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Adding CrIII or AlIII salts into the water suspension of platinum group metal (PGM) catalysts accelerated oxyanion pollutant reduction by up to 600%. Our initial attempts of adding K2CrVIO4, K2CrVI2O7, or KCrIII(SO4)2 into Pd/C enhanced BrO3- reduction with 1 atm H2 by 6-fold. Instrument characterizations and kinetic explorations collectively confirmed the immobilization of reduced CrVI as CrIII(OH)3 on the catalyst surface. This process altered the ζ-potentials from negative to positive, thus substantially enhancing the Langmuir-Hinshelwood adsorption equilibrium constant for BrO3- onto Pd/C by 37-fold. Adding AlIII(OH)3 from alum at pH 7 achieved similar enhancements. The Cr-Pd/C and Al-Pd/C showed top-tier efficiency of catalytic performance (normalized with Pd dosage) among all the reported Pd catalysts on conventional and nanostructured support materials. The strategy of adding inert metal hydroxides works for diverse PGMs (palladium and rhodium), substrates (BrO3- and ClO3-), and support materials (carbon, alumina, and silica). This work shows a simple, inexpensive, and effective example of enhancing catalyst activity and saving PGMs for environmental applications.

A Z-scheme Fe2O3@C@1T/2H-MoS2 heterostructured catalyst is constructed using carbon and 1T-MoS2 as bridging layers, realizing high-performance H2O2 generation and a self-sufficient heterogeneous photo-Fenton reaction.

In this paper, a blind background calibration technique for super-regenerative receivers (SRRs) is presented. The proposed calibration scheme is designed to help SRRs to maintain their high sensitivity and immunity to negative transconductance ( -Gm ) variations under process-voltagetemperature (PVT) variations. Unlike the conventional foreground -Gm variations calibration techniques that require interruption of the receiver input, the proposed calibration technique employs input signal statistics and does not require interruption of the input bit-stream for extraction of the errors. The proposed scheme is based on an adaptive algorithm that compares the probability distribution of the pseudorandom-input (PI) stream and the output of the super-regenerative oscillator (SRO) and forces them to coincide at the end of the calibration. The proposed technique is implemented using a mixed-signal detection circuit and a finite state machine (FSM) that drives an 8-bit successive approximation register (SAR) to adjust the compensation current in the SRO. The simulation results successfully verify the effectiveness and reliability of the proposed calibration technique and show significant improvements in terms of SRR sensitivity under different process corners.

Colloidal self-assembly refers to a solution-processed assembly of nanometer-/micrometer-sized, well-dispersed particles into secondary structures, whose collective properties are controlled by not only nanoparticle property but also the superstructure symmetry, orientation, phase, and dimension. This combination of characteristics makes colloidal superstructures highly susceptible to remote stimuli or local environmental changes, representing a prominent platform for developing stimuli-responsive materials and smart devices. Chemists are achieving even more delicate control over their active responses to various practical stimuli, setting the stage ready for fully exploiting the potential of this unique set of materials. This review addresses the assembly of colloids into stimuli-responsive or smart nanostructured materials. We first delineate the colloidal self-assembly driven by forces of different length scales. A set of concepts and equations are outlined for controlling the colloidal crystal growth, appreciating the importance of particle connectivity in creating responsive superstructures. We then present working mechanisms and practical strategies for engineering smart colloidal assemblies. The concepts underpinning separation and connectivity control are systematically introduced, allowing active tuning and precise prediction of the colloidal crystal properties in response to external stimuli. Various exciting applications of these unique materials are summarized with a specific focus on the structure-property correlation in smart materials and functional devices. We conclude this review with a summary of existing challenges in colloidal self-assembly of smart materials and provide a perspective on their further advances to the next generation.

Platinum (Pt) has found wide use as an electrocatalyst for sustainable energy conversion systems1–3. The activity of Pt is controlled by its electronic structure (typically, the d-band centre), which depends sensitively on lattice strain4,5. This dependence can be exploited for catalyst design4,6–8, and the use of core–shell structures and elastic substrates has resulted in strain-engineered Pt catalysts with drastically improved electrocatalytic performances7,9–13. However, it is challenging to map in detail the strain–activity correlations in Pt-catalysed conversions, which can involve a number of distinct processes, and to identify the optimal strain modification for specific reactions. Here we show that when ultrathin Pt shells are deposited on palladium-based nanocubes, expansion and shrinkage of the nanocubes through phosphorization and dephosphorization induces strain in the Pt(100) lattice that can be adjusted from −5.1 per cent to 5.9 per cent. We use this strain control to tune the electrocatalytic activity of the Pt shells over a wide range, finding that the strain–activity correlation for the methanol oxidation reaction and hydrogen evolution reaction follows an M-shaped curve and a volcano-shaped curve, respectively. We anticipate that our approach can be used to screen out lattice strain that will optimize the performance of Pt catalysts—and potentially other metal catalysts—for a wide range of reactions. By depositing platinum shells on palladium-based nanocubes, the strain can be controlled by through phosphorization and dephosphorization, making it possible to tune the electrocatalytic activity of the platinum shells.

Drop-casting manganese oxide (MnO

We report a method for fast Fourier transform (FFT)-weighted optical coherence tomography (OCT) in the second biological tissue transparency window by actively modulating the plasmonic scattering of Fe

Engineering the nucleation and growth of plasmonic metals (Ag and Au) on their pre-existing seeds is expected to produce nanostructures with unconventional morphologies and plasmonic properties that may find unique applications in sensing, catalysis, and broadband energy harvesting. Typical seed-mediated growth processes take advantage of the perfect lattice match between the deposited metal and seeds to induce conformal coating, leading to either simple size increases (e.g., Au on Au) or the formation of core-shell structures (e.g., Ag on Au) with limited morphology change. In this work, we show that the introduction of a thin layer of metal with considerable lattice mismatch can effectively induce the nucleation of well-defined Au islands on Au nanocrystal seeds. By controlling the interfacial energy between the seed and the deposited material, the oxidative ripening, and the surface diffusion of metal precursors, we can regulate the number of islands on the seeds and produce complex Au nanostructures with morphologies tunable from core-satellites to tetramers, trimers, and dimers. This surface engineering strategy is of great significance in nanomaterial synthesis as it is general and can be used to create secondary structures of many other nanocrystals in a controllable manner.

Nanocomposites containing FeS as catalyst and MoS2 as cocatalyst have been synthesized toward efficient heterogeneous Fenton reaction. The deposition of FeS nanoparticles in situ on the surface of MoS2 nanosheets creates strong contact between the two components and generates a large number of exposed Mo6+ sites and sulfur vacancies, which contribute to the enhanced degradation rate by accelerating Fe3+/Fe2+ cycling and ensuring rapid electron transfer. In addition, the MoS2/FeS nanocomposite catalysts exhibit the best performance at near-neutral conditions (pH 6.5), which solves the challenges in conventional Fenton reactions such as leaching of metal ions, the formation of iron slurry, and the need of adjusting solution pH. Further, the nanocomposite can maintain high efficiency after many recycling experiments. It is believed that the MoS2/FeS nanocomposite represents an efficient heterogeneous Fenton catalyst that can greatly promote the performance of advanced oxidation processes (AOPs) for solving practical environmental issues.

Photoacoustic (PA) imaging uses photon-phonon conversion for high-resolution tomography of biological tissues and functions. Exogenous contrast agents are often added to improve the image quality, but the interference from endogenous molecules diminishes the imaging sensitivity and specificity. We report a background-free PA imaging technique based on the active modulation of PA signals via magnetic alignment of Fe

Summary Controllable assembly of molecular and nanoscale building blocks into uniform superstructures up to bulk dimensions remains a key challenge in the next phase of nanotechnology development. Here, we report the self-assembly of superstructures at all scales by taking advantage of the partial miscibility of water and 1-butanol to generate transient aqueous emulsion droplets that can encapsulate the target materials and introduce them into template holes. Further diffusion of water into 1-butanol depletes the emulsion droplets, assembling the building blocks into one well-defined superstructure in each hole. Superstructuring of various types and shapes of nanoparticles, biomolecules, and inorganic compounds could be achieved without the need for surfactants and chemical modifications. The versatility, scalability, low-cost, and accurate positioning are crucial advantages for the future development of advanced precision manufacturing.

Conventional templating synthesis confines the growth of seeds in rigid spaces to achieve faithful morphological replication. Herein, we explore the use of spherical shape-deformable polymeric nanoshells to regulate the anisotropic growth of Ag nanoplates. The flexible shells deform adaptively to accommodate the initial overgrowth of the seeds but restrict the growth in the directions where the shells are fully stretched, eventually producing nanoplates with an unconventional circular profile. The diameter of the final Ag nanoplates can be precisely predicted by stretching and flattering the nanoshells into a plate-like capsule while retaining their original internal surface area. Furthermore, unlike conventional templates, the polymer shells eventually turn themselves into a conformal coating that binds to the surface of the full-grown Ag nanoplates and significantly enhances their stability against oxidative etching.

The unprecedented development of inorganic nanostructure synthesis has paved the way toward their broad applications in areas such as food science, agroforestry, energy conversion, and biomedicine. The precise manipulation of the nucleation and subsequent growth has been recognized as the central guiding principle for controlling the size and morphology of the nanostructures. However, conventional colloid syntheses based on direct precipitation reactions still have limitations in their versatility and extendibility. The crystal structure of a material determines the limited number of possible morphologies that its nanostructures can adopt. Further, as nucleation and growth kinetics are sensitive to not only the nature of the precipitation reactions but also ligands and ripening effect, rigorous control of reaction conditions must be established for every specific synthesis. In addition, multiple experimental parameters are entangled with each other, thereby requiring rigorous control of all reaction conditions. As a result, it is usually challenging to extend a synthetic recipe from one material to another. As an alternative method, the direct transformation of existing nanostructures into target ones has become an effective and robust approach capable of creating various complex nanostructures that are otherwise challenging to obtain using conventional methods. To this end, an in-depth understanding of nanoscale transformation toward the synthesis of inorganic nanostructures with diverse properties and applications is highly desirable.In this Account, we aim to reveal the critical effect of the interfacial diffusion on controlled nanoscale transformation. We first discuss how the interdiffusion rates determine the morphology and properties of bimetallic nanostructures. While equal interdiffusion rates lead to perfect mixing and generate fully alloyed nanostructures, interdiffusion at unequal rates creates vacancies in the fast diffusion side, which may cause dramatic morphological transformation to the nanostructures. Then, we introduce interfacial reactions, including the Kirkendall cavitation process, elimination reaction, and solid-state reaction, to promote the unbalanced interdiffusion and generalize nanoscale transformations in materials of various compositions, morphologies, and crystal structures. Finally, we discuss the use of capping ligands to inhibit the diffusion of atoms on one side of the interface in order to enable selective etching or transformation of the nanostructures. By modifying the nanostructured surface with specific capping ligands, the diffusion of surface atoms is restricted. When nanoparticles undergo chemical reactions (such as etching or heating), the outward diffusion of substances dominates, thereby successfully achieving chemical and morphological transformations. We believe that controlled interfacial diffusion can effectively manipulate nanoscale transformations, thus providing new strategies for the custom synthesis of multifunctional nanomaterials for various specific applications.

The slow kinetics at the cathode of oxygen reduction reaction (ORR) seriously limits the efficiencies of fuel cells and metal-air batteries. Pt, the state-of-the-art ORR electrocatalyst, suffers from high cost, low earth abundance, and poor stability. Here a self-templated strategy based on metal-organic frameworks (MOFs) is proposed for the fabrication of hollow nitrogen-doped carbon spheres that are embedded with cobalt nanoparticles (Co/HNC). The Co/HNC manifests better ORR activities, methanol tolerance, and stability than commercial Pt/C. The high ORR performance of Co/NHC can be attributed to the hollow structure which provides enlarged electrochemically active surface area, the formation of more Co-N species, and the introduction of defects. This work highlights the significance of rational engineering of MOFs for enhanced ORR activity and stability and offers new routes to the design and synthesis of high-performance electrocatalysts.

International audience; Over the last three decades, photonic crystals (PhCs) have attracted intense interests thanks to their broad potential applications in optics and photonics. Generally, these structures can be fabricated via either ‘‘top-down’’ lithographic or ‘‘bottom-up’’ self-assembly approaches. The self-assembly approaches have attracted particular attention due to their low cost, simple fabrication processes, relative convenience of scaling up, and the ease of creating complex structures with nanometer precision. The self-assembled colloidal crystals (CCs), which are good candidates for PhCs, have offered unprecedented opportunities for photonics, optics, optoelectronics, sensing, energy harvesting, environmental remediation, pigments, and many other applications. The creation of high-quality CCs and their mass fabrication over large areas are the critical limiting factors for real-world applications. This paper reviews the state-of-the-art techniques in the self-assembly of colloidal particles for the fabrication of large-area high-quality CCs and CCs with unique symmetries. The first part of this review summarizes the types of defects commonly encountered in the fabrication process and their effects on the optical properties of the resultant CCs. Next, the mechanisms of the formation of cracks/defects are discussed, and a range of versatile fabrication methods to create large-area crack/defect-free twodimensional and three-dimensional CCs are described. Meanwhile, we also shed light on both the advantages and limitations of these advanced approaches developed to fabricate high-quality CCs. The self-assembly routes and achievements in the fabrication of CCs with the ability to open a complete photonic bandgap, such as cubic diamond and pyrochlore structure CCs, are discussed as well. Then emerging applications of large-area high-quality CCs and unique photonic structures enabled by the advanced self-assembly methods are illustrated. At the end of this review, we outlook the future approaches in the fabrication of perfect CCs and highlight their novel real-world applications.

We report the unconventional space-free confined growth of Au nanoshells with well-defined plasmonic properties and active tuning of their plasmon coupling by the nanoscale magnetic assembly. The seeded growth of Au exclusively occurred at the hard-soft interfaces between the Fe3O4 core and phenolic resin without the need of creating a limiting space, which represents a general and elegant approach to various core-shell nanostructures. The deformability of permeable phenolic layers plays an essential role in regulating the interfacial growth of Au nanoshells. While the polymer elasticity suppresses the radial deposition of Au atoms, their high deformability can afford enough spaces for the formation of conformal metallic shells. The coupled magnetic-plasmonic properties allow active tuning of the plasmon coupling and the resonant scattering of Au nanoshells by the magnetic assembly of the hybrid nanoparticles into plasmonic chains, whose potentials in applications have been demonstrated in designing transparent displays and anticounterfeiting devices.

Pristine titanium dioxide (TiO

We demonstrate a bio-inspired coating for novel imaging and sensing designs: the coating sorts different colors and linear polarizations. This coating, composed of conducting, nanofibrous polyaniline in an inverse opal film (PANI-IOF), is inexpensive and can feasibly be deposited over large areas on a range of flexible and non-flat substrates. With PANI IOFs, light is scattered into azimuthally polarized Debye rings. Subsequently, the diffracted speckle patterns carry compressed representations of the polarized illumination, which we reconstruct using shallow neural networks.

Plasmonic nanomaterials with strong absorption at near-infrared frequencies are promising photothermal therapy agents (PTAs). The pursuit of high photothermal conversion efficiency has been the central focus of this research field. Here, we report the development of plasmonic nanoparticle clusters (PNCs) as highly efficient PTAs and provide a semiquantitative approach for calculating their resonant frequency and absorption efficiency by combining the effective medium approximation (EMA) theory and full-wave electrodynamic simulations. Guided by the theoretical prediction, we further develop a universal strategy of space-confined seeded growth to prepare various PNCs. Under optimized growth conditions, we achieve a record photothermal conversion efficiency of up to ∼84% for gold-based PNCs, which is attributed to the collective plasmon-coupling-induced near-unity absorption efficiency. We further demonstrate the extraordinary photothermal therapy performance of the optimized PNCs iniin vivo/iapplication. Our work demonstrates the high feasibility and efficacy of PNCs as nanoscale PTAs.

We demonstrate polarization-switching in conducting, electrochromic photonic-crystal films. These ordered, multi-scale structures offer numerous opportunities for inexpensive, large-area, active metasurfaces and fabrication over flexible and non-flat substrates.

Expensive instruments and complicated data processing are often required to discriminate solvents with similar structures and properties. Colorimetric sensors with high selectivity, low cost, and good portability are highly desirable to simplify such detection tasks. Herein, we report the fabrication of a photonic crystal sensor based on the self-assembled resorcinol formaldehyde (RF) hollow spheres to realize colorimetric sensing of polar solvents, including homologs and isomers based on the saturated diffusion time. The diffusion of solvent molecules through the photonic crystal film exhibits a unique three-step diffusion profile accompanied by a dynamic color change, as determined by the physicochemical properties of the solvent molecules and their interactions with the polymer shells, making it possible to accurately identify the solvent type based on the dynamic reflection spectra or visual perception. With its superior selectivity and sensitivity, this single-component colorimetric sensor represents a straightforward tool for convenient solvent detection and identification.

Mn4+ ion-doped red-emitting oxides are promising candidates for light-emitting-diode phosphors, but the formation and stabilization of Mn4+ in the oxide matrix remain a challenge due to the spontan...

Solar-driven interfacial steam generation is a promising technique for clean water production because it can minimize thermal loss by localizing solar-to-heat conversion at the air/liquid interface. Here we report an integrated solar evaporator by partially growing 2D polypyrrole microsheets within a melamine foam through chemical vapor polymerization. These microsheets can induce multiple light reflections within the foam, enable omnidirectional light absorption, provide abundant surfaces to promote heat transfer, and achieve spatially defined hydrophobicity to facilitate vapor escape. Meanwhile, the inherent hydrophilicity of the bottom part of the foam promotes spontaneous upward water transport and suppresses heat loss. The composite foam exhibits an excellent apparent evaporation rate of ∼2 kg/(m

Metal nanoparticles have drawn great attention in heterogeneous catalysis. One challenge is that they are easily deactivated by migration-coalescence during the catalysis process because of their high surface energy. With the rapid development of nanoscience, encapsulating metal nanoparticles in nanoshells or nanopores becomes one of the most promising strategies to overcome the stability issue of the metal nanoparticles. Besides, the activity and selectivity could be simultaneously enhanced by taking advantage of the synergy between the metal nanoparticles and the encapsulating materials as well as the molecular sieving property of the encapsulating materials. In this review, we provide a comprehensive summary of the recent progress in the synthesis and catalytic properties of the encapsulated metal nanoparticles. This review begins with an introduction to the synthetic strategies for encapsulating metal nanoparticles with different architectures developed to date, including their encapsulation in nanoshells of inorganic oxides and carbon, porous materials (zeolites, metal-organic frameworks, and covalent organic frameworks), and organic capsules (dendrimers and organic cages). The advantages of the encapsulated metal nanoparticles are then discussed, such as enhanced stability and recyclability, improved selectivity, strong metal-support interactions, and the capability of enabling tandem catalysis, followed by the introduction of some representative applications of the encapsulated metal nanoparticles in thermo-, photo-, and electrocatalysis. At the end of this review, we discuss the remaining challenges associated with the encapsulated metal nanoparticles and provide our perspectives on the future development of the field.

Thermal treatment is generally a desirable process to improve the properties of nanomaterials, which however often leads to undesirable problems such as aggregation and shape deformation. Here, we ...

We report a remarkable thickness-dependent wrinkling behavior of oxygen plasma-treated polydimethylsiloxane (PDMS) films, in which an energy barrier separates the wrinkling mechanics into two regimes. For thick films, the film wrinkles with a constant periodicity which can be precisely predicted by the classic nonlinear finite mechanics. Reducing the film thickness below 1 mm leads to nonuniform wrinkles with an increasing periodicity which gives rise to random scattering and transparency changes under mechanical strains. By tuning the film thickness, we were able to control both the quality and size of the periodic wrinkles and further design mechanochromic devices featuring brilliant structural colors and programmable colorimetric responses. This work sheds light on the fundamental understanding of the wrinkling mechanics of bilayer systems and their intriguing mechanochromic applications.

The application of electrocatalysts with high activity to a practical water electrolysis cell is a crucial challenge for the production of pure hydrogen and commercialization of the water electrolyzer. Herein, a nanosized Cu0.5Co2.5O4 catalyst synthesized by co-precipitation by adjusting pH is applied to the anion exchange membrane water electrolysis (AEMWE) cell as an anode, which is demonstrated to have higher efficiency and stability than noble metal-based anodes. The composition (Cu/Co) and morphology of Cu0.5Co2.5O4 change as the pH increases and then nanoparticles are formed at pH 11, where oxygen vacancies are formed by the etching of Cu. In the density functional theory study, the electronic structure of Co modified by Cu in the Co3O4 lattice leads to an optimal adsorption strength, resulting in a free energy diagram in which the potential of Cu0.5Co2.5O4 (1.756 V vs. reversible hydrogen electrode, RHE) is more thermodynamically favorable than that of Co3O4 (1.951 V vs. RHE). The Cu0.5Co2.5O4 catalyst has a recorded overpotential of 285 mV at 10 mA cm−2 in 1 M KOH. Furthermore, the AEMWE cell using Cu0.5Co2.5O4 as an anode exhibited a current density of 1.3 A cm−2 at 1.8 V, which is the highest performance among the reported papers and maintains around 80% energy conversion efficiency for 100 hours.