Scale-up of cluster beam deposition to the gram scale with the matrix assembly cluster source for heterogeneous catalysis (propylene combustion)

Cluster beam deposition is a solvent-free method to prepare films of nanoparticles, one obvious application being heterogeneous catalysis. To address the problem of low cluster deposition rates, a novel cluster beam source, the “Matrix Assembly Cluster Source” was invented recently. Following the proof of principle studies, here, we demonstrate a further scale-up by 2 orders of magnitude, equivalent to reaching a production of ∼10 mg of clusters (Au100) per hour. This allows the preparation of cluster-decorated powder catalysts at the gram scale, comfortably sufficient for practical catalysis studies of novel materials at the research level, as demonstrated here by the catalytic combustion of propylene.We are thankful for financial support from the EPSRC (Grant Reference No. EP/K006061/2) and the European Union’s Horizon 2020 program through the CritCat project under Grant Agreement No. 686053

Catalytic activity of physically deposited metal clusters and their atomic structure study

The deposition of preformed clusters onto suitable support materials represents a new technique for the precision synthesis of heterogeneous catalysts. Benefitting from the successful scale-up of the cluster production, this thesis directly explores the catalytic performance of physically produced metal clusters for liquid-phase and vapour-phase model reactions, particularly under realistic conditions. The catalyst powders used in the experiments were produced using two kinds of cluster beam sources: a magnetron sputtering gas condensation cluster source and a matrix assembly cluster source (MACS). The cluster atomic structure, chemical composition and size evolution due to the reaction were characterized by aberration-corrected scanning transmission electron microscopy (STEM), coupled with energy dispersive X-ray spectroscopy (EDS), and correlated with the cluster chemical activities. In the first part, Au/Cu binary clusters with variable controlled composition were deposited onto magnesium oxide supports using a magnetron sputtering gas condensation cluster source. It was found that Au/Cu cluster catalysts are highly active for the liquid-phase 4-nitrophenol reduction. Electron microscopy revealed that the Au/Cu clusters produced have an alloy structure, which results in a random distribution of Au and Cu atoms on the cluster surface. Combined with theoretical calculations of the binding energies, the interplay between Au and Cu atoms at the cluster surface, resulting in an enhanced catalytic activity, is proposed. In the second part, we demonstrated the catalyst preparation with a new type of cluster beam source, MACS. Pd nanoclusters were deposited onto diced carbon tape supports and used for catalyzing vapour-phase selective 1-pentyne hydrogenation. The catalysis results showed that the Pd cluster catalyst from MACS is more active (per unit weight) than the Pd reference sample synthesized by traditional wet impregnation. Cluster size evolution before and after reaction suggested that the superior activity derived from the smaller cluster size and better stability against sintering compared to the Pd reference sample. In addition, no synergetic effect was found in Pd/Au clusters. The observed similar cluster activity (per surface atom) for Pd and Pd/Au cluster catalysts may be due to the oxidation in air, which could drive Pd atoms to the cluster surface, thus leading to a Pd cluster surface as pure Pd clusters. Finally, a new method to prepare metal colloids from the cluster beam technique is introduced, in which metal clusters made using MACS were directly deposited onto soluble polymer films, followed by dissolving the polymer films in suitable solvents. The Pd colloids produced were also used to catalyze the reduction of 4-nitrophenol to demonstrate the catalytic performance. Only a small activity was observed which was attributed to the protecting polymers blocking a high fraction of the active sites on the cluster surface

Electrocatalytic Behavior of PtCu Clusters Produced by Nanoparticle Beam Deposition

State-of-the-art electrocatalysts for electrolyzer and fuel cell applications currently rely on platinum group metals, which are costly and subject to supply risks. In recent years, a vast collection of research has explored the possibility of reducing the Pt content in such catalysts by alloying with earth-abundant and cheap metals, enabling co-optimization of cost and activity. Here, using nanoparticle beam deposition, we explore the electrocatalytic performance of PtCu alloy clusters in the hydrogen evolution reaction (HER). Elemental compositions of the produced bimetallic clusters were shown by X-ray photoelectron spectroscopy (XPS) to range from 2 at. % to 38 at. % Pt, while high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) combined with energy dispersive X-ray (EDX) spectroscopy indicated that the predominant cluster morphologies could be characterized as either a fully mixed alloy or as a mixed core with a Cu-rich shell. In contrast with previous studies, a monotonic decrease in HER activity with increasing Cu content was observed over the composition range studied, with the current density measured at -0.3 V (vs reversible hydrogen electrode) scaling approximately linearly with Pt at. %. This trend opens up the possibility that PtCu could be used as a reference system for comparing the composition-dependent activity of other bimetallic catalysts

Scale-Up of Cluster Beam Deposition to the Gram Scale with the Matrix Assembly Cluster Source for Heterogeneous Catalysis (Catalytic Ozonation of Nitrophenol in Aqueous Solution)

The deposition of precisely controlled clusters from the beam onto suitable supports represents a novel method to prepare advanced cluster-based catalysts. In principle, cluster size, composition, and morphology can be tuned or selected prior to deposition. The newly invented matrix assembly cluster source (MACS) offers one solution to the long-standing problem of low cluster deposition rate. Demonstrations of the cluster activities under realistic reaction conditions are now needed. We deposited elemental silver (Ag) and gold (Au) clusters onto gram-scale powders of commercial titanium dioxide (TiO2) to investigate the catalytic oxidation of nitrophenol (a representative pollutant in water) by ozone in aqueous solution, as relevant to the removal of waste drugs from the water supply. A range of techniques, including scanning transmission electron microscopy (STEM), Brunauer–Emmett–Teller (BET) surface area test, and X-ray photoelectron spectroscopy (XPS), were employed to reveal the catalyst size, morphology, surface area, and oxidation state. Both the Ag and Au cluster catalysts proved active for the nitrophenol ozonation. The cluster catalysts showed activities at least comparable to those of catalysts made by traditional chemical methods in the literature, demonstrating the potential applications of the cluster beam deposition method for practical heterogeneous catalysis in solution

Synthesis without Solvents: The Cluster (Nanoparticle) Beam Route to Catalysts and Sensors

It is hard to predict the future of science. For example, when C60 and its structure were identified from the mass spectra of gas phase carbon clusters, few could have predicted the era of carbon nanotechnology which the discovery introduced. The solubilization and functionalization of C60, the identification and then synthesis of carbon nanotubes, and the generation and physics of graphene have made a scale of impact on the international R&D (and to some extent industrial) landscape which could not have been foreseen. Technology emerged from a search for molecules of astrochemical interest in the interstellar gas. This little sketch provides the authors with the confidence to present here a status report on progress toward another radical future—the synthesis of nanoparticles (typically metals) on an industrial scale without solvents and consequently effluents, without salts and their sometimes accompanying toxicity, with minimal prospects for unwanted nanoparticle escape into the environment, with a high degree of precision in the control of the size, shape and composition of the nanoparticles produced and with applications from catalysts and sensors to photonics, electronics and theranostics. In fact, our story begins in exactly the same place as the origin of the nanocarbon era—the generation and mass selection of free atomic clusters in a vacuum chamber. The steps along the path so far include deposition of such beams of clusters onto surfaces in vacuum, elucidation of the key elements of the cluster–surface interaction, and demonstrations of the potential applications of deposited clusters. The principal present challenges, formidable but solvable, are the necessary scale-up of cluster beam deposition from the nanogram to the gram scale and beyond, and the processing and integration of the nanoclusters into appropriate functional architectures, such as powders for heterogeneous catalysis, i.e., the formulation engineering problem. The research which is addressing these challenges is illustrated in this Account by examples of cluster production (on the traditional nanogram scale), emphasizing self-selection of size, controlled generation of nonspherical shapes, and nonspherical binary nanoparticles; by the scale-up of cluster beam production by orders of magnitude with the magnetron sputtering, gas condensation cluster source, and especially the Matrix Assembly Cluster Source (MACS); and by promising demonstrations of deposited clusters in gas sensing and in heterogeneous catalysis (this on the gram scale) in relevant environments (both liquid and vapor phases). The impact on manufacturing engineering of the new paradigm described here is undoubtedly radical; the prospects for economic success are, as usual, full of uncertainties. Let the readers form their own judgements

Visible-light induced photocatalytic degradation of estrone (E1) with hexagonal copper selenide nanoflakes in water

Steroid hormones, being potent endocrine-disruptors, are a menace to human health and aquatic life. Herein, visible-light induced photocatalytic degradation of estrone (E1) by hexagonal copper selenide (CuSe) nanoflakes has been reported. CuSe was synthesised by a facile and low-temperature (100 oC) co-precipitation method and was characterised. The nanocrystals were of stoichiometric Cu:Se ratio with Se2- and Cu in the + 1/+ 2 mixed-valence state and exhibited laminar, flake-like morphology with a preferred hexagonal close-packed structure (P63/mmc) having average particle size and thickness of 0.229 ± 0.146 µm and 0.05 ± 0.02 µm, respectively. The adsorption isotherms of E1 were linear and the adsorption process was exothermic. The reactivity of E1 under aqueous suspensions of CuSe exposed to visible light exhibited pseudo-first-order kinetics with a rate constant, k, that varied with initial E1 concentration, light power, catalyst dose, and pH. Particularly, k was almost constant over the range pH5–9 but substantially increased as pH rose to 11, while light power and catalyst dose increased k up to a maximum, and the initial concentration reduced k. Surprisingly, CuSe oxidised E1, even in the absence of light, and leached species that were identified and their time-dependency was determined. We concluded that the disappearance of E1 by CuSe is attributed to synergetic effects of adsorption, oxidation by CuSe, and photocatalytic degradation. Supported by liquid-mass spectrometry analysis and molecular chemistry calculations, we also suggested a possible mechanism for E1 degradation. Thus, hexagonal CuSe nanocrystals can be a promising candidate for the treatment of endocrine-disrupting chemicals (EDC)-contaminated wastewaters

Machine Learning Approaches to Predict Risks of Diabetic Complications and Poor Glycemic Control in Nonadherent Type 2 Diabetes

Purpose: The objective of this study was to evaluate the efficacy of machine learning algorithms in predicting risks of complications and poor glycemic control in nonadherent type 2 diabetes (T2D).Materials and Methods: This study was a real-world study of the complications and blood glucose prognosis of nonadherent T2D patients. Data of inpatients in Sichuan Provincial People’s Hospital from January 2010 to December 2015 were collected. The T2D patients who had neither been monitored for glycosylated hemoglobin A nor had changed their hyperglycemia treatment regimens within the last 12 months were the object of this study. Seven types of machine learning algorithms were used to develop 18 prediction models. The predictive performance was mainly assessed using the area under the curve of the testing set.Results: Of 800 T2D patients, 165 (20.6%) met the inclusion criteria, of which 129 (78.2%) had poor glycemic control (defined as glycosylated hemoglobin A ≥7%). The highest area under the curves of the testing set for diabetic nephropathy, diabetic peripheral neuropathy, diabetic angiopathy, diabetic eye disease, and glycosylated hemoglobin A were 0.902 ± 0.040, 0.859 ± 0.050, 0.889 ± 0.059, 0.832 ± 0.086, and 0.825 ± 0.092, respectively.Conclusion: Both univariate analysis and machine learning methods reached the same conclusion. The duration of T2D and the duration of unadjusted hypoglycemic treatment were the key risk factors of diabetic complications, and the number of hypoglycemic drugs was the key risk factor of glycemic control of nonadherent T2D. This was the first study to use machine learning algorithms to explore the potential adverse outcomes of nonadherent T2D. The performances of the final prediction models we developed were acceptable; our prediction performances outperformed most other previous studies in most evaluation measures. Those models have potential clinical applicability in improving T2D care

Active site manipulation in MoS2 cluster electrocatalysts by transition metal doping

The development of non-platinum group metal catalysts for the hydrogen evolution reaction (HER) in water electrolyser devices is essential for their widespread and sustainable deployment. In recent years, molybdenum disulfide (MoS2) catalysts have received significant attention as they not only exhibit good electrocatalytic HER activity but also, crucially, acid-stability. However, further performance enhancement is required for these materials to be competitive with Pt and to that end transition metal doping of MoS2 has been explored as a route to further increasing its catalytic activity. In this work, cluster beam deposition was employed to produce controlled cobalt-doped MoS2 clusters (MoS2–Co). We demonstrate that, in contrast to previous observations of performance enhancement in MoS2 resulting from nickel doping (MoS2–Ni), the introduction of Co has a detrimental effect on HER activity. The contrasting behaviours of Ni and Co doping are rationalized by density functional theory (DFT) calculations, which suggest that HER-active surface vacancies are deactivated by combination with Co dopant atoms, whilst their activity is retained, or even partially enhanced, by combination with Ni dopant atoms. Furthermore, the adatom dopant–vacancy combination kinetics appear to be more than three orders of magnitude faster in MoS2–Co than for MoS2–Ni. These findings highlight a fundamental difference in the influence of transition metal dopants on the HER performance of MoS2 electrocatalysts and stress the importance of considering surface atomic defects when predicting their behaviour

Gas-Phase Deposition of Gold Nanoclusters to Produce Heterogeneous Glycerol Oxidation Catalysts

Gold nanoparticles prepared by colloidal methods are effective catalysts for selective glycerol oxidation under basic conditions. Large-scale synthesis of catalysts by wet chemical methods leads to large amounts of waste and can result in polymer or salt residues remaining on the catalyst. In contrast, gas-phase cluster deposition (cluster beam deposition) offers a solvent-free method to synthesize controlled nanoparticles/clusters. We show that the deposition of bare gas-phase gold clusters onto carbon powder leads to a catalyst comparable to that prepared by colloidal methods. This shows the feasibility of the synthesis method to produce oxidation catalysts with reduced waste