Electrocatalytic Selenate Transformation to Tunable Products Using Affordable Catalysts
Authors: Xie Ao , Martinez Vargas David Ricardo , Yang Zilan , Zou Shiqiang (Nick) 
Published: August 2024

Anthropogenic selenium (Se) pollution has profound ecosystem and human health impacts. Compared to selenite or Se(IV), selenate or Se(VI) is chemically inert and more challenging for selective removal from the complex aquatic environment.1 Current Se(VI) removal efforts seek intensive resource and energy input to drive Se(VI) transformation, and are subject to environmental and operating conditions.2 The potential solution for sustainable Se(VI) transformation involves catalytic reduction of Se(VI). In current catalytic approaches, the reduction of Se(VI) is achieved using either abiotic photocatalysts (e.g., TiO2) or biotic enzymes (e.g., nitrate reductase).3

Here, we explored the opportunities of electrified Se(VI) transformation with functionalized catalysts to manage aquatic selenate pollution. Se(VI) can be removed through phase transformation into solid Se(0) that could cover reactive surfaces and prevent further catalysis, or gaseous Se(-II) that is toxic and needs to be captured. Alternatively, the reduction of Se(VI) into reactive Se(IV) allows exposure of active interfaces for continuous electrochemcial transformation. Therefore, a controlled reduction of Se(VI) to Se(IV) would be ideal in aquatic Se(VI) management and potential Se recovery. To the best of our knowledge, controlled Se(VI) transformation has not been fully achieved in the literature. In this study, we evaluated five affordable catalysts on graphite cathodes, including TiO2,3 underpotentially deposited Cu (UPD Cu),4 underpotentially deposited Cd (UPD Cd), Co, and CuFe nanoarrays.5 Among these five candidates, characteristic Se(VI) reduction peaks were identified for TiO2, UPD Cu, and UPD Cd through cyclic voltammetry. Less than 5% of 1-mM Se was removed using UPD Cu and UPD Cd, based on 24-hour chronoamperometry tests at corresponding potentials. Unfortunately, ppm-level Cu or Cd were detected in the treated effluent. In contrast, more than 90% of Se(VI) was removed using TiO2 as the catalyst after 24 hours. TiO2 was more robust and stable in electrocatalytic reactions with minimal catalyst dissolution and, therefore, was selected for further electrocatalytic Se(VI) reduction studies.
During the TiO2-catalyzed reduction, Se(VI) would first transform into Se(IV) at a relatively positive potential. A maximum of 97% Se(VI) was found to be converted to Se(IV) in a 6-hour electrocatalytic Se(VI) reduction at -0.18 V. Decreasing electrode potential to -0.35 V, solid deposits of Se(0) appeared on a TiO2-modified graphite cathode. With a more negative electrode potential, further Se(0) reduction to Se(-II) was identified. The findings spotlight the opportunities to control Se(VI) transformation and harvest tunable products per removal demand and strategies. The effect of operational conditions was investigated at various TiO2 loading and solution pH. Higher TiO2 loading and lower solution pH favored the electrocatalytic Se(VI) transformation. The removal kinetics and performance were then studied under optimal operational conditions at -0.45 V, where Se(0) was dominant among Se(VI) reduction products, and -0.70 V, where Se(-II) was abundant. Kinetics analysis revealed that electrocatalytic Se(VI) reduction at -0.70 V was roughly four times faster as compared to that at -0.45 V. A total of 88.7 ± 2.3% of Se(VI) was removed after 24 hours of electrocatalysis at -0.70 V. In contrast, 48.2 ± 9.3% of Se(VI) was removed after 24 hours of electrocatalysis at -0.45 V. These results warrant further evaluation of the regenerability and lifespan of TiO2-modified graphite electrodes, an optimized electrode/reactor design, and an integrated Se removal/recovery system.

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