Direct Environmental Lead Detection by Photoluminescent Perovskite Formation with Nanogram Sensitivity.

Although the global ban on leaded gasoline has markedly reduced lead poisoning, many other environmental sources of lead exposure, such as paint, pipes, mines, and recycling sites remain. Existing methods to identify these sources are either costly or unreliable. We report here a new, sensitive, and inexpensive lead detection method that relies on the formation of a perovskite semiconductor. The method only requires spraying the material of interest with methylammonium bromide and observing whether photoluminesence occurs under UV light to indicate the presence of lead. The method detects as little as 1.0 ng/mm2 of lead by the naked eye and 50 pg/mm2 using a digital photo camera. We exposed more than 50 different materials to our reagent and found no false negatives or false positives. The method readily detects lead in soil, paint, glazing, cables, glass, plastics, and dust and could be widely used for testing the environment and preventing lead poisoning.

Architected Metal Selenides via Sequential Cation and Anion Exchange on Self-Organizing Nanocomposites.

Shape-preserving conversion reactions have the potential to unlock new routes for self-organization of complex three-dimensional (3D) nanomaterials with advanced functionalities. Specifically, developing such conversion routes toward shape-controlled metal selenides is of interest due to their photocatalytic properties and because these metal selenides can undergo further conversion reactions toward a wide range of other functional chemical compositions. Here, we present a strategy toward metal selenides with controllable 3D architectures using a two-step self-organization/conversion approach. First, we steer the coprecipitation of barium carbonate nanocrystals and silica into nanocomposites with controllable 3D shapes. Second, using a sequential exchange of cations and anions, we completely convert the chemical composition of the nanocrystals into cadmium selenide (CdSe) while preserving the initial shape of the nanocomposites. These architected CdSe structures can undergo further conversion reactions toward other metal selenides, which we demonstrate by developing a shape-preserving cation exchange toward silver selenide. Moreover, our conversion strategy can readily be extended to convert calcium carbonate biominerals into metal selenide semiconductors. Hence, the here-presented self-assembly/conversion strategy opens exciting possibilities toward customizable metal selenides with complex user-defined 3D shapes.

Contraction and Expansion of Nanocomposites during Ion Exchange Reactions.

The next generation of advanced functional materials can greatly benefit from methods for realizing the right chemical composition at the right place. Nanocomposites of amorphous silica and metal carbonate nanocrystals (BaCO3/SiO2) form an attractive starting point as they can straightforwardly be assembled in different controllable three-dimensional (3D) shapes, while the chemical composition of the nanocrystals can be completely converted via ion exchange. Nevertheless, it is still unknown-let alone predictable-how nanoscopic changes in the lattice volume of the nanocrystals translate to changes in the microscopic dimensions of 3D BaCO3/SiO2 structures during ion exchange. Here, we demonstrate that the microscopic shape adapts to contraction and expansion of the atomic spacing of nanocrystals. Starting from BaCO3/SiO2, we systematically decrease and increase lattice volumes by converting the BaCO3 nanocrystals into a range of chalcogenides and perovskites. Based on geometrical analysis, we obtain a precise prediction for how the microscopic nanocomposite volume follows the change in nanoscopic crystal volume. The silica matrix facilitates mechanical flexibility to adapt to nanoscopic volume changes, while preserving the 3D morphology and fine details of the original composite with high fidelity. The versatility and predictability of shape-preserving conversion reactions open up exciting opportunities for using nanocomposites as functional components.

Rational Design of Bioinspired Nanocomposites with Tunable Catalytic Activity.

Biological assembly processes offer inspiration for ordering building blocks across multiple length scales into advanced functional materials. Such bioinspired strategies are attractive for assembling supported catalysts, where shaping and structuring across length scales are essential for their performance but still remain tremendously difficult to achieve. Here, we present a simple bioinspired route toward supported catalysts with tunable activity and selectivity. We coprecipitate shape-controlled nanocomposites with large specific surface areas of barium carbonate nanocrystals that are uniformly embedded in a silica support. Subsequently, we exchange the barium carbonate to cobalt while preserving the nanoscopic layout and microscopic shape, and demonstrate their catalytic performances in the Fischer-Tropsch synthesis as a case study. Control over the crystal size between 10 and 17 nm offers tunable activity and selectivity for shorter (C5-C11) and longer (C20+) hydrocarbons, respectively. Hence, these results open simple, versatile, and scalable routes to tunable and highly reactive bioinspired catalysts.

Shape-Preserving Chemical Conversion of Architected Nanocomposites.

Forging customizable compounds into arbitrary shapes and structures has the potential to revolutionize functional materials, where independent control over shape and composition is essential. Current self-assembly strategies allow impressive levels of control over either shape or composition, but not both, as self-assembly inherently entangles shape and composition. Herein, independent control over shape and composition is achieved by chemical conversion reactions on nanocrystals, which are first self-assembled in nanocomposites with programmable microscopic shapes. The multiscale character of nanocomposites is crucial: nanocrystals (5-50 nm) offer enhanced chemical reactivity, while the composite layout accommodates volume changes of the nanocrystals (≈25%), which together leads to complete chemical conversion with full shape preservation. These reactions are surprisingly materials agnostic, allowing a large diversity of chemical pathways, and development of conversion pathways yielding a wide selection of shape-controlled transition metal chalcogenides (cadmium, manganese, iron, and nickel oxides and sulfides). Finally, the versatility and application potential of this strategy is demonstrated by assembling: 1) a scalable and highly reactive nickel catalyst for the dry reforming of butane, 2) an agile magnetic-controlled particle, and 3) an electron-beam-controlled reversible microactuator with sub-micrometer precision. Previously unimaginable customization of shape and composition is now achievable for assembling advanced functional components.

Autonomous mesoscale positioning emerging from myelin filament self-organization and Marangoni flows.

Out-of-equilibrium molecular systems hold great promise as dynamic, reconfigurable matter that executes complex tasks autonomously. However, translating molecular scale dynamics into spatiotemporally controlled phenomena emerging at mesoscopic scale remains a challenge-especially if one aims at a design where the system itself maintains gradients that are required to establish spatial differentiation. Here, we demonstrate how surface tension gradients, facilitated by a linear amphiphile molecule, generate Marangoni flows that coordinate the positioning of amphiphile source and drain droplets floating at air-water interfaces. Importantly, at the same time, this amphiphile leads, via buckling instabilities in lamellar systems of said amphiphile, to the assembly of millimeter long filaments that grow from the source droplets and get absorbed at the drain droplets. Thereby, the Marangoni flows and filament organization together sustain the autonomous positioning of interconnected droplet-filament networks at the mesoscale. Our concepts provide potential for the development of non-equilibrium matter with spatiotemporal programmability.