Challenging thermodynamics: combining immiscible elements in a single-phase nano-ceramic.

The Hume-Rothery rules governing solid-state miscibility limit the compositional space for new inorganic material discovery. Here, we report a non-equilibrium, one-step, and scalable flame synthesis method to overcome thermodynamic limits and incorporate immiscible elements into single phase ceramic nanoshells. Starting from prototype examples including (NiMg)O, (NiAl)Ox, and (NiZr)Ox, we then extend this method to a broad range of Ni-containing ceramic solid solutions, and finally to general binary combinations of elements. Furthermore, we report an "encapsulated exsolution" phenomenon observed upon reducing the metastable porous (Ni0.07Al0.93)Ox to create ultra-stable Ni nanoparticles embedded within the walls of porous Al2O3 nanoshells. This nanoconfined structure demonstrated high sintering resistance during 640 h of catalysis of CO2 reforming of methane, maintaining constant 96% CH4 and CO2 conversion at 800 °C and dramatically outperforming conventional catalysts. Our findings could greatly expand opportunities to develop novel inorganic energy, structural, and functional materials.

Branching phenomena in nanostructure synthesis illuminated by the study of Ni-based nanocomposites.

Branching phenomena are ubiquitous in both natural and artificial crystallization processes. The branched nanostructures' emergent properties depend upon their structures, but their structural tunability is limited by an inadequate understanding of their formation mechanisms. Here we developed an ensemble of Nickel-Based nano-Composites (NBCs) to investigate branching phenomena in solution-phase synthesis with precision and in depth. NBCs of 24 morphologies, including dots, core@shell dots, hollow shells, clusters, polyhedra, platelets, dendrites, urchins, and dandelions, were synthesized through systematic adjustment of multiple synthesis parameters. Relationships between the synthesis parameters and the resultant morphologies were analyzed. Classical or non-classical models of nucleation, nascent growth, 1D growth, 2D growth, 3D reconstruction, aggregation, and carburization were defined individually and then integrated to provide a holistic view of the formation mechanism of branched NBCs. Finally, guidelines were extracted and verified to guide the rational solution-phase syntheses of branched nanomaterials with emergent biological, chemical, and physical properties for potential applications in immunology, catalysis, energy storage, and optics. Demonstrating a systematic approach for deconvoluting the formation mechanism and enhancing the synthesis tunability, this work is intended to benefit the conception, development, and improvement of analogous artificial branched nanostructures. Moreover, the progress on this front of synthesis science would, hopefully, deepen our understanding of branching phenomena in nature.

Ultrasensitive Room-Temperature NO2 Detection Using SnS2/MWCNT Composites and Accelerated Recovery Kinetics by UV Activation.

High performance with lower power consumption is one among the essential features of a sensing device. Minute traces of hazardous gases such as NO2 are difficult to detect. Tin disulfide (SnS2) nanosheets have emerged as a promising NO2 sensor. However, their poor room-temperature conductivity gives rise to inferior sensitivity and sluggish recovery rates, thereby hindering their applications. To mitigate this problem, we present a low-cost ultrasensitive NO2 gas sensor with tin disulfide/multiwalled carbon nanotube (SnS2/MWCNT) nanocomposites, prepared using a single-step hydrothermal method, as sensing elements. Relative to pure SnS2, the conductivity of nanocomposites improved significantly. The sensor displayed a decrease in resistance when exposed to NO2, an oxidizing gas, and exhibited p-type conduction, also confirmed in separate Mott-Schottky measurements. At a temperature of 20 °C, the sensor device has a relative response of about ≈5% (3%) for 25 ppb (1 ppb) of NO2 with complete recovery in air (10 min) and excellent recovery rates with UV activation (0.3 min). A theoretical lower limit of detection (LOD) of 7 ppt implies greater sensitivity than all previously reported SnS2-based gas sensors, to the best of our knowledge. The improved sensing characteristics were attributed to the formation of nano p-n heterojunctions, which enhances the charge transport and gives rise to faster response. The composite sensor also demonstrated good NO2 selectivity against a variety of oxidizing and reducing gases, as well as excellent stability and long-term durability. This work will provide a fresh perspective on SnS2-based composite materials for practical gas sensors.

Humidity-Tolerant Room-Temperature Selective Dual Sensing and Discrimination of NH3 and NO Using a WS2/MWCNT Composite.

Continuous detection of toxic and hazardous gases like nitric oxide (NO) and ammonia (NH3) is needed for environmental management and noninvasive diagnosis of various diseases. However, to the best of our knowledge, dual detection of these two gases has not been previously reported. To address the challenge, we demonstrate the design and fabrication of low-cost NH3 and NO dual gas sensors using tungsten disulfide/multiwall carbon nanotube (WS2/MWCNT) nanocomposites as sensing channels which maintained their performance in a humid environment. The composite-based device has shown successful dual detection at temperatures down to 18 °C and relative humidity of 90%. For 0.1 ppm ammonia, it exhibited a p-type conduction with response and recovery times of 102 and 261 s, respectively; on the other hand, with NO (10 ppb, n-type), these times were 285 and 198 s, respectively. The device with 5 mg MWCNTs possesses a superior selectivity along with a relative response of ≈7% (5 ppb) and ≈5% (0.1 ppm) for NO and NH3, respectively, at 18 °C. The response is less affected by relative humidity, and this is attributed to the presence of MWCNTs that are hydrophobic in nature. Upon simultaneous exposure to NO (5-10 ppb) and NH3 (0.1-5 ppm), the response was dominated by NO, implying clear discrimination to the simultaneous presence of these two gases. We propose a sensing mechanism based on adsorption/desportion and accompanied charge transfer between the adsorbed gas molecules and sensing surface. The results suggest that an optimized weight ratio of WS2 and MWCNTs could govern favorable sensing conditions for a particular gas molecule.

A General Route to Flame Aerosol Synthesis and In Situ Functionalization of Mesoporous Silica.

Mesoporous silica is a versatile material for energy, environmental, and medical applications. Here, for the first time, we report a flame aerosol synthesis method for a class of mesoporous silica with hollow structure and specific surface area exceeding 1000 m2 g-1 . We show its superior performance in water purification, as a drug carrier, and in thermal insulation. Moreover, we propose a general route to produce mesoporous nanoshell-supported nanocatalysts by in situ decoration with active nanoclusters, including noble metal (Pt/SiO2 ), transition metal (Ni/SiO2 ), metal oxide (CrO3 /SiO2 ), and alumina support (Co/Al2 O3 ). As a prototypical application, we perform dry reforming of methane using Ni/SiO2 , achieving constant 97 % CH4 and CO2 conversions for more than 200 hours, dramatically outperforming an MCM-41 supported Ni catalyst. This work provides a scalable strategy to produce mesoporous nanoshells and proposes an in situ functionalization mechanism to design and produce flexible catalysts for many reactions.

Magnetically Controllable Flowerlike, Polyhedral Ag-Cu-Co3O4 for Surface-Enhanced Raman Scattering.

Syntheses of Cu-, Ag-, and Ag-Cu-Co3O4 nanomaterials are of interest for a wide range of applications including electrochemistry, thermal catalysis, energy storage, and electronics. However, Co3O4-based nanomaterials have not been explored for surface-enhanced Raman scattering (SERS). Here, we present Cu-, Ag-, and Ag-Cu-Co3O4 nanomaterials of a hierarchical flower shape comprising two separate phases: a pure Cu or Ag core and multiple Co3O4 branches, in which the optical properties of the core and the magnetic properties of the branches are integrated. In addition, a series of nonmagnetic Cu-dominant Cu-Co-O polyhedra without Co3O4 branches were derived from Cu-Co3O4. The polyhedron morphology can be controlled and transformed among cubes, cuboctahedra, and truncated octahedra by tuning the amounts of ligands and additives to vary the potential energy and growth rate of specific crystal facets. The flowerlike Cu-, Ag-, and Ag-Cu-Co3O4 were characterized for SERS enhancement, showing that Ag-Cu-Co3O4 does not enhance SERS from 4-mercaptobenzoic acid (4-MBA) but dramatically and selectively does so for adsorbed rhodamine 6G. Obviously, the synergy of Ag and Cu within the Co3O4 flower constraint promotes the SERS activity. This type of spinel with not only excellent SERS activity but also ferromagnetism could be of great potential in tandem SERS detection/magnetic separation and related applications.