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We systematically study the explicit roles of noble metal catalysts in steering the gas selectivity of metal oxides toward specific target analytes by using highly dispersed catalysts on In2O3 nanofibers as a consistent synthetic platform.

Smart wearable electronic textiles (e-textiles) that can detect and differentiate multiple stimuli, while also collecting and storing the diverse array of data signals using highly innovative, multifunctional, and intelligent garments, are of great value for personalized healthcare applications. However, material performance and sustainability, complicated and difficult e-textile fabrication methods, and their limited end-of-life processability are major challenges to wide adoption of e-textiles. In this review, we explore the potential for sustainable materials, manufacturing techniques, and their end-of-the-life processes for developing eco-friendly e-textiles. In addition, we survey the current state-of-the-art for sustainable fibers and electronic materials (i.e., conductors, semiconductors, and dielectrics) to serve as different components in wearable e-textiles and then provide an overview of environmentally friendly digital manufacturing techniques for such textiles which involve less or no water utilization, combined with a reduction in both material waste and energy consumption. Furthermore, standardized parameters for evaluating the sustainability of e-textiles are established, such as life cycle analysis, biodegradability, and recyclability. Finally, we discuss the current development trends, as well as the future research directions for wearable e-textiles which include an integrated product design approach based on the use of eco-friendly materials, the development of sustainable manufacturing processes, and an effective end-of-the-life strategy to manufacture next generation smart and sustainable wearable e-textiles that can be either recycled to value-added products or decomposed in the landfill without any negative environmental impacts.

The massive production of polymer-based respiratory masks during the COVID-19 pandemic has rekindled the issue of environmental pollution from nonrecyclable plastic waste. To mitigate this problem, conventional filters should be redesigned with improved filtration performance over the entire operational life while also being naturally degradable at the end. Herein, we developed a functional and biodegradable polymeric filter membrane consisting of a polybutylene adipate terephthalate (PBAT) matrix blended with cetyltrimethylammonium bromide (CTAB) and montmorillonite (MMT) clay, whose surface properties have been modified through cation exchange reactions for good miscibility with PBAT in an organic solvent. Particularly, the spontaneous evolution of a partial core-shell structure (i.e., PBAT core encased by CTAB-MMT shell) during the electrospinning process amplified the triboelectric effect as well as the antibacterial/antiviral activity that was not observed in naive PBAT. Unlike the conventional face mask filter that relies on the electrostatic adsorption mechanism, which deteriorates over time and/or due to external environmental factors, the PBAT@CTAB-MMT nanofiber membrane (NFM)-based filter continuously retains electrostatic charges on the surface due to the triboelectric effect of CTAB-MMT. As a result, the PBAT@CTAB-MMT NFM-based filter showed high filtration efficiencies (98.3%, PM

The process of exsolution for the synthesis of strongly anchored metal nanoparticles (NPs) on host oxide lattices has been proposed as a promising strategy for designing robust catalyst-support composite systems. However, because conventional exsolution processes occur in harsh reducing environments at high temperatures for long periods of time, the choice of support materials and dopant metals are limited to those with inherently high thermal and chemical stability. Herein, we report the exsolution of a series of noble metal catalysts (Pt, Rh, and Ir) from metal oxide nanofibers (WO

This work presents the synthesis of LaFeO3/SnO2 nanotubes (NTs) based on the GRR process, with perovskite LaFeO3 NTs prepared by electrospun nanofibers as the starting material resulting in a significantly enhanced catalytic activity.

Noble-metal nanoframes consisting of interconnected, ultrathin ridges have received considerable attention in the field of heterogeneous catalysis. The enthusiasm arises from the high utilization efficiency of atoms for significantly reducing the material loading while enhancing the catalytic performance. In this review article, we offer a comprehensive assessment of research endeavors in the design and rational synthesis of noble-metal nanoframes for applications in catalysis. We start with a brief introduction to the unique characteristics of nanoframes, followed by a discussion of the synthetic strategies and their controls in terms of structure and composition. We then present case studies to elucidate mechanistic details behind the synthesis of mono-, bi-, and multimetallic nanoframes, as well as heterostructured and hybrid systems. We discuss their performance in electrocatalysis, thermal catalysis, and photocatalysis. Finally, we highlight recent progress in addressing the structural and compositional stability issues of nanoframes for the assurance of robustness in catalytic applications.

Most respiratory masks are made of fabrics, which only capture the infectious virus carriers into the matrix. However, these contagious viruses stay active for a long duration (∼7 days) within the fabric matrix possibly inducing post-contact transmissions. Moreover, conventional masks are vulnerable to bacterial growth with prolonged exposure to exhaled breaths. Herein, we combined violacein, a naturally-occurring antimicrobial agent, with porous nanofiber membranes to develop a series of functional filters that autonomously sterilizes viruses and bacteria. The violacein-embedded membrane inactivates viruses within 4 h (99.532 % reduction for influenza and 99.999 % for human coronavirus) and bacteria within 2 h (75.5 % reduction). Besides, its nanofiber structure physically filters out the nanoscale (0.8 μm) and micron-scale (0.8 μm - 3 μm) particulates, providing high filtration efficiencies (99.7 % and 100 % for PM 1.0 and PM 10, respectively) with long-term stability (for 25 days). In addition, violacein provides additional UV-resistant property, which protects the skin from sunlight. The violacein-embedded membrane not only proved the sterile efficacy of microbe extracted pigments for biomedical products but also provided insights to advance the personal protective equipment (PPE) to fight against contagious pathogens.

Though highly promising as powerful gas sensors, oxide semiconductor chemiresistors have low surface reactivity, which limits their selectivity, sensitivity, and reaction kinetics, particularly at room temperature (RT) operation. It is proposed that a hybrid design involving the nanostructuring of oxides and passivation with selective gas filtration layers can potentially overcome the issues with surface activity. Herein, unique bi-stacked heterogeneous layers are introduced; that is, nanostructured oxides covered by conformal nanoporous gas filters, on ultrahigh-density nanofiber (NF) yarns via sputter deposition with indium tin oxide (ITO) and subsequent self-assembly of zeolitic imidazolate framework (ZIF-8) nanocrystals. The NF yarn composed of ZIF-8-coated ITO films can offer heightened surface activity at RT because of high porosity, large surface area, and effective screening of interfering gases. As a case study, the hybrid sensor demonstrated remarkable sensing performances characterized by high NO selectivity, fast response/recovery kinetics (60-fold improvement), and large responses (12.8-fold improvement @ 1 ppm) in comparison with pristine yarn@ITO, especially under highly humid conditions. Molecular modeling reveals an increased penetration ratio of NO over O

We report the fabrication of Ag–Au cuboctahedral nanoboxes enclosed by {100} and {111} facets, respectively, through the orthogonal deposition of Au on two different facets of Ag cuboctahedra. Specifically, we titrate aqueous HAuCl4 into an aqueous mixture containing Ag cuboctahedra, ascorbic acid, and NaOH (under basic conditions), in the presence of poly(vinylpyrrolidone) (PVP) and cetyltrimethylammonium chloride (CTAC), respectively. In the case of PVP, the oxidation of Ag was initiated from the {111} facets of the cuboctahedra through the galvanic replacement reaction between Au(III) and Ag, accompanied by the deposition of Au onto the {100} facets. Because the dissolved Ag(I) ions could react with NaOH to form Ag2O on the {111} facets and thus terminate the galvanic reaction, the Au(III) ions would be further reduced by the ascorbate monoanion (HAsc−) to generate Au atoms for their continuing deposition on the {100} facets, converting Ag cuboctahedra to Ag@Au{100} cuboctahedra. Upon the etching of Ag from the core, we obtained Ag–Au cuboctahedral nanoboxes enclosed by {100} facets. In contrast, when CTAC was present, the oxidation of Ag through a galvanic reaction could continuously proceed on {100} facets as the dissolved Ag(I) ions would react with the excessive amount of Cl− ions derived from CTAC to produce soluble AgCl2− ions rather than insoluble Ag2O. As a result, the dissolved Ag(I) and Au(III) ions would be co-reduced by HAsc− for the generation of Ag and Au atoms, followed by their co-deposition onto {111} facets for the generation of Ag@Au{111} concave cuboctahedra. After the removal of Ag from the core by etching, we obtained Ag–Au{111} cuboctahedral nanoboxes enclosed by {111} facets. Both samples of cuboctahedral nanoboxes exhibited strong optical absorption in the infrared region. Interestingly, the cuboctahedral nanoboxes enclosed by {111} facets showed significantly enhanced catalytic activity toward the reduction of 4-nitrophenol by NaBH4 relative to their counterparts encased by {100} facets.

Silver is an excellent catalyst for oxidation reactions such as ethylene epoxidation, but it shows limited activity toward reduction reactions. Here we report a strategy to revitalize Ag nanocrystals as a redox catalyst for the production of an aromatic azo compound by modifying their surface with an isocyanide-based compound. We also leverage in situ fingerprint spectroscopy to acquire molecular insights into the reaction mechanism by probing the vibrational modes of all chemical species at the catalytic surface with surface-enhanced Raman spectroscopy. We establish that binding of isocyanide to Ag nanocrystals makes it possible for Ag to extract the oxygen atoms from the nitro-groups of nitroaromatics and then use these atoms to oxidize isocyanide to isocyanate. Concurrently, the coupling between two adjacent deoxygenated nitroaromatic molecules leads to the formation of an aromatic azo compound., Ag nanocrystals can serve as a redox catalyst for the production of an aromatic azo compound when their surface is modified with an isocyanide-based molecule.

We report an investigation of the adsorption of thiol and isocyanide molecules on colloidal Ag nanocubes through surface-enhanced Raman scattering (SERS). Specifically, we collect SERS spectra in situ at different time points from a mixture of Ag nanocubes and ligand molecules at a specific concentration. We demonstrate that 4-nitrothiophenol could readily bind to the Ag surface through strong thiol–Ag interaction. We also observe red shifts for the SERS peaks as the concentration decreases, suggesting a change to the molecular orientation relative to the surface. Likewise, 4-aminothiophenol also adsorbs onto Ag quickly, but gives much weaker SERS signals relative to 4-nitrothiophenol because the electron-donating amine group would retard the chemical enhancement of SERS. Different from thiols, 1,4-phenylene diisocyanide binds to Ag surface through a relatively weak, σ-donation bond. With an increase in concentration, molecules tend to adsorb on the nanocubes with the benzene ring tilting away from the su...

Ex-solution catalysts, in which a host oxide is decorated with confined metallic nanoparticles, have exhibited breakthrough activity in various catalytic reactions. However, catalysts prepared by conventional ex-solution processes are limited by the low surface area of host oxides, the limited solubility of dopants, and the incomplete conversion of doped cations into metal catalysts. Here, the design of the host oxide structure is reconceptualized using a metal-organic framework (MOF) as an oxide precursor that can absorb a large quantity of ions while also promoting ex-solution at low temperatures (400-500 °C). The MOF-derived metal oxide host can readily incorporate metal cations, from which catalytic nanoparticles can be uniformly ex-solved owing to the short diffusion length in the nano-sized oxides. The distinct ex-solution behaviors of Pt, Pd, and Rh, and their bimetallic combinations are investigated. The MOF-driven mesoporous ZnO particles functionalized with PdPt catalysts ex-solved at 500 °C show benchmark-level of acetone oxidation activity as well as acetone-sensing characteristics by accelerating both oxygen chemisorption and acetone dissociation. Their findings provide a new route for the preparation of highly active catalysts by engineering the architecture and composition of the host oxide to facilitate the ex-solution process rationally.

Silver nanocubes have found use in an array of applications but their performance has been plagued by the shape instability arising from the oxidation and dissolution of Ag atoms from the edges and corners. Here we demonstrate that the shape of Ag nanocubes can be well preserved by covering their edges and corners with a corrosion-resistant metal such as Ir. In a typical process, we titrate a Na3IrCl6 solution in ethylene glycol (EG) into a suspension of Ag nanocubes in an EG solution in the presence of poly(vinylpyrrolidone) (PVP) held at 110 °C. The Ir atoms derived from the reduction of Na3IrCl6 by EG and Ag are deposited onto the edges and then corners for the generation of Ag–Ir core-frame nanocubes. Remarkably, our results indicate that a small amount of Ir atoms on the edges and corners is adequate to prevent the Ag nanocubes from transforming into nanospheres when heated in a PVP/EG solution up to 110 °C. We further demonstrate that these Ag–Ir nanocubes embrace plasmonic properties comparable to those of the original Ag nanocubes, making them immediately useful in a variety of applications. This strategy for stabilizing the shape of Ag nanocubes should be extendible to Ag nanocrystals with other shapes or nanocrystals comprised of other metals.

We report the defect-assisted deposition of Au on Ag nanocubes for the generation of Ag@Au core–shell nanocubes with three to eight atomic layers. In a standard protocol, we disperse Ag nanocubes in an ethylene glycol (EG) solution containing poly(vinylpyrrolidone) and then titrate aqueous HAuCl4 at 110 °C. Initially, the galvanic replacement reaction between HAuCl4 and Ag allows the deposition of Au on the edges of the nanocubes with highest surface energy as the Ag atoms on the side faces are dissolved into the aqueous suspension in the form of Ag(I) ions to create surface defects. These defects then become preferential sites for the codeposition of Ag and Au atoms derived from the coreduction of both the Ag(I) and Au(III) ions in the reaction solution by EG. Once the defect sites have been filled, the additional Ag and Au atoms will rapidly diffuse across the entire surface of each nanocube for the generation of a nanocube with a relatively thin shell made of a Ag–Au alloy. Afterward, the chemical redu...

We report the fabrication of Ag-Pd concave nanocrystals by introducing the Pd(ii) precursor into an aqueous suspension of Ag nanocubes in the presence of cetyltrimethylammonium chloride (CTAC) under ambient conditions. Different from the previously reported work that involved the oxidation of Ag and deposition of Pd at random sites on the surface for the generation of Ag-Pd hollow nanocrystals, we demonstrate that the Cl- ions from CTAC can confine the oxidation of Ag atoms to the side faces of a nanocube while the resultant Pd atoms are deposited on the edges in an orthogonal manner. By controlling the amount of the Pd(ii) precursor involved in a synthesis, we can transform Ag nanocubes into Ag-Pd nanocrystals with different degrees of concaveness for the side faces and controllable Pd contents. We characterize the outermost layer of concave surfaces for the as-obtained Ag-Pd nanocrystals by surface-enhanced Raman scattering (SERS) through the use of an isocyanide probe. This facile approach would enable the fabrication of Ag-based concave nanocrystals for applications in plasmonics and catalysis.

We report a simple and general method for the production of Ag–Rh bimetallic nanostructures with a unique integration of the plasmonic and catalytic properties exemplified by these two metals, respectively. When a Rh(III) precursor is titrated into a polyol suspension of Ag nanocubes held at 110 °C in the presence of ascorbic acid and poly(vinylpyrrolidone), Rh atoms are generated and deposited on the nanocubes. When the amount of Rh(III) precursor is relatively low, the Rh atoms tend to nucleate from the edges of the Ag nanocubes and then follow an island growth mode because of the relatively low temperature involved and the high cohesive energy of Rh. The Rh islands can be maintained with an ultrafine size of only several nanometers, presenting an extremely large specific surface area for catalytic applications. As the amount of Rh(III) precursor is increased, the galvanic replacement reaction between the Rh(III) and Ag nanocubes will kick in, leading to the formation of increasingly concaved side faces...

We report a facile synthesis of Ag nanocubes with concave side faces and Au–Ag alloy frames, namely Ag@Au–Ag concave nanocrystals, by titrating HAuCl4 solution into an aqueous mixture of Ag nanocubes, ascorbic acid (H2Asc), NaOH, and cetyltrimethylammonium chloride (CTAC) at an initial pH of 11.6 under ambient conditions. Different from all previous studies involving poly(vinylpyrrolidine), the use of CTAC at a sufficiently high concentration plays an essential role in carving away Ag atoms from the side faces through galvanic replacement. Concurrent co-deposition of Au and Ag atoms via chemical reduction at orthogonal sites on the surface of Ag nanocubes leads to the generation of Ag@Au–Ag concave nanocrystals with well-defined and controllable structures. Specifically, in the presence of CTAC-derived Cl– ions, the titrated HAuCl4 is maintained in the AuCl4– species, enabling its galvanic replacement with the Ag atoms located on the side faces of nanocubes. The released Ag+ ions can be retained in the so...

For the proliferation of the supercapacitor technology, it is essential to attain superior areal and volumetric performance. Nevertheless, maintaining stable areal/volumetric capacitance and rate capability, especially for thick electrodes, remains a fundamental challenge. Here, for the first time, a rationally designed porous monolithic electrode is reported with high thickness of 800 µm (46.74 mg cm-2 , with high areal mass loading of NiCo2 S4 6.9 mg cm-2 ) in which redox-active Ag nanoparticles and NiCo2 S4 nanosheets are sequentially decorated on highly conductive wood-derived carbon (WC) substrates. The hierarchically assembled WC@Ag@NiCo2 S4 electrode exhibits outstanding areal capacitance of 6.09 F cm-2 and long-term stability of 84.5% up to 10 000 cycles, as well as exceptional rate capability at 50 mA cm-2 . The asymmetric cell with an anode of WC@Ag and a cathode of WC@Ag@NiCo2 S4 delivers areal/volumetric energy density of 0.59 mWh cm-2 /3.93 mWh cm-3 , which is much-improved performance compared to those of most reported thick electrodes at the same scale. Theoretical calculations verify that the enhanced performance could be attributed to the decreased adsorption energy of OH- and the down-shifted d-band of Ag atoms, which can accelerate the electron transport and ion transfer.

A facile method is described herein for generating a mineral gradient in a biodegradable polymer scaffold. The gradient is achieved by swelling a composite film made of polycaprolactone (PCL) and hydroxyapatite (HAp) nanoparticles with a PCL solution. During the swelling process, the solvent and PCL polymer chains diffuse into the composite film, generating a gradient in HAp density at their interface. The thickness of the mineral gradient can be tuned by varying the extent of swelling to match the length scale of the natural tendon-to-bone attachment (20-60 µm). When patterned with an array of funnel-shaped channels, the mineral gradient presents stem cells with spatial gradations in both biochemical cues (e.g., osteoinductivity and conductivity associated with the HAp nanoparticles) and mechanical cues (e.g., substrate stiffness) to stimulate their differentiation into a graded distribution of cell phenotypes. This new class of biomimetic scaffolds holds great promise for facilitating the regeneration of the injured tendon-to-bone attachment by stimulating the formation of a functionally graded interface.

We report a facile route to the synthesis of Ag@Au–Pt trimetallic nanocubes in which the Ag, Au, and Pt atoms are exposed at the corners, side faces, and edges, respectively. Our success relies on the use of Ag@Au nanocubes, with Ag2O patches at the corners and Au on the side faces and edges, as seeds for the site-selective deposition of Pt on the edges only in a reaction system containing ascorbic acid (H2Asc) and poly(vinylpyrrolidone). At an initial pH of 3.2, H2Asc can dissolve the Ag2O patches, exposing the Ag atoms at the corners of a nanocube. Upon the injection of the H2PtCl6 precursor, the Pt atoms derived from the reduction by both H2Asc and Ag are preferentially deposited on the edges, leading to the formation of Ag@Au–Pt trimetallic nanocubes. We demonstrate the use of 2,6-dimethylphenyl isocyanide as a molecular probe to confirm and monitor the deposition of Pt atoms on the edges of nanocubes through surface-enhanced Raman scattering (SERS). We further explore the use of these bifunctional trimetallic nanoparticles with integrated plasmonic and catalytic properties for in situ SERS monitoring the reduction of 4-nitrothiophenol by NaBH4. Upon the removal of Ag via H2O2 etching, the Ag@Au–Pt nanocubes evolve into trimetallic nanoboxes with a wall thickness of about 2 nm and well-defined openings at the corners. The trimetallic nanoboxes embrace plasmon resonance peaks in the near-infrared region with potential in biomedical applications.

We report the development of an isocyanide-based molecular probe for in situ characterizing the overgrowth of a second metal on silver nanocrystal seeds in solution by surface-enhanced Raman scattering (SERS). As the first demonstration, we elucidate that the vibrational frequency of 2,6-dimethylphenyl isocyanide (2,6-DMPI) can serve as a distinctive reporter for capturing the nucleation of Pt on the edges of Ag nanocubes in the aqueous solution containing a Pt precursor, ascorbic acid, and poly(vinylpyrrolidone) under ambient conditions. Our success relies on the difference in stretching frequency for the NC bond when the isocyanide group binds to the Ag and Pt atoms. Specifically, σ donation from the antibonding σ* orbital of the -NC group to the d-band of Ag would strengthen the NC bond, blue shifting the stretching frequency. In contrast, π-back-donation from the d-band of Pt to the π* antibonding orbital of the -NC group would weaken the NC bond, leading to a red shift of stretching frequency. Therefore, it is feasible to in situ characterize the outermost surface that consists of both newly deposited Pt atoms and remaining Ag atoms by following the stretching frequencies and intensities of 2,6-DMPI in real time. Because the SERS hot spots on the edges of Ag nanocubes coincide with the {110} facets preferred for the nucleation of Pt atoms, this technique is capable of resolving 27 Pt atoms being deposited on each edge of a 39 nm Ag nanocube in the original growth solution. Collectively, in situ SERS, with its consummate sensitivity to molecular structure and bonding of isocyanide-based molecular probe, could elucidate the mechanistic details involved in the seeded overgrowth of a catalytically significant metal, such as Pt, Pd, Ir, Rh, and Ru, on the surface of a Ag or Au nanocrystal seed.