Here, a unique step-scheme (S-scheme) heterojunction array involving C 4 N and aligned TiO 2 nanorods, namely C 4 N@TiO 2 NR, is explored as an advanced photoelectrode for developing an innovative acid–base/Zn–air hybrid cell capable of harvesting light and chemical neutralization energy (CNE) in one integrated system to boost the charge/discharge performance. The properly staggered band arrangement with a built-in electric field in C 4 N@TiO 2 NR induces an S-type charge migration path to ensure superior redox ability of photogenerated carriers with efficient spatial separation. This coupled with the structural merits of 3D hierarchical arrays enables remarkable photocurrent response and facilitates oxygen evolution kinetics upon irradiation. Paring this heterojunction photoelectrode with an alkaline Zn electrode and an acidic air electrode produces a light and CNE dual-assisted cell with two switchable modes of light-assisted acid-base/air battery (LABAB) and acid-base battery (LAB). By capturing light during charge and CNE during discharge, LABAB breaks the limit of the equilibrium potential (1.65 V) of conventional Zn–air batteries (ZABs) to deliver impressive charge/discharge voltages of 0.43/2.02 and 0.87/1.86 V at 0.1 and 10 mA cm −2 , superior to all reported ZABs. respectively. When LABAB is switched to LAB, it can harvest light and CNE simultaneously to afford markedly increased output voltage relative to common acid–base batteries.
The uniform pH reaction environment of both acid proton-exchange membrane and alkaline anion-exchange membrane direct liquid fuel cells (DLFCs) substantially lowers the cell performance. Herein we propose a high-performance pH-disparate DLFC (ΔpH-DLFC), which can harvest the neutralization energy to maximize the thermodynamic voltage of DLFCs. Benefiting from the construction of oxygen-electrolyte interfaces, the triple-phase boundary density of cathode is significantly increased. The ΔpH-DLFCs yield peak power densities of 279, 341 and 610 mW cm −2 when methanol, ethanol and sodium formate are fed into the anode respectively. The stable operation of direct formate fuel cell at 200 mA cm −2 for 24 h further confirms the feasibility of the ΔpH-DLFCs. Moreover, the flexibility of the ΔpH-DLFC in oxidants and catalysts was also investigated. The experimental result indicates that the air-based pH-disparate direct formate fuel cell with non-platinum catalyst obtains a peak power density of 140 mW cm −2 at 80 °C, suggesting the great potential for practical application.
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