Microwave-Assisted ultrafast Synthesis of Bimetallic Nickel-Cobalt Metal-Organic Frameworks for Application in the Oxygen Evolution Reaction.

A series of monometallic Ni-, Co- and Zn-MOFs and bimetallic NiCo-, NiZn- and CoZn-MOFs M2(BDC)2DABCO and (M,M')2(BDC)2DABCO, respectively, with the same pillar and layer linkers 4-diazabicyclo[2.2.2]octane (DABCO) and benzene-1,4-dicarboxylate (BDC) were prepared through a fast microwave-assisted thermal conversion synthesis method within only 12 min. In the bimetallic MOFs the ratio M:M' was 4:1. The mono- and bimetallic MOFs were selected to systematically explore the catalytic-activity of their derived metal oxide/hydroxides for the oxygen evolution reaction (OER). The NiCoMOF exhibits superior catalytic activity for the OER with the lowest overpotentials of 301 mV and Tafel slopes of 42 mV dec-1 on a glassy carbon electrode in 1 mol L-1 KOH electrolyte at a current density of 10 mA cm-2. In addition, NiCoMOF was in situ grown in just 25 min by the MW synthesis on the surface of nickel foam (NF) where overpotentials of 313 and 328 mV at current densities of 50 and 300 mA cm-2, respectively, were delivered and superior long-term stability for practical OER application. The low Tafel slope of 27 mV dec-1, as well as a low reaction resistance from electrochemical impedance spectroscopy measurement (Rfar = 2 Ω), confirm the excellent OER performance of this NiCoMOF/NF composite.

Bimetallic CPM-37(Ni,Fe) metal-organic framework: enhanced porosity, stability and tunable composition.

A newly synthesized series of bimetallic CPM-37(Ni,Fe) metal-organic frameworks with different iron content (Ni/Fe ≈ 2, 1, 0.5, named CPM-37(Ni2Fe), CPM-37(NiFe) and CPM-37(NiFe2)) demonstrated high N2-based specific SBET surface areas of 2039, 1955, and 2378 m2 g-1 for CPM-37(Ni2Fe), CPM-37(NiFe), and CPM-37(NiFe2), having much higher values compared to the monometallic CPM-37(Ni) and CPM-37(Fe) with 87 and 368 m2 g-1 only. It is rationalized that the mixed-metal nature of the materials increases the structural robustness due to the better charge balance at the coordination bonded cluster, which opens interesting application-oriented possibilities for mixed-metal CPM-37 and other less-stable MOFs. In this work, the CPM-37-derived α,ß-Ni(OH)2, γ-NiO(OH), and, plausibly, γ-FeO(OH) phases obtained via decomposition in the alkaline medium demonstrated a potent electrocatalytic activity in the oxygen evolution reaction (OER). The ratio Ni : Fe ≈ 2 from CPM-37(Ni2Fe) showed the best OER activity with a small overpotential of 290 mV at 50 mA cm-2, low Tafel slope of 39 mV dec-1, and more stable OER performance compared to RuO2 after 20 h chronopotentiometry at 50 mA cm-2.

Exceptionally Stable And Super-Efficient Electrocatalysts Derived From Semiconducting Metal Phosphonate Frameworks.

Two new isostructural semiconducting metal-phosphonate frameworks are reported. Co2 [1,4-NDPA] and Zn2 [1,4-NDPA] (1,4-NDPA4- is 1,4-naphthalenediphosphonate) have optical bandgaps of 1.7 eV and 2.5 eV, respectively. The electrocatalyst derived from Co2 [1,4-NPDA] as a precatalyst generated a low overpotential of 374 mV in the oxygen evolution reaction (OER) with a Tafel slope of 43 mV dec-1 at a current density of 10 mA cm-2 in alkaline electrolyte (1 mol L-1 KOH), which is indicative of remarkably superior reaction kinetics. Benchmarking of the OER of Co2 [1,4-NPDA] material as a precatalyst coupled with nickel foam (NF) showed exceptional long-term stability at a current density of 50 mA cm-2 for water splitting compared to the state-of-the-art Pt/C/RuO2 @NF after 30 h in 1 mol L-1 KOH. In order to further understand the OER mechanism, the transformation of Co2 [1,4-NPDA] into its electrocatalytically active species was investigated.

A New Family of Layered Metal-Organic Semiconductors: Cu/V-Organophosphonates.

Herein, we report the design and synthesis of a layered redox-active, antiferromagnetic metal organic semiconductor crystals with the chemical formula [Cu(H2 O)2 V(µ-O)(PPA)2 ] (where PPA is phenylphosphonate). The crystal structure of [Cu(H2 O)2 V(µ-O)(PPA)2 ] shows that the metal phosphonate layers are separated by phenyl groups of the phenyl phosphonate linker. Tauc plotting of diffuse reflectance spectra indicates that [Cu(H2 O)2 V(µ-O)(PPA)2 ] has an indirect band gap of 2.19 eV. Photoluminescence (PL) spectra indicate a complex landscape of energy states with PL peaks at 1.8 and 2.2 eV. [Cu(H2 O)2 V(µ-O)(PPA)2 ] has estimated hybrid ionic and electronic conductivity values between 0.13 and 0.6 S m-1 . Temperature-dependent magnetization measurements show that [Cu(H2 O)2 V(µ-O)(PPA)2 ] exhibits short range antiferromagnetic order between Cu(II) and V(IV) ions. [Cu(H2 O)2 V(µ-O)(PPA)2 ] is also photoluminescent with photoluminescence quantum yield of 0.02%. [Cu(H2 O)2 V(µ-O)(PPA)2 ] shows high electrochemical, and thermal stability.

Synthesis of Ketjenblack Decorated Pillared Ni(Fe) Metal-Organic Frameworks as Precursor Electrocatalysts for Enhancing the Oxygen Evolution Reaction.

Metal-organic frameworks (MOFs) have been investigated with regard to the oxygen evolution reaction (OER) due to their structure diversity, high specific surface area, adjustable pore size, and abundant active sites. However, the poor conductivity of most MOFs restricts this application. Herein, through a facile one-step solvothermal method, the Ni-based pillared metal-organic framework [Ni2(BDC)2DABCO] (BDC = 1,4-benzenedicarboxylate, DABCO = 1,4-diazabicyclo[2.2.2]octane), its bimetallic nickel-iron form [Ni(Fe)(BDC)2DABCO], and their modified Ketjenblack (mKB) composites were synthesized and tested toward OER in an alkaline medium (KOH 1 mol L-1). A synergistic effect of the bimetallic nickel-iron MOF and the conductive mKB additive enhanced the catalytic activity of the MOF/mKB composites. All MOF/mKB composite samples (7, 14, 22, and 34 wt.% mKB) indicated much higher OER performances than the MOFs and mKB alone. The Ni-MOF/mKB14 composite (14 wt.% of mKB) demonstrated an overpotential of 294 mV at a current density of 10 mA cm-2 and a Tafel slope of 32 mV dec-1, which is comparable with commercial RuO2, commonly used as a benchmark material for OER. The catalytic performance of Ni(Fe)MOF/mKB14 (0.57 wt.% Fe) was further improved to an overpotential of 279 mV at a current density of 10 mA cm-2. The low Tafel slope of 25 mV dec-1 as well as a low reaction resistance due to the electrochemical impedance spectroscopy (EIS) measurement confirmed the excellent OER performance of the Ni(Fe)MOF/mKB14 composite. For practical applications, the Ni(Fe)MOF/mKB14 electrocatalyst was impregnated into commercial nickel foam (NF), where overpotentials of 247 and 291 mV at current densities of 10 and 50 mA cm-2, respectively, were realized. The activity was maintained for 30 h at the applied current density of 50 mA cm-2. More importantly, this work adds to the fundamental understanding of the in situ transformation of Ni(Fe)DMOF into OER-active α/ß-Ni(OH)2, ß/γ-NiOOH, and FeOOH with residual porosity inherited from the MOF structure, as seen by powder X-ray diffractometry and N2 sorption analysis. Benefitting from the porosity structure of the MOF precursor, the nickel-iron catalysts outperformed the solely Ni-based catalysts due to their synergistic effects and exhibited superior catalytic activity and long-term stability in OER. In addition, by introducing mKB as a conductive carbon additive in the MOF structure, a homogeneous conductive network was constructed to improve the electronic conductivity of the MOF/mKB composites. The electrocatalytic system consisting of earth-abundant Ni and Fe metals only is attractive for the development of efficient, practical, and economical energy conversion materials for efficient OER activity.

Microwave-assisted synthesis of iridium oxide and palladium nanoparticles supported on a nitrogen-rich covalent triazine framework as superior electrocatalysts for the hydrogen evolution and oxygen reduction reaction.

Iridium oxide (IrOx-NP) and palladium nanoparticles (Pd-NP) were supported on a 2,6-dicyanopyridine-based covalent-triazine framework (DCP-CTF) by energy-saving and sustainable microwave-assisted thermal decomposition reactions in propylene carbonate and in the ionic liquid [BMIm][NTf2]. Transmission electron microscopy (TEM), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS) confirm well-distributed NPs with sizes from 2 to 13 nm stabilized on the CTF particles. Metal contents between 10 and 41 wt% were determined by flame atomic absorption spectroscopy (AAS). Nitrogen sorption measurements of the metal-loaded CTFs revealed Brunauer-Emmett-Teller (BET) surface areas between 904 and 1353 m2 g-1. The composites show superior performance toward the hydrogen evolution reaction (HER) with low overpotentials from 47 to 325 mV and toward the oxygen reduction reaction (ORR) with high half-wave potentials between 810 and 872 mV. IrOx samples in particular show high performances toward HER while the Pd samples show better performance toward ORR. In both reactions, electrocatalysts can compete with the high performance of Pt/C. Exemplary cyclic voltammetry durability tests with 1000 cycles and subsequent TEM analyses show good long-term stability of the materials. The results demonstrate the promising synergistic effects of NP-decorated CTF materials, resulting in a high electrocatalytic activity and stability.

Synthesis and Characterization of a Crystalline Imine-Based Covalent Organic Framework with Triazine Node and Biphenyl Linker and Its Fluorinated Derivate for CO2/CH4 Separation.

A catalyst-free Schiff base reaction was applied to synthesize two imine-linked covalent organic frameworks (COFs). The condensation reaction of 1,3,5-tris-(4-aminophenyl)triazine (TAPT) with 4,4'-biphenyldicarboxaldehyde led to the structure of HHU-COF-1 (HHU = Heinrich-Heine University). The fluorinated analog HHU-COF-2 was obtained with 2,2',3,3',5,5',6,6'-octafluoro-4,4'-biphenyldicarboxaldehyde. Solid-state NMR, infrared spectroscopy, X-ray photoelectron spectroscopy, and elemental analysis confirmed the successful formation of the two network structures. The crystalline materials are characterized by high Brunauer-Emmett-Teller surface areas of 2352 m2/g for HHU-COF-1 and 1356 m2/g for HHU-COF-2. The products of a larger-scale synthesis were applied to prepare mixed-matrix membranes (MMMs) with the polymer Matrimid. CO2/CH4 permeation tests revealed a moderate increase in CO2 permeability at constant selectivity for HHU-COF-1 as a dispersed phase, whereas application of the fluorinated COF led to a CO2/CH4 selectivity increase from 42 for the pure Matrimid membrane to 51 for 8 wt% of HHU-COF-2 and a permeability increase from 6.8 to 13.0 Barrer for the 24 wt% MMM.