The heavy metal ion adsorption performance of birnessite (a layer-structured manganese oxide) can be enhanced by decreasing the Mn average oxidation state (Mn AOS) and dissolution−recrystallization during electrochemical redox reactions. However, the electrochemical adsorption processes of heavy metal ions by tunnel-structured manganese oxides are still enigmatic. Here, tunnel-structured manganese oxides including pyrolusite (2.3 Å × 2.3 Å tunnel), cryptomelane (4.6 Å × 4.6 Å tunnel) and todorokite (6.9 Å × 6.9 Å tunnel) were synthesized, and their electrochemical adsorptions for Cd²⁺ were performed through galvanostatic charge−discharge. The influence of both supporting ion species in the tunnel and tunnel size on the electrochemical adsorption performance was also studied. The adsorption capacity of tunnel-structured manganese oxides for Cd²⁺ was remarkably enhanced by electrochemical redox reactions. Relative to K⁺ in the tunnel of cryptomelane, the supporting ion H⁺ was more favorable to the electrochemical adsorption of Cd²⁺. With increasing initial pH and specific surface area, the electrochemical adsorption capacity of cryptomelane increased. The cryptomelane electrode could be regenerated by galvanostatic charge−discharge in Na₂SO₄ solution. Due to the differences in their tunnel size and supporting ion species, the tunnel-structured manganese oxides follow the order of cryptomelane (192.0 mg g⁻¹) > todorokite (44.8 mg g⁻¹) > pyrolusite (13.5 mg g⁻¹) in their electrochemical adsorption capacities for Cd²⁺.

The heavy metal ion adsorption performance of birnessite (a layer-structured manganese oxide) can be enhanced by decreasing the Mn average oxidation state (Mn AOS) and dissolution−recrystallization during electrochemical redox reactions. However, the electrochemical adsorption processes of heavy metal ions by tunnel-structured manganese oxides are still enigmatic. Here, tunnel-structured manganese oxides including pyrolusite (2.3 Å × 2.3 Å tunnel), cryptomelane (4.6 Å × 4.6 Å tunnel) and todorokite (6.9 Å × 6.9 Å tunnel) were synthesized, and their electrochemical adsorptions for Cd²⁺ were performed through galvanostatic charge−discharge. The influence of both supporting ion species in the tunnel and tunnel size on the electrochemical adsorption performance was also studied. The adsorption capacity of tunnel-structured manganese oxides for Cd²⁺ was remarkably enhanced by electrochemical redox reactions. Relative to K⁺ in the tunnel of cryptomelane, the supporting ion H⁺ was more favorable to the electrochemical adsorption of Cd²⁺. With increasing initial pH and specific surface area, the electrochemical adsorption capacity of cryptomelane increased. The cryptomelane electrode could be regenerated by galvanostatic charge−discharge in Na₂SO₄ solution. Due to the differences in their tunnel size and supporting ion species, the tunnel-structured manganese oxides follow the order of cryptomelane (192.0 mg g⁻¹) > todorokite (44.8 mg g⁻¹) > pyrolusite (13.5 mg g⁻¹) in their electrochemical adsorption capacities for Cd²⁺.