Design and Application of a Gas Diffusion Electrode (GDE) Cell for Operando and In Situ Studies

Presented here is an electrochemical three-electrode Gas Diffusion Electrode (GDE) cell tailored for operandoand in situ investigations of electrocatalytic processes, with a particular focus on X-ray scattering studies. The optimized cell is engineered to accommodate the minimal sample-detector distances requisite for comprehensive X-ray total scattering investigations. An in-depth understanding of catalytic processes requires their study under ‘working’ conditions. Configured as a flow-cell, the setup therefore enables the examination of electrocatalysts under high current densities and associated gas evolution phenomena, particularly pertinent for reactions like the oxygen evolution reaction (OER). Notably, its transparency simplifies cell alignment, troubleshooting, and facilitates scans through the catalyst layer, crucial for background corrections. Demonstrating its versatility, we showcase its utility through Small Angle X-ray Scattering (SAXS), X-ray Diffraction (XRD), and X-ray Pair Distribution Function (PDF) analyses of total scattering data

Surfactant-Free Colloidal Syntheses of Gold-Based Nanomaterials in Alkaline Water and Mono-alcohol Mixtures [Dataset]

120 pages. -- SA. Synthesis of Au NPs using ROH. -- SB. Experimental section. -- SC. Effect of mono-alcohol, mono-alcohol content and cation. -- SD. Effect of experimental parameters: HAuCl4 concentration, volume of solution, type of container used, light. -- SE. Effect of the nature of the alcohols. -- SF. Kinetics of the reduction. -- SG. Influence of the temperature. -- SH. Influence of base concentration. -- SI. Influence of gas atmosphere. -- SJ. Influence of the order of addition of the chemicals. -- SK. Discussion of Au NP formation. -- SL. Reproducibility. -- SM. Scalability. -- SN. Mixture of mono-alcohols. -- SO. Cation and surfactant effects . -- SP. Electrochemical characterization of Au NPs. -- SQ. Supported NPs. -- SR. Pd and bimetallic NPs. -- SS. Nanocomposites. -- ST. Electrochemical characterization of AuxPdy NPs and [x Au + y Pd] nanocomposites. -- SU. Outlook into multi-metallic nanomaterials. -- SV. Comparison of different catalysts. -- SW. ReferencesGold nanoparticles (Au NPs) and gold-based nanomaterials combine unique properties relevant for medicine, imaging, optics, sensing, catalysis, and energy conversion. While the Turkevich–Frens and Brust–Schiffrin methods remain the state-of-the-art colloidal syntheses of Au NPs, there is a need for more sustainable and tractable synthetic strategies leading to new model systems. In particular, stabilizers are almost systematically used in colloidal syntheses, but they can be detrimental for fundamental and applied studies. Here, a surfactant-free synthesis of size-controlled colloidal Au NPs stable for months is achieved by the simple reduction of HAuCl4 at room temperature in alkaline solutions of low-viscosity mono-alcohols such as ethanol or methanol and water, without the need for any other additives. Palladium (Pd) and bimetallic AuxPdy NPs, nanocomposites and multimetallic samples, are also obtained and are readily active (electro)­catalysts. The multiple benefits over the state-of-the-art syntheses that this simple synthesis bears for fundamental and applied research are highlighted.Peer reviewe

Formation and growth mechanism for niobium oxide nanoparticles: atomistic insight from in situ X-ray total scattering

Understanding the mechanisms for nanoparticle nucleation and growth is crucial for the development of tailormade nanomaterials. Here, we use X-ray total scattering and Pair Distribution Function analysis to follow the formation and growth of niobium oxide nanoparticles. We study the solvothermal synthesis from niobium chloride in benzyl alcohol, and through investigations of the influence of reaction temperature, a formation pathway can be suggested. Upon dissolution of niobium chloride in benzyl alcohol, octahedral [NbCl$_{6−x}$O$_x$] complexes form through exchange of chloride ligands. Heating of the solution results in polymerization, where larger clusters built from multiple edge-sharing [NbCl$_{6−x}$O$_x$] octahedra assemble. This leads to the formation of a nucleation cluster with the ReO$_3$ type structure, which grows to form nanoparticles of the Wadsley–Roth type H-Nb$_2$O$_5$ structure, which in the bulk phase usually only forms at high temperature. Upon further growth, structural defects appear, and the presence of shear-planes in the structure appears highly dependent on nanoparticle size

Monoalkyl phosphinic acids as ligands in nanocrystal synthesis

Ligands play a crucial role in the synthesis of colloidal nanocrystals. Nevertheless, only a handful molecules are currently used, oleic acid being the most typical example. Here, we show that monoalkyl phosphinic acids are another interesting ligand class, forming metal complexes with a reactivity that is intermediate between the traditional carboxylates and phosphonates. We first present the synthesis of n-hexyl, 2-ethylhexyl, n-tetradecyl, n-octadecyl, and oleylphosphinic acid. These compounds are suitable ligands for high-temperature nanocrystal synthesis (240-300 degrees C) since, in contrast to phosphonic acids, they do not form anhydride oligomers. Consequently, CdSe quantum dots synthesized with octadecylphosphinic acid are conveniently purified, and their UV-vis spectrum is free from background scattering. The CdSe nanocrystals have a low polydispersity and a photoluminescence quantum yield up to 18% (without shell). Furthermore, we could synthesize CdSe and CdS nanorods using phosphinic acid ligands with high shape purity. We conclude that the reactivity toward TOP-S and TOP-Se precursors decreases in the following series: cadmium carboxylate > cadmium phosphinate > cadmium phosphonate. By introducing a third and intermediate class of surfactants, we enhance the versatility of surfactant-assisted syntheses

Elucidating the Steady-State OER Activity of (Ni1-xFex)OOH Binary Nanoparticles in As-prepared and Purified KOH Electrolyte Solutions

Replacing critical raw materials employed in water electrolysis applications as electrocatalysts with earth-abundant materials is paramount for the future upscaling to industrial dimensions. In that regard, Ni and Ni-based multimetallic hydroxides, above all NiFe-hydroxides, have shown promising performance towards the oxygen evolution reaction (OER) in alkaline conditions. However, it has been shown that the extraordinary performance of these materials is owed largely to Fe impurities found in commercial KOH from which electrolyte solutions are prepared. The mechanism of action of these impurities is still not fully understood, and therefore, at the heart of ongoing discussions. In this study, we investigate the OER activity of different nanostrcutured (Ni1-xFex)OOH samples and find their activities to be influenced differently by the presence of Fe impurities in the electrolyte. From the gathered data, we conclude that the presence of Fe impurities impacts gravely the structure sensitivity of the OER. In purified electrolyte solutions the OER appears to be a structure-sensitive reaction while this seems not to be the case in the presence of said impurities

A Reproducible and Scalable Method for Producing Fluorescent Polystyrene Nanoparticles

In this work polystyrene nanoparticles (PS NPs) were fabricated from an emulsion of PS/toluene in water using various surfactants, and purified via dialysis in a simple procedure. The synthesis process was carried out at room temperature, without hazardous chemicals, and with a workload of 5 hours. The investigation was performed to evaluate the limits for production of PS NPs with comparable properties. A robust PS NP synthesis procedure was developed, repeated, and tested by three independent researches. The procedure was up-scaled to prove the applicability of the method and the NPs were prepared with four different hydrophobic dyes. All products were found to be comparable, and it was concluded that the method reported here can provide PS NPs with or without dye dopants, and that it provides access to PS NPs with an average diameter of 25 nm in a reproducible size distribution

Influence of precursor structure on the formation of tungsten oxide polymorphs

Understanding material nucleation processes is crucial for the development of synthesis pathways for tailormade materials. However, we currently have little knowledge of the influence of the precursor solution structure on the formation pathway of materials. We here use in situ total scattering to show how the precursor solution structure influences which crystal structure is formed during the hydrothermal synthesis of tungsten oxides. We investigate the synthesis of tungsten oxide from the two polyoxometalate salts, ammonium metatungstate and ammonium paratungstate. In both cases, a hexagonal ammonium tungsten bronze (NH4)0.25WO3, is formed as the final product. If the precursor solution contains metatungstate clusters, this phase forms directly in the hydrothermal synthesis. However, if the paratungstate B cluster is present at the time of crystallization, a metastable intermediate phase in the form of a pyrochlore-type tungsten oxide, WO30*5H2O, initially forms. The pyrochlore structure then undergoes a phase transformation into the tungsten bronze phase. Our studies thus experimentally show that the precursor cluster structure present at the moment of crystallization directly influences the formed crystalline phase and suggest that the precursor structure just prior to crystallization can be used as a tool for targeting specific crystalline phases of interest

Unveiling polyamorphism and polyamorphic interconversions in pharmaceuticals: the peculiar case of hydrochlorothiazide

Polyamorphism has been a controversial and highly debated solid-state phenomenon in both material and pharmaceutical communities. Although some evidence of this fascinating phenomenon has been reported for several inorganic systems, and more recently also for a few organic compounds, the occurrence of polyamorphism is poorly understood and the molecular-level organization of polyamorphic forms is still unknown. Here we have investigated the occurrence of polyamorphism and polyamorphic interconversions in hydrochlorothiazide (HCT), using both experimental and computational methods. Three distinct HCT polyamorphs, presenting distinct physical and thermal stabilities as well as distinct relaxation properties, were systematically prepared using spray-drying (SD), quench-cooling (QC) and ball milling (BM) methods. HCT polyamorph II (obtained by QC) was found to be more physically stable than polyamorphs I and III (obtained by SD and BM, respectively). Furthermore, polyamorphs I and III could be converted into polyamorph II after QC, while polyamorph II did not convert to any other polyamorph after SD or BM. Molecular dynamics simulations show that HCT dihedral angle distributions are significantly different for polyamorphs I and II, which is postulated as a possible explanation for their different physicochemical properties

From Gel to Crystal: Mechanism of HfO2 and ZrO2 Nanocrystal Synthesis in Benzyl Alcohol

Nonaqueous sol-gel syntheses have been used to make many types of metal oxide nanocrystals. According to the current paradigm, nonaqueous syntheses have slow kinetics, thus favoring the thermodynamic (crystalline) product. Here we investigate the synthesis of hafnium (and zirconium) oxide nanocrystals from the metal chloride in benzyl alcohol. We follow the transition from precursor to nanocrystal through a combination of rheology, EXAFS, NMR, TEM and X-ray total scattering (PDF analysis). Upon dissolving the metal chloride precursor, the exchange of chloride ligands for benzylalkoxide liberates HCl. The latter catalyzes the etherification of benzyl alcohol, eliminating water. During the temperature ramp to the reaction temperature (220 °C), sufficient water is produced to turn the reaction mixture into a macroscopic gel. Rheological analysis shows a network consisting of strong interactions with temperature dependent restructuring. After a few minutes at the reaction temperature, crystalline particles emerge from the gel, and nucleation and growth are complete after 30 minutes. In contrast, four hours are required to obtain the highest isolated yield, which we attribute to the slow in situ formation of water (the extraction solvent). We used our mechanistic insights to optimize the synthesis, achieving high yields with a reduced reaction time. In summation, our results oppose the idea that nonaqueous sol-gel syntheses necessarily form crystalline products slowly, without a transient gel state

Unveiling polyamorphism and polyamorphic interconversions in pharmaceuticals : the peculiar case of hydrochlorothiazide

Polyamorphism has been a controversial and highly debated solid-state phenomenon in both material and pharmaceutical communities. Although some evidence of this fascinating phenomenon has been reported for several inorganic systems, and more recently also for a few organic compounds, the occurrence of polyamorphism is poorly understood and the molecular-level organization of polyamorphic forms is still unknown. Here we have investigated the occurrence of polyamorphism and polyamorphic interconversions in hydrochlorothiazide (HCT), using both experimental and computational methods. Three distinct HCT polyamorphs, presenting distinct physical and thermal stabilities as well as distinct relaxation properties, were systematically prepared using spray-drying (SD), quench-cooling (QC) and ball milling (BM) methods. HCT polyamorph II (obtained by QC) was found to be more physically stable than polyamorphs I and III (obtained by SD and BM, respectively). Furthermore, polyamorphs I and III could be converted into polyamorph II after QC, while polyamorph II did not convert to any other polyamorph after SD or BM. Molecular dynamics simulations show that HCT dihedral angle distributions are significantly different for polyamorphs I and II, which is postulated as a possible explanation for their different physicochemical properties.Three polyamorphs of hydrochlorothiazide with distinct physicochemical properties were discovered. MD simulations show different dihedral angle distributions in polyamorphs I and II. Polyamorphs I and III were converted into polyamorph II.Peer reviewe