Multifunctional Ultrathin Pd_<i>x</i>Cu_1–<i>x</i> and Pt∼Pd_<i>x</i>Cu_1–<i>x</i> One-Dimensional Nanowire Motifs for Various Small Molecule Oxidation Reactions

Developing novel electrocatalysts for small molecule oxidation processes, including formic acid oxidation (FAOR), methanol oxidation reaction (MOR), and ethanol oxidation reaction (EOR), denoting the key anodic reactions for their respective fuel cell configurations, is a significant and relevant theme of recent efforts in the field. Herein, in this report, we demonstrated a concerted effort to couple and combine the benefits of small size, anisotropic morphology, and tunable chemical composition in order to devise a novel “family” of functional architectures. In particular, we have fabricated not only ultrathin 1-D Pd_1–<i>x</i>Cu_<i>x</i> alloys but also Pt-coated Pd_1–<i>x</i>Cu_<i>x</i> (i.e., Pt∼Pd_1–<i>x</i>Cu_<i>x</i>; herein the ∼ indicates an intimate association, but not necessarily actual bond formation, between the inner bimetallic core and the Pt outer shell) core–shell hierarchical nanostructures with readily tunable chemical compositions by utilizing a facile, surfactant-based, wet chemical synthesis coupled with a Cu underpotential deposition technique. Our main finding is that our series of as-prepared nanowires are functionally flexible. More precisely, we demonstrate that various examples within this “family” of structural motifs can be tailored for exceptional activity with all 3 of these important electrocatalytic reactions. In particular, we note that our series of Pd_1–<i>x</i>Cu_<i>x</i> nanowires all exhibit enhanced FAOR activities as compared with not only analogous Pd ultrathin nanowires but also commercial Pt and Pd standards, with Pd₉Cu representing the “optimal” composition. Moreover, our group of Pt∼Pd_1–<i>x</i>Cu_<i>x</i> nanowires consistently outperformed not only commercial Pt NPs but also ultrathin Pt nanowires by several fold orders of magnitude for both the MOR and EOR reactions in alkaline media. The variation of the MOR and EOR performance with the chemical composition of our ultrathin Pt∼Pd_1–<i>x</i>Cu_<i>x</i> nanowires was also discussed

Probing Ultrathin One-Dimensional Pd–Ni Nanostructures As Oxygen Reduction Reaction Catalysts

An ambient, surfactant-based synthetic means was used to prepare ultrathin binary (<i>d</i> ∼ 2 nm) Pd–Ni nanowires, which were subsequently purified using a novel butylamine-based surfactant-exchange process coupled with an electrochemical CO adsorption and stripping treatment to expose active surface sites. We were able to systematically vary the chemical composition of as-prepared Pd–Ni nanowires from pure elemental Pd to Pd_0.50Ni_0.50 (atomic ratio), as verified using EDS analysis. The overall morphology of samples possessing >60 atom % Pd consisted of individual, discrete one-dimensional nanowires. The electrocatalytic performances of elemental Pd, Pd_0.90Ni_0.10, Pd_0.83Ni_0.17, and Pd_0.75Ni_0.25 nanowires in particular were examined. Our results highlight a “volcano”-type relationship between chemical composition and corresponding ORR activities with Pd_0.90Ni_0.10, yielding the highest activity (i.e., 1.96 mA/cm² at 0.8 V) among all nanowires tested. Moreover, the Pd_0.90Ni_0.10 sample exhibited outstanding methanol tolerance ability. In essence, there was only a relatively minimal 15% loss in the specific activity in the presence of 4 mM methanol, which was significantly better than analogous data on Pt nanoparticles and Pt nanowires. In addition, we also studied ultrathin, core–shell Pt∼Pd_0.90Ni_0.10 nanowires, which exhibited a specific activity of 0.62 mA/cm² and a corresponding mass activity of 1.44 A/mg_Pt at 0.9 V. Moreover, our as-prepared core–shell electrocatalysts maintained excellent electrochemical durability. We postulate that one-dimensional Pd–Ni nanostructures represent a particularly promising platform for designing ORR catalysts with high performance

Synthesis, Characterization, and Formation Mechanism of Crystalline Cu and Ni Metallic Nanowires under Ambient, Seedless, Surfactantless Conditions

In this report, crystalline elemental Cu and Ni nanowires have been successfully synthesized through a simplistic, malleable, solution-based protocol involving the utilization of a U-tube double diffusion apparatus under ambient conditions. The nanowires prepared within the 50 and 200 nm template membrane pore channels maintain diameters ranging from ∼90–230 nm with lengths attaining the micrometer scale. To mitigate for the unwanted but very facile oxidation of these nanomaterials to their oxide analogues, our synthesis mechanism relies on a carefully calibrated reaction between the corresponding metal precursor solution and an aqueous reducing agent solution, resulting in the production of pure, monodisperse metallic nanostructures. These as-prepared nanowires were subsequently characterized from an applications’ perspective so as to investigate their optical and photocatalytic properties

Robust but On-Demand Detachable Wet Tissue Adhesive Hydrogel Enhanced with Modified Tannic Acid

Adhesives with robust but readily detachable wet tissue adhesion are of great significance for wound closure. Polyelectrolyte complex adhesive (PECA) is an important wet tissue adhesive. However, its relatively weak cohesive and adhesive strength cannot satisfy clinical applications. Herein, modified tannic acid (mTA) with a catechol group, a long alkyl hydrophobic chain, and a phenyl group was prepared first, and then, it was mixed with acrylic acid (AA) and polyethylenimine (PEI), followed by UV photopolymerization to make a wet tissue adhesive hydrogel with tough cohesion and adhesion strength. The hydrogel has a strong wet tissue interfacial toughness of ∼1552 J/m2, good mechanical properties (∼7220 kPa cohesive strength, ∼873% strain, and ∼33,370 kJ/m3 toughness), and a bursting pressure of ∼1575 mmHg on wet porcine skin. The hydrogel can realize quick and effective adhesion to various wet biological tissues including porcine skin, liver, kidney, and heart and can be changed easily with triggering urea solution to avoid tissue damage or uncomfortable pain to the patient. This biosafe adhesive hydrogel is very promising for wound closure and may provide new ideas for the design of robust wet tissue adhesives

Robust but On-Demand Detachable Wet Tissue Adhesive Hydrogel Enhanced with Modified Tannic Acid

Adhesives with robust but readily detachable wet tissue adhesion are of great significance for wound closure. Polyelectrolyte complex adhesive (PECA) is an important wet tissue adhesive. However, its relatively weak cohesive and adhesive strength cannot satisfy clinical applications. Herein, modified tannic acid (mTA) with a catechol group, a long alkyl hydrophobic chain, and a phenyl group was prepared first, and then, it was mixed with acrylic acid (AA) and polyethylenimine (PEI), followed by UV photopolymerization to make a wet tissue adhesive hydrogel with tough cohesion and adhesion strength. The hydrogel has a strong wet tissue interfacial toughness of ∼1552 J/m2, good mechanical properties (∼7220 kPa cohesive strength, ∼873% strain, and ∼33,370 kJ/m3 toughness), and a bursting pressure of ∼1575 mmHg on wet porcine skin. The hydrogel can realize quick and effective adhesion to various wet biological tissues including porcine skin, liver, kidney, and heart and can be changed easily with triggering urea solution to avoid tissue damage or uncomfortable pain to the patient. This biosafe adhesive hydrogel is very promising for wound closure and may provide new ideas for the design of robust wet tissue adhesives

Robust but On-Demand Detachable Wet Tissue Adhesive Hydrogel Enhanced with Modified Tannic Acid

Adhesives with robust but readily detachable wet tissue adhesion are of great significance for wound closure. Polyelectrolyte complex adhesive (PECA) is an important wet tissue adhesive. However, its relatively weak cohesive and adhesive strength cannot satisfy clinical applications. Herein, modified tannic acid (mTA) with a catechol group, a long alkyl hydrophobic chain, and a phenyl group was prepared first, and then, it was mixed with acrylic acid (AA) and polyethylenimine (PEI), followed by UV photopolymerization to make a wet tissue adhesive hydrogel with tough cohesion and adhesion strength. The hydrogel has a strong wet tissue interfacial toughness of ∼1552 J/m2, good mechanical properties (∼7220 kPa cohesive strength, ∼873% strain, and ∼33,370 kJ/m3 toughness), and a bursting pressure of ∼1575 mmHg on wet porcine skin. The hydrogel can realize quick and effective adhesion to various wet biological tissues including porcine skin, liver, kidney, and heart and can be changed easily with triggering urea solution to avoid tissue damage or uncomfortable pain to the patient. This biosafe adhesive hydrogel is very promising for wound closure and may provide new ideas for the design of robust wet tissue adhesives

Robust but On-Demand Detachable Wet Tissue Adhesive Hydrogel Enhanced with Modified Tannic Acid

Adhesives with robust but readily detachable wet tissue adhesion are of great significance for wound closure. Polyelectrolyte complex adhesive (PECA) is an important wet tissue adhesive. However, its relatively weak cohesive and adhesive strength cannot satisfy clinical applications. Herein, modified tannic acid (mTA) with a catechol group, a long alkyl hydrophobic chain, and a phenyl group was prepared first, and then, it was mixed with acrylic acid (AA) and polyethylenimine (PEI), followed by UV photopolymerization to make a wet tissue adhesive hydrogel with tough cohesion and adhesion strength. The hydrogel has a strong wet tissue interfacial toughness of ∼1552 J/m2, good mechanical properties (∼7220 kPa cohesive strength, ∼873% strain, and ∼33,370 kJ/m3 toughness), and a bursting pressure of ∼1575 mmHg on wet porcine skin. The hydrogel can realize quick and effective adhesion to various wet biological tissues including porcine skin, liver, kidney, and heart and can be changed easily with triggering urea solution to avoid tissue damage or uncomfortable pain to the patient. This biosafe adhesive hydrogel is very promising for wound closure and may provide new ideas for the design of robust wet tissue adhesives

Robust but On-Demand Detachable Wet Tissue Adhesive Hydrogel Enhanced with Modified Tannic Acid

Adhesives with robust but readily detachable wet tissue adhesion are of great significance for wound closure. Polyelectrolyte complex adhesive (PECA) is an important wet tissue adhesive. However, its relatively weak cohesive and adhesive strength cannot satisfy clinical applications. Herein, modified tannic acid (mTA) with a catechol group, a long alkyl hydrophobic chain, and a phenyl group was prepared first, and then, it was mixed with acrylic acid (AA) and polyethylenimine (PEI), followed by UV photopolymerization to make a wet tissue adhesive hydrogel with tough cohesion and adhesion strength. The hydrogel has a strong wet tissue interfacial toughness of ∼1552 J/m2, good mechanical properties (∼7220 kPa cohesive strength, ∼873% strain, and ∼33,370 kJ/m3 toughness), and a bursting pressure of ∼1575 mmHg on wet porcine skin. The hydrogel can realize quick and effective adhesion to various wet biological tissues including porcine skin, liver, kidney, and heart and can be changed easily with triggering urea solution to avoid tissue damage or uncomfortable pain to the patient. This biosafe adhesive hydrogel is very promising for wound closure and may provide new ideas for the design of robust wet tissue adhesives

Robust but On-Demand Detachable Wet Tissue Adhesive Hydrogel Enhanced with Modified Tannic Acid

Adhesives with robust but readily detachable wet tissue adhesion are of great significance for wound closure. Polyelectrolyte complex adhesive (PECA) is an important wet tissue adhesive. However, its relatively weak cohesive and adhesive strength cannot satisfy clinical applications. Herein, modified tannic acid (mTA) with a catechol group, a long alkyl hydrophobic chain, and a phenyl group was prepared first, and then, it was mixed with acrylic acid (AA) and polyethylenimine (PEI), followed by UV photopolymerization to make a wet tissue adhesive hydrogel with tough cohesion and adhesion strength. The hydrogel has a strong wet tissue interfacial toughness of ∼1552 J/m2, good mechanical properties (∼7220 kPa cohesive strength, ∼873% strain, and ∼33,370 kJ/m3 toughness), and a bursting pressure of ∼1575 mmHg on wet porcine skin. The hydrogel can realize quick and effective adhesion to various wet biological tissues including porcine skin, liver, kidney, and heart and can be changed easily with triggering urea solution to avoid tissue damage or uncomfortable pain to the patient. This biosafe adhesive hydrogel is very promising for wound closure and may provide new ideas for the design of robust wet tissue adhesives

Synthesis of Compositionally Defined Single-Crystalline Eu³⁺-Activated Molybdate–Tungstate Solid-Solution Composite Nanowires and Observation of Charge Transfer in a Novel Class of 1D CaMoO₄–CaWO₄:Eu³⁺–0D CdS/CdSe QD Nanoscale Heterostructures

As a first step, we have synthesized and optically characterized a systematic series of one-dimensional (1D) single-crystalline Eu³⁺-activated alkaline-earth metal tungstate/molybdate solid-solution composite CaW_1–<i>x</i>­Mo_<i>x</i>O₄ (0 ≤ “<i>x</i>” ≤ 1) nanowires of controllable chemical composition using a modified template-directed methodology under ambient room-temperature conditions. Extensive characterization of the resulting nanowires has been performed using X-ray diffraction, electron microscopy, and optical spectroscopy. The crystallite size and single crystallinity of as-prepared 1D CaW_1–<i>x</i>­Mo_<i>x</i>O₄:Eu³⁺ (0 ≤ “<i>x</i>” ≤ 1) solid-solution composite nanowires increase with increasing Mo component (“<i>x</i>”). We note a clear dependence of luminescence output upon nanowire chemical composition with our 1D CaW_1–<i>x</i>Mo_<i>x</i>O₄:Eu³⁺ (0 ≤ “<i>x</i>” ≤ 1) evincing the highest photoluminescence (PL) output at “<i>x</i>” = 0.8, among samples tested. Subsequently, coupled with either zero-dimensional (0D) CdS or CdSe quantum dots (QDs), we successfully synthesized and observed charge transfer processes in 1D CaW_1–<i>x</i>Mo_<i>x</i>­O₄:Eu³⁺ (“<i>x</i>” = 0.8)–0D QD composite nanoscale heterostructures. Our results show that CaW_1–<i>x</i>­Mo_<i>x</i>O₄:Eu³⁺ (“<i>x</i>” = 0.8) nanowires give rise to PL quenching when CdSe QDs and CdS QDs are anchored onto the surfaces of 1D CaWO₄–CaMoO₄:Eu³⁺ nanowires. The observed PL quenching is especially pronounced in CaW_1–<i>x</i>Mo_<i>x</i>O₄:Eu³⁺ (“<i>x</i>” = 0.8)–0D CdSe QD heterostructures. Conversely, the PL output and lifetimes of CdSe and CdS QDs within these heterostructures are not noticeably altered as compared with unbound CdSe and CdS QDs. The differences in optical behavior between 1D Eu³⁺ activated tungstate and molybdate solid-solution nanowires and the semiconducting 0D QDs within our heterostructures can be correlated with the relative positions of their conduction and valence energy band levels. We propose that the PL quenching can be attributed to a photoinduced electron transfer process from CaW_1–<i>x</i>­Mo_<i>x</i>O₄:Eu³⁺ (“<i>x</i>” = 0.8) to both CdSe and CdS QDs, an assertion supported by complementary near edge X-ray absorption fine structure (NEXAFS) spectroscopy measurements