A simple
one-step chemical
method is employed for the successful synthesis of CuO(50%)–ZnO(50%)
nanocomposites (NCs) and investigation of their gas sensing properties.
The X-ray diffraction studies revealed that these CuO–ZnO NCs
display a hexagonal wurtzite-type crystal structure. The average width
of 50–100 nm and length of 200–600 nm of the NCs were
confirmed by transmission electron microscopic images, and the 1:1
proportion of Cu and Zn composition was confirmed by energy-dispersive
spectra, i.e., CuO(50%)–ZnO(50%) NC studies. The CuO(50%)–ZnO(50%)
NCs exhibit superior gas sensing performance with outstanding selectivity
toward NO2 gas at a working temperature of 200 °C. Moreover, these
NCs were used for the indirect evaluation of NO2 via electrochemical
detection of NO2– (as NO2 converts
into NO2– once it reacts with moisture,
resulting into acid rain, i.e., indirect evaluation of NO2). As compared with other known modified electrodes, CuO(50%)–ZnO(50%)
NCs show an apparent oxidation of NO2– with a larger peak current for a wider linear range of nitrite concentration
from 20 to 100 mM. We thus demonstrate that the as-synthesized CuO(50%)–ZnO(50%)
NCs act as a promising low-cost NO2 sensor and further
confirm their potential toward tunable gas sensors (electrochemical
and solid state) (Scheme 1).
An underexplored
reaction of pyrazine (rigid and linear) and succinic
acid (flexible) with Co(NO3)2·6H2O afforded four new coordination polymers (CPs): [Co(H2O)(pyz)(suc)] (1), [Co(H2O)2(pyz)(suc)]
(2), [Co(H2O)4(pyz)](suc) (3) and [Co2(H2O)2(pyz)(suc)2] (4), as well as [Co(HCO2)2(pyz)] (5) being lately reported along with well-known 6 and 7. The CPs were obtained as stable crystalline
materials and characterized by conventional solid-state techniques,
including X-ray crystallography. Hydrothermally produced compounds 1 and 2 were both 3D CPs. While 3 and 4 obtained under ambient/solvothermal conditions
in DMSO generated 1D and 3D structures, 5 isolated from
DMF under solvothermal conditions had a 3D structure. The topologies
of the coordination polymers 1–7 were
described by underlying nets 3D 5-c fet, 3D 4-c cds, 1D 2-c 2C1, 3D 5-c bnn, 3D
6-c rob, 1D 2-c 2C1, and 3D 6-c pcu, respectively. The plot of χM
–1 versus T was essentially linear in the entire temperature
range following the Curie–Weiss law with a Curie constant (C) of 2.525 and a negative Weiss constant (ϕ) of −46.24
K, suggesting weak antiferromagnetic (AF) exchange interactions. CO2 and N2 adsorption studies of 1–5 featured type III isotherms. 1 was found to
show remarkably higher quenching efficiencies for nitrophenols (η
= 98% for o-NP) over other NACs. The Stern–Volmer
plot exhibited deviation in linearity with K
sv values about 200 times greater than that for the simplest
nitroaromatic compound (NB), signifying its exclusive quenching ability
toward 1. The LOD for p-NP addition
to 1 was found to be 0.995 ppm.
Bipyridine glycoluril (BPG), a urea-fused bipyridine tecton, forms a square-pyramidal secondary building unit with copper(ii) which further self-assembles to give a porous hydrogen-bonded complex. This complex displays a high proton conductivity of 4.45 × 10 S cm at 90 °C and 95% relative humidity (RH). Chains consisting of coordinated water, solvent water and nitrate anions embedded in the complex are responsible for high proton conduction. The proton conduction pathway was corroborated by ab initio electronic structure calculations with molecular dynamics (MD) simulations using the Nudged Elastic Band (NEB) method. The theoretical activation energy estimated to be 0.18 eV is in close agreement with the experimental value of 0.15 eV which evidences a Grotthuss proton hopping mechanism. We thus demonstrate that the hydrogen-bonded complex encapsulating appropriate counter ions, coordinated water and solvent water molecules exhibts superprotonic conductivity.
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