

A quantitative in vitro method to predict the adhesion lifetime of diamond-like carbon thin films on biomedical implants.

A quantitative method using Rockwell C indentation was developed to study the adhesion of diamond-like carbon (DLC) protective coatings to the CoCrMo biomedical implant alloy when immersed in phosphate-buffered saline (PBS) solution at 37 degrees C. Two kinds of coatings with thicknesses ranging from 0.5 up to 16 microns were investigated, namely DLC and DLC/Si-DLC, where Si-DLC denotes a 90 nm thick DLC interlayer containing Si. The time-dependent delamination of the coating around the indentation was quantified by means of optical investigations of the advancing crack front and calculations of the induced stress using the finite element method (FEM). The cause of delamination for both types of coatings was revealed to be stress-corrosion cracking (SCC) of the interface material. For the DLC coating a typical SCC behavior was observed, including a threshold region (60J m(-2)) and a "stage 1" crack propagation with a crack-growth exponent of 3.0, comparable to that found for ductile metals. The DLC/Si-DLC coating exhibits an SCC process with a crack-growth exponent of 3.3 and a threshold region at 470 Jm(-2), indicating an adhesion in PBS at 37 degrees C that is about eight times better than that of the DLC coating. The SCC curves were fitted to the reaction controlled model typically used to explain the crack propagation in bulk soda lime glass. As this model falls short of accurately describing all the SCC curves, limitations of its application to the interface between a brittle coating and a ductile substrate are discussed.

Probing the interface in vapor-deposited bimetallic Pd-Au and Pt-Au films by CO adsorption from the liquid phase.

Bimetallic Pd-Au and Pt-Au and monometallic Pd, Pt, and Au films were prepared by physical vapor deposition. The resulting surfaces were characterized by means of XPS, AFM, and CO adsorption from the liquid phase (CH2Cl2) monitored by ATR-IR spectroscopy. CO adsorption combined with ATR-IR proved to be a very sensitive method for probing the degree of interdiffusion occurring at the interfaces whose properties were altered by variation of the Pd and Pt film thickness from 0.2 to 2 nm. Because no CO adsorption was observed on Au, the evaporation of Pt-group metals on Au allowed us to study the effect of dilution on the adsorption properties of the surfaces. At equivalent Pd film thickness, the evaporation of Au reduced the amount of adsorbed CO and caused the formation of 2-fold bridging CO, which was almost absent in monometallic surfaces. Additionally, the average particle size on Pd-Au surfaces was smaller than that on monometallic Pd surfaces. The results indicate that a Pd/Au diffuse interface is formed that affects the Pd particle size even more drastically than the simple decrease in Pd film thickness in monometallic surfaces. Pt-Au surfaces were less sensitive to CO adsorption, indicating that the two metals do not mix to a significant extent. The difference in the interfacial behavior of Pd and Pt in the bimetallic gold films is traced to the largely different Pd-Au and Pt-Au miscibility gaps.

In vitro studies on the effect of delaminated a-C:H film fragments on bone marrow cell cultures.

Amorphous hydrogenated carbon (a-C:H) films have many outstanding properties required for a protective coating material on load bearing medical implants. Recently, titanium doped a-C:H films have been evaluated regarding their effects on bone marrow cell cultures. But many materials that are well-tolerated in bulk form are able to induce toxic reaction if present particulate form. In order to further assess biocompatibility aspects of these two coatings, film delamination has been mimicked in exposure to fluids. In the present study, particles from a-C:H, a-C:H/Ti and a-C:H-a-C:H/Ti bilayer films were added to bone marrow cell cultures in vitro. The results showed that plain a-C:H and to a certain extent a-CH/Ti particles were inert. Both kinds of particles did not significantly stimulate the osteoclast-related enzyme tartrate resistant acid phosphatase (TRAP). A slight increase in cell proliferation and total culture TRAP was found in cultures treated by a-C:H-a-C:H/Ti bilayer films. Latter effect can probably be traced back by the relative high percentage of small particles of a size of around 2 microm. However, if corrected by the cell number also no differences between particle-treated and untreated control cultures could be found, indicating the absence of a toxic effect from delaminated a-C:H coatings.