Electrochemical sensing is considered as one of the most
promising
approaches for quick, reliable, and on-site detection and monitoring
of arsenic (As) levels in water. However, the unavailability of stable,
selective, and affordable electrode materials hampers the development
of portable, cost-effective, reliable, and practically applicable
arsenic-sensing electrochemical devices. In this article, we describe
a straightforward biphasic synthesis method for the crafting of sulfur-doped
reduced graphene oxide (S-rGO)-supported Prussian blue (PB) nanodeposits
(S-rGO/PB), a nanocomposite with exceptional stability and activity
for selective and sensitive electrochemical sensing of As. The S-rGO/PB
is demonstrated to selectively and sensitively electrocatalyze the
As(0)/As(III) and As(III)/As(V) charge transfer processes via the
participation of the Fe(II)/Fe(III) cycle as revealed by X-ray photoelectron
spectroscopy, thereby ensuring accurate and sensitive electrochemical
sensing of As in water samples. We demonstrate that with the S-rGO/PB
electrode, As(III) can be sensed via differential pulse voltammetry
(DPV) with sensitivity values of 1.79 (As(0)–As(III)) and 10.69
μA ppb–1 cm–2 (As(III)–As(V))
and limits of detection as low as 0.0104 and 0.0536 ppb, respectively.
Alongside real-time applicability, the S-rGO/PB is demonstrated to
exhibit excellent stability and specificity toward arsenic sensing
even in the presence of other interferents. Importantly, the As(III)
estimates obtained for real water samples using DPV over S-rGO/PB
closely match the estimates obtained with atomic absorption spectrometry,
a highly expensive and sophisticated state-of-the-art technique known
for its accuracy in estimation of the sub-ppb traces of heavy metals.
The presented results suggest that the S-rGO/PB composite is a promising
electrode material that can facilitate the design and development
of portable, affordable, reliable, and practically applicable electrochemical
setups for on-site sensing and electrodetoxification of As(III) in
water samples. The availability and accessibility of such setups are
a must for the worldwide success of arsenic mitigation initiatives,
particularly in underdeveloped and impoverished nations.