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.

Inverse Adsorption Separation of N2 O/CO2 in AgZK-5 Zeolite.

Nitrous oxide (N2 O), as the third largest greenhouse gas in the world, also has great applications in daily life and industrial production, like anesthetic, foaming agent, combustion supporting agent, N or O atomic donor. The capture of N2 O in adipic acid tail gas is of great significance but remains challenging due to the similarity with CO2 in molecular size and physical properties. Herein, the influence of cation types on CO2 -N2 O separation in zeolite was studied comprehensively. In particular, the inverse adsorption of CO2 -N2 O was achieved by AgZK-5, which preferentially adsorbs N2 O over CO2 , making it capable of trapping N2 O from an N2 O/CO2 mixture. AgZK-5 shows a recorded N2 O/CO2 selectivity of 2.2, and the breakthrough experiment indicates excellent performance for N2 O/CO2 separation. The density functional theory (DFT) calculation shows that Ag+ has stronger adsorption energy with N2 O, and the kinetics of N2 O is slightly faster than that of CO2 on AgZK-5.

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.

Capture and Separation of SO2 Traces in Metal-Organic Frameworks via Pre-Synthetic Pore Environment Tailoring by Methyl Groups.

Herein, we report a pre-synthetic pore environment design strategy to achieve stable methyl-functionalized metal-organic frameworks (MOFs) for preferential SO2 binding and thus enhanced low (partial) pressure SO2 adsorption and SO2 /CO2 separation. The enhanced sorption performance is for the first time attributed to an optimal pore size by increasing methyl group densities at the benzenedicarboxylate linker in [Ni2 (BDC-X)2 DABCO] (BDC-X=mono-, di-, and tetramethyl-1,4-benzenedicarboxylate/terephthalate; DABCO=1,4-diazabicyclo[2,2,2]octane). Monte Carlo simulations and first-principles density functional theory (DFT) calculations demonstrate the key role of methyl groups within the pore surface on the preferential SO2 affinity over the parent MOF. The SO2 separation potential by methyl-functionalized MOFs has been validated by gas sorption isotherms, ideal adsorbed solution theory calculations, simulated and experimental breakthrough curves, and DFT calculations.