High capacity adsorption of antimony in biomass-based composite and its consequential utilization as battery anode.

Antimony is more than an emerging pollutant in water but a scare resource. In this study, we report an adsorbent with the record capacity so far from the balanced view of Sb(III) and Sb(V). The composite adsorbent was fabricated by encapsulating hollow Fe3O4 nanosphere with the EDTA grafted chitosan, and it has superhigh adsorption capacity of for 657.1 mg/g for Sb(III) and 467.3 mg/g for Sb(V), respectively. The mechanism study reveals that the adsorption of Sb initializes from the Fe3O4, propagates along the chitosan with hydrogen bond, and terminates at the inner sphere complex with the EDTA moiety in the adsorbent. In view of the ultra-high adsorption capacity of the adsorbent, the recovered adsorbent that contains abundant (>36.4%) highly dispersed antimony nanoparticles (600-FCSE-Sb) is applied to Li-ion battery anode after reduction. This article provides a new idea for connecting water treatment and electric energy storage.

Biochar microtube interconnected hydrotalcite nanosheets for the adsorption of aqueous Sb(III).

Actuated by the non-ionic heavy metal of antimony (Sb) contaminants with undesired toxicity to the environment and human health, capturing Sb is urgent to remedy contaminated water. Herein, the lamellar MnCo hydrotalcite was grown on catkin-derived biochar through the in situ etching of ZIF-L to construct a hierarchical microtube@nanosheet hybrid (CLMH) for Sb immobilization. The adsorption behaviour and mechanism of trivalent antimony (Sb (III)) on the CLMH were investigated. The CLMH shows good pH applicability for capturing Sb(III) at pH from 2 to 9. The excellent adsorption capacity of CLMH for Sb(III) is 247.62 mg g-1at 303 K, and the endothermic process is proved by the positive value of ΔH0(10.54 kJ mol-1). The adsorption process is fitted with the intra-particle diffusion model, which can be described with external mass transfer, intraparticle diffusion in pores, and equilibrium stage. The adsorption mechanism is proved, which includes the bind of Metal-O-Sb bonds by inner-sphere complex, the embedding of Sb in the intercalation of hydrotalcite, redox between Mn and Sb, and functional groups dependent anchoring effect. The work benefits the understanding of the antimony removal behaviour over the hierarchical microtube@nanosheet hybrids.

Phylogenetic position of Bopyroides hippolytes, with comments on the rearrangement of the mitochondrial genome in isopods (Isopoda: Epicaridea: Bopyridae).

BACKGROUND: Classification of parasitic bopyrids has traditionally been based on morphological characteristics, but phylogenetic relationships have remained elusive due to limited information provided by morphological data and tendency for loss of morphological features as a result of parasitic lifestyle. Subfamily Argeiinae was separated from Bopyrinae based on morphological evidence, although the assignment of all genera has not been phylogenetically evaluated. Bopyroides hippolytes has been traditionally classified in Bopyrinae, but divergent morphological characters make this assignment questionable. To investigate the relationship of bopyrines, we sequenced the complete mitochondrial genome of B. hippolytes and four mitochondrial genes of two other Bopyrinae. RESULTS: The phylogenetic trees based on separate and combined cox1and 18S sequence data recovered Bopyridae as robustly monophyletic, but Bopyrinae as polyphyletic. Bopyroides hippolytes was a close sister to Argeia pugettensis, type species to Argeiinae. Mitochondrial phylogenomics also suggested that B. hippolytes was close to Argeiinae. We also found a novel gene order in B. hippolytes compared to other isopods. CONCLUSIONS: Bopyroides hippolytes should be excluded from the Bopyrinae and has a close affinity with Argeia pugettensis based on molecular and morphological data. The conserved syntenic blocks of mitochondrial gene order have distinctive characteristics at a subordinal level and may be helpful for understanding the higher taxonomic level relationships of Isopoda.

Iron Catalyzed Cascade Construction of Molybdenum Carbide Heterointerfaces for Understanding Hydrogen Evolution.

The intercrystalline interfaces have been proven vital in heterostructure catalysts. However, it is still challenging to generate specified heterointerfaces and to make clear the mechanism of a reaction on the interface. Herein, this work proposes a strategy of Fe-catalyzed cascade formation of heterointerfaces for comprehending the hydrogen evolution reaction (HER). In the pure solid-phase reaction system, Fe catalyzes the in situ conversion of MoO2 to MoC and then Mo2 C, and the consecutive formation leaves lavish intercrystalline interfaces of MoO2 -MoC (in Fe-MoO2 /MoC@NC) or MoC-Mo2 C (in Fe-MoC/ß-Mo2 C@NC), which contribute to HER activity. The improved HER activity on the interface leads to further checking of the mechanism with density functional theory calculation. The computation results reveal that the electroreduction (Volmer step) produced H* prefers to be adsorbed on Mo2 C; then two pathways are proposed for the HER on the interface of MoC-Mo2 C, including the single-molecular adsorption pathway (Rideal mechanism) and the bimolecular adsorption pathway (Langmuir-Hinshelwood mechanism). The calculation results further show that the former is favorable, and the reaction on the MoC-Mo2 C heterointerface significantly lowers the energy barriers of the rate-determining steps.

Encapsulating Electron-Rich Pd NPs with Lewis Acidic MOF: Reconciling the Electron-Preference Conflict of the Catalyst for Cascade Condensation via Nitro Reduction.

Cascade reactions take advantage of step-saving and facile operation for obtaining chemicals. Herein, catalytic hydrogenation of nitroarene coupled condensation with ß-diketone to afford ß-ketoenamines is achieved by an integrated nanocatalyst, Pd-e@UiO-66. The catalyst has the structure of an acid-rich metal-organic framework (MOF), UiO-66-encapsulated electron-rich Pd nanoparticles, and it reconciles the electron-effect contradiction of cascade catalytic reactions: catalytic hydrogenation requires an electron-rich catalyst, while condensation requires electron-deficient Lewis acid sites. The catalyst showed good activity, high chemoselectivity, and universal applicability for the synthesis of ß-ketoenamines using nitroarenes. More than 30 ß-ketoenamines have been successfully prepared with up to 99% yield via the methodology of relay catalysis. The catalyst exhibited excellent stability to maintain its catalytic performance for more than five cycles. Furthermore, we conducted an in-depth exploration of the reaction mechanism with theoretical calculations.

Investigation of antimony adsorption on a zirconium-porphyrin-based metal-organic framework.

A zirconium-porphyrin based organic framework PCN-222 was employed for investigating the adsorption performance of Sb(III) in aqueous solution. It is proved that the adsorbent has the advantages of rapid adsorption and high capacity. Interestingly, we discover that PCN-222 shows pH-dependent adsorption performance, with higher capacity at pH = 2 and 8 than at pH = 5. According to XPS and FT-IR analyses, an adsorption model of PCN-222 with pH = 2, 5, and 8 is proposed, that is, zirconium clusters combine with antimony at different pH values with bidentate complexes, monodentate complexes, and alkaline monodentate complexes, thus producing an excellent adsorption effect. Moreover, the porphyrin ring is also beneficial for the adsorption of antimony. In addition, PCN-222 shows good regeneration and recycling performance, and it is a promising adsorbent as well as a platform for investigating the removal of Sb(III) in water treatment.

Metal-Organic Framework-Encapsulated CoCu Nanoparticles for the Selective Transfer Hydrogenation of Nitrobenzaldehydes: Engineering Active Armor by the Half-Way Injection Method.

A novel armor-type composite of metal-organic framework (MOF)-encapsulated CoCu nanoparticles with a Fe3 O4 core (Fe3 O4 @SiO2 -NH2 -CoCu@UiO-66) has been designed and synthesized by the half-way injection method, which successfully serves as an efficient and recyclable catalyst for the selective transfer hydrogenation. In this half-way injection approach, the pre-synthetic Fe3 O4 @SiO2 -NH2 -CoCu was injected into the UiO-66 precursor solution halfway through the MOF budding period. The formed MOF armor could play a role of providing significant additional catalytic sites besides CoCu nanoparticles, protecting CoCu nanoparticles, and improving the catalyst stability, thus facilitating the selective transfer hydrogenation of nitrobenzaldehydes into corresponding nitrobenzyl alcohols in high selectivity (99 %) and conversion (99 %) rather than nitro group reduction products. Notably, this method achieves the precise assembly of a MOF-encapsulated composite, and the ingenious combination of MOF and nanoparticles exhibits excellent catalytic performance in the selective hydrogen transfer reaction, implementing a "1+1>2" strategy in catalysis.

Selective Synthesis of Symmetrical Secondary Amines from Nitriles with a Pt-CuFe/Fe3 O4 Catalyst and Ammonia Borane as Hydrogen Donor.

Hydrogenation of nitriles is an efficient and environmentally friendly route to synthesize symmetrical secondary amines, but it usually produces a mixture of amines, imines, and hydrogenolysis by-products. Herein we report a magnetic quaternary-component Pt-CuFe/Fe3 O4 nanocatalyst system for the selective synthesis of symmetrical secondary amines with ammonia borane as hydrogen donor. The catalyst with a low Pt loading (0.456 wt%) is the source of the activity, and the d-band electron transfer from Cu to Fe enhances the selectivity. This synergistic effect results in the transformation of benzonitrile to dibenzylamine with excellent conversion (up to 99 %) and nearly quantitative selectivity (up to 96 %) under mild reaction conditions, nevertheless, the reaction TOF is as high as up to 1409.9 h-1 . A variety of nitriles are suitable for the synthesis of symmetrical secondary amines. More importantly, unwanted hydrogenolysis byproducts, especially toluene, is not detected at all. In addition, the catalyst is magnetically recoverable, and it can be reused up to five times.

Facile and Large-Scale Fabrication of Sub-3†nm PtNi Nanoparticles Supported on Porous Carbon Sheet: A Bifunctional Material for the Hydrogen Evolution Reaction and Hydrogenation.

Facile and large-scale preparation of materials with uniform distributions of ultrafine particles for catalysis is a challenging task, and it is even more difficult to obtain catalysts that excel in both the hydrogen evolution reaction (HER) and hydrogenation, which are the corresponding merging and splitting procedures of hydrogen, respectively. Herein, the fabrication of ultrafine bimetallic PtNi nanoparticles embedded in carbon nanosheets (CNS) by means of in situ self-polymerization and annealing is reported. This bifunctional catalyst shows excellent performance in the hydrogen evolution reaction (HER) and the hydrogenation of p-nitrophenol. Remarkably PtNi bimetallic catalyst with low metal loading (PtNi2 @CNS-600, 0.074 wt % Pt) exhibited outstanding HER activity with an overpotential as low as 68 mV at a current density of 10 mA cm-2 with a platinum loading of only 0.612 µgPt cm-2 and Tafel slope of 35.27 mV dec-1 in a 0.5 m aqueous solution of H2 SO4 , which is comparable to that of the 20 % Pt/C catalyst (31 mV dec-1 ). Moreover, it also shows superior long-term electrochemical durability for at least 30 h with negligible degradation compared with 20 % Pt/C. In addition, the material with increased loading (mPtNi2 @CNS-600, 2.88 % Pt) showed robust catalytic activity for hydrogenation of p-nitrophenol at ambient pressure and temperature. The catalytic activity towards hydrogen splitting is a circumstantial evidence that agrees with the Volmer-Tafel reaction path in the HER.