Aqueous redox flow batteries that employ organic molecules as redox couples hold great promise for mitigating the intermittency of renewable electricity through efficient, low-cost diurnal storage. However, low cell potentials and sluggish ion transport often limit the achievable power density. Here, we explore bipolar membrane (BPM)-enabled acid–base redox flow batteries in which the positive and negative electrodes operate in the alkaline and acidic electrolytes, respectively. This new configuration adds the potential arising from the pH difference across the membrane and enables an open circuit voltage of ∼1.6 V. In contrast, the same redox molecules operating at a single pH generate ∼0.9 V. Ion transport in the BPM is coupled to the water dissociation and acid–base neutralization reactions. Interestingly, experiments and numerical modeling show that both of these processes must be catalyzed in order for the battery to function efficiently. The acid–base concept provides a potentially powerful approach to increase the energy storage capacity of aqueous redox flow batteries, and insights into the catalysis of the water dissociation and neutralization reactions in BPMs may be applicable to related electrochemical energy conversion devices.
In water-splitting dye-sensitized photoelectrochemical cells (WS-DSPECs), charge recombination competes with catalytic water oxidation to determine the overall efficiency of the system. The kinetics of these processes have been difficult to understand because transient absorbance (TA) experiments typically show nearly complete charge recombination on the submillisecond time scale; in contrast, electrochemical measurements such as open circuit photovoltage decay suggest a charge recombination time scale that is 2-3 orders of magnitude longer. Here we explore these processes with dye-sensitized nanocrystalline TiO and TiO/TaO core-shell photoanodes in aqueous electrolytes using TA spectroscopy, intensity-modulated photovoltage spectroscopy (IMVS), and photoelectrochemical impedance spectroscopy (PEIS). The fast recombination rates measured by TA result from strong laser excitation that leads to high electron occupancy in TiO, whereas IMVS modulates the concentration of charge-separated states near solar irradiance levels. The recombination processes measured by electrochemical methods such as IMVS, PEIS, and transient photovoltage are the discharging of injected electrons in TiO, as evidenced by the close agreement between the nearly first-order recombination rates probed by IMVS and the RC time constants derived from PEIS data. However, IMVS measurements at variable probe light intensity reveal that the reaction orders for the recombination of injected electrons with oxidized sensitizer molecules are far from unity. This kinetic analysis is relevant to understanding steady-state recombination rates in full WS-DSPECs in which molecular and nanoparticle catalysts are used to oxidize water.
We report a precious-metal-free molecular catalyst-based photocathode that is active for aqueous CO 2 reduction to CO and methanol. The photoelectrode is composed of cobalt phthalocyanine molecules anchored on graphene oxide which is integrated via a (3aminopropyl)triethoxysilane linker to p-type silicon protected by a thin film of titanium dioxide. The photocathode reduces CO 2 to CO with high selectivity at potentials as mild as 0 V versus the reversible hydrogen electrode (vs RHE). Methanol production is observed at an onset potential of À 0.36 V vs RHE, and reaches a peak turnover frequency of 0.18 s À 1 . To date, this is the only molecular catalyst-based photoelectrode that is active for the six-electron reduction of CO 2 to methanol. This work puts forth a strategy for interfacing molecular catalysts to p-type semiconductors and demonstrates state-of-the-art performance for photoelectrochemical CO 2 reduction to CO and methanol.
A molecularly thin layer of 2‐aminobenzenethiol (2‐ABT) was adsorbed onto nanoporous p‐type silicon (b‐Si) photocathodes decorated with Ag nanoparticles (Ag NPs). The addition of 2‐ABT alters the balance of the CO2 reduction and hydrogen evolution reactions, resulting in more selective and efficient reduction of CO2 to CO. The 2‐ABT adsorbate layer was characterized by Fourier transform infrared (FTIR) spectroscopy and modeled by density functional theory calculations. Ex situ X‐ray photoelectron spectroscopy (XPS) of the 2‐ABT modified electrodes suggests that surface Ag atoms are in the +1 oxidation state and coordinated to 2‐ABT via Ag−S bonds. Under visible light illumination, the onset potential for CO2 reduction was −50 mV vs. RHE, an anodic shift of about 150 mV relative to a sample without 2‐ABT. The adsorption of 2‐ABT lowers the overpotentials for both CO2 reduction and hydrogen evolution. A comparison of electrodes functionalized with different aromatic thiols and amines suggests that the primary role of the thiol group in 2‐ABT is to anchor the NH2 group near the Ag surface, where it serves to bind CO2 and also to assist in proton transfer.
While dye-sensitized metal oxides are good candidates as H 2 evolution photocatalysts for solar-driven Z-scheme water splitting, their solar-to-hydrogen (STH) energy conversion efficiencies remain low because of uncontrolled charge recombination reactions. Here, we show that modification of Ru dye–sensitized, Pt-intercalated HCa 2 Nb 3 O 10 nanosheets ( Ru /Pt/HCa 2 Nb 3 O 10 ) with both amorphous Al 2 O 3 and poly(styrenesulfonate) (PSS) improves the STH efficiency of Z-scheme overall water splitting by a factor of ~100, when the nanosheets are used in combination with a WO 3 -based O 2 evolution photocatalyst and an I 3 − /I − redox mediator, relative to an analogous system that uses unmodified Ru /Pt/HCa 2 Nb 3 O 10 . By using the optimized photocatalyst, PSS/ Ru /Al 2 O 3 /Pt/HCa 2 Nb 3 O 10 , a maximum STH of 0.12% and an apparent quantum yield of 4.1% at 420 nm were obtained, by far the highest among dye-sensitized water splitting systems and comparable to conventional semiconductor-based suspended particulate photocatalyst systems.
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