Balancing act: influence of Cu content in NiCu/C catalysts for methane decomposition.

Thermal catalytic decomposition of methane is an innovative pathway to produce CO2-free hydrogen from natural gas. We investigated the role of Cu content in carbon-supported bimetallic NiCu catalysts. A graphitic carbon material was used as a model support, and we combined operando methane decomposition experiments in a thermogravimetric analyzer with in situ electron microscopy measurements. The carbon yield was maximum with around 30% Cu in the nanoparticles. Adding more Cu drastically lowered the carbon solubility in the metal nanoparticles, which lowered the initial reaction rate and overall carbon yield. In situ TEM measurements showed that the addition of Cu to the catalysts strongly influenced the metal nanoparticle shape and size during carbon growth, and the growth mode. NiCu particles were larger, remained spherical and facilitated steady CNF growth. In contrast, pure Ni nanoparticles fluctuated in shape, sometimes fragmented, and showed stuttering CNF growth. This was ascribed to fluctuating coverage of part of the Ni nanoparticle surface with amorphous carbon, which increased the chance of total encapsulation and hence deactivation of the individual Ni nanoparticles. This supports a picture where balancing the carbon supply, transport, and nucleation of amorphous and crystalline carbon is crucial. Our results also highlight the importance of combining statistically relevant measurements with microscopic information on individual nanoparticles to understand overall catalytic trends from the combined behavior of individual catalyst nanoparticles.

Cation Exchange and Spontaneous Crystal Repair Resulting in Ultrathin, Planar CdS Nanosheets.

Cation exchange has become a major postsynthetic tool to obtain nanocrystals with a combination of stoichiometry, size, and shape that is challenging to achieve by direct wet-chemical synthesis. Here, we report on the transformation of highly anisotropic, ultrathin, and planar PbS nanosheets into CdS nanosheets of the same dimensions. We monitor the evolution of the Cd-for-Pb exchange by ex-situ TEM, HAADF-STEM, and EDX. We observe that in the early stages of the exchange the sheets show large in-sheet voids that repair spontaneously upon further exchange and annealing, resulting in ultrathin, planar, and crystalline CdS nanosheets. After cation exchange, the nanosheets show broad sub-band gap luminescence, as often observed in CdS nanocrystals. The photoluminescence excitation spectrum reveals the heavy- and light-hole exciton features, with very strong quantum confinement and large electron-hole Coulomb energy, typical for 2D ultrathin Cd-chalcogenide nanosheets.

Adaptive insertion of a hydrophobic anchor into a poly(ethylene glycol) host for programmable surface functionalization.

Covalent and non-covalent molecular binding are two strategies to tailor surface properties and functions. However, the lack of responsiveness and requirement for specific binding groups makes spatiotemporal control challenging. Here, we report the adaptive insertion of a hydrophobic anchor into a poly(ethylene glycol) (PEG) host as a non-covalent binding strategy for surface functionalization. By using polycyclic aromatic hydrocarbons as the hydrophobic anchor, hydrophilic charged and non-charged functional modules were spontaneously loaded onto PEG corona in 2 min without the assistance of any catalysts and binding groups. The thermodynamically favourable insertion of the hydrophobic anchor can be reversed by pulling the functional module, enabling programmable surface functionalization. We anticipate that the adaptive molecular recognition between the hydrophobic anchor and the PEG host will challenge the hydrophilic understanding of PEG and enhance the progress in nanomedicine, advanced materials and nanotechnology.

Room-Temperature Interconversion Between Ultrathin CdTe Magic-Size Nanowires Induced by Ligand Shell Dynamics.

The formation mechanisms of colloidal magic-size semiconductor nanostructures have remained obscure. Herein, we report the room temperature synthesis of three species of ultrathin CdTe magic-size nanowires (MSNWs) with diameters of 0.7 ± 0.1 nm, 0.9 ± 0.2 nm, and 1.1 ± 0.2 nm, and lowest energy exciton transitions at 373, 418, and 450 nm, respectively. The MSNWs are obtained from Cd(oleate)2 and TOP-Te, provided diphenylphosphine and a primary alkylamine (RNH2) are present at sufficiently high concentrations, and exhibit sequential, discontinuous growth. The population of each MSNW species is entirely determined by the RNH2 concentration [RNH2] so that single species are only obtained at specific concentrations, while mixtures are obtained at concentrations intermediate between the specific ones. Moreover, the MSNWs remain responsive to [RNH2], interconverting from thinner to thicker upon [RNH2] decrease and from thicker to thinner upon [RNH2] increase. Our results allow us to propose a mechanism for the formation and interconversion of CdTe MSNWs and demonstrate that primary alkylamines play crucial roles in all four elementary kinetic steps (viz., monomer formation, nucleation, growth in length, and interconversion between species), thus being the decisive element in the creation of a reaction pathway that leads exclusively to CdTe MSNWs. The insights provided by our work thus contribute toward unravelling the mechanisms behind the formation of shape-controlled and atomically precise magic-size semiconductor nanostructures.

Maximizing noble metal utilization in solid catalysts by control of nanoparticle location.

Maximizing the utilization of noble metals is crucial for applications such as catalysis. We found that the minimum loading of platinum for optimal performance in the hydroconversion of n-alkanes for industrially relevant bifunctional catalysts could be reduced by a factor of 10 or more through the rational arranging of functional sites at the nanoscale. Intentionally depositing traces of platinum nanoparticles on the alumina binder or the outer surface of zeolite crystals, instead of inside the zeolite crystals, enhanced isomer selectivity without compromising activity. Separation between platinum and zeolite acid sites preserved the metal and acid functions by limiting micropore blockage by metal clusters and enhancing access to metal sites. Reduced platinum nanoparticles were more active than platinum single atoms strongly bonded to the alumina binder.

Unraveling the Emission Pathways in Copper Indium Sulfide Quantum Dots.

Semiconductor copper indium sulfide quantum dots are emerging as promising alternatives to cadmium- and lead-based chalcogenides in solar cells, luminescent solar concentrators, and deep-tissue bioimaging due to their inherently lower toxicity and outstanding photoluminescence properties. However, the nature of their emission pathways remains a subject of debate. Using low-temperature single quantum dot spectroscopy on core-shell copper indium sulfide nanocrystals, we observe two subpopulations of particles with distinct spectral features. The first class shows sharp resolution-limited emission lines that are attributed to zero-phonon recombination lines of a long-lived band-edge exciton. Such emission results from the perfect passivation of the copper indium sulfide core by the zinc sulfide shell and points to an inversion in the band-edge hole levels. The second class exhibits ultrabroad spectra regardless of the temperature, which is a signature of the extrinsic self-trapping of the hole assisted by defects in imperfectly passivated quantum dots.

Synthesis and Formation Mechanism of Colloidal Janus-Type Cu2-xS/CuInS2 Heteronanorods via Seeded Injection.

Colloidal heteronanocrystals allow for the synergistic combination of properties of different materials. For example, spatial separation of the photogenerated electron and hole can be achieved by coupling different semiconductors with suitable band offsets in one single nanocrystal, which is beneficial for improving the efficiency of photocatalysts and photovoltaic devices. From this perspective, axially segmented semiconductor heteronanorods with a type-II band alignment are particularly attractive since they ensure the accessibility of both photogenerated charge carriers. Here, a two-step synthesis route to Cu2-xS/CuInS2 Janus-type heteronanorods is presented. The heteronanorods are formed by injection of a solution of preformed Cu2-xS seed nanocrystals in 1-dodecanethiol into a solution of indium oleate in oleic acid at 240 °C. By varying the reaction time, Janus-type heteronanocrystals with different sizes, shapes, and compositions are obtained. A mechanism for the formation of the heteronanocrystals is proposed. The first step of this mechanism consists of a thiolate-mediated topotactic, partial Cu+ for In3+ cation exchange that converts one of the facets of the seed nanocrystals into CuInS2. This is followed by homoepitaxial anisotropic growth of wurtzite CuInS2. The Cu2-xS seed nanocrystals also act as sacrificial Cu+ sources, and therefore, single composition CuInS2 nanorods are eventually obtained if the reaction is allowed to proceed to completion. The two-stage seeded growth method developed in this work contributes to the rational synthesis of Cu2-xS/CuInS2 heteronanocrystals with targeted architectures by allowing one to exploit the size and faceting of premade Cu2-xS seed nanocrystals to direct the growth of the CuInS2 segment.

Seeded Growth Combined with Cation Exchange for the Synthesis of Anisotropic Cu2-x S/ZnS, Cu2-x S, and CuInS2 Nanorods.

Colloidal copper(I) sulfide (Cu2-x S) nanocrystals (NCs) have attracted much attention for a wide range of applications because of their unique optoelectronic properties, driving scientists to explore the potential of using Cu2-x S NCs as seeds in the synthesis of heteronanocrystals to achieve new multifunctional materials. Herein, we developed a multistep synthesis strategy toward Cu2-x S/ZnS heteronanorods. The Janus-type Cu2-x S/ZnS heteronanorods are obtained by the injection of hexagonal high-chalcocite Cu2-x S seed NCs in a hot zinc oleate solution in the presence of suitable surfactants, 20 s after the injection of sulfur precursors. The Cu2-x S seed NCs undergo rapid aggregation and coalescence in the first few seconds after the injection, forming larger NCs that act as the effective seeds for heteronucleation and growth of ZnS. The ZnS heteronucleation occurs on a single (100) facet of the Cu2-x S seed NCs and is followed by fast anisotropic growth along a direction that is perpendicular to the c-axis, thus leading to Cu2-x S/ZnS Janus-type heteronanorods with a sharp heterointerface. Interestingly, the high-chalcocite crystal structure of the injected Cu2-x S seed NCs is preserved in the Cu2-x S segments of the heteronanorods because of the high-thermodynamic stability of this Cu2-x S phase. The Cu2-x S/ZnS heteronanorods are subsequently converted into single-component Cu2-x S and CuInS2 nanorods by postsynthetic topotactic cation exchange. This work expands the possibilities for the rational synthesis of colloidal multicomponent heteronanorods by allowing the design principles of postsynthetic heteroepitaxial seeded growth and nanoscale cation exchange to be combined, yielding access to a plethora of multicomponent heteronanorods with diameters in the quantum confinement regime.

Bad neighbour, good neighbour: how magnetic dipole interactions between soft and hard ferrimagnetic nanoparticles affect macroscopic magnetic properties in ferrofluids.

Fluids responding to magnetic fields (ferrofluids) offer a scene with no equivalent in nature to explore long-range magnetic dipole interactions. Here, we studied the very original class of binary ferrofluids, embedding soft and hard ferrimagnetic nanoparticles. We used a combination of X-ray magnetic spectroscopy measurements supported by multi-scale experimental techniques and Monte-Carlo simulations to unveil the origin of the emergent macroscopic magnetic properties of the binary mixture. We found that the association of soft and hard magnetic nanoparticles in the fluid has a considerable influence on their inherent magnetic properties. While the ferrofluid remains in a single phase, magnetic interactions at the nanoscale between both types of particles induce a modification of their respective coercive fields. By connecting the microscopic properties of binary ferrofluids containing small particles, our findings lay the groundwork for the manipulation of magnetic interactions between particles at the nanometer scale in magnetic liquids.

Tailoring Cu+ for Ga3+ Cation Exchange in Cu2-xS and CuInS2 Nanocrystals by Controlling the Ga Precursor Chemistry.

Nanoscale cation exchange (CE) has resulted in colloidal nanomaterials that are unattainable by direct synthesis methods. Aliovalent CE is complex and synthetically challenging because the exchange of an unequal number of host and guest cations is required to maintain charge balance. An approach to control aliovalent CE reactions is the use of a single reactant to both supply the guest cation and extract the host cation. Here, we study the application of GaCl3-L complexes [L = trioctylphosphine (TOP), triphenylphosphite (TPP), diphenylphosphine (DPP)] as reactants in the exchange of Cu+ for Ga3+ in Cu2-xS nanocrystals. We find that noncomplexed GaCl3 etches the nanocrystals by S2- extraction, whereas GaCl3-TOP is unreactive. Successful exchange of Cu+ for Ga3+ is only possible when GaCl3 is complexed with either TPP or DPP. This is attributed to the pivotal role of the Cu2-xS-GaCl3-L activated complex that forms at the surface of the nanocrystal at the onset of the CE reaction, which must be such that simultaneous Ga3+ insertion and Cu+ extraction can occur. This requisite is only met if GaCl3 is bound to a phosphine ligand, with a moderate bond strength, to allow facile dissociation of the complex at the nanocrystal surface. The general validity of this mechanism is demonstrated by using GaCl3-DPP to convert CuInS2 into (Cu,Ga,In)S2 nanocrystals, which increases the photoluminescence quantum yield 10-fold, while blue-shifting the photoluminescence into the NIR biological window. This highlights the general applicability of the mechanistic insights provided by our work.

Synthesis and Characterization of Ru-Loaded Anodized Aluminum Oxide for Hydrogenation Catalysis.

Anodized aluminum oxides (AAOs) are synthesized and used as catalyst support in combination with Ru as metal in hydrogenation catalysis. SEM and TEM analysis of the as-synthesized AAOs reveal uniform, ordered nanotubes with pore diameters of 18 nm, which are further characterized with Kr physisorption, XRD and FTIR spectroscopy. After impregnation of the AAOs with Ru, the presence of Ru nanoparticles inside the tubular pores is evidenced clearly for the first time via HAADF-STEM-EDX. The Ru-AAOs have been tested for catalytic activity, which showed high conversion and selectivity for the hydrogenation of toluene and butanal.

Shaping Silica Rods by Tuning Hydrolysis and Condensation of Silica Precursors.

We present the synthesis of colloidal silica particles with new shapes by manipulating the growth conditions of rods that are growing from polyvinylpyrrolidone-loaded water-rich droplets containing ammonia and ethanol. The silica rods grow by ammonia-catalyzed hydrolysis and condensation of tetraethoxysilane (TEOS). The lengthwise growth of these silica rods gives us the opportunity to change the conditions at any time during the reaction. In this work, we vary the availability of hydrolyzed monomers as a function of time and study how the change in balance between the hydrolysis and condensation reactions affects a typical synthesis (as described in more detail by our group earlier1). First, we show that in a "standard" synthesis, there are two silica growth processes occurring; one in the oil phase and one in the droplet. The growth process in the water droplet causes the lengthwise growth of the rods. The growth process in the oil phase produces a thin silica layer around the rods, but also causes the nucleation of 70 nm silica spheres. During a typical rod growth, silica formation mainly takes place in the droplet. The addition of partially hydrolyzed TEOS or tetramethoxysilane (TMOS) to the growth mixture results in a change in balance between the hydrolysis and condensation reaction. As a result, the growth also starts to take place on the surface of the water droplet and thus from the oil phase, not only from inside the droplet onto a silica rod sticking out of the droplet. Carefully tuning the growth from the droplet and the growth from the oil phase allowed us to create nanospheres, hollow silica rods, hollow sphere rod systems (colloidal matchsticks), and bent silica rods.

Anisotropic 2D Cu2-x Se Nanocrystals from Dodecaneselenol and Their Conversion to CdSe and CuInSe2 Nanoparticles.

We present the synthesis of colloidal anisotropic Cu2-x Se nanocrystals (NCs) with excellent size and shape control, using the unexplored phosphine-free selenium precursor 1-dodecaneselenol (DDSe). This precursor forms lamellar complexes with Cu(I) that enable tailoring the NC morphology from 0D polyhedral to highly anisotropic 2D shapes. The Cu2-x Se NCs are subsequently used as templates in postsynthetic cation exchange reactions, through which they are successfully converted to CdSe and CuInSe2 quantum dots, nanoplatelets, and ultrathin nanosheets. The shape of the template hexagonal nanoplatelets is preserved during the cation exchange reaction, despite a substantial reorganization of the anionic sublattice, which leads to conversion of the tetragonal umangite crystal structure of the parent Cu2-x Se NCs into hexagonal wurtzite CdSe and CuInSe2, accompanied by a change of both the thickness and the lateral dimensions of the nanoplatelets. The crystallographic transformation and reconstruction of the product NCs are attributed to a combination of the unit cell dimensionalities of the parent and product crystal phases and an internal ripening process. This work provides novel tools for the rational design of shape-controlled colloidal anisotropic Cu2-x Se NCs, which, besides their promising optoelectronic properties, also constitute a new family of cation exchange templates for the synthesis of shape-controlled NCs of wurtzite CdSe, CuInSe2, and other metal selenides that cannot be attained through direct synthesis approaches. Moreover, the insights provided here are likely applicable also to the direct synthesis of shape-controlled NCs of other metal selenides, since DDSe may be able to form lamellar complexes with several other metals.

Intra- and Interparticle Heterogeneities in Solid Activators for Single-Site Olefin Polymerization Catalysis as Revealed by Micro-Spectroscopy.

Methylaluminoxane (MAO) is an activator for single-site olefin polymerization catalysts. Structural characterization of MAO, and in particular the influence of its heterogenization on a silica support, is pivotal for the understanding and optimization of this versatile co-catalyst. In this work, we demonstrate that by varying the MAO loading on a silica support, we can tune the single particle characteristics in terms of MAO distribution and consequent activity. At low MAO loading we reveal two possible intraparticle MAO distributions: a homogeneous and an Al-shell type distribution. With increasing MAO loading, the interparticle MAO distribution becomes more homogeneous. Acidity probing measurements on the single particle level explain how a different intraparticle MAO distribution results in a different activity in metallocene activation. Al-shell particles contain remaining silanol groups and a negligible amount of acid sites and are, therefore, considered inactive for metallocene activation. Only the solid activator particles with a homogeneous intraparticle MAO distribution contain a sufficient number of acid sites, capable of activating the deposited metallocenes.

Luminescent Gold Nanocluster-Decorated Polymeric Hybrid Particles with Assembly-Induced Emission.

Ultrasmall gold atom clusters (<2 nm in diameter) or gold nanoclusters exhibit emergent photonic properties (near-infrared absorption and emission) compared to larger plasmonic gold particles because of the significant quantization of their conduction band. Although single gold nanocluster properties and applications are being increasingly investigated, little is still known about their behavior and properties when assembled into suprastructures, and even fewer studies are investigating their use for biomedical applications. Here, a simple synthetic pathway combines gold nanoclusters with thermosensitive diblock copolymers of poly(ethylene glycol) (PEG) and poly( N-isopropylacrylamide) (PNIPAm) to form a new class of gold-polymer, micelle-forming, hybrid nanoparticle. The nanohybrids' design is uniquely centered on enabling the temperature-dependent self-assembly of gold nanoclusters into the hydrophobic cores of micelles. This nonbulk assembly not only preserves but also enhances the attractive near-infrared photonics of the gold nanoclusters by significantly increasing their native fluorescent signal. In parallel to the fundamental insights into gold nanocluster ordering and assembly, the gold-polymer nanohybrids also demonstrated great potential as fluorescent live-imaging probes in vitro. This innovative material design based on the temperature-dependent, self-assembly of gold nanoclusters within a polymeric micelle's core shows great promise toward bioassays, nanosensors, and nanomedicine.

Interplay between Surface Chemistry, Precursor Reactivity, and Temperature Determines Outcome of ZnS Shelling Reactions on CuInS2 Nanocrystals.

ZnS shelling of I-III-VI2 nanocrystals (NCs) invariably leads to blue-shifts in both the absorption and photoluminescence spectra. These observations imply that the outcome of ZnS shelling reactions on I-III-VI2 colloidal NCs results from a complex interplay between several processes taking place in solution, at the surface of, and within the seed NC. However, a fundamental understanding of the factors determining the balance between these different processes is still lacking. In this work, we address this need by investigating the impact of precursor reactivity, reaction temperature, and surface chemistry (due to the washing procedure) on the outcome of ZnS shelling reactions on CuInS2 NCs using a seeded growth approach. We demonstrate that low reaction temperatures (150 °C) favor etching, cation exchange, and alloying regardless of the precursors used. Heteroepitaxial shell overgrowth becomes the dominant process only if reactive S- and Zn-precursors (S-ODE/OLAM and ZnI2) and high reaction temperatures (210 °C) are used, although a certain degree of heterointerfacial alloying still occurs. Remarkably, the presence of residual acetate at the surface of CIS seed NCs washed with ethanol is shown to facilitate heteroepitaxial shell overgrowth, yielding for the first time CIS/ZnS core/shell NCs displaying red-shifted absorption spectra, in agreement with the spectral shifts expected for a type-I band alignment. The insights provided by this work pave the way toward the design of improved synthesis strategies to CIS/ZnS core/shell and alloy NCs with tailored elemental distribution profiles, allowing precise tuning of the optoelectronic properties of the resulting materials.

Superior Stability of Au/SiO2 Compared to Au/TiO2 Catalysts for the Selective Hydrogenation of Butadiene.

Supported gold nanoparticles are highly selective catalysts for a range of both liquid-phase and gas-phase hydrogenation reactions. However, little is known about their stability during gas-phase catalysis and the influence of the support thereon. We report on the activity, selectivity, and stability of 2-4 nm Au nanoparticulate catalysts, supported on either TiO2 or SiO2, for the hydrogenation of 0.3% butadiene in the presence of 30% propene. Direct comparison of the stability of the Au catalysts was possible as they were prepared via the same method but on different supports. At full conversion of butadiene, only 0.1% of the propene was converted for both supported catalysts, demonstrating their high selectivity. The TiO2-supported catalysts showed a steady loss of activity, which was recovered by heating in air. We demonstrated that the deactivation was not caused by significant metal particle growth or strong metal-support interaction, but rather, it is related to the deposition of carbonaceous species under reaction conditions. In contrast, all the SiO2-supported catalysts were highly stable, with very limited formation of carbonaceous deposits. It shows that SiO2-supported catalysts, despite their 2-3 times lower initial activities, clearly outperform TiO2-supported catalysts within a day of run time.

Promoted Iron Nanocrystals Obtained via Ligand Exchange as Active and Selective Catalysts for Synthesis Gas Conversion.

Colloidal synthesis routes have been recently used to fabricate heterogeneous catalysts with more controllable and homogeneous properties. Herein a method was developed to modify the surface composition of colloidal nanocrystal catalysts and to purposely introduce specific atoms via ligands and change the catalyst reactivity. Organic ligands adsorbed on the surface of iron oxide catalysts were exchanged with inorganic species such as Na2S, not only to provide an active surface but also to introduce controlled amounts of Na and S acting as promoters for the catalytic process. The catalyst composition was optimized for the Fischer-Tropsch direct conversion of synthesis gas into lower olefins. At industrially relevant conditions, these nanocrystal-based catalysts with controlled composition were more active, selective, and stable than catalysts with similar composition but synthesized using conventional methods, possibly due to their homogeneity of properties and synergic interaction of iron and promoters.

Highly Luminescent Water-Dispersible NIR-Emitting Wurtzite CuInS2/ZnS Core/Shell Colloidal Quantum Dots.

Copper indium sulfide (CIS) quantum dots (QDs) are attractive as labels for biomedical imaging, since they have large absorption coefficients across a broad spectral range, size- and composition-tunable photoluminescence from the visible to the near-infrared, and low toxicity. However, the application of NIR-emitting CIS QDs is still hindered by large size and shape dispersions and low photoluminescence quantum yields (PLQYs). In this work, we develop an efficient pathway to synthesize highly luminescent NIR-emitting wurtzite CIS/ZnS QDs, starting from template Cu2-x S nanocrystals (NCs), which are converted by topotactic partial Cu+ for In3+ exchange into CIS NCs. These NCs are subsequently used as cores for the overgrowth of ZnS shells (≤1 nm thick). The CIS/ZnS core/shell QDs exhibit PL tunability from the first to the second NIR window (750-1100 nm), with PLQYs ranging from 75% (at 820 nm) to 25% (at 1050 nm), and can be readily transferred to water upon exchange of the native ligands for mercaptoundecanoic acid. The resulting water-dispersible CIS/ZnS QDs possess good colloidal stability over at least 6 months and PLQYs ranging from 39% (at 820 nm) to 6% (at 1050 nm). These PLQYs are superior to those of commonly available water-soluble NIR-fluorophores (dyes and QDs), making the hydrophilic CIS/ZnS QDs developed in this work promising candidates for further application as NIR emitters in bioimaging. The hydrophobic CIS/ZnS QDs obtained immediately after the ZnS shelling are also attractive as fluorophores in luminescent solar concentrators.