A General Strategy toward Metal Sulfide Nanoparticles Confined in a Sulfur-Doped Ti3 C2 Tx MXene 3D Porous Aerogel for Efficient Ambient N2 Electroreduction.

Three-dimensional (3D) porous MXene-based aerogel architectures have attracted great interest for many applications, despite limits in renewable energy conversion owing to the lack of multifunctionality in their components. Herein, a simple and general strategy for constructing a novel functional 3D MXene-based composite heterojunction aerogel (MS@S-MAs) is presented via divalent metal-ion assembly and subsequent thermal sulfidation, and its application in electrochemical nitrogen reduction reaction (NRR) is studied. The as-prepared MS@S-MAs comprises metal sulfide nanoparticles uniformly confined in 3D interconnected conductive S-doped MXene sheets with intimate interfacial interaction. Benefiting from the unique properties and an interfacial interaction, MS@S-MAs exhibit significantly improved NRR catalytic performance and excellent stability because of the higher exposure of electrochemically active sites coupled with easier accessibility, faster mass diffusion, and quicker carrier transport at the interface. Remarkably, CoS@S-MAs show an NH3 yield rate and a Faradaic efficiency of 12.4 µg h-1 mg-1 cat and 27.05% at the lower potential of -0.15 V versus a reversible hydrogen electrode in 0.1 m Na2 SO4 solution under ambient conditions, which rivals or exceeds most of the previously reported MXene-based and Co-based catalysts. This work will open avenues to construct 3D MXene-based materials with rich functionalities for energy storage and conversion, catalysis, and other applications.

Phosphine-Built-in Porous Organic Cage for Stabilization and Boosting the Catalytic Performance of Palladium Nanoparticles in Cross-Coupling of Aryl Halides.

Herein, we report first a novel phosphine-containing porous organic cage (PPOC) from a [2 + 3] self-assembly of triphenyl phosphine-based trialdehyde and (S,S)-1,2-diaminocyclohexane via dynamic imine chemistry, which was employed as a porous material for the controlled growth of palladium nanoparticles (NPs) due to the strong affinity of Pd to the phosphine ligand based on the principle of hard and soft acids and bases. Comprehensive characterizations including X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, NMR, and X-ray absorption spectroscopy reveal that ultrafine Pd NPs with narrow size distribution (1.7 ± 0.3 nm) and enhanced surface electronic density via a strong interaction between NPs and phosphine were homogeneously dispersed in the PPOC. The resultant catalyst Pd@PPOC exhibits remarkably superior catalytic activities for various cross-coupling reactions of aryl halides, for example, Sonogashira, Suzuki, Heck, and carbonylation. The catalytic activity of Pd@PPOC outperforms the state-of-the-art Pd complexes and other Pd NPs supported on N-containing porous cages under identical conditions, owing to the enhanced surface electronic density of Pd NPs and their high stability and dispersibility in solution. More importantly, Pd@PPOC is highly stable and easily recycled and reused without loss of their catalytic activity. This work provides a new functional POC with extended potentials in catalysis and material science.

Rh-catalyzed highly regioselective hydroformylation to linear aldehydes by employing porous organic polymer as a ligand.

In this work, we developed a new structural porous organic polymer containing biphosphoramidite unit, which can be used as a solid bidentate phosphorous ligand for rhodium-catalyzed solvent-free higher olefins hydroformylation. The resultant catalyst demonstrated unprecedently high regioselectivity to linear aldehydes and could be readily recovered for successive reuses with good stability in both catalytic activity and regioselectivity.

Hydrogenation of Functionalized Nitroarenes Catalyzed by Single-Phase Pyrite FeS2 Nanoparticles on N,S-Codoped Porous Carbon.

Catalytic hydrogenation of nitroarenes is an industrially very important and environmentally friendly process for the production of anilines; however, highly chemoselective reduction of nitroarenes decorated with one or more reducible groups in a nitroarene molecule remains a challenge. Herein, a novel hybrid non-noble iron-based nanocatalyst (named as FeS2 /NSC) was developed, which was prepared from biomass as C and N source together with inexpensive Fe(NO3 )3 as Fe source through high-temperature pyrolysis in a straightforward and cost-effective procedure. Comprehensive characterization revealed that single-phase pyrite FeS2 nanoparticles with precisely defined composition and uniform size were homogeneously dispersed on N,S-codoped porous carbon with large specific surface area, hierarchical porous channels, and high pore volume. The resultant catalyst FeS2 /NSC demonstrated good catalytic activity for hydrogenation of functionalized nitroarenes with good tolerance of various functional groups in water as a sustainable and green solvent. Compared with bulk pyrite FeS2 and other non-noble metal-based heterogeneous catalysts reported in the literature, a remarkably enhanced activity was observed under mild reaction conditions. More importantly, FeS2 /NSC displayed exclusive chemoselectivity for the reduction of nitro groups for nitroarenes bearing varying readily reducible groups.

One-pot selective N-formylation of nitroarenes to formamides catalyzed by core-shell structured cobalt nanoparticles.

One-pot direct N-formylation of readily available nitroarenes with ammonium formate catalyzed by core-shell structured cobalt nanoparticles has been developed. A broad set of nitroarenes was successfully converted to their corresponding formamides in good to high yields with various functional group tolerance. This heterogeneous catalyst can be easily removed from the reaction medium and can be reused several times without a significant loss of reaction efficiency.

A new porous magnetic chitosan modified by melamine for fast and efficient adsorption of Cu(II) ions.

A new porous magnetic chitosan modified by melamine (MA-CS/Fe3O4) was synthesized. The compositions and surface topographies were characterized by infrared (IR) spectroscopy, X-ray diffraction (XRD) analysis, thermogravimetric (TG) analysis and scanning electron microscope (SEM), respectively. The results of adsorption kinetics showed the adsorption behavior could be better described by the pseudo-second-order equation (R>0.999). The adsorption isotherm was well fitted by the Langmuir equation (R>0.999), and the values of separation factors were in the range of 0-1.0. The maximum adsorption capacity for Cu(II) was 2.58mmolg(-1) at the optimal experimental conditions, which were pH=5.5, t=25min, C0=5.0mmolL(-1). The rate-controlling step was supposed to be chemical adsorption rather than mass transport. The adsorbent still exhibited high adsorption capacity after five regeneration cycles. The adsorption mechanism was due to coordination between Cu(II) and N atoms.

Preparation of triethylene-tetramine grafted magnetic chitosan for adsorption of Pb(II) ion from aqueous solutions.

In this paper, a novel triethylene-tetramine grafted magnetic chitosan was synthesized. The chemical structure and the percentage content of each element of chitosan and its derivatives were characterized by elemental analysis, infrared spectroscopy, solid state (13)C NMR, X-ray diffraction analysis and thermogravimetric analysis, respectively. Their surface topography was observed by the transmission electron microscope. The results of adsorption kinetics and adsorption thermodynamics showed the adsorption mechanism could be better described by the pseudo-second-order equation (R>0.999). The adsorption isotherm was well fitted by the Langmuir equation (R>0.999), and 0