Search

As a narrow bandgap semiconductor, transition metal selenides are promising as excellent electrocatalysts for hydrogen evolution reactions (HERs). Herein, using an ultra-thin MOF as the precursor, a Co-doped core–shell shaped NiSe2 based catalyst is successfully constructed by a two-step calcination method as an efficient HER catalyst. Experiments and theoretical calculations indicate that the introduction of Co adjusts the electronic structure of Ni and Se, promoting charge transfer and reducing the energy barrier of the rate-limiting step to accelerate the hydrogen precipitation reaction. In addition, the core–shell structure contributes to mass transport, and the outer carbon layer improves the stability of the catalyst. The optimal catalyst (Ni0.75Co0.25Se2@NC) exhibited satisfactory electrocatalytic activity as evidenced by a low overpotential of −143 mV at a current density of −10 mA cm−2 and a small Tafel slope of 37.5 mV dec−1. This work provides a valuable strategy for fabricating efficient NiSe2 based electrocatalysts for the HER. [ABSTRACT FROM AUTHOR]

The evolution of cost-effective hydrogen evolution reaction (HER) electrocatalysts is of great significance for the development of clean energy. Exploring effective synthesis strategies to optimize the performance of non-noble metal electrocatalysts has always attracted our attention. Herein, ultrathin coordination polymers were used as precursors to controllably synthesize two-dimensional (2D) ultrathin dual-phase transition metal selenide (TMSs)/carbon–nitrogen (CN) composites (CoSe2–NiSe2/CN) by a two-step method (first a low temperature hydrothermal method for selenization, and then high temperature calcination selenization). Benefiting from its large specific surface area (49 m2 g−1), abundant catalytically active sites and synergistic effects, CoSe2–NiSe2/CN can significantly enhance the HER catalytic activity and exhibits good electrocatalytic activity with an overpotential of 150 mV at −10 mA cm−2, and a small Tafel slope of 42 mV dec−1 in an acidic electrolyte for the HER. This work provides a new strategy for optimizing the HER catalytic activity of TMSs by preparing 2D ultrathin dual-phase TMS composite materials. [ABSTRACT FROM AUTHOR]

Two series of lanthanide-based metal–organic frameworks, namely {[Ln(BIPA-TC)0.5(DMA)2(NO3)]·DMA·H2O}n (1-Ln, Ln = Eu, Dy, Sm, Nd) and {[Ln2(BIPA-TC)1.5(DMA)3(H2O)2]·2DMA·2H2O}n (2-Ln, Ln = Eu, Dy, Sm, Nd), were successfully constructed via a solvent regulation strategy based on a π-electron rich tetra-carboxylate ligand (H4BIPA-TC). 1-Ln shows a 4-connected lvt topology with the point symbol of {42·84}, but 2-Ln displays a new 4,4,6-connected wxk1 topology with the point symbol of {43·83}4{46·66·83}2{86}. The solid-state luminescence property and the microporous nature of Eu-MOFs (1-Eu and 2-Eu) indicate that they can potentially be used as luminescent sensors. Fluorescence measurements indicate that Fe3+ exhibits the quenching effect for 1-Eu with the quenching efficiency of 93.1%. 2-Eu is the first MOF sensor for Mg2+ with the lowest detection limit of 1.53 × 10−10 mol L−1 and displays good recyclable capability. Simultaneously, in the presence of other metal ions (Ca2+, Mn2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Pd2+, Al3+, Cr3+and Fe3+), 2-Eu can maintain the selective sensing of Mg2+, indicating its potential for Mg2+ turn-on sensing. [ABSTRACT FROM AUTHOR]

A ligand with a flexible conformation can be obtained by modifying functional groups. We modified H4DCBA with –CH3/–CF3 groups to construct three Zr-MOFs; the torsion of the central benzene ring changes the topologies. The three Zr-MOFs showed high adsorption rates for Cr2O72−, and the CF3-functional groups enhanced the adsorption capacity of UPC-49 for Cr2O72−. [ABSTRACT FROM AUTHOR]

A ligand with a flexible conformation can be obtained by modifying functional groups. We modified H4DCBA with –CH3/–CF3 groups to construct three Zr-MOFs; the torsion of the central benzene ring changes the topologies. The three Zr-MOFs showed high adsorption rates for Cr2O72−, and the CF3-functional groups enhanced the adsorption capacity of UPC-49 for Cr2O72−. [ABSTRACT FROM AUTHOR]

The evolution of cost-effective hydrogen evolution reaction (HER) electrocatalysts is of great significance for the development of clean energy. Exploring effective synthesis strategies to optimize the performance of non-noble metal electrocatalysts has always attracted our attention. Herein, ultrathin coordination polymers were used as precursors to controllably synthesize two-dimensional (2D) ultrathin dual-phase transition metal selenide (TMSs)/carbon-nitrogen (CN) composites (CoSe2-NiSe2/CN) by a two-step method (first a low temperature hydrothermal method for selenization, and then high temperature calcination selenization). Benefiting from its large specific surface area (49 m2 g-1), abundant catalytically active sites and synergistic effects, CoSe2-NiSe2/CN can significantly enhance the HER catalytic activity and exhibits good electrocatalytic activity with an overpotential of 150 mV at -10 mA cm-2, and a small Tafel slope of 42 mV dec-1 in an acidic electrolyte for the HER. This work provides a new strategy for optimizing the HER catalytic activity of TMSs by preparing 2D ultrathin dual-phase TMS composite materials.

Two series of lanthanide-based metal-organic frameworks, namely {[Ln(BIPA-TC)0.5(DMA)2(NO3)]·DMA·H2O}n (1-Ln, Ln = Eu, Dy, Sm, Nd) and {[Ln2(BIPA-TC)1.5(DMA)3(H2O)2]·2DMA·2H2O}n (2-Ln, Ln = Eu, Dy, Sm, Nd), were successfully constructed via a solvent regulation strategy based on a π-electron rich tetra-carboxylate ligand (H4BIPA-TC). 1-Ln shows a 4-connected lvt topology with the point symbol of {42·84}, but 2-Ln displays a new 4,4,6-connected wxk1 topology with the point symbol of {43·83}4{46·66·83}2{86}. The solid-state luminescence property and the microporous nature of Eu-MOFs (1-Eu and 2-Eu) indicate that they can potentially be used as luminescent sensors. Fluorescence measurements indicate that Fe3+ exhibits the quenching effect for 1-Eu with the quenching efficiency of 93.1%. 2-Eu is the first MOF sensor for Mg2+ with the lowest detection limit of 1.53 × 10-10 mol L-1 and displays good recyclable capability. Simultaneously, in the presence of other metal ions (Ca2+, Mn2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Pd2+, Al3+, Cr3+and Fe3+), 2-Eu can maintain the selective sensing of Mg2+, indicating its potential for Mg2+ turn-on sensing.