Shifting Emphasis from Electro- to Catalytically Active Sites: Effects of Pore Size of Flow-Through Anodes on Water Purification.

A flow-through anode has demonstrated high efficiency for micropollutant abatement in water purification. In addition to developing novel electrode materials, a rational design of its porous structure is crucial to achieve high electrooxidation kinetics while sustaining a low cost for flow-through operation. However, our knowledge of the relationship between the pore structure and its performance is still incomplete. Therefore, we systematically explore the effect of pore size (with a median from 4.7 to 49.4 μm) on the flow-through anode efficiency. Results showed that when the pore size was <26.7 μm, the electrooxidation kinetics was insignificantly improved, but the permeability declined dramatically. Traditional empirical evidence from hydrodynamic modeling and electrochemical tests indicated that a flow-through anode with a smaller pore size (e.g., 4.7 μm) had a high mass transfer capability and large electroactive area. However, this did not further accelerate the micropollutant removal. Combining an overpotential distribution model and an imprinting method has revealed that the reactivity of a flow-through anode is related to the catalytically active volume/sites. The rapid overpotential decay as a function of depth in the anode would offset the merits arising from a small pore size. Herein, we demonstrate an optimal pore size distribution (∼20 μm) of typical flow-through anodes to maximize the process performance at a low energy cost, providing insights into the design of advanced flow-through anodes in water purification applications.