Altering the morphology of electrochemically
active nanostructured
materials could fundamentally influence their subsequent catalytic
as well as oxygen evolution reaction (OER) performance. Enhanced OER
activity for mixed-metal spinel-type sulfide (CuCo2S4) nanorods is generally done by blending the material that
has high conductive supports together with those having a high surface
volume ratio, for example, graphitic carbon nitrides (g-C3N4). Here, we report a noble-metal-free CuCo2S4 nanorod-based electrocatalyst appropriate for basic
OER and neutral media, through a simple one-step thermal decomposition
approach from its molecular precursors pyrrolidine dithiocarbamate-copper(II),
Cu[PDTC]2, and pyrrolidine dithiocarbamate-cobalt(II),
Co[PDTC]2 complexes. Transmission electron microscopy (TEM)
images as well as X-ray diffraction (XRD) patterns suggest that as-synthesized
CuCo2S4 nanorods are highly crystalline in nature
and are connected on the g-C3N4 support. Attenuated
total reflectance–Fourier-transform infrared (ATR-FTIR), X-ray
photoelectron spectroscopy (XPS), and Raman spectroscopy studies affirm
the successful formation of bonds that bridge (Co–N/S–C)
at the interface of CuCo2S4 nanorods and g-C3N4. The kinetics of the reaction are expedited,
as these bridging bonds function as an electron transport chain, empowering
OER electrocatalytically under a low overpotential (242 mV) of a current
density at 10 mA cm–2 under basic conditions, resulting
in very high durability. Moreover, CuCo2S4/g-C3N4 composite nanorods exhibit a high catalytic
activity of OER under a neutral medium at an overpotential of 406
mV and a current density of 10 mA cm–2.
The racemase enzymes convert l-amino acids to their d-isomer. The reaction proceeds through a stepwise deprotonation-reprotonation mechanism that is assisted by a pyridoxal phosphate (PLP) coenzyme. This work reports a PLP-photoswitch-imidazole triad where the racemization reaction can be controlled by light by tweaking the distance between the basic residue and the reaction centre.
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