Compressibility Studies of Copper Selenides Obtained by Cation Exchange Reaction Revealing the New CsCl Phase.

In this study, we conducted a high-pressure investigation of Cu2-xSe nanostructures with pyramid- and plate-like morphologies, created through cation exchange from zinc-blende CdSe nanocrystals and wurtzite CdSe nanoplatelets respectively. Using a diamond anvil cell setup at the APS synchrotron, we observed the phase transitions in the Cu2-xSe nanostructures up to 40 GPa, identifying a novel CsCl-type lattice with Pm3̅m symmetry above 4 GPa. This CsCl-type structure, previously unreported in copper selenides, was partially retained after decompression. Our results indicate that the initial crystalline structure of CdSe does not affect the stability of Cu2-xSe nanostructures formed via cation exchange. Both morphologies of Cu2-xSe sintered under compression, potentially contributing to the stabilization of the high-pressure phase through interfacial defects. These findings are significant for discovering new phases with potential applications in future technologies.

Self-Cleaning Highly Porous TiO2 Coating Designed by Swelling-Assisted Sequential Infiltration Synthesis (SIS) of a Block Copolymer Template.

Photocatalytic self-cleaning coatings with a high surface area are important for a wide range of applications, including optical coatings, solar panels, mirrors, etc. Here, we designed a highly porous TiO2 coating with photoinduced self-cleaning characteristics and very high hydrophilicity. This was achieved using the swelling-assisted sequential infiltration synthesis (SIS) of a block copolymer (BCP) template, which was followed by polymer removal via oxidative thermal annealing. The quartz crystal microbalance (QCM) was employed to optimize the infiltration process by estimating the mass of material infiltrated into the polymer template as a function of the number of SIS cycles. This adopted swelling-assisted SIS approach resulted in a smooth uniform TiO2 film with an interconnected network of pores. The synthesized film exhibited good crystallinity in the anatase phase. The resulting nanoporous TiO2 coatings were tested for their functional characteristics. Exposure to UV irradiation for 1 h induced an improvement in the hydrophilicity of coatings with wetting angle reducing to unmeasurable values upon contact with water droplets. Furthermore, their self-cleaning characteristics were tested by measuring the photocatalytic degradation of methylene blue (MB). The synthesized porous TiO2 nanostructures displayed promising photocatalytic activity, demonstrating the degradation of approximately 92% of MB after 180 min under ultraviolet (UV) light irradiation. Thus, the level of performance was comparable to the photoactivity of commercial anatase TiO2 nanoparticles of the same quantity. Our results highlight a new robust approach for designing hydrophilic self-cleaning coatings with controlled porosity and composition.

Binder-Free Cnt Cathodes for Li-O2 Batteries with More Than One Life.

Li-O2 batteries (LOB) performance degradation ultimately occurs through the accumulation of discharge products and irreversible clogging of the porous electrode during the cycling. Electrode binder degradation in the presence of reduced oxygen species can result in additional coating of the conductive surface, exacerbating capacity fading. Herein, a facile method to fabricate free-standing is established, binder-free electrodes for LOBs in which multi-wall carbon nanotubes form cross-linked networks exhibiting high porosity, conductivity, and flexibility. These electrodes demonstrate high reproducibility upon cycling in LOBs. After cell death, efficient and inexpensive methods to wash away the accumulated discharge products are demonstrated, as reconditioning method. The second life usage of these electrodes is validated, without noticeable loss of performance. These findings aim to assist in the development of greener high energy density batteries while reducing manufacturing and recycling costs.

Accessibility and Mechanical Stability of Nanoporous Zinc Oxide and Aluminum Oxide Coatings Synthesized via Infiltration of Polymer Templates.

The conformal nanoporous inorganic coatings with accessible pores that are stable under applied thermal and mechanical stresses represent an important class of materials used in the design of sensors, optical coatings, and biomedical systems. Here, we synthesize porous AlOx and ZnO coatings by the sequential infiltration synthesis (SIS) of two types of polymers that enable the design of porous conformal coatings-polymers of intrinsic microporosity (PIM) and block co-polymer (BCP) templates. Using quartz crystal microbalance (QCM), we show that alumina precursors infiltrate both polymer templates four times more efficiently than zinc oxide precursors. Using the quartz crystal microbalance (QCM) technique, we provide a comprehensive study on the room temperature accessibility to water and ethanol of pores in block copolymers (BCPs) and porous polymer templates using polystyrene-block-poly-4-vinyl pyridine (PS75-b-P4VP25) and polymers of intrinsic microporosity (PIM-1), polymer templates modified by swelling, and porous inorganic coatings such as AlOx and ZnO synthesized by SIS using such templates. Importantly, we demonstrate that no structural damage occurs in inorganic nanoporous AlOx and ZnO coatings synthesized via infiltration of the polymer templates during the water freezing/melting cycling tests, suggesting excellent mechanical stability of the coatings, even though the hardness of the inorganic nanoporous coating is affected by the polymer and precursor selections. We show that the hardness of the coatings is further improved by their annealing at 900 °C for 1 h, though for all the cases except ZnO obtained using the BCP template, this annealing has a negligible effect on the porosity of the material, as is confirmed by the consistency in the optical characteristics. These findings unravel new potential for the materials being used across various environment and temperature conditions.

Optical anisotropy of CsPbBr3 perovskite nanoplatelets.

The two-dimensional CsPbBr3 nanoplatelets have a quantum well electronic structure with a band gap tunable with sample thicknesses in discreet steps based upon the number of monolayers. The polarized optical properties of CsPbBr3 nanoplatelets are studied using fluorescence anisotropy and polarized transient absorption spectroscopies. Polarized spectroscopy shows that they have absorption and emission transitions which are strongly plane-polarized. In particular, photoluminescence excitation and transient absorption measurements reveal a band-edge polarization approaching 0.1, the limit of isotropic two-dimensional ensembles. The degree of anisotropy is found to depend on the thickness of the nanoplatelets: multiple measurements show a progressive decrease in optical anisotropy from 2 to 5 monolayer thick nanoplatelets. In turn, larger cuboidal CsPbBr3 nanocrystals, are found to have consistently positive anisotropy which may be attributed to symmetry breaking from ideal perovskite cubes. Optical measurements of anisotropy are described with respect to the theoretical framework developed to describe exciton fine structure in these materials. The observed planar absorption and emission are close to predicted values at thinner nanoplatelet sizes and follow the predicted trend in anisotropy with thickness, but with larger anisotropy than theoretical predictions. Dominant planar emission, albeit confined to the thinnest nanoplatelets, is a valuable attribute for enhanced efficiency of light-emitting devices.

Macroscale Superlubricity Induced by MXene/MoS2 Nanocomposites on Rough Steel Surfaces under High Contact Stresses.

Toward the goal of achieving superlubricity, or near-zero friction, in industrially relevant material systems, solution-processed multilayer Ti3C2Tx-MoS2 blends are spray-coated onto rough 52100-grade steel surfaces as a solid lubricant. The tribological performance was assessed in a ball-on-disk configuration in a unidirectional sliding mode. The test results indicate that Ti3C2Tx-MoS2 nanocomposites led to superlubricious states, which has hitherto been unreported for both individual pristine materials, MoS2 and Ti3C2Tx, under macroscale sliding conditions, indicating a synergistic mechanism enabling the superlative performance. The processing, structure, and property correlation were studied to understand the underlying phenomena. Raman spectroscopy, scanning electron microscopy, and transmission electron microscopy revealed the formation of an in situ robust tribolayer that was responsible for the performance at high contact pressures (>1.1 GPa) and sliding speeds (0.1 m/s). This report presents the lowest friction obtained by either MoS2 or MXene or any combination of the two so far.

Porous but Mechanically Robust All-Inorganic Antireflective Coatings Synthesized using Polymers of Intrinsic Microporosity.

Here, we introduce polymer of intrinsic microporosity 1 (PIM-1) to design single-layer and multilayered all-inorganic antireflective coatings (ARCs) with excellent mechanical properties. Using PIM-1 as a template in sequential infiltration synthesis (SIS), we can fabricate highly uniform, mechanically stable conformal coatings of AlOx with porosities of ∼50% and a refractive index of 1.41 compared to 1.76 for nonporous AlOx that is perfectly suited for substrates commonly used in high-end optical systems or touch screens (e.g., sapphire, conductive glass, bendable glass, etc.). We show that such films can be used as a single-layer ARC capable of reduction of the Fresnel reflections of sapphire to as low as 0.1% at 500 nm being deposited only on one side of the substrate. We also demonstrate that deposition of the second layer with higher porosity using block copolymers enables the design of graded-index double-layered coatings. AlOx structures with just two layers and a total thickness of less than 200 nm are capable of reduction of Fresnel reflections under normal illumination to below 0.5% in a broad spectral range with 0.1% reflection at 700 nm. Additionally, and most importantly, we show that highly porous single-layer and graded-index double-layered ARCs are characterized by high hardness and scratch resistivity. The hardness and the maximum reached load were 7.5 GPa and 13 mN with a scratch depth of about 130 nm, respectively, that is very promising for the structures consisting of two porous AlOx layers with 50% and 85% porosities, correspondingly. Such mechanical properties of coatings can also allow their application as protective layers for other optical coatings.

Swelling-Assisted Sequential Infiltration Synthesis of Nanoporous ZnO Films with Highly Accessible Pores and Their Sensing Potential for Ethanol.

Here, we report a swelling-assisted sequential infiltration synthesis (SIS) approach for the design of highly porous zinc oxide (ZnO) films by infiltration of block copolymer templates such as polystyrene-block-polyvinyl pyridine with inorganic precursors followed by UV ozone-assisted removal of the polymer template. We show that porous ZnO coatings with the thickness in the range between 140 and 420 nm can be obtained using only five cycles of SIS. The pores in ZnO fabricated via swelling-assisted SIS are highly accessible, and up to 98% of pores are available for solvent penetration. The XPS data indicate that the surface of nanoporous ZnO films is terminated with -OH groups. Density functional theory calculations show a lower energy barrier for ethanol-induced release of the oxygen restricted depletion layer in the case of the presence of -OH groups at the ZnO surface, and hence, it can lead to higher sensitivity in sensing of ethanol. We monitored the response of ZnO porous coatings with different thicknesses and porosities to ethanol vapors using combined mass-based and chemiresistive approaches at room temperature and 90 °C. The porous ZnO conformal coatings reveal a promising sensitivity toward detection of ethanol at low temperatures. Our results suggest the excellent potential of the SIS approach for the design of conformal ZnO coatings with controlled porosity, thickness, and composition that can be adapted for sensing applications.

Effect of Polymer Removal on the Morphology and Phase of the Nanoparticles in All-Inorganic Heterostructures Synthesized via Two-Step Polymer Infiltration.

Polymer templates play an essential role in the robust infiltration-based synthesis of functional multicomponent heterostructures with controlled structure, porosity, and composition. Such heterostructures are be used as hybrid organic-inorganic composites or as all-inorganic systems once the polymer templates are removed. Using iron oxide/alumina heterostructures formed by two-step infiltration of polystyrene-block-polyvinyl pyridine block copolymer with iron and aluminum precursors from the solution and vapor-phases, respectively, we show that the phase and morphology of iron oxide nanoparticles dramatically depend on the approach used to remove the polymer. We demonstrate that thermal and plasma oxidative treatments result in iron oxide nanoparticles with either solid or hollow morphologies, respectively, that lead to different magnetic properties of the resulting materials. Our study extends the boundaries of structure manipulations in multicomponent heterostructures synthesized using polymer infiltration synthesis, and hence their properties.

Visualizing Heterogeneity of Monodisperse CdSe Nanocrystals by Their Assembly into Three-Dimensional Supercrystals.

We show that the self-assembly of monodisperse CdSe nanocrystals synthesized at lower temperature (∼310 °C) into three-dimensional supercrystals results in the formation of separate regions within the supercrystals that display photoluminescence at two distinctly different wavelengths. Specifically, the central portions of the supercrystals display photoluminescence and absorption in the orange region of the spectrum, around 585 nm, compared to the 575 nm photoluminescence maximum for the nanocrystals dispersed in toluene. Distinct domains on the surfaces and edges of the supercrystals, by contrast, display photoluminescence and absorption in the green region of the spectrum, around 570 nm. We attribute the different-colored domains to two subpopulations of NCs in the monodisperse ensemble: the nanocrystals in the "orange" regions are chemically stable, whereas the nanocrystals in the "green" regions are partially oxidized. The susceptibility of the "green" nanocrystals to oxidation indicates a lower coverage of capping molecules on these nanocrystals. We propose that the two subpopulations correspond to nanocrystals with different surfaces that we attribute to the polytypism of CdSe.

Hypoxia-induced biosynthesis of gold nanoparticles in the living brain.

While a large number of studies deal with biomedical applications of various types of nanoparticles synthesized using wet chemistry, we propose the concept of targeted biosynthesis of nanoparticles in the living brain. Here we demonstrate that the pathological biochemical process of accumulation of reduced pyridine nucleotides under deleterious conditions of brain hypoxia can be redirected to drive the biosynthesis of biocompatible Au nanoparticles from a precursor salt in situ in the immediate vicinity of the hypoxia site, thereby restoring the redox status of the brain.

Revealing the Effects of the Non-solvent on the Ligand Shell of Nanoparticles and Their Crystallization.

When nanoparticles (NPs) are assembled from solution, a common assembly method of choice is either solution destabilization or solvent evaporation technique. The destabilization of the NP solution by non-solvents results in the formation of faceted supercrystals (SCs) while periodic film-like assemblies are typically formed by solvent evaporation. Here, we reveal the effect of non-solvents in washing, dispersing, and crystallizing NPs. Small angle neutron scattering (SANS) is employed for monitoring the ligand shell of NPs in solutions upon introduction of various non-solvents. The SC crystallization process is traced in situ with small-angle X-ray scattering (SAXS), and the structures of the resulting single-crystalline SCs are examined in detail by mapping the reciprocal space using SAXS and wide-angle X-ray scattering. Our study suggests that the relative miscibility of the non-solvent with solvents and ligands determines the solvation and thickness of the ligand shell and thereby the resulting structure of SCs. In the early stage of crystallization, truncated octahedral PbS NPs form SCs with face-centered cubic (fcc) symmetry. In the later stage, the fcc symmetry is preserved in the SC formed by larger (5.60 nm) NPs, but the SC assembled from smaller (4.14 nm) NPs undergoes a phase transition into body-centered cubic (bcc) lattice via Bain transformation, becoming a polycrystalline SC containing three structurally correlated bcc domains and one untransformed fcc domain. Our study provides the detailed understanding of the non-solvent effect that impacts beyond the formation of SCs, enabling the judicious selection of solvent/non-solvent mixtures for NP purification.

Block-Co-polymer-Assisted Synthesis of All Inorganic Highly Porous Heterostructures with Highly Accessible Thermally Stable Functional Centers.

Here, we propose a simple approach for the design of highly porous multicomponent heterostructures by infiltration of block-co-polymer templates with inorganic precursors in swelling solvents followed by gas-phase sequential infiltration synthesis and thermal annealing. This approach can prepare conformal coatings, free-standing membranes, and powders consisting of uniformly sized metal or metal oxide nanoparticles (NPs) well dispersed in a porous oxide matrix. We employed this new, versatile synthetic concept to synthesize catalytically active heterostructures of uniformly dispersed ∼4.3 nm PdO nanoparticles accessible through three-dimensional pore networks of the alumina support. Importantly, such materials reveal high resistance against sintering at 800 °C, even at relatively high loadings of NPs (∼10 wt %). At the same time, such heterostructures enable high mass transport due to highly interconnected nature of the pores. The surface of synthesized nanoparticles in the porous matrix is highly accessible, which enables their good catalytic performance in methane and carbon monoxide oxidation. In addition, we demonstrate that this approach can be utilized to synthesize heterostructures consisting of different types of NPs on a highly porous support. Our results show that swelling-based infiltration provides a promising route toward the robust and scalable synthesis of multicomponent structures.

Ligand dynamics control structure, elasticity, and high-pressure behavior of nanoparticle superlattices.

Precise engineering of nanoparticle superlattices (NPSLs) for energy applications requires a molecular-level understanding of the physical factors governing their morphology, periodicity, mechanics, and response to external stimuli. Such knowledge, particularly the impact of ligand dynamics on physical behavior of NPSLs, is still in its infancy. Here, we combine coarse-grained molecular dynamics simulations, and small angle X-ray scattering experiments in a diamond anvil cell to demonstrate that coverage density of capping ligands (i.e., number of ligands per unit area of a nanoparticle's surface), strongly influences the structure, elasticity, and high-pressure behavior of NPSLs using face-centered cubic PbS-NPSLs as a representative example. We demonstrate that ligand coverage density dictates (a) the extent of diffusion of ligands over NP surfaces, (b) spatial distribution of the ligands in the interstitial spaces between neighboring NPs, and (c) the fraction of ligands that interdigitate across different nanoparticles. We find that below a critical coverage density (1.8 nm-2 for 7 nm PbS NPs capped with oleic acid), NPSLs collapse to form disordered aggregates via sintering, even under ambient conditions. Above the threshold ligand coverage density, NPSLs surprisingly preserve their crystalline order even under high applied pressures (∼40-55 GPa), and show a completely reversible pressure behavior. This opens the possibility of reversibly manipulating lattice spacing of NPSLs, and in turn, finely tuning their collective electronic, optical, thermo-mechanical, and magnetic properties.

Effect of the Micelle Opening in Self-assembled Amphiphilic Block Co-polymer Films on the Infiltration of Inorganic Precursors.

Infiltration of the polymer templates with inorganic precursors using the selective vapor-phase infiltration approach, or sequential infiltration synthesis (SIS), allows the design of materials with advanced properties. Swelling of the block co-polymer (BCP) templates enables the additional control of the structure, porosity, and thickness of the composite or inorganic materials. Here, we use the highly precise quartz crystal microbalance (QCM) technique to investigate quantitatively the effect of the micelle opening by swelling and inorganic precursor infiltrating on the evolution of porosity in amphiphilic BCPs. We show that swelling of the polystyrene- block-poly-4-vinyl pyridine (PS- b-P4VP) BCP in ethanol at 75 °C occurs rapidly and results in a stable polymer structure in 30 min. By using an alumina model system, we found that swelling enables access to all available polar domains of the PS- b-P4VP film leading to an increase in the SIS-infiltrated alumina mass as compared to the nonswelled BCP layer. Our results demonstrate that swelling of the 110 nm thick BCP template results in the formation of 192 nm thick alumina films with 2 times larger alumina mass and 4 times larger effective pore volume than in case of the nonswelled sample. In the case of the thicker polymer template, the difference due to swelling becomes even more substantial because the fraction of accessible polymer is increased much more than in thin films. Our findings provide important insights into the mechanism of the infiltration of the inorganic precursors into swelled and nonswelled, spin-coated BCP templates enabling the design of highly porous thick ceramic films by SIS.

Accessibility of the pores in highly porous alumina films synthesized via sequential infiltration synthesis.

Inorganic nanoporous materials with highly accessible pores are of great interest for the design of efficient catalytic, purification and detection systems. Limited access to the pores is a common problem associated with traditional approaches for the synthesis of porous materials, affecting the functionality of the low-density structure. Recently, infiltration of a nanoporous polymer template with inorganic precursors followed by oxidative annealing was proposed as a new and efficient approach to creating porous inorganic structures with controlled thickness, composition and pore sizes. Here, we report an ultra-high accessibility of the pores in porous films prepared via polymer-swelling-assisted sequential infiltration synthesis (SIS). Using a quartz crystal microbalance technique, we show the increased solvent adsorbing capabilities of highly porous alumina films as a result of high interconnectivity of the pores in such structures. The directionality and highly interconnected nature of the pores are demonstrated in experiments with the partial blocking of pore access by the deposition of a single-layer graphene that is not transparent to solvent. 60% of the pores remain accessible when only 20% of the surface is exposed to solvent. Using humidity detection as an example, we also show that highly porous alumina produced by polymer-swelling-assisted SIS is a promising candidate for sensing applications.

Binary Transition-Metal Oxide Hollow Nanoparticles for Oxygen Evolution Reaction.

Low-cost transition metal oxides are actively explored as alternative materials to precious metal-based electrocatalysts for the challenging multistep oxygen evolution reaction (OER). We utilized the Kirkendall effect allowing the formation of hollow polycrystalline, highly disordered nanoparticles (NPs) to synthesize highly active binary metal oxide OER electrocatalysts in alkali media. Two synthetic strategies were applied to achieve compositional control in binary transition metal oxide hollow NPs. The first strategy is capitalized on the oxidation of transition-metal NP seeds in the presence of other transition-metal cations. Oxidation of Fe NPs treated with Ni (+2) cations allowed the synthesis of hollow oxide NPs with a 1-4.7 Ni-to-Fe ratio via an oxidation-induced doping mechanism. Hollow Fe-Ni oxide NPs also reached a current density of 10 mA/cm2 at 0.30 V overpotential. The second strategy is based on the direct oxidation of iron-cobalt alloy NPs which allows the synthesis of hollow Fe xCo100- x-oxide NPs where x can be tuned in the range between 36 and 100. Hollow Fe36Co64-oxide NPs also revealed the current density of 10 mA/cm2 at 0.30 V overpotential in 0.1 M KOH.

Unexpected compositional and structural modification of CoPt3 nanoparticles by extensive surface purification.

We combined synchrotron small angle X-ray scattering, X-ray fluorescence and extended X-ray absorption fine structure spectroscopy to probe the structure of chemically synthesized CoPt3 nanoparticles (NPs) after ligand removal via the commonly accepted solvent/nonsolvent approach. We showed that the improved catalytic activity of extensively purified NPs could not be explained only in terms of a "cleaner" surface. We found that extensive surface purification results in the substantial leaching of the Co atoms from the chemically synthesized CoPt3 NPs transforming them into CoPt3/Pt core/shell structures with an unexpectedly thick (∼0.5 nm) Pt shell. We indicated that the improved catalytic activity of extensively purified NPs in octyne hydrogenation reaction can be explained by the formation of CoPt3/Pt core/shell structures. Also, we demonstrated that drastic compositional and structural transformation of water transferred CoPt3 NPs was rather a result of extensive removal of native ligands via a solvent/nonsolvent approach than leaching of cobalt atoms in aqueous media. We expect that these findings can be relevant to other transition metal based multicomponent NPs.

Strain-Driven Stacking Faults in CdSe/CdS Core/Shell Nanorods.

Colloidal semiconductor nanocrystals are commonly grown with a shell of a second semiconductor material to obtain desired physical properties, such as increased photoluminescence quantum yield. However, the growth of a lattice-mismatched shell results in strain within the nanocrystal, and this strain has the potential to produce crystalline defects. Here, we study CdSe/CdS core/shell nanorods as a model system to investigate the influence of core size and shape on the formation of stacking faults in the nanocrystal. Using a combination of high-angle annular dark-field scanning transmission electron microscopy and pair-distribution-function analysis of synchrotron X-ray scattering, we show that growth of the CdS shell on smaller, spherical CdSe cores results in relatively small strain and few stacking faults. By contrast, growth of the shell on larger, prolate spheroidal cores leads to significant strain in the CdS lattice, resulting in a high density of stacking faults.