Au@AuPd Core-Alloyed Shell Nanoparticles for Enhanced Electrocatalytic Activity and Selectivity under Visible Light Excitation.

Plasmonic catalysis has been employed to enhance molecular transformations under visible light excitation, leveraging the localized surface plasmon resonance (LSPR) in plasmonic nanoparticles. While plasmonic catalysis has been employed for accelerating reaction rates, achieving control over the reaction selectivity has remained a challenge. In addition, the incorporation of catalytic components into traditional plasmonic-catalytic antenna-reactor nanoparticles often leads to a decrease in optical absorption. To address these issues, this study focuses on the synthesis of bimetallic core@shell Au@AuPd nanoparticles (NPs) with ultralow loadings of palladium (Pd) into gold (Au) NPs. The goal is to achieve NPs with an Au core and a dilute alloyed shell containing both Au and Pd, with a low Pd content of around 10 atom %. By employing the (photo)electrocatalytic nitrite reduction reaction (NO2RR) as a model transformation, experimental and theoretical analyses show that this design enables enhanced catalytic activity and selectivity under visible light illumination. We found that the optimized Pd distribution in the alloyed shell allowed for stronger interaction with key adsorbed species, leading to improved catalytic activity and selectivity, both under no illumination and under visible light excitation conditions. The findings provide valuable insights for the rational design of antenna-reactor plasmonic-catalytic NPs with controlled activities and selectivity under visible light irradiation, addressing critical challenges to enable sustainable molecular transformations.

Ultralow Catalytic Loading for Optimised Electrocatalytic Performance of AuPt Nanoparticles to Produce Hydrogen and Ammonia.

The hydrogen evolution and nitrite reduction reactions are key to producing green hydrogen and ammonia. Antenna-reactor nanoparticles hold promise to improve the performances of these transformations under visible-light excitation, by combining plasmonic and catalytic materials. However, current materials involve compromising either on the catalytic activity or the plasmonic enhancement and also lack control of reaction selectivity. Here, we demonstrate that ultralow loadings and non-uniform surface segregation of the catalytic component optimize catalytic activity and selectivity under visible-light irradiation. Taking Pt-Au as an example we find that fine-tuning the Pt content produces a 6-fold increase in the hydrogen evolution compared to commercial Pt/C as well as a 6.5-fold increase in the nitrite reduction and a 2.5-fold increase in the selectivity for producing ammonia under visible light excitation relative to dark conditions. Density functional theory suggests that the catalytic reactions are accelerated by the intimate contact between nanoscale Pt-rich and Au-rich regions at the surface, which facilitates the formation of electron-rich hot-carrier puddles associated with the Pt-based active sites. The results provide exciting opportunities to design new materials with improved photocatalytic performance for sustainable energy applications.

Reductive Thermal Atomic Layer Deposition Process for Gold.

In this work, we developed an atomic layer deposition (ALD) process for gold metal thin films from chloro(triethylphosphine)gold(I) [AuCl(PEt3)] and 1,4-bis(trimethylgermyl)-1,4-dihydropyrazine [(Me3Ge)2DHP]. High purity gold films were deposited on different substrate materials at 180 °C for the first time with thermal reductive ALD. The growth rate is 1.7 Å/cycle after the film reaches full coverage. The films have a very low resistivity close to the bulk value, and a minimal amount of impurities could be detected. The reaction mechanism of the process is studied in situ with a quartz crystal microbalance and a quadrupole mass spectrometer.

Atomic layer deposition of PbCl2, PbBr2 and mixed lead halide (Cl, Br, I) PbXnY2-n thin films.

Atomic layer deposition offers outstanding film uniformity and conformality on substrates with high aspect ratio features. These qualities are essential for mixed-halide perovskite films applied in tandem solar cells, transistors and light-emitting diodes. The optical and electronic properties of mixed-halide perovskites can be adjusted by adjusting the ratios of different halides. So far ALD is only capable of depositing iodine-based halide perovskites whereas other halide processes are lacking. We describe six new low temperature (≤100 °C) ALD processes for PbCl2 and PbBr2 that are crucial steps for the deposition of mixed-halide perovskites with ALD. Lead bis[bis(trimethylsilyl)amide]-GaCl3 and -TiBr4 processes yield the purest, crystalline, uniform and conformal films of PbCl2 and PbBr2 respectively. We show that these two processes in combination with a PbI2 process from the literature deposit mixed lead halide films. The four less optimal processes revealed that reaction by-products in lead halide deposition processes may cause film etching or incorporate themselves into the film.

A low-temperature thermal ALD process for nickel utilizing dichlorobis(triethylphosphine)nickel(II) and 1,4-bis(trimethylgermyl)-1,4-dihydropyrazine.

In this work, we developed a new ALD process for nickel metal from dichlorobis(triethylphosphine)nickel(II) (NiCl2(PEt3)2) and 1,4-bis(trimethylgermyl)-1,4-dihydropyrazine ((Me3Ge)2DHP). A series of phosphine adducts of nickel and cobalt halides were synthesized and characterized for their volatility and thermal stability. Also (Me3Ge)2DHP is a novel reducing agent in ALD. Smooth nickel films were deposited on different substrate materials at 110 °C, which is the lowest deposition temperature for Ni metal found in the literature. The growth rate is 0.2 Å per cycle when the film is not continuous and decreases to 0.1 Å per cycle after the film becomes pinhole-free. Besides a small amount (7 at%) of carbidic carbon, the films have only small amounts of impurities. Most notably, the chlorine content is below 0.2 at%, indicating efficient reduction. Furthermore, we think that (Me3Ge)2DHP can open new avenues for the ALD of other metals at low temperatures.

Deposition of Intact and Active Proteins In Vacuo Using Large Argon Cluster Ion Beams.

Providing inert materials with a biochemical function, for example using proteins, is a cornerstone technology underlying many applications. However, the controlled construction of protein thin films remains a major challenge. Here, an innovative solvent-free approach for protein deposition is reported, using lysozyme as a model. By diverting a time-of-flight secondary ion mass spectrometer (ToF-SIMS) from its standard analytical function, large argon clusters were used to achieve protein transfer. A target consisting of a pool of proteins was bombarded with 10 keV Ar5000+ ions, and the ejected proteins were collected on a silicon wafer. The ellipsoidal deposition pattern was evidenced by ToF-SIMS analysis, while SDS-PAGE electrophoresis confirmed the presence of intact lysozyme on the collector. Finally, enzymatic activity assays demonstrated the preservation of the three-dimensional structure of the transferred proteins. These results pave the way to well-controlled protein deposition using ion beams and to the investigation of more complex multilayer architectures.

Large cluster ions: soft local probes and tools for organic and bio surfaces.

Ionised cluster beams have been produced and employed for thin film deposition and surface processing for half a century. In the last two decades, kiloelectronvolt cluster ions have also proved to be outstanding for surface characterisation by secondary ion mass spectrometry (SIMS), because their sputter and ion yields are enhanced in a non-linear fashion with respect to monoatomic projectiles, with a resulting step change of sensitivity for analysis and imaging. In particular, large gas cluster ion beams, or GCIB, have now become a reference in organic surface and thin film analysis using SIMS and X-ray photoelectron spectroscopy (XPS). The reason is that they induce soft molecular desorption and offer the opportunity to conduct damageless depth-profiling and 3D molecular imaging of the most sensitive organic electronics and biological samples, with a nanoscale depth resolution. In line with these recent developments, the present review focuses on rather weakly-bound, light-element cluster ions, such as noble or other gas clusters, and water or alcohol nanodroplets (excluding clusters made of metals, inorganic salts or ionic liquids) and their interaction with surfaces (essentially, but not exclusively, organic). The scope of this article encompasses three aspects. The first one is the fundamentals of large cluster impacts with surfaces, using the wealth of information provided by molecular dynamics simulations and experimental observations. The second focus is on recent applications of large cluster ion beams in surface characterisation, including mass spectrometric analysis and 2D localisation of large molecules, molecular depth-profiling and 3D molecular imaging. Finally, the perspective explores cutting edge developments, involving (i) new types of clusters with a chemistry designed to enhance performance for mass spectrometry imaging, (ii) the use of cluster fragment ion backscattering to locally retrieve physical surface properties and (iii) the fabrication of new biosurface and thin film architectures, where large cluster ion beams are used as tools to transfer biomolecules in vacuo from a target reservoir to any collector substrate.

Growth and composition of nanostructured and nanoporous cerium oxide thin films on a graphite foil.

The morphology and composition of CeOx films prepared by r.f. magnetron sputtering on a graphite foil have been investigated mainly by using microscopy methods. This study presents the formation of nanocrystalline layers with porous structure due to the modification of a carbon support and the formation of cerium carbide crystallites as a result of the deposition process. Chemical analyses of the layers with different thicknesses performed by energy dispersive X-ray spectroscopy, electron energy loss spectroscopy and X-ray photoelectron spectroscopy have pointed to the reduction of the cerium oxide layers. In the deposited layers, cerium was present in mixed Ce(3+) and Ce(4+) valence. Ce(3+) species were located mainly at the graphite foil-CeOx interface and the chemical state of cerium was gradually changing to Ce(4+) going to the layer surface. It became more stoichiometric in the case of thicker layers except for the surface region, where the presence of Ce(3+) was associated with oxygen vacancies on the surface of cerium oxide grains. The degree of cerium oxide reduction is discussed in the context of particle size.