Enzymatic Mesoporous Metal Nanocavities for Concurrent Electrocatalysis of Nitrate to Ammonia Coupled with Polyethylene Terephthalate Upcycling.

Electrochemical upcycling of waste pollutants into high value-added fuels and/or chemicals is recognized as a green and sustainable solution that can address the resource utilization on earth. Despite great efforts, their progress has seriously been hindered by the lack of high-performance electrocatalysts. In this work, bimetallic PdCu mesoporous nanocavities (MCs) are reported as a new bifunctional enzymatic electrocatalyst that realizes concurrent electrocatalytic upcycling of nitrate wastewater and polyethylene terephthalate (PET) plastic waste. Abundant metal mesopores and open nanocavities of PdCu MCs provide the enzymatic confinement of key intermediates for the deeper electroreduction of nitrate and accelerate the transport of reactants/products within/out of electrocatalyst, thus affording high ammonia Faradic efficiency (FENH3) of 96.6% and yield rate of 5.6 mg h-1 mg-1 at the cathode. Meanwhile, PdCu MC nanozymes trigger the selective electrooxidation of PET-derived ethylene glycol (EG) into glycolic acid (GA) and formic acid with high FEs of >90% by a facile regulation of potentials at the anode. Moreover, concurrent electrosynthesis of value-added NH3 and GA is disclosed in the two-electrode coupling system, further confirming the high efficiency of bifunctional PdCu MC nanozymes in producing value-added fuels and chemicals from waste pollutants in a sustainable manner.

Micromechanics and Ultrasonic Propagation in Consolidated Earthen-Site Soils.

Although nondestructive ultrasonic technologies have been applied in laboratory and field tests in the field of heritage conservation, few studies have quantified the relationship among the real microstructures, micromechanical properties, and macroscopic acoustic responses of earthen-site soils. This paper develops a micromechanics-based multiscale model for quantitatively exploring the ultrasonic propagation characteristics of elastic waves in untreated and consolidated earthen-site soils. Scanning electron microscope images and image processing technology are integrated into the finite-element simulation. The effects of microstructure and wave features on the acoustic characteristics of soils are quantitatively investigated under pulsive loading. The simulation results of untreated and consolidated soils are efficiently compared to ultrasonic test data. It is demonstrated that the integration of microstructure image processing and multiscale modeling can predict the ultrasonic pulse velocity well, which improves the accuracy of laboratory testing and field monitoring and better serves the evaluation and implementation of engineering practice in the field of heritage conservation.

Growing recyclable and healable piezoelectric composites in 3D printed bioinspired structure for protective wearable sensor.

Bionic multifunctional structural materials that are lightweight, strong, and perceptible have shown great promise in sports, medicine, and aerospace applications. However, smart monitoring devices with integrated mechanical protection and piezoelectric induction are limited. Herein, we report a strategy to grow the recyclable and healable piezoelectric Rochelle salt crystals in 3D-printed cuttlebone-inspired structures to form a new composite for reinforcement smart monitoring devices. In addition to its remarkable mechanical and piezoelectric performance, the growth mechanisms, the recyclability, the sensitivity, and repairability of the 3D-printed Rochelle salt cuttlebone composite were studied. Furthermore, the versatility of composite has been explored and applied as smart sensor armor for football players and fall alarm knee pads, focusing on incorporated mechanical reinforcement and electrical self-sensing capabilities with data collection of the magnitude and distribution of impact forces, which offers new ideas for the design of next-generation smart monitoring electronics in sports, military, aerospace, and biomedical engineering.

A general protocol for precise syntheses of ordered mesoporous intermetallic nanoparticles.

Intermetallic nanomaterials consist of two or more metals in a highly ordered atomic arrangement. There are many possible combinations and morphologies, and exploring their properties is an important research area. Their strict stoichiometry requirement and well-defined atom binding environment make intermetallic compounds an ideal research platform to rationally optimize catalytic performance. Making mesoporous intermetallic materials is a further advance; crystalline mesoporosity can expose more active sites, facilitate the mass and electron transfer, and provide the distinguished mesoporous nanoconfinement environment. In this Protocol, we describe how to prepare ordered mesoporous intermetallic nanomaterials with controlled compositions, morphologies/structures and phases by a general concurrent template strategy. In this approach, the concurrent template used is a hybrid of mesoporous platinum or palladium and Korea Advanced Institute of Science and Technology-6 (KIT-6) (meso-Pt/KIT-6 or meso-Pd/KIT-6) that can be transformed by the second precursors under reducing conditions. The second precursor can either be a second metal or a metalloid/non-metal, e.g., boron/phosphorus. KIT-6 is a silica scaffold that is removed using NaOH or HF to form the mesoporous product. Procedures for example catalytic applications include the 3-nitrophenylacetylene semi-hydrogenation reaction, p-nitrophenol reduction reaction and electrochemical hydrogen evolution reaction. The synthetic strategy for preparation of ordered mesoporous intermetallic nanoparticles would take almost 5 d; the physical characterization by electron microscope, X-ray diffraction and inductively coupled plasma-mass spectrometry takes ~2 days and the function characterization depends on the research question, but for catalysis it takes 1-5 h.

Creatine phosphate improves myocardial function and myocardial enzyme profile in children with myocarditis.

Myocarditis in children is more common in clinical practice, which can cause different degrees of cardiac function damage. We investigated the effects of creatine phosphate in the treatment of myocarditis in children. Children in the control group were treated with sodium fructose diphosphate, and children in the observation group were treated with creatine phosphate on the basis of the control group. After treatment, the myocardial enzyme profile and cardiac function of children in the observation group were better than the control group. The total effective rate of treatment for children in the observation group was higher than that in the control group. In conclusion, creatine phosphate could significantly improve myocardial function, improve myocardial enzyme profile and reduce myocardial damage in children with pediatric myocarditis and had a high safety of use, which was worthy of clinical promotion.

Application of periodontal tissue regeneration combined with orthodontics in oral prosthodontics and its influence and significance on the expressions of IL-1ß, TNF-α and IL-5 in periodontal tissue.

The aim is to investigate the application of periodontal tissue regeneration combined with orthodontics in oral restoration, and explore its effect and significance on the expressions of Interleukin-1ß (IL-1ß), tumor necrosis factor-α (TNF-α) and interleukin-5 (IL-5) in periodontal tissue. The patients in observation group were treated with orthodontics combined with periodontal tissue regeneration, and the control group was treated with periodontal tissue regeneration. The total effective rate, adverse reactions, recurrence rate and treatment satisfaction were compared. The masticatory function, language function, aesthetic level, VAS score, quality of life, gingival index (GI), plaque index (PLI), periodontal pocket probing depth (PD), sulcus bleeding index (SBI), IL-1ß, TNF-α and IL-5 levels were compared. The recurrence rate of observation group was lower than control group, while the treatment satisfaction was higher after treatment. After treatment, the scores of masticatory, language, aesthetics, physiological, social, emotional, cognitive, and emotional functions and overall health score were higher than before treatment. After treatment, the scores of masticatory and language functions, aesthetics and quality of life of observation group were significantly higher than control group. After treatment, the VAS score, GI, PLI, SBI, PD, IL-1ß, TNF-α and IL-5 levels were lower than before. The VAS score, GI, PLI, SBI, PD levels, IL-1ß, TNF-α and IL-5 levels of observation group were lower after treatment. Orthodontics combined with periodontal tissue regeneration can help improve the periodontal condition of patients with periodontitis, reduce inflammatory response, improve the level of efficacy and overall safety, and further improve patients' quality of life and treatment satisfaction.

AURKB promotes tumorigenesis and carboplatin resistance by regulating the ERK pathway in neuroblastoma cells.

BACKGROUND: Previous research has revealed that activation or aberrant expression of kinases can lead to tumorigenesis of various cancers, including neuroblastoma (NB). Suppression of kinase expression can reduce drug resistance. We explored the potential role and mechanism of the aurora kinase B (AURKB) gene in the acquisition of carboplatin resistance in NB. METHODS: Immunohistochemistry (IHC) and qRT-PCR were used to explore the AURKB expression in NB patients. Subsequently, we structured Carboplatin-resistant NB cells. The potential biological functions of AURKB in carboplatin resistance were examined through knockdown of AURKB combined with CCK8, flow cytometry, immunohistochemistry, and western blot. Finally, overexpression of AURKB combined with ERK inhibitor (U0126) was carried out to explore the role of downstream signaling pathways. RESULTS: Overexpression of AURKB was closely correlated to poor prognosis in NB patients. In vitro, knockdown of AURKB could lead to a decline in IC50 value and restrain the invasion and the expression of MRP1 and Ki67, while promotes apoptosis in carboplatin-resistant cells (IMR-32-R and SK-N-AS-R). Additionally, AURKB overexpression could potentiate the invasion and the expression of MRP1 and Ki67, while suppresses apoptosis in SK-N-AS-R and IMR-32-R, whereas ERK inhibitor U0126 could reverse the phenomenon caused by AURKB overexpression. CONCLUSION: AURKB overexpression was strongly associated with poor prognosis and carboplatin resistant acquisition. Additionally, suppression of AURKB-ERK axis might be a potential therapy for carboplatin resistance in NB patients.

Mesoporous PdN Alloy Nanocubes for Efficient Electrochemical Nitrate Reduction to Ammonia.

Developing highly active and selective electrocatalysts for electrochemical nitrate reduction reaction (NITRR) is very important for synthesizing recyclable ammonia (NH3 ) in an economic and environmentally friendly manner. Despite some encouraging progress, their activity and selectivity have been remarkably slower than expected. In this manuscript, mesoporous palladium-nonmetal (meso-PdX) nanocubes (NCs) are reported as a new series of highly efficient electrocatalysts for selective nitrate reduction reaction (NITRR) electrocatalysis to NH3 . The samples feature uniformly alloyed compositions and highly penetrated mesopores with abundant highly active sites and optimized electronic structures. The best meso-PdN NCs hold an outstanding NITRR activity and selectivity with a remarkable NH3 Faradaic efficiency of 96.1% and a yield rate of 3760 µg h-1 mg-1 , suppressing the state-of-the-art electrocatalysts. Meanwhile, meso-PdN NCs are electrocatalytically stable, retaining well the activity and selectivity of NO3 - -to-NH3 electrocatalysis for more than 20 cycles. Detailed mechanism studies ascribe the superior performance to combined compositional and structural synergies of meso-PdN NCs that not only promote the adsorption (reactivity) of NO3 - and the desorption of NH3 but also increase the retention time of key intermediates for the deeper NITRR electrocatalysis to NH3 through an eight-electron pathway.

Relation between Microstructures and Macroscopic Mechanical Properties of Earthen-Site Soils.

While the macroscopic mechanical properties of earthen-site soils have undergone extensive experimental and modeling studies, few research efforts focus on the relationship between the overall mechanical behavior and micro-pore structure. We developed a microstructure-based finite element model to investigate the influence of micro-pore structure on the macroscopic mechanical behavior of earthen-site soils. Scanning electron microscopy images of the untreated and consolidated soils were processed to compare the changes in equivalent diameter, sphericity, and porosity of the soils after consolidation. According to the pore parameter range of the untreated and consolidated soils, the effects of micro-pores on the soil behavior are specifically conducted under both static and dynamic loads. The relationships between pore characteristics and stiffness, strength, and ultrasonic wave velocity are established.

Looseness Identification of Track Fasteners Based on Ultra-Weak FBG Sensing Technology and Convolutional Autoencoder Network.

Changes in the geological environment and track wear, and deterioration of train bogies may lead to the looseness of subway fasteners. Identifying loose fasteners randomly distributed along the subway line is of great significance to avoid train derailment. This paper presents a convolutional autoencoder (CAE) network-based method for identifying fastener loosening features from the distributed vibration responses of track beds detected by an ultra-weak fiber Bragg grating sensing array. For an actual subway tunnel monitoring system, a field experiment used to collect the samples of fastener looseness was designed and implemented, where a crowbar was used to loosen or tighten three pairs of fasteners symmetrical on both sides of the track within the common track bed area and the moving load of a rail inspection vehicle was employed to generate 12 groups of distributed vibration signals of the track bed. The original vibration signals obtained from the on-site test were converted into two-dimensional images through the pseudo-Hilbert scan to facilitate the proposed two-stage CAE network with acceptable capabilities in feature extraction and recognition. The performance of the proposed methodology was quantified by accuracy, precision, recall, and F1-score, and displayed intuitively by t-distributed stochastic neighbor embedding (t-SNE). The raster scan and the Hilbert scan were selected to compare with the pseudo-Hilbert scan under a similar CAE network architecture. The identification performance results represented by the four quantification indicators (accuracy, precision, recall, and F1-score) based on the scan strategy in this paper were at least 23.8%, 9.5%, 20.0%, and 21.1% higher than those of the two common scan methods. As well as that, the clustering visualization by t-SNE further verified that the proposed approach had a stronger ability in distinguishing the feature of fastener looseness.

Noble-Metal-Based Hollow Mesoporous Nanoparticles: Synthesis Strategies and Applications.

As second-generation mesoporous materials, mesoporous noble metals (NMs) are of significant interest for their wide applications in catalysis, sensing, bioimaging, and biotherapy owing to their structural and metallic features. The introduction of interior hollow cavity into NM-based mesoporous nanoparticles (MNs), which subtly integrate hierarchical hollow and mesoporous structure into one nanoparticle, produces a new type of hollow MNs (HMNs). Benefiting from their higher active surface, better electron/mass transfer, optimum electronic structure, and nanoconfinement space, NM-based HMNs exhibit their high efficiency in enhancing catalytic activity and stability and tuning catalytic selectivity. In this review, recent progress in the design, synthesis, and catalytic applications of NM-based HMNs is summarized, including the findings of the groups. Five main strategies for synthesizing NM-based HMNs, namely silica-assisted surfactant-templated nucleation, surfactant-templated sequential nucleation, soft "dual"-template, Kirkendall effect in synergistic template, and galvanic-replacement-assisted surfactant template, are described in detail. In addition, the applications in ethanol oxidation electrocatalysis and hydrogenation reactions are discussed to highlight the high activity, enhanced stability, and optimal selectivity of NM-based HMNs in (electro)catalysis. Finally, the further outlook that may lead the directions of synthesis and applications of NM-based HMNs is prospected.

Highly Curved, Quasi-Single-Crystalline Mesoporous Metal Nanoplates Promote CC Bond Cleavage in Ethanol Oxidation Electrocatalysis.

The ability to manipulate metal nanocrystals with well-defined morphologies and structures is greatly important in material chemistry, catalysis chemistry, nanoscience, and nanotechnology. Although 2D metals serve as interesting platforms, further manipulating them in solution with highly penetrated mesopores and ideal crystallinity remains a huge challenge. Here, an easy yet powerful synthesis strategy for manipulating the mesoporous structure and crystallinity of 2D metals in a controlled manner with cetyltrimethylammonium chloride as the mesopore-forming surfactant and extra iodine-ion as the structure/facet-selective agent is reported. This strategy allows for preparing an unprecedented type of 2D quasi-single-crystalline mesoporous nanoplates (SMPs) with highly curved morphology and controlled metal composition. The products, for example, PdCu SMPs, feature abundant undercoordinated sites, optimized electronic structures, excellent electron/mass transfers, and confined mesopore environments. Curved PdCu SMPs exhibit remarkable electrocatalytic activity of 6.09 A mgPd -1 and stability for ethanol oxidation reaction (EOR) compared with its counterpart catalysts and commercial Pd/C. More importantly, PdCu SMPs are highly selective for EOR electrocatalysis that dramatically promotes C-C bond cleavage with a superior C1 pathway selectivity as high as 72.1%.

Mesoporous Gold Nanostructures: Synthesis and Beyond.

Mesoporous metal nanostructures have offered multiple advantages that cannot be realized elsewhere. These materials have been attracting more research attention in catalysis and electrocatalysis owing to their functional structures and compositions. Of the various mesoporous metals available, mesoporous gold (mesoAu) nanostructures are of special interest in surface-enhanced Raman scattering (SERS) and related applications because of their strong electromagnetic field (localized surface plasmon resonance). In the last few decades, various synthesis strategies have been developed to prepare mesoAu nanostructures with controllable morphologies that exhibit fascinating physicochemical properties and increase applications in SERS, catalysis, and electrocatalysis. In this Perspective, we systematically summarize recent advances in synthesis and applications of mesoAu nanostructures. Four synthesis strategies, including dealloying, nanocasting, electrochemical deposition, and intermediate template, are discussed in detail. Moreover, physicochemical properties and promising applications of mesoAu nanostructures are presented. Finally, we describe current challenges and give a general outlook to explore further directions in synthesis and applications of mesoAu nanostructures.

Effects of lifestyle interventions on glucose regulation and diabetes risk in adults with impaired glucose tolerance or prediabetes: a meta-analysis

ABSTRACT The prevalence of diabetes mellitus is increasing and is related to sedentary lifestyles and obesity. Many studies were published on the effect of lifestyle interventions on glucose regulation and delay the onset of diabetes in adults with impaired glucose tolerance (IGT) or prediabetes. This study aimed to investigate the role of lifestyle interventions in individuals with IGT or prediabetes using a meta-analytic approach. PubMed, Embase, and the Cochrane Central Register of Controlled Trials databases were searched from their inception up to January 2020 to select eligible randomized controlled trials (RCTs). The weighted mean difference (WMD; for fasting plasma glucose (FPG) and 2-hour plasma glucose (2hPPG)) or relative risk (RR; for the risk of diabetes) with 95% confidence interval (CI) were calculated for pooled effect estimates using the random-effects model. Thirteen RCTs involving 3376 individuals with IGT or prediabetes were selected for this meta-analysis. The results showed that lifestyle interventions were associated with lower FPG (WMD: -0.14; 95% CI: -0.24 to -0.05 mmol/L; p=0.004) and 2hPPG (WMD: -0.66; 95% CI: -1.12 to -0.20 mmol/L; p=0.005) in adults with IGT or prediabetes. Moreover, the risk of diabetes was significantly reduced in individuals who received lifestyle interventions (RR: 0.75; 95% CI: 0.60-0.95; p=0.015). Lifestyle interventions could help improve glucose dysregulation and prevent the progression of diabetes in adults with IGT or prediabetes. Further large-scale RCTs should be conducted to assess the effects of long-term lifestyle interventions on diabetic complications in adults with IGT or prediabetes.

Effects of lifestyle interventions on glucose regulation and diabetes risk in adults with impaired glucose tolerance or prediabetes: a meta-analysis.

The prevalence of diabetes mellitus is increasing and is related to sedentary lifestyles and obesity. Many studies were published on the effect of lifestyle interventions on glucose regulation and delay the onset of diabetes in adults with impaired glucose tolerance (IGT) or prediabetes. This study aimed to investigate the role of lifestyle interventions in individuals with IGT or prediabetes using a meta-analytic approach. PubMed, Embase, and the Cochrane Central Register of Controlled Trials databases were searched from their inception up to January 2020 to select eligible randomized controlled trials (RCTs). The weighted mean difference (WMD; for fasting plasma glucose (FPG) and 2-hour plasma glucose (2hPPG)) or relative risk (RR; for the risk of diabetes) with 95% confidence interval (CI) were calculated for pooled effect estimates using the random-effects model. Thirteen RCTs involving 3376 individuals with IGT or prediabetes were selected for this meta-analysis. The results showed that lifestyle interventions were associated with lower FPG (WMD: -0.14; 95% CI: -0.24 to -0.05 mmol/L; p=0.004) and 2hPPG (WMD: -0.66; 95% CI: -1.12 to -0.20 mmol/L; p=0.005) in adults with IGT or prediabetes. Moreover, the risk of diabetes was significantly reduced in individuals who received lifestyle interventions (RR: 0.75; 95% CI: 0.60-0.95; p=0.015). Lifestyle interventions could help improve glucose dysregulation and prevent the progression of diabetes in adults with IGT or prediabetes. Further large-scale RCTs should be conducted to assess the effects of long-term lifestyle interventions on diabetic complications in adults with IGT or prediabetes.

Mesoporous Noble Metal-Metalloid/Nonmetal Alloy Nanomaterials: Designing Highly Efficient Catalysts.

Mesoporous metals have received increasing attention in catalysis and related applications because of their novel physicochemical properties and functional geometric features. Control of multicomponent compositions and crystalline structures of mesoporous metals is critical for their applications. Recently, mesoporous metals have gradually expanded from traditional metal-metal alloys to metal-metalloid/nonmetal alloys with random solids and/or ordered intermetallics. As new, highly efficient nanocatalysts, mesoporous metal-metalloid/nonmetal alloys not only increase the utilization efficiency of precious noble metals and accelerate electron/mass transfer but also introduce new functions and optimize the surface electronic structure of metal sites, all of which enhance their catalytic activity and stability and tune their catalytic selectivity. In this Perspective, we focus on the latest developments in this area, including the findings from our group regarding the rational design and targeted synthesis of mesoporous noble metal-metalloid/nonmetal alloy nanocatalysts. We summarize the current synthetic strategies for mesoporous noble metal-metalloid/nonmetal alloys and discuss key effects of crystalline mesoporosity and metalloid/nonmetal alloys in enhancing catalytic performances of noble metal catalysts. We also describe the current bottlenecks and major challenges to explore further directions in synthesis and applications of mesoporous noble metal-metalloid/nonmetal alloys.

MicroRNA-195-5p suppresses the proliferation, migration, invasion and epithelial-mesenchymal transition of laryngeal cancer cells in vitro by targeting E2F3.

Increasing evidence has indicated that microRNAs (miRNAs/miRs) play an important role in the occurrence and development of various types of cancer. The aim of the present study was to investigate the role and underlying molecular mechanisms of miR-195-5p in laryngeal cancer cell proliferation, migration and invasion. Reverse transcription-quantitative PCR (RT-qPCR) was performed to measure the expression levels of miR-195-5p in laryngeal carcinoma cell lines. The expression levels of miR-195-5p and E2F transcription factor 3 (E2F3) were modified by transfection with miR-195-5p mimics and pcDNA3.1-E2F3. A luciferase reporter assay was used to verify the association between miR-195a-5p and E2F3. Cell Counting Kit-8, cell wound healing and Transwell invasion assays were used to detect the biological functions of laryngeal cancer cells. The expression of epithelial-mesenchymal transition (EMT)-associated genes was evaluated by western blotting and RT-qPCR. The results revealed that the expression of miR-195-5p was decreased in laryngeal cancer cell lines. The overexpression of miR-195-5p inhibited the proliferation, migration, invasion and EMT of laryngeal cancer cells. Dual-luciferase reporter assays revealed that miR-195-5p could directly target E2F3 and that there was a negative association between them. E2F3 overexpression significantly attenuated the inhibitory effects of the overexpression of miR-195-5p on the proliferation, migration, invasion and EMT of laryngeal cancer cells. Collectively, the findings of the present study demonstrated that the overexpression of miR-195-5p significantly inhibited the progression of laryngeal cancer cells, and these effects may be mediated via the downregulation of the expression of E2F3.

Highly Efficient Dehydrogenation of Formic Acid over Binary Palladium-Phosphorous Alloy Nanoclusters on N-Doped Carbon.

Highly efficient dehydrogenation of formic acid (FA) at room temperature is a safe and suitable way to obtain hydrogen and promote the development of hydrogen storage application. Herein, the phosphorous-alloyed Pd nanoclusters loading on nitrogen-doped carbon (PdP/NC) were prepared and recognized as the highly active nanocatalysts for the dehydrogenation of FA. The PdP/NCs with controlled sizes and compositions were prepared by an easy self-limiting synthesis in an aqueous solution. The best PdP/NC exhibited a remarkable catalytic activity with a high turnover frequency of ∼3253.0 h-1 than the compared nanocatalysts for the dehydrogenation of FA at room temperature. The catalytic kinetics and durability studies showed that both the alloyed P in Pd crystals and doped N in the carbon support could effectively tailor the electronic states of the Pd surface and further optimize the adsorption energy of FA. Based on the Sabatier principle, the proper adsorption energy accelerated the dehydrogenation reaction and correspondingly enhanced the activity and durability. The work proposed a high-efficiency nanocatalyst for safe hydrogen generation and may be extended to create other similar nanocatalysts with different compositions and nanostructures.

Ultrathin and Wavy PdB Alloy Nanowires with Controlled Surface Defects for Enhanced Ethanol Oxidation Electrocatalysis.

Engineering crystalline structures/defects and elemental compositions is synthetically critical to optimize surface features of noble metal nanocrystals and thus improve their catalytic performances in various reactions. In this manuscript, we report a facile one-step aqueous synthesis of one-dimensional (1D) noble metal-metalloid alloy nanowires (NWs) with an ultrathin and wavy morphology, controlled crystalline defects, and binary PdB compositions as a highly efficient catalyst toward the electrochemical ethanol oxidation reaction (EOR). We show that the utilization of hexadecylpyridinium chloride as functional surfactant is of great importance to confine in-the-columnar epitaxial nucleation of anisotropic ultrathin PdB NWs, while the attachment growth precisely controls their surface crystalline defects with a wavy morphology. Meanwhile, this strategy is synthetically universal and can be readily extended to engineer an ultrathin wavy morphology and crystalline defect of ternary PdMB (M = Cu and Pt) alloy NWs. Owing to multiple structural and compositional merits, resultant PdB alloy NWs synergistically expose more electrocatalytically active sites and also kinetically accelerate the removal of CO-related poisons, remarkably improving electrocatalytic EOR activity and stability compared to their counterpart catalysts. Besides, wavy PdB alloy NWs are also electrochemically more active for electrocatalytic oxidation of other alcohols (methanol, glycerol, and glucose). The findings reported here thus shed a bright light on rational design of the high-performance metal alloy catalysts for their potential applications in fine chemical synthesis, fuel cells, and beyond.

Ultrafine RhNi Nanocatalysts Confined in Hollow Mesoporous Carbons for a Highly Efficient Hydrogen Production from Ammonia Borane.

Ammonia borane (AB) has received growing research interest as one of the most promising hydrogen-storage carrier materials. However, fast dehydrogenation of AB is still limited by sluggish catalytic kinetics over current catalysts. Herein, highly uniform and ultrafine bimetallic RhNi alloy nanoclusters encapsulated within nitrogen-functionalized hollow mesoporous carbons (defined as RhNi@NHMCs) are developed as highly active, durable, and selective nanocatalysts for fast hydrolysis of AB under mild conditions. Remarkable activity with a high turnover frequency (TOF) of 1294 molH2 molRh-1 min-1 and low activation energy (Ea) of 18.6 kJ mol-1 is observed at room temperature, surpassing the previous Rh-based catalysts. The detailed mechanism studies reveal that when catalyzed by RhNi@NHMCs, a covalently stable O-H bond by H2O first cleaves in electropositive H* and further attacks B-H bond of AB to stoichiometrically produce 3 equiv of H2, whose catalytic kinetics is restricted by the oxidation cleavage of the O-H bond. Compositional and structural features of RhNi@NHMCs result in synergic electronic, functional, and support add-in advantages, kinetically accelerating the cleavage of the attacked H2O (O-H bond) and remarkably promoting the catalytic hydrolysis of AB accordingly. This present work represents a new and effective strategy for exploring high-performance supported metal-based alloy nanoclusters for (electro)catalysis.