Ultrathin Rh Nanosheets with Rich Grain Boundaries for Efficient Hydrogen Oxidation Electrocatalysis.

Two-dimensional (2D) Pt-group ultrathin nanosheets (NSs) are promising advanced electrocatalysts for energy-related catalytic reactions. However, improving the electrocatalytic activity of 2D Pt-group NSs through the addition of abundant grain boundaries (GBs) and understanding the underlying formation mechanism remain significant challenges. Herein, we report the controllable synthesis of a series of Rh-based nanocrystals (e.g., Rh nanoparticles, Rh NSs, and Rh NSs with GBs) through a CO-mediated kinetic control synthesis route. In light of the 2D NSs' structural advantages and GB modification, the Rh NSs with rich GBs exhibit an enhanced electrocatalytic activity compared to pure Rh NSs and commercial Pt/C toward the hydrogen oxidation reaction (HOR) in alkaline media. Both experimental results and theoretical computations corroborate that the GBs in the Rh NSs have the capacity to ameliorate the adsorption free energy of reaction intermediates during the HOR, thus resulting in outstanding HOR catalytic performance. Our work offers novel perspectives in the realm of developing sophisticated 2D Pt-group metal electrocatalysts with rich GBs for the energy conversion field.

Tuning Electron Transfer in Atomic-Scale Pt-Supported Catalysts for the Alkaline Hydrogen Oxidation Reaction.

Developing efficient atomic-scale metal-supported catalysts is of great significance for energy conversion technologies. However, the precise modulation of electron transfer between the metal and supporter in atomic-scale metal-supported catalysts to further improve the catalytic activity is still a major challenge. Herein, we show tunable electron transfer between atomic-scale Pt and tungsten nitride/oxide supports (namely, Pt/WN and Pt/W18O49). Pt/WN with modest electron exchange and Pt/W18O49 with aggressive electron exchange exhibit notably different catalytic activities for the alkaline hydrogen oxidation reaction (HOR), in which Pt/WN shows a 5.7-fold enhancement in HOR intrinsic catalytic performance in comparison to Pt/W18O49. Additionally, the tunable electronic transfer at the interface of Pt/WN and Pt/W18O49, as proven by the theoretical calculation, resulted in the discrepancy of the adsorption free energy of the reaction intermediates, as well as catalytic activity, for the HOR process. Our work provides new insights into the design of advanced atomic-scale metal-supported catalysts for electrocatalysis.

Water-Stable Hybrid Lead-Free Perovskite for Negative Temperature Coefficient Thermistors.

Negative temperature coefficient (NTC) thermistors feature higher sensitivities and faster response speeds and thereby have particular applications in many fields. However, current NTC thermistors are mostly based on inorganic ceramic materials, which show obvious drawbacks in material synthesis, property modulation, and flexible film fabrication. Herein, we report, for the first time, the promising application of an inorganic-organic hybrid NTC thermistor. A new lead-free hybrid iodo bismuthate [1,1',1″-(benzene-1,3,5-triyl)tris(3-methyl-1H-imidazol-3-ium)]Bi2I9 [denoted as (Me3TMP)Bi2I9] was synthesized by a "double-free" strategy. (Me3TMP)Bi2I9 features a lead-free binuclear bismuth iodine anion charge compensated by a "classic hydrogen-bond-free" cation. (Me3TMP)Bi2I9 exhibits remarkable stability in water and UV light irradiation and shows the largest temperature sensitivity coefficient among all reported NTC materials. Theoretical calculation and detailed structural analysis disclose that the seriously distorted (BiI6) octahedra are responsible for the intriguing NTC effect for (Me3TMP)Bi2I9.

Corrigendum: Superparamagnetic enhancement of thermoelectric performance.

This corrects the article DOI: 10.1038/nature23667.

Superparamagnetic enhancement of thermoelectric performance.

The ability to control chemical and physical structuring at the nanometre scale is important for developing high-performance thermoelectric materials. Progress in this area has been achieved mainly by enhancing phonon scattering and consequently decreasing the thermal conductivity of the lattice through the design of either interface structures at nanometre or mesoscopic length scales or multiscale hierarchical architectures. A nanostructuring approach that enables electron transport as well as phonon transport to be manipulated could potentially lead to further enhancements in thermoelectric performance. Here we show that by embedding nanoparticles of a soft magnetic material in a thermoelectric matrix we achieve dual control of phonon- and electron-transport properties. The properties of the nanoparticles-in particular, their superparamagnetic behaviour (in which the nanoparticles can be magnetized similarly to a paramagnet under an external magnetic field)-lead to three kinds of thermoelectromagnetic effect: charge transfer from the magnetic inclusions to the matrix; multiple scattering of electrons by superparamagnetic fluctuations; and enhanced phonon scattering as a result of both the magnetic fluctuations and the nanostructures themselves. We show that together these effects can effectively manipulate electron and phonon transport at nanometre and mesoscopic length scales and thereby improve the thermoelectric performance of the resulting nanocomposites.

Ru Colloidosome Catalysts for the Hydrogen Oxidation Reaction in Alkaline Media.

Developing efficient hydrogen oxidation reaction (HOR) electrocatalysts in alkaline media is of great significance for anion exchange membrane fuel cells. Herein, we report the synthesis of hollow colloidosomes composed of Ru nanocrystals based on a novel gas/liquid interface self-assembly strategy. Structural characterizations reveal that much defects are present in the building block (Ru nanocrystals) of Ru colloidosomes. Theoretical calculations suggest that the defects in the Ru structure can optimize the adsorption binding energy of reaction intermediates for the HOR. Benefiting from the assembled colloidosome and optimized electronic structure, the Ru colloidosomes exhibit remarkable HOR catalytic performance in alkaline media with a mass activity higher than that of benchmark Pt/C. Our work may shed new light on the rational design of advanced electrocatalysts with an assembled structure for energy-related applications.

Magnetically enhanced thermoelectrics: a comprehensive review.

Thermoelectric (TE) materials have great potential for waste-energyrecycling and solid-state cooling. Their conversion efficiency has attracted huge attention to the development of TE devices, and largely depends on the thermal and electrical transport properties. Magnetically enhanced thermoelectrics open up the possibility of making thermoelectricity a future leader in sustainable energy development and offer an intriguing platform for both fundamental physics and prospective applications. In this review, state-of-the-art TE materials are summarized from the magnetism point of view, via diagrams of the charges, lattices, orbits and spin degrees of freedom. Our fundamental knowledge of magnetically induced TE effects is discussed. The underlying thermo-electro-magnetic merits are discussed in terms of superparamagnetism- and magnetic-transition-enhanced electron scattering, field-dependent magnetoelectric coupling, and the magnon- and phonon-drag Seebeck effects. After these topics, we finally review several thermal-electronic and spin current-induced TE materials, highlight future possible strategies for further improvingZT, and also give a brief outline of ongoing research challenges and open questions in this nascent field.

Nitrogen-Doped Cobalt Diselenide with Cubic Phase Maintained for Enhanced Alkaline Hydrogen Evolution.

The introduction of heteroatoms is one of the most important ways to modulate the intrinsic electronic structure of electrocatalysts to improve their catalytic activity. However, for transition metal chalcogenides with highly symmetric crystal structure (HS-TMC), the introduction of heteroatoms, especially those with large atomic radius, often induces large lattice distortion and vacancy defects, which may lead to structural phase transition of doped materials or structural phase reconstruction during the catalytic reaction. Such unpredictable situations will make it difficult to explore the connection between the intrinsic electronic structure of doped catalysts and catalytic activity. Herein, taking thermodynamically stable cubic CoSe2 phase as an example, we demonstrate that nitrogen incorporation can effectively regulate the intrinsic electronic structure of HS-TMC with structural phase stability and thus promote its electrocatalytic activity for the hydrogen evolution activity (HER). In contrast, the introduction of phosphorus can lead to structural phase transition from cubic CoSe2 to orthorhombic phase, and the structural phase of phosphorus-doped CoSe2 is unstable for HER.

Tandem Catalysis of Ammonia Borane Dehydrogenation and Phenylacetylene Hydrogenation Catalyzed by CeO2 Nanotube/Pd@MIL-53(Al).

Heterogeneously catalyzed, selective hydrogenation in the liquid phase is widely used in industry for the synthesis of chemicals. However, it can be a challenge to prevent active nanoparticles (e.g., palladium) from aggregation/leaching and meanwhile achieve high conversion as well as selectivity, especially under mild conditions. To address these issues, a CeO2 nanotube/Pd@MIL-53(Al) sandwich-structured catalyst has been prepared in which the MIL-53(Al) porous shell can efficiently stabilize the palladium nanoparticles. When this catalyst was used in a tandem catalytic reaction involving the dehydrogenation of ammonia borane and the hydrogenation of phenylacetylene, remarkably, the hydrogen released from the dehydrogenation of ammonia borane boosted the catalytic process, with 100 % conversion of phenylacetylene and a selectivity of 96.2 % for styrene, even at room temperature and atmospheric pressure, within 1 min. This work therefore provides an alternative strategy for balancing the conversion and selectivity of liquid-phase hydrogenation reactions.

Implanting Atomic Dispersed Ru in PtNi Colloidal Nanocrystal Clusters for Efficient Catalytic Performance in Electro-oxidation of Liquid Fuels.

Although PtRu alloy nanocatalysts have been certified to possess excellent electrocatalytic performance and CO-poisoning tolerance toward formic acid and methanol electro-oxidation, the unaffordable usages of ruthenium (Ru) and platinum (Pt) have greatly limited their widespread adoption. Here, a facile one-pot method is reported for implanting atomic dispersed Ru in PtNi colloidal nanocrystal clusters with different Ru/Pt/Ni molar ratios, greatly reducing the dosages of Pt and Ru, and further improving the catalytic performances for the electro-oxidation of formic acid and methanol. Through simple control of the amount of Ni(acac)2 precursor, trimetallic Ru0.3 Pt70.5 Ni29.2 , Ru0.6 Pt55.9 Ni43.5 , Ru0.2 Pt77.3 Ni22.5 , and Ru0.9 Pt27.3 Ni71.8 colloidal nanocrystal clusters (CNCs) are obtained. In particular, the Ru0.3 Pt70.5 Ni29.2 CNCs exhibit excellent specific activities for formic acid and methanol electro-oxidation, that is, 14.2 and 15.3 times higher, respectively, than those of the Pt/C catalyst. Moreover, the Ru0.3 Pt70.5 Ni29.2 CNCs also possess better anti-CO-poisoning properties and diffusion ability than the other RuPtNi CNCs. The excellent formic acid and methanol electro-oxidation activities of RuPtNi CNCs are ascribed to the optimal ligand effects derived from the Pt, Ni, and atomic dispersed Ru atoms, which can improve the OH adsorption ability and further the anti-CO-poisoning capability. This research opens a new door for increasing the electro-oxidation properties of liquid fuels by using lower dosages of noble metals in Pt-based catalysts.

Metal-Organic Framework (MOF)-Derived Carbon-Mediated Interfacial Reaction for the Synthesis of CeO2 -MnO2 Catalysts.

CeO2 -based catalysts are widely studied in catalysis fields. Developing one novel synthetic approach to increase the intimate contact between CeO2 and secondary species is of particular importance for enhancing catalytic activities. Herein, an interfacial reaction between metal-organic framework (MOF)-derived carbon and KMnO4 to synthesize CeO2 -MnO2 , in which carbon is derived from the pyrolysis of Ce-MOFs under an inert atmosphere, is described. The MOF-derived carbon is found to restrain the growth of CeO2 crystallites under a high calcination temperature and, more importantly, intimate contact within CeO2 /C is conveyed to CeO2 /MnO2 after the interfacial reaction; this is responsible for the high catalytic activity of CeO2 -MnO2 towards CO oxidation.

Laser irradiation-induced laminated graphene/MoS2 composites with synergistically improved tribological properties.

Engineering lubricant additives that have extraordinary friction reduction and anti-wear performance is critical to almost any modern mechanical machines. Here, we demonstrate the fabrication of laminated lubricant additives that can combine the advantages of zero-dimensional nanospheres and two-dimensional nanosheets. A simple in situ laser irradiation method is developed to prepare the laminated composite structure composed of ideally ultrasmooth MoS2 sub-microspheres embedded within multiple layers of graphene. These ultrasmooth MoS2 spheres within the laminated structure can change sliding friction into rolling friction under strong shear force created by moving contact surfaces to significantly reduce the friction. Meantime, the graphene layers can behave as 'protection pads' to efficiently avoid the formation of scars on the metal-to-metal contact surfaces. Overall, the laminated composites as lubricant additives synergistically improve the friction reduction and anti-wear properties. Additionally, due to the unique loosely packed laminated structure, the composites can stably disperse in the lubricant for more than 15 d and work under high temperatures without being oxidized. Such constructed laminated composites with outstanding tribological properties by an in situ laser irradiation method supply a new concept in designing lubricant additives that can combine the advantages of 0D and 2D structures.

Water Stability Studies of Hybrid Iodoargentates Containing N-Alkylated or N-Protonated Structure Directing Agents: Exploring Noncentrosymmetric Hybrid Structures.

In situ alkylation or protonation reactions on the thiazolyl-N donors of benzothiazole (btz) and its derivative 2-aminobenzothiazole (abtz) occurred to form four structure directing agents (SDAs), which feature different structure directing abilities and hydrophobicities. The thiazolyl-N alkylated and protonated btz cations direct to form an α-type (AgI2)- iodoargentate chain in (Etbtz)(AgI2) (1), (Prbtz)(AgI2) (2), and (Hbtz)(AgI2) (3), respectively, while the thiazolyl-N protonated abtz cation directs to form a new type of (Ag2I3)- anionic chain in (Habtz)(Ag2I3) (4). Compounds 1 and 4 represent the first noncentrosymmetric (NCS) hybrid iodoargentates with organic S-containing N-heterocycle derivative cations as SDAs. Further, 1 exhibits high water stability and is second harmonic generation (SHG) active with a response about twice that of KDP (KH2PO4). Importantly, the water stability studies indicate that hybrid iodoargentates with hydrophobic N-alkylated SDAs are more stable in water than those with relative hydrophilic N-protonated SDAs.

Optical sensing properties of Au nanoparticle/hydrogel composite microbeads using droplet microfluidics.

Uniform Au nanoparticle (NP)/poly (acrylamide-co-acrylic acid) [P(AAm-co-AA)] hydrogel microbeads were successfully prepared using droplet microfluidics technology. The microbeads exhibited a good stimuli-responsive behavior to pH value. Particularly in the pH value ranging from pH 2-pH 9, the composite microbead sizes gradually increased along with the increase of pH value. The homogeneous Au NPs, which were encapsulated in the P(AAm-co-AA) hydrogel microbeads, could transform the volume changes of hydrogel into optical signals by a tested single microbead with a microspectrometre system. The glucose was translated into gluconic acid by glucose oxidase. Thus, the Au NP/P(AAm-co-AA) hydrogel microbeads were used for detecting glucose based on pH effects on the composite microbeads. For this, the single Au NP/P(AAm-co-AA) hydrogel microbead could act as a good pH- or glucose-visualizing sensor.

Black Gold: Plasmonic Colloidosomes with Broadband Absorption Self-Assembled from Monodispersed Gold Nanospheres by Using a Reverse Emulsion System.

A facile approach for the fabrication of novel black plasmonic colloidosomes assembled from Au nanospheres is developed by an emulsion-templating strategy. This self-assembly process is based on a new reverse water-in-1-butanol emulsion system, in which the water emulsion droplets can dissolve into 1-butanol (oil) phase at an appropriate rate. These Au colloidosomes possess hexagonal close-packed multilayer shells and show a low reflectivity and intense broadband absorption owing to the strong interparticle plasmonic coupling, which is further investigated by a finite-difference time-domain method. This method is universal and is suitable for self-assembly of different noble-metal nanoparticles into different colloidosomes. These colloidosomes have important applications in photothermal therapy, biosensors, and drug delivery.

A dual-mode label-free electrochemical immunosensor for ultrasensitive detection of procalcitonin by on-site vulcanization of dual-MOF heterostructure.

Detection of procalcitonin (PCT) is crucial for the early identification of sepsis. PCT is primarily utilized in the multiple diagnosis of bacterial and viral illnesses along with to guide the application of antibiotics. Considering their advantages of high specificity and straightforward usage, electrochemical immunosensors offer significant application prospects in the detection of disease indicators. A dual-mode electrochemical immunosensor was constructed in this study to reliably identify PCT. In light of the synergistic effect of the dual-MOF derived heterostructure, the immunosensor demonstrating excellent square wave voltammetry (SWV) signals as well as significant catalytic activity for the H2O2 redox process. In addition to maintaining a low detection limit (SWV: 0.31 fg/mL and i-t: 0.098 fg/mL), the immunosensor offers an extensive linear response range (0.000001-100 ng/mL). The excellent performance is on account of the introduction of the local on-site sulfurized dual-MOF heterostructure with abundant metal chalcogenides/MOF interfaces, which boosts the specific surface area, offers an abundance of active sites, enhances conductivity, and raises catalytic activity. Furthermore, the immunosensor exhibits outstanding specificity, stability and reproducibility for the determination of PCT in serum, which is of great crucial for the clinical screening and diagnosis of sepsis.

Enhanced photocatalytic CO2 conversion over 0D/2D CsPbBr3/BiOCl S-scheme heterojunction via boosting charge separation.

The stable contact of heterogeneous interfaces and the substantial exposure of active sites are crucial for enhancing the photocatalytic performance of semiconductor catalysts. However, most reported two-dimensional (2D)/2D CsPbBr3 and BiOCl heterostructures are fabricated using electrostatic self-assembly methods, which exhibit significant deficiencies in precise interface quality control and effective active site exposure. In this study, we fabricate a zero-dimensional (0D)/2D CsPbBr3/BiOCl heterojunction via a two-step calcination method, achieving an efficient direct S-scheme configuration. Optimizing interfacial contact and band alignment between CsPbBr3 quantum dots and BiOCl nanosheets enhances cross-plane charge transfer, promoting superior charge separation. This 0D/2D CsPbBr3/BiOCl heterojunction exhibits enhanced carrier mobility and high conversion rates without cocatalysts or sacrificial agents. The mechanism underlying the accelerated S-scheme charge transfer is comprehensively elucidated through a combination of analytical techniques and density functional theory (DFT) calculations. This study offers a novel approach for managing charge carrier segregation and mobility in CO2 reduction photocatalysts.

Checkerboard-like nickel nanoislands/defect graphene aerogel with enhanced surface plasmon resonance for superior microwave absorption.

To solve the problem of dispersion of magnetic nanoparticles in ultralight electromagnetic absorption field, checkerboard-like nickel nanoislands/defect graphene aerogel (NIDG) with enhanced surface plasmon resonance was designed and prepared through electrostatic self-assembly method. This special structure successfully overcame the aggregation phenomenon of magnetic metals and built high-density gap regions to enhance surface plasmon resonance. And the NIDG has achieved excellent electromagnetic wave absorption performance in C band. Specially, NIDG is superior in ultra-lightness with only 6.2 wt%, compared to some recently reported magnetic electromagnetic wave absorbers. Such great performance can be attributed to the enhanced surface plasmon resonance and improved impedance matching. This work is significant for achieving effective dielectric loss and designing lightweight low-frequency EMW absorbing materials.

Encapsulated ruthenium nanoparticles activated few-layer carbon frameworks as high robust oxygen evolution electrocatalysts in acidic media.

Noble metals have been extensively employed as high active catalysts for oxygen evolution reaction (OER), are usually subjected to serious surface transformation and poor structural stability, especially in acid media, which need imperatively remedied. Herein, the interfacial engineering of Ru via few-layer carbon (Ru@FLC) was carried out, in which FLC can significantly suppress the corrosion of Ru in acid media, ensuring the efficient interfacial charge transport between Ru and FLC. As a result, a low overpotentials@10 mA cm-2 of 258 mV and small Tafel slopes of 53.1 mV dec-1 for oxygen evolution OER were achieved in acid media. DFT calculations disclose that outer FLC could induce charge redistribution and effectively optimize intermediates free energy adsorption, resulting in greatly reduce the energy barrier for OER. Our work may offer a new avenue to produce progressive OER electrocatalysts for energy-related applications in acid solution.

Ultrathin covalent and cuprophilic interaction-assembled copper-sulfur monolayer in organic metal chalcogenide for oriented photoconductivity.

We report the thinnest copper sulfur atomic monolayer in an organic copper chalcogenide [Cu(CMP)]n (CMP = 5-chloro-2-mercaptopyridine). The layer features a new type of copper sulfur structure woven by both covalent bond and cuprophilic interaction and shows an intriguing oriented photoconductivity.