One-Step Pyrolysis Transformation of Mulberry Leaves Followed by Electrochemical Treatment: Preparing of M (M = Pt, Au) Nanoparticles Incorporated Nitrogen-Doped Carbon Nanoporous Structures as Efficient Electrocatalyst for Hydrogen Evolution Reaction.

To facilely develop low-cost and efficient hydrogen evolution electrocatalysts, catalyst with low content of platinum on nitrogen-doped carbon nanoporous structures were prepared for hydrogen evolution reaction (HER). This study firstly demonstrated the one-step pyrolysis transformation of conveniently accessible mulberry leaves to obtain nitrogen-doped nanoporous carbons (N-NPCs) for hydrogen evolution reaction. After electrochemical treatment, the obtained N-NPCs-ET with Pt as counter electrode exhibited an unexpected high hydrogen evolution activity, which had low onset overpotential of 100 mV and a Tafel slope of 60 mV dec-1. N-NPCs-ET maintained catalytic activity for at least 10 h in 0.5 M H2SO4 solution. The enhanced HER performance was relevant to the incorporation of Pt nanoparticles, which were dissolved from anodic Pt counter electrode in acid media and precipitated into cathodic N-NPCs surface again. Moreover, for the first time, we found that with a gold electrode as the counter electrode, Au nanoparticles could be incorporated into N-NPCs by electrochemical treatments and the formed Au nanoparticles decorated N-NPCs possessed efficient catalytic activity toward HER.

Oxygen Vacancy-Rich 2D TiO2 Nanosheets: A Bridge Toward High Stability and Rapid Hydrogen Storage Kinetics of Nano-Confined MgH2.

MgH2 has attracted intensive interests as one of the most promising hydrogen storage materials. Nevertheless, the high desorption temperature, sluggish kinetics, and rapid capacity decay hamper its commercial application. Herein, 2D TiO2 nanosheets with abundant oxygen vacancies are used to fabricate a flower-like MgH2/TiO2 heterostructure with enhanced hydrogen storage performances. Particularly, the onset hydrogen desorption temperature of the MgH2/TiO2 heterostructure is lowered down to 180 °C (295 °C for blank MgH2). The initial desorption rate of MgH2/TiO2 reaches 2.116 wt% min-1 at 300 °C, 35 times of the blank MgH2 under the same conditions. Moreover, the capacity retention is as high as 98.5% after 100 cycles at 300 °C, remarkably higher than those of the previously reported MgH2-TiO2 composites. Both in situ HRTEM observations and ex situ XPS analyses confirm that the synergistic effects from multi-valance of Ti species, accelerated electron transportation caused by oxygen vacancies, formation of catalytic Mg-Ti oxides, and stabilized MgH2 NPs confined by TiO2 nanosheets contribute to the high stability and kinetically accelerated hydrogen storage performances of the composite. The strategy of using 2D substrates with abundant defects to support nano-sized energy storage materials to build heterostructure is therefore promising for the design of high-performance energy materials.

Nanoconfined and in Situ Catalyzed MgH2 Self-Assembled on 3D Ti3C2 MXene Folded Nanosheets with Enhanced Hydrogen Sorption Performances.

MXenes are considered as potential support materials for nanoconfinement of MgH2/Mg to improve the hydrogen storage properties. However, it has never been realized so far due to the stacking and oxidation problems caused by unexpected surface terminations (-OH, -O, etc.) on MXenes. In this study, hexadecyl trimethylammonium bromide was used to build a 3D Ti3C2Tx architecture of folded nanosheets to reduce the stacking risk of flakes, and a bottom-up self-assembly strategy was successfully applied to synthesize ultradispersed MgH2 nanoparticles anchored on the surface of the annealed 3D Ti3C2Tx (Ti-MX). The composite with a 60 wt % loading of MgH2 NPs, 60MgH2@Ti-MX, starts to decompose at 140 °C and is capable of releasing 3.0 wt % H2 at 150 °C within 2.5 h. In addition, a reversible capacity up to 4.0 wt % H2 was still maintained after 60 cycles at 200 °C without obvious loss in kinetics. In situ high-resolution TEM observations of the decomposition process together with other analyses revealed that the nanosize effect caused by the nanoconfinement and the multiphasic interfaces between MgH2(Mg) and Ti-MX, especially the in situ formed catalytic TiH2, were main reasons accounting for the superior hydrogen sorption performances.

Using a Self-Assembled Two-Dimensional MXene-Based Catalyst (2D-Ni@Ti3C2) to Enhance Hydrogen Storage Properties of MgH2.

In this work, we report the remarkable catalytic effects of a novel Ti3C2 MXene-based catalyst (Ni@Ti-MX), which was prepared via self-assembling of Ni nanoparticles onto the surface of exfoliated Ti3C2 nanosheets. The resultant Ni@Ti-MX catalyst, characterized by ultradispersed Ni nanoparticles being anchored on the monolayer Ti3C2 flakes, was introduced into MgH2 through ball milling. In situ transmission electron microscopy (TEM) analysis revealed that a synergetic catalytic effect of multiphase components (Mg2Ni, TiO2, metallic Ti, etc.) derived in the MgH2 + Ni@Ti-MX composite exhibits remarkable improvements in the hydrogen sorption kinetics of MgH2. In particular, the MgH2 + Ni@Ti-MX composite can absorb 5.4 wt % H2 in 25 s at 125 °C and release 5.2 wt % H2 in 15 min at 250 °C. Interestingly, it can uptake 4 wt % H2 in 5 h even at room temperature. Furthermore, the dehydrogenation peak temperature of the MgH2 + Ni@Ti-MX composite is about 221 °C, which is 50 and 122 °C lower than that of MgH2 + Ti-MX and MgH2, respectively. The excellent hydrogen sorption properties of the MgH2 + Ni@Ti-MX composite are primarily attributed to the peculiar core-shell nanostructured MgH2@Mg2NiH4 hybrid materials and the interfacial coupling effects from different catalyst-matrix interfaces. The results obtained in this study demonstrate that using self-assembling of transition-metal elements on two-dimensional (2D) materials as a catalyst is a promising approach to enhance the hydrogen storage properties of MgH2.

Heterogeneous Nanostructure Design Based on the Epitaxial Growth of Spongy MoS x on 2D Co(OH)2 Nanoflakes for Triple-Enzyme Mimetic Activity: Experimental and Density Functional Theory Studies on the Dramatic Activation Mechanism.

In this study, we present a three-in-one catalytic platform for intrinsic oxidase-, peroxidase-, and catalase-like activity, which is enabled by epitaxial growth of the MoS x nanosponge on 2D Co(OH)2 nanoflakes [2D Co(OH)2 NFs] (CoMo hybrids). First, the 2D Co(OH)2 NFs are stripped from hierarchical three-dimensional Co(OH)2 nanoflowers which are synthesized in an eco-friendly way via one-step surfactant-free chemical route. Next, the porous MoS x nanosponge is decorated on the 2D Co(OH)2 NFs' surface using a solvothermal process forming heterogeneous nanostructured CoMo hybrids. Finally, because of the host-guest interaction, that is, after the epitaxial growth of spongy MoS x on 2D Co(OH)2 NFs, the heterogeneous nanostructure of CoMo hybrids exhibits unpredictable triple-enzyme mimetic activity simultaneously. The mechanisms of the oxidase-like properties are investigated by density functional theory (DFT) calculations, and it is discovered that a simple reaction/dissociation of O2 absorbed on Co-Mo thin films can explain the enhanced oxidase-like activity of the CoMo hybrids. In addition, the CoMo hybrids are also reproducible, stable, and reusable, that is, after 10 cycle uses, >90% mimic enzyme activity of the CoMo hybrids is still maintained. The oxidase-like activity of the CoMo hybrids enables it to oxidize 3,3',5,5'-tetramethylbenzidine (TMB) producing the blue oxTMB, which can selectively oxidize ascorbic acid (AA) and pave a new avenue for colorimetric sensing of AA. The proposed colorimetric strategy has been successfully utilized to measure AA in rat brain during the cerebral calm/ischemia process. Our findings provide in-depth insight into the future research of enzyme-like activities and might help to elucidate the mechanism and understand the role of epitaxial growth on the properties and application of hybrid nanostructures.

Co3O4 nanoparticles anchored on nitrogen-doped reduced graphene oxide as a multifunctional catalyst for H2O2 reduction, oxygen reduction and evolution reaction.

This study describes a facile and effective route to synthesize hybrid material consisting of Co3O4 nanoparticles anchored on nitrogen-doped reduced graphene oxide (Co3O4/N-rGO) as a high-performance tri-functional catalyst for oxygen reduction reaction (ORR), oxygen evolution reaction (OER) and H2O2 sensing. Electrocatalytic activity of Co3O4/N-rGO to hydrogen peroxide reduction was tested by cyclic voltammetry (CV), linear sweep voltammetry (LSV) and chronoamperometry. Under a reduction potential at -0.6 V to H2O2, this constructing H2O2 sensor exhibits a linear response ranging from 0.2 to 17.5 mM with a detection limit to be 0.1 mM. Although Co3O4/rGO or nitrogen-doped reduced graphene oxide (N-rGO) alone has little catalytic activity, the Co3O4/N-rGO exhibits high ORR activity. The Co3O4/N-rGO hybrid demonstrates satisfied catalytic activity with ORR peak potential to be -0.26 V (vs. Ag/AgCl) and the number of electron transfer number is 3.4, but superior stability to Pt/C in alkaline solutions. The same hybrid is also highly active for OER with the onset potential, current density and Tafel slope to be better than Pt/C. The unusual catalytic activity of Co3O4/N-rGO for hydrogen peroxide reduction, ORR and OER may be ascribed to synergetic chemical coupling effects between Co3O4, nitrogen and graphene.

Highly luminescent organosilane-functionalized carbon dots as a nanosensor for sensitive and selective detection of quercetin in aqueous solution.

The organosilane-functionalized carbon dots (SiCDs) were synthesized using citric acid with N-(b-aminoethyl)-g-aminopropyl methyldimethoxy silane (AEAPMS). The as-synthesized SiCDs were characterized by IR, TEM, XPS, NMR and fluorescence. The SiCDs showed a strong emission at 455 nm with excitation at 365 nm. The SiCDs exhibited analytical potential as sensing probes for quercetin (QCT) determination. pH effect, temperature effect, interferences, and analytical performance of the method were investigated. It suggested that SiCDs exhibited high sensitivity and selectivity toward QCT: the linear ranges of SiCDs were estimated to be 0-40 µM while the limit of detection (LOD) was calculated to be 79 nM.