Reutilizing Methane Reforming Spent Catalysts as Efficient Overall Water-Splitting Electrocatalysts.

It is extremely prudent and highly challenging to design a greener bifunctional electrocatalyst that shows effective electrocatalytic activity and high stability toward electrochemical water splitting. As several hundred tons of catalysts are annually deactivated by deposition of carbon, herein, we came up with a strategy to reutilize spent methane reforming catalysts that were deactivated by the formation of graphitic carbon (GC) and carbon nanofibers (CNF). An electrocatalyst was successfully synthesized by in situ deposition of noble metal-free MoS2 over spent catalysts via a hydrothermal method that showed exceptional performance regarding the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). At 25 mA cm-2, phenomenal OER overpotentials (η25) of 128 and 154 mV and modest HER overpotentials of 186 and 207 mV were achieved for MoS2@CNF and MoS2@GC, respectively. Moreover, OER Tafel slopes of 41 and 71 mV dec-1 and HER Tafel slopes of 99 and 107 mV dec-1 were obtained for MoS2@CNF and MoS2@GC, respectively. Furthermore, the synthesized catalysts exhibited good long-term durability for about 18 h at 100 µA cm-2 with unnoticeable changes in the linear sweep voltammetry (LSV) curve of the HER after 1000 cycles. The carbon on the spent catalyst increased the conductivity, while MoS2 enhanced the electrocatalytic activity; hence, the synergistic effect of both materials resulted in enhanced electrocatalysts for overall water splitting. This work of synthesizing enhanced nanostructured electrocatalysts with minimal usage of inexpensive MoS2 gives a rationale for engineering potent greener electrocatalysts.

Perylene diimide/MXene-modified graphitic pencil electrode-based electrochemical sensor for dopamine detection.

The synthesis of novel architecture comprising perylene diimide (PDI)-MXene (Ti3C2TX)-integrated graphitic pencil electrode for electrochemical detection of dopamine (DA) is reported. The good electron passage between PDI-MXene resulted in an unprecedented nano-adduct bearing enhanced electrocatalytic activity with low-energy electronic transitions. The anionic groups of PDI corroborated enhanced active surface area for selective binding and robust oxidation of DA, thereby decreasing the applied potential. Meanwhile, the MXene layers acted as functional conducive support for PDI absorption via strong H-bonding. The considerable conductivity of MXene enhanced electron transportation thus increasing the sensitivity of sensing interface. The inclusively engineered nano-adduct resulted in robust DA oxidation with ultra-sensitivity (38.1 µAµM-1cm-2), and low detection limit (240 nM) at very low oxidation potential (-0.135 V). Moreover, it selectively signaled DA in the presence of physiological interferents with wide linearity (100-1000 µM). The developed transducing interface performed well in human serum samples with RSD (0.1 to 0.4%) and recovery (98.6 to 100.2%) corroborating the viability of the practical implementation of this integrated system. Graphical abstract Schematic illustration of the oxidative process involved on constructed sensing interface for the development of a non-enzymatic dopamine sensor.