Free-standing Nanosheets Research Articles

Freestanding Penta-Twinned Pd-Ag Nanosheets.

2D metal nanosheets have attracted significant attention as efficient catalysts for various important chemical reactions. However, the development of metal nanosheets with controlled compositions and morphologies has been slow due to the challenges associated with synthesizing thermodynamically unfavorable 2D structures. Herein, we report a synthesis route of freestanding Pd-Ag penta-twinned nanosheets (Pd-Ag ptNSs) with distinct 5-fold twin boundaries. Through the coreduction of Ag and Pd precursors on presynthesized Pd ptNSs, Ag could be homogeneously alloyed with Pd, leading to the formation of well-defined Pd-Ag ptNSs. The promotional effects of the bimetallic composition, 2D structure, and twin boundaries on catalysis were studied by using Pd-Ag ptNS-catalyzed H2 production from formic acid decomposition as a model reaction. Notably, the catalytic activity of the Pd-Ag ptNSs drastically outperformed those of monometallic, bimetallic, and 3D counterparts, such as Pd ptNSs, Pd-Ag nanosheets without a TB, and Pd-Ag octahedral nanocrystals, demonstrating the promising potential of the integration of twin boundaries and multiple compositions in the development of high-performance 2D nanocatalysts.

Solution Synthesis of NdTe3 Magnetic Nanosheets.

Neodymium tritelluride is a layered van der Waals material, with correlated electronic properties including high electronic mobility, charge density waves, and antiferromagnetism. We developed a solution synthesis method to form free-standing nanosheets of NdTe3, with nanosheet lateral dimensions of 200-400 nm. The morphology of the nanosheet was influenced by the neodymium precursor. When Nd[(N(SiMe3)2]3 was used as the metal source the nanosheet thickness average was 12 ± 2.5 nm, alternatively the combination of NdCl3 and Li(N(SiMe3)2) led to thicker nanosheets, approximately 19 ± 2.4 nm. We believe that the difference in thickness and changes in surface chemistry point to the role of chloride in accelerating nanocrystal growth for the synthesis with NdCl3 (and Li(N(SiMe3)2). Both types of nanosheets exhibit charge density wave (CDW) distortions as measured using electron diffraction and investigated using variable temperature Raman scattering. Interestingly, the magnetic studies suggest a distinct change in properties between 12 and 19 nm thickness in antiferromagnetic NdTe3.

"Hard" Emulsion-Induced Interface Super-Assembly: A General Strategy for Two-Dimensional Hierarchically Porous Metal-Organic Framework Nanoarchitectures.

Two-dimensional (2D) hierarchically porous metal-organic framework (MOF) nanoarchitectures with tailorable meso-/macropores hold great promise for enhancing mass transfer kinetics, augmenting accessible active sites, and thereby boosting performance in heterogeneous catalysis. However, achieving the general synthesis of 2D free-standing MOF nanosheets with controllable hierarchical porosity and thickness remains a challenging task. Herein, we present an ingenious "hard" emulsion-induced interface super-assembly strategy for preparing 2D hierarchically porous UiO-66-NH2 nanosheets with highly accessible pore channels, tunable meso-/macropore sizes, and adjustable thicknesses. The methodology relies on transforming the geometric shape of oil droplet templates within appropriate oil-in-water emulsions from conventional zero-dimensional (0D) "soft" liquid spheres to 2D "hard" solid sheets below the oil's melting/freezing point. Subsequent surfactant exchange on the surface of 2D "hard" emulsions facilitates the heterogeneous nucleation and interfacial super-assembly of in situ formed mesostructured MOF nanocomposites, serving as structural units, in a loosely packed manner to produce 2D MOF nanosheets with multimodal micro/meso-/macroporous systems. Importantly, this strategy can be extended to prepare other 2D hierarchically porous MOF nanosheets by altering metal-oxo clusters and organic ligands. Benefiting from fast mass transfer and highly accessible Lewis acidic sites, the resultant 2D hierarchically porous UiO-66-NH2 nanosheets deliver a fabulous catalytic yield of approximately 96% on the CO2 cycloaddition of glycidyl-2-methylphenyl ether, far exceeding the yield of approximately 29% achieved using conventional UiO-66-NH2 microporous crystals. This "hard" emulsion-induced interface super-assembly strategy paves a new path toward the rational construction of elaborate 2D nanoarchitecture of hierarchical MOFs with tailored physicochemical properties for diverse potential applications.

Capture and Storage of Cell-Free DNA via Bio-Informational Hydrogel Microspheres.

Excessive cell-free DNA (cfDNA) can induce chronic inflammation by activating intracellular nucleic acid sensors. Intervention in cfDNA-mediated "pro-inflammatory signaling transduction" could be a potential alleviating strategy for chronic inflammation, such as in diabetic wounds. However, effectively and specifically downgrading cfDNA concentration in the pathological microenvironment remains a challenge. Therefore, this work prepares free-standing polydopamine nanosheets through DNA-guided assembly and loaded them into microfluidic hydrogel microspheres. The π─π stacking/hydrogen bonding interactions between polydopamine nanosheets and the π-rich bases of cfDNA, along with the cage-like spatial confinement created by the hydrogel polymer network, achieved cfDNA capture and storage, respectively. Catechol in polydopamine nanosheets can also assist in reducing reactive oxygen species (ROS) levels. Efficient cfDNA binding independent of serum proteins, specific interdiction of abnormal activation of cfDNA-associated toll-like receptor 9, as well as down-regulation of inflammatory cytokines and ROS levels are shown in this system. The chronic inflammation alleviating and the pro-healing effects on the mice model with diabetic wounds are also investigated. This work presents a new strategy for capturing and storing cfDNA to intervene in cell signaling transduction. It also offers new insights into the regulatory mechanisms between inflammatory mediators and biomaterials in inflammation-related diseases.

Deeper Insights into the Morphology Effect of Na2Ti3O7 Nanoarrays on Sodium-Ion Storage.

Na2Ti3O7-based anodes show great promise for Na+ storage in sodium-ion batteries (SIBs), though the effect of Na2Ti3O7 morphology on battery performance remains poorly understood. Herein, hydrothermal syntheses is used to prepare free-standing Na2Ti3O7 nanosheets or Na2Ti3O7 nanotubes on Ti foil substrates, with the structural and electrochemical properties of the resulting electrodes explored in detail. Results show that the Na2Ti3O7 nanosheet electrode (NTO NSs) delivered superior performance in terms of reversible capacity, rate capability, and especially long-term durability in SIBs compared to its nanotube counterpart (NTO NTs). Electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM) investigations, combined with density functional theory calculations, demonstrated that the flexible 2D Na2Ti3O7 nanosheets are mechanically more robust than the rigid Na2Ti3O7 nanotube arrays during prolonged battery cycling, explaining the superior durability of the NTO NSs electrode. This work prompts the use of anodes based on Na2Ti3O7 nanosheets in the future development of high-performance SIBs.

Defect-Free, Few-Atomic-Layer Thin ZnO Nanosheets with Superior Excitonic Properties for Optoelectronic Devices.

Two-dimensional (2D) wide bandgap materials are gaining significant interest for next-generation optoelectronic devices. However, fabricating electronic-grade 2D nanosheets from non-van der Waals (n-vdW) oxide semiconductors poses a great challenge due to their stronger interlayer coupling compared with vdW crystals. This strong coupling typically introduces defects during exfoliation, impairing the optoelectronic properties. Herein, we report the liquid-phase exfoliation of few-atomic-layer thin, defect-free, free-standing ZnO nanosheets. These micron-sized, ultrathin ZnO structures exhibit three different orientations aligned along both the polar c-plane as well as the nonpolar a- and m-planes. The superior crystalline quality of the ZnO nanosheets is validated through comprehensive characterization techniques. This result is supported by density functional theory (DFT) calculations, which reveals that the formation of oxygen vacancies is energetically less favorable in 2D ZnO and that the c-plane loses its polarity upon exfoliation. Unlike bulk ZnO, which is typically dominated by defect-induced emission, the exfoliated nanosheets exhibit a strong, ambient-stable excitonic UV emission. We further demonstrate the utility of solution processing of ZnO nanosheets by their hybrid integration with organic components to produce stable light emitting diodes (LEDs) for display applications.

Hydrogenation driven ultra-low lattice thermal conductivity in β 12 borophene

Borophene gathered large interest owing to its polymorphism and intriguing properties such as Dirac point, inherent metallicity, etc but oxidation limits its capabilities. Hydrogenated borophene was recently synthesised experimentally to harness its applications. Motivated by experimental work, in this paper, using first-principles calculations and Boltzmann transport theory, we study the freestanding β 12 borophene nanosheet doped and functionalised with hydrogen (H), lithium (Li), beryllium (Be), and carbon (C) atoms at different β 12 lattice sites. Among all possible configurations, we screen two stable candidates, pristine and hydrogenated β 12 borophene nanosheets. Both nanosheets possess dynamic and mechanical stability while the hydrogenated sheet has different anisotropic metallicity compared to pristine sheet leading to enhancement in brittle behaviour. Electronic structure calculations reveal that both nanosheets host Dirac cones (DCs), while hydrogenation leads to shift and enhancement in tilt of the DCs. Further hydrogenation leads to the appearance of additional Fermi pockets in the Fermi surface. Transport calculations reveals that the lattice thermal conductivity changes from 12.51 to 0.22 W m−1 K−1 (along armchair direction) and from 4.42 to 0.07 W m−1 K−1 (along zigzag direction) upon hydrogenation at room temperature (300 K), demonstrating a large reduction by two orders of magnitude. Such reduction is mainly attributed to decreased phonon mean free path and relaxation time along with the enhanced phonon scattering rates stemming from high frequency phonon flat modes in hydrogenated nanosheet. Comparatively larger weighted phase space leads to increased anharmonic scattering in hydrogenated nanosheet contributing to ultra-low lattice thermal conductivity. Consequently, hydrogenated β 12 nanosheet exhibits a comparatively higher thermoelectric figure of merit (∼0.75) at room temperature along armchair direction. Our study demonstrates the effects of functionalisation on transport properties of freestanding β 12 borophene nanosheets which can be utilised to enhance the thermoelectric performance in two-dimensional (2D) systems and expand the applications of boron-based 2D materials.

Electrodeposited graphene@Co3O4 nanosheets for oxygen evolution reaction

With the increasing demand for renewable and clean energy, highly efficient and low-cost electrocatalysts for oxygen evolution reaction (OER) have attracted great interest in the field of hydrogen energy. In this work, we report a novel strategy to prepare graphene (Gr, rather than graphene oxide)-supported highly efficient catalyst for OER. Gr-supported Co3O4 free-standing nanosheets (Gr@eCo3O4) are fabricated by electrodeposition. SiO2 is used as a template for co-electrodeposition, and is further etched by alkali. Gr provides large electrochemical surface area and abundant catalytically active sites, as well as enhances the conductivity of Co3O4. Meanwhile, the charge transfer kinetics of OER is improved on Co3O4 electrodeposited on Gr. Gr@eCo3O4 exhibits superior OER performance with a Tafel slope of 45 mV dec−1 at 10 mA cm−2.

Cactus-like NC/CoxP electrode enables efficient and stable hydrogen evolution for saline water splitting

Designing efficient and robust catalysts for hydrogen evolution reaction (HER) is imperative for saline water electrolysis technology. A catalyst composed of CoxP nanowires array with N-doped carbon nanosheets (NC) was fabricated on Ni foam (NF) by an in-situ growth strategy. The material is designated as NC/CoxP@NF. In the preparation process, Co(OH)2 nanowires were transformed into a metal organic framework of cobalt (ZIF-67) on NF by the dissolution-coordination of endogenous Co2+ and 2-methylimidazole. The resulting cactus-like microstructure gives NC/CoxP@NF abundant exposed active sites and ion transport channels, which improve the HER catalytic reaction kinetics. Furthermore, the interconnected alternating nanowires and free-standing nanosheets in NC/CoxP@NF improve its structural stability, and the formation of surface polyanions (phosphate) and a NC nanosheet protective layer improve the anti-corrosive properties of catalysts. Thus, the NC/CoxP@NF has an excellent performance, requiring overpotentials of 107 and 133 mV for HER to achieve 10 mA cm−2 in 1.0 mol L−1 KOH and 1.0 mol L−1 KOH + 0.5 mol L−1 NaCl, respectively. This in-situ transformation strategy is a new way of constructing highly-efficient HER catalysts for saline water electrolysis.

DNA Framework-Templated Fabrication of Ultrathin Electroactive Gold Nanosheets.

Generally, two-dimensional gold nanomaterials have unique properties and functions that offer exciting application prospects. However, the crystal phases of these materials tend to be limited to the thermodynamically stable crystal structure. Herein, we report a DNA framework-templated approach for the ambient aqueous synthesis of freestanding and microscale amorphous gold nanosheets with ultrathin sub-nanometer thickness. We observe that extended single-stranded DNA on DNA nanosheets can induce site-specific metallization and enable precise modification of the metalized nanostructures at predefined positions. More importantly, the as-prepared gold nanosheets can serve as an electrocatalyst for glucose oxidase-catalyzed aerobic oxidation, exhibiting enhanced electrocatalytic activity (~3-fold) relative to discrete gold nanoclusters owing to a larger electrochemical active area and wider band gap. The proposed DNA framework-templated metallization strategy is expected to be applicable in a broad range of fields, from catalysis to new energy materials.

DNA Framework‐Templated Fabrication of Ultrathin Electroactive Gold Nanosheets

AbstractGenerally, two‐dimensional gold nanomaterials have unique properties and functions that offer exciting application prospects. However, the crystal phases of these materials tend to be limited to the thermodynamically stable crystal structure. Herein, we report a DNA framework‐templated approach for the ambient aqueous synthesis of freestanding and microscale amorphous gold nanosheets with ultrathin sub‐nanometer thickness. We observe that extended single‐stranded DNA on DNA nanosheets can induce site‐specific metallization and enable precise modification of the metalized nanostructures at predefined positions. More importantly, the as‐prepared gold nanosheets can serve as an electrocatalyst for glucose oxidase‐catalyzed aerobic oxidation, exhibiting enhanced electrocatalytic activity (~3‐fold) relative to discrete gold nanoclusters owing to a larger electrochemical active area and wider band gap. The proposed DNA framework‐templated metallization strategy is expected to be applicable in a broad range of fields, from catalysis to new energy materials.

Multivalency-induced structural variations of 2D selenium nanosheets: facile solution-phase synthesis and optical properties.

The structural stability of two-dimensional (2D) phases derived from bulk selenium (Se) is intrinsically rooted in the multivalent nature of the material. The emergence of 2D Se, as its morphology evolves from 1D to 2D, was initially inspired by theoretical predictions of various quasi-stable structural phases of 2D Se. Here, we report a facile liquid-phase synthesis of free-standing few-layer selenium nanosheets (SeNS) employing a simple magnetic stirring of their bulk counterpart in N-methyl pyrrolidone (NMP). The synthesized SeNS possess lateral dimensions ranging from several hundreds of nanometers to a few microns, with a minimum thickness of ∼1 nm. High-resolution transmission electron microscopy reveals the existence of α- and β-selenene. Fourier transform infrared analysis suggests that the inherent surface/edge functionalization of 2D SeNS by NMP enhances their dispersion stability. The UV-vis-NIR absorption spectrum of SeNS exhibits a shoulder peak at 330 nm, attributed to surface/edge functionalization, and multiple peaks across the vis-NIR region, stemming from size quantization effects. The functionalized selenium nanosheets generate photoluminescence that spans the blue-green range, while the size quantization of SeNS leads to green-orange luminescence. The non-linear optical studies following Z-scan experiments with an open aperture revealed reverse saturable absorption (RSA) and strong optical limiting in 2D SeNS under 532 nm, 10 ns laser pulses. Notably, a transition from RSA to saturable absorption (SA) has also been observed in samples stirred over an extended period. In this perspective, the results illustrate the first experimental realization of free-standing multivalent 2D selenium in allotropic forms with unique optical properties.

Gold Nanoparticle-Loaded Porous Poly(ethylene glycol) Nanosheets for Electrochemical Detection of H2O2.

The effective detection of hydrogen peroxide (H2O2) in different environments and, above all, in biological media, is an important practical issue. To this end, we designed a novel electrochemical sensor for H2O2 detection by introducing gold nanoparticles (AuNPs) into the porous poly(ethylene glycol) (PEG) matrix formed by the thermally activated crosslinking of amino- and epoxy-decorated STAR-PEG precursors. The respective composite PEG-AuNP films could be readily prepared on oxidized Si substrates, separated from them as free-standing nanosheets, and transferred as H2O2 sensing elements onto the working electrode of the electrochemical cell, with the performance of the sensing element relied on the established catalytic activity of AuNPs with respect to H2O2 decomposition. The sensitivity, detection limit, and the operation range of the composite PEG-AuNP sensors were estimated at ~3.4 × 102 μA mM-1 cm-2, 0.17 μM of H2O2, and 20 μM-3.5 mM of H2O2, respectively, which are well comparable with the best values for other types of H2O2 sensors reported recently in literature. The particular advantages of the composite PEG-AuNP sensors are commercial source materials, a simple fabrication procedure, the bioinert character of the PEG matrix, the 3D character of the AuNP assembly, and the possibility of transferring the nanosheet sensing element to any secondary substrate, including the glassy carbon electrode of the electrochemical cell. In particular, the bioinert character of the PEG matrix can be of importance for potential biological and biomedical applications of the designed sensing platform.

In-situ free-standing inorganic 2D Cs2PbI2Cl2 nanosheets for efficient self-powered photodetectors with carbon electrode

Inorganic two-dimensional (2D) perovskites possess excellent thermal stability and high charge mobility, making them an attractive choice for stable optoelectronic devices such as photodetectors (PDs). The formation of an appropriate inorganic 2D perovskite structure is of great importance to efficient PDs, especially to that of planar self-powered photovoltaic PDs featuring perpendicular charge transport channels. Herein, we implemented morphological engineering on wide bandgap inorganic 2D perovskite, Cs2PbI2Cl2, demonstrating a successful preparation of in-situ free-standing nanosheets structure with proper charge channels for photovoltaic type self-powered PDs. Compared with its counterpart with a nanoblock morphology, the 2D nanosheet Cs2PbI2Cl2 film exhibits enhanced charge mobility and purified Ruddlesden-Popper phase that can withstand high-energy electron beam radiation, accelerated thermal aging and long-term shelf storage. Sandwiching Cs2PbI2Cl2 nanosheet film in between tin oxide (SnO2) and polythiophene (P3HT) as electron and hole acceptors, respectively, the constructed photovoltaic type structure exhibits effective dissociation of excitons at the cascade type-II interface. The nanosheets enable lower dark current and more efficient charge collection than the nanoblock structure. As a result, the self-powered photodetectors with 2D Cs2PbI2Cl2 nanosheets deliver an outstanding responsivity of 698 mW/cm2 and a detectivity of 8.6×1012 Jones. The stable PDs can be applied to monitor ultraviolet irradiation in real outdoor conditions. Our work demonstrates the significant role of morphology tuning of 2D inorganic perovskite in stable, cost-effective and efficient photodetectors.

In situ immobilization of δ-MnO2 nanosheets on a porous support for rapid and continuous cleaning of bisphenol A-spiked water

Bisphenol A (BPA), a building block of various plastics, is invading biosystems through drinking water and raising concerns about their adverse impacts on human health. Filtration, biological, and oxidation methods have been developed to decontaminate BPA, but high energy demand or lengthy biodegradation process acts as limiting factors. Recently, δ-MnO2 with layered structure has emerged as a promising tool for BPA degradation. However, the reaction rate of BPA degradation suffers from the nature of aggregation in free-standing δ-MnO2 nanosheets with limited accessible active sites towards BPA. To overcome this critical challenge, this study demonstrates that the immobilization of δ-MnO2 nanosheets on a porous support can enhance BPA degradation rate due to the increased exposure of active sites of δ-MnO2. As a result, the δ-MnO2 nanosheets immobilized on porous diatom particles via polydopamine (PDA) binder degrades BPA (k’ ∼0.774 L g−1 min−1) 14 times faster than free-standing δ-MnO2 (k’ ∼0.056 L g−1 min−1). Furthermore, the resulting δ-MnO2-PDA-diatom degrades ∼ 99 % of BPA within 20 min and can be recycled without any performance loss up to 7 times, providing the reusability towards BPA removal in a sustainable and eco-friendly manner. More importantly, the degraded products of BPA resulting from radical transfers, coupling, and fragmentation reactions do not cause any estrogenic response or toxicity to ecological systems, as examined with human and fish cells. Finally, a column packed with δ-MnO2-PDA-diatom demonstrates 99 % BPA removal with continuous flows of BPA-spiked wastewater. We propose that this advanced system will be readily extended to remove a broad array of water contaminants that will disrupt the physiological function of organs and their roles in the endocrine cross-talk between the reproductive hormones.

Supercurrent, Multiple Andreev Reflections and Shapiro Steps in InAs Nanosheet Josephson Junctions.

We report an experimental study of proximity induced superconductivity in planar Josephson junction devices made from free-standing InAs nanosheets. The nanosheets are grown by molecular beam epitaxy, and the Josephson junction devices are fabricated by directly contacting the nanosheets with superconductor Al electrodes. The fabricated devices are explored by low-temperature carrier transport measurements. The measurements show that the devices exhibit a gate-tunable supercurrent, multiple Andreev reflections, and a good quality superconductor-semiconductor interface. The superconducting characteristics of the Josephson junctions are investigated at different magnetic fields and temperatures and are analyzed based on the Bardeen-Cooper-Schrieffer (BCS) theory. The measurements of the ac Josephson effect are also conducted under microwave radiations with different radiation powers and frequencies, and integer Shapiro steps are observed. Our work demonstrates that InAs nanosheet based hybrid devices are desired systems for investigating the forefront of physics, such as two-dimensional topological superconductivity.

Free‐Standing Molecularly Thin Amorphous Silica Nanosheets (Small 22/2023)

Amorphous Silica Nanosheets In article number 2300022, Eisuke Yamamoto, Minoru Osada, and co-workers establish a chemical protocol for free-standing molecularly thin nanosheets; solid-state surfactant lamellae can serve as templates guiding amorphous silica nanosheets. Exfoliation of the lamellar hybrids with ordered alkyl-chain arrangement allows into free-standing amorphous silica nanosheets with 0.9 nm in thickness. In addition, the nanosheets show high colloidal stability that enables atomic layer engineering of film with a low leakage current density.

Two-Dimensional Supramolecular Polymerization of DNA Amphiphiles is Driven by Sequence-Dependent DNA-Chromophore Interactions.

Two-dimensional (2D) assemblies of water-soluble block copolymers have been limited by a dearth of systematic studies that relate polymer structure to pathway mechanism and supramolecular morphology. Here, we employ sequence-defined triblock DNA amphiphiles for the supramolecular polymerization of free-standing DNA nanosheets in water. Our systematic modulation of amphiphile sequence shows the alkyl chain core forming a cell membrane-like structure and the distal π-stacking chromophore block folding back to interact with the hydrophilic DNA block on the nanosheet surface. This interaction is crucial to sheet formation, marked by a chiral "signature", and sensitive to DNA sequence, where nanosheets form with a mixed sequence, but not with a homogeneous poly(thymine) sequence. This work opens the possibility of forming well-ordered, bilayer-like assemblies using a single DNA amphiphile for applications in cell sensing, nucleic acid therapeutic delivery and enzyme arrays.

Observation of ferrimagnetic ordering in chemically synthesized 2D Cr2S3 nanosheets

It is established that 2D magnetic materials are the ideal platform for building up modern-day electronic and spintronic devices. The popular ways to achieve 2D magnetic materials are mechanical exfoliation and chemical vapor deposition. However, the direct chemical synthesis route of such magnetic 2D materials on a large scale is relatively unexplored. This article reports an easy and cost-effective facile chemical synthesis with a proper capping agent and magnetic study of free-standing 2D Cr2S3 nanosheets and Cr2S3 nanoparticles within the temperature range of 2–300 K under the magnetic field of up to 5 T. Although few magnetic results on 2D Cr2S3 are available in the literature, there is enough scope to work for an in-depth understanding of the magnetic aspects of this 2D material. Here, ferrimagnetic ordering with a sufficiently high coercivity of up to 0.139 T at 2 K along with a tendency to the saturation in magnetization down to a certain temperature limit is observed. Contrary to the strong antiferromagnetic coupling with a Néel temperature, as observed by previous researchers, is also observed for this chemically synthesized 2D Cr2S3 nanosheets. A transition temperature of 117 K is observed for the Cr2S3 nanosheets, whereas for Cr2S3 nanoparticles, a transition temperature of 101.7 K is observed with negligible coercivity. This facile synthesis technique may be applied to achieve other non-van der Waals type 2D magnetic materials. These kinds of non-van der Waals type 2D magnets will be useful to modern-day spintronic devices.

Atomic-thick metastable phase RhMo nanosheets for hydrogen oxidation catalysis

Metastable phase two-dimensional catalysts provide great flexibility for modifying their chemical, physical, and electronic properties. However, the synthesis of ultrathin metastable phase two-dimensional metallic nanomaterials is highly challenging, mainly due to the anisotropic nature of metallic materials and their thermodynamically unstable ground-state. Here, we report free-standing RhMo nanosheets with atomic thickness and a unique core/shell (metastable phase/stable phase) structure. The polymorphic interface between the core region and shell region stabilizes and activates metastable phase catalysts; the RhMo Nanosheets/C shows excellent hydrogen oxidation activity and stability. Specifically, the mass activities of RhMo Nanosheets/C is 6.96 A mgRh−1; this is 21.09 times higher than that of commercial Pt/C (0.33 A mgPt−1). Density functional theory calculations suggest that the interface aids in the dissociation of H2 and the H species can then spillover to weak H binding sites for desorption, providing excellent hydrogen oxidation activity for RhMo nanosheets. This work advances the highly controlled synthesis of two-dimensional metastable phase noble metals and provides great directions for the design of high-performance catalysts for fuel cells and beyond.