Pre-phase transition of a Cu2-xS template enables polymorph selective synthesis of MS (M = Zn, Cd, Mn) nanocrystals via cation exchange reactions.

Utilization of copper-deficient Cu2-xS nanocrystals (NCs) with diverse crystal phases and stoichiometries as cation exchange (CE) templates is a potential route to overcome the current limitations in the polymorph selective synthesis of desired nanomaterials. Among the Cu2-xS NCs, covellite CuS is emerging as an attractive CE template to produce complicated and metastable metal sulfide NCs. The presence of a reducing agent is essential to induce a phase transition of CuS into other Cu2-xS phases prior to the CE reactions. Nevertheless, the effect of the reducing agent on the phase transition of CuS, especially into the hexagonal close packing (hcp) phase and the cubic close packing (ccp) phase, has been scarcely exploited, but it is highly important for the polymorphic production of metal sulfides with the wurtzite phase and zinc blende phase. Herein, we report a reducing agent dependent pre-phase transition of CuS nanodisks (NDs) into hcp and ccp Cu2-xS NCs. 1-Dodecanethiol molecules and oleylamine molecules selectively reduced CuS NDs into hcp djurleite Cu1.94S NDs and ccp digenite Cu1.8S NCs. Afterward, the hcp Cu1.94S NDs and ccp Cu1.8S NCs were exchanged by Zn2+/Cd2+/Mn2+, and the wurtzite phase and the zinc blende phase of ZnS, CdS, and MnS NCs were produced. Without the pre-phase transition, direct CE reactions of CuS NDs are incapable of synthesizing the above wurtzite and zinc blende metal sulfide NCs. Therefore, our findings suggest the importance of the pre-phase transition of the CE template in polymorphic syntheses, holding great promise in the fabrication of other polymorphic nanomaterials with novel physical and chemical properties.

Cross-linking and self-assembly synthesis of tannin-based carbon frameworks cathode for Zn-ion hybrid supercapacitors.

Carbon frameworks with well-developed porosity present broad application prospects in energy-related materials, and green preparation still face challenges. Herein, the tannins-derived framework-like carbon material is obtained by cross-linking and self-assembly strategy.The phenolic hydroxyl and quinones in tannin cross-linking react with the amine groups in the methenamine by simple stirring, which drives the self-assembly of tannins and methenamine,contributing to the reaction products being precipitated in solution as aggregates with framework-like structure. The porosity and micromorphology of framework-like structures are further enriched by the thermal stability difference between tannin and methenamine. The methenamine of framework-like structures is entirely removed by the sublimation and decomposition and the tannin is transformed into carbon materials inheriting framework-like structures after the carbonization, which offers the path for rapid electron transport. The framework-like structure, excellent specific surface area and nitrogen doping give the assembled Zn-ion hybrid supercapacitors a superior specific capacitance of 165.3 mAh·g-1 (350.4 F·g-1). This device could be charged to 1.87 V to power the bulb by using solar panels. This study proves that the tannin-derived framework-like carbon is a promising electrode of the Zn-ion hybrid supercapacitors, which is beneficial for value-added and industrial supercapacitors application of green feedstocks.

Interfacial Electronic Effects in Co@N-Doped Carbon Shells Heterojunction Catalyst for Semi-Hydrogenation of Phenylacetylene.

Metal-supported catalyst with high activity and relatively simple preparation method is given priority to industrial production. In this work, this study reported an easily accessible synthesis strategy to prepare Mott-Schottky-type N-doped carbon encapsulated metallic Co (Co@Np+gC) catalyst by high-temperature pyrolysis method in which carbon nitride (g-C3N4) and dopamine were used as support and nitrogen source. The prepared Co@Np+gC presented a Mott-Schottky effect; that is, a strong electronic interaction of metallic Co and N-doped carbon shell was constructed to lead to the generation of Mott-Schottky contact. The metallic Co, due to high work function as compared to that of N-doped carbon, transferred electrons to the N-doped outer shell, forming a new contact interface. In this interface area, the positive and negative charges were redistributed, and the catalytic hydrogenation mainly occurred in the area of active charges. The Co@Np+gC catalyst showed excellent catalytic activity in the hydrogenation of phenylacetylene to styrene, and the selectivity of styrene reached 82.4%, much higher than those of reference catalysts. The reason for the promoted semi-hydrogenation of phenylacetylene was attributed to the electron transfer of metallic Co, as it was caused by N doping on carbon.

Metal 3D printing technology for functional integration of catalytic system.

Mechanical properties and geometries of printed products have been extensively studied in metal 3D printing. However, chemical properties and catalytic functions, introduced by metal 3D printing itself, are rarely mentioned. Here we show that metal 3D printing products themselves can simultaneously serve as chemical reactors and catalysts (denoted as self-catalytic reactor or SCR) for direct conversion of C1 molecules (including CO, CO2 and CH4) into high value-added chemicals. The Fe-SCR and Co-SCR successfully catalyze synthesis of liquid fuel from Fischer-Tropsch synthesis and CO2 hydrogenation; the Ni-SCR efficiently produces syngas (CO/H2) by CO2 reforming of CH4. Further, the Co-SCR geometrical studies indicate that metal 3D printing itself can establish multiple control functions to tune the catalytic product distribution. The present work provides a simple and low-cost manufacturing method to realize functional integration of catalyst and reactor, and will facilitate the developments of chemical synthesis and 3D printing technology.