Spatiotemporal pH imaging using fluorescence lifetime imaging microscopy (FLIM) is an excellent technique for investigating dynamic (electro)chemical processes. However, probes that are responsive at high pH values are not available. Here, we describe the development and application of dedicated pH probes based on the 1-methyl-7-amino-quinolinium fluorophore. The high fluorescence lifetime and quantum yield, the high (photo)stability, and the inherent water solubility make the quinolinium fluorophore well suited for the development of FLIM probes. Due to the flexible fluorophore-spacer-receptor architecture, probe lifetimes are tunable in the pH range between 5.5 and 11. An additional fluorescence lifetime response, at tunable pH values between 11 and 13, is achieved by deprotonation of the aromatic amine at the quinolinium core. Probe lifetimes are hardly affected by temperature and the presence of most inorganic ions, thus making FLIM imaging highly reliable and convenient. At 0.1 mM probe concentrations, imaging at rates of 3 images per second, at a resolution of 4 μm, while measuring pH values up to 12 is achieved. This enables the pH imaging of dynamic electrochemical processes involving chemical reactions and mass transport.@en

Electrochemical CO2 reduction poses a promising pathway to produce hydrocarbon chemicals and fuels without relying on fossil fuels. Gas diffusion electrodes allow high selectivity for desired carbon products at high current density by ensuring a sufficient CO2 mass transfer rate to the catalyst layer. In addition to CO2 mass transfer, the product selectivity also strongly depends on the local pH at the catalyst surface. In this work, we directly visualize for the first time the two-dimensional (2D) pH profile in the catholyte channel of a gas-fed CO2 electrolyzer equipped with a bipolar membrane. The pH profile is imaged with operando fluorescence lifetime imaging microscopy (FLIM) using a pH-sensitive quinolinium-based dye. We demonstrate that bubble-induced mixing plays an important role in the Faradaic efficiency. Our concentration measurements show that the pH at the catalyst remains lower at −100 mA cm-2 than at −10 mA cm-2, implying that bubble-induced advection outweighs the additional OH- flux at these current densities. We also prove that the pH buffering effect of CO2 from the gas feed and dissolved CO2 in the catholyte prevents the gas diffusion electrode from becoming strongly alkaline. Our findings suggest that gas-fed CO2 electrolyzers with a bipolar membrane and a flowing catholyte are promising designs for scale-up and high-current-density operation because they are able to avoid extreme pH values in the catalyst layer.@en

To make green hydrogen more economically attractive, the energy losses in alkaline electrolysis need to be minimized while operating at high current densities (1 A cm−2). At these current densities the ohmic resistance and gas bubbles effects contribute largely to the energy losses. To mitigate the gas bubbles losses, we demonstrate, for the first time, a pressure swing to remove gas bubbles in a zero-gap alkaline water electrolyzer. The pressure swing leverages the ideal gas law to increase the volume of gas in the system periodically, for a short duration (<2 s). This temporal volume increase effectively removes bubbles from the electrolyzer. We show that pressure swing can be used to measure the effect of bubbles on the ohmic resistance (RBubbles). Our results reveal that foam electrodes have a significantly larger RBubbles than perforated plate electrodes (1.8 Ω cm2 vs 0.3 Ω cm2). The time-averaged cell voltage reduces by 170 mV when applying pressure swings to an electrolyzer operating at 200 mA cm−2 in 1 M KOH with foam electrodes. The bubble resistance further depends on the electrolyte conductivity (inversely proportional) and is only moderately affected by operating pressure (25 % lower when increasing pressure amplitude from 1–2 to 1–5 bar). By implementing these findings in a model, we estimate that the pressure swing could reduce the cell voltage by ∼0.1 V for an electrolyzer operating at industrial conditions (6 M KOH, 80 °C, 1 A cm−2) for foam electrodes. For perforated plate electrodes, however, the reduced cell voltage is lower and does not outweigh the additional compression energy.@en

We report here the synthesis and photophysical study of a series of electron donor–acceptor molecules, in which electron-donating 4-methoxyphenoxy groups are attached to the 1,7-bay positions of four different perylene tetracarboxylic acid derivatives, namely, perylene tetraesters 1, perylene monoimide diesters 2, perylene bisimides 3, and perylene monobenzimidazole monoimides 4. These perylene derivatives are used because of their increasing order of electron-accepting capability upon moving from 1 to 4. Two additional donor–acceptor molecules are synthesized by linking electron-donating 4-methoxyphenyl groups to the imide position of perylene monoimide diester 2 and perylene bisimide 3. The motivation for this study is to achieve a good control over the photoinduced charge-transfer (CT) process in perylene-based systems by altering the position of electron donors and tuning the electron deficiency of perylene core. A comprehensive study of the photophysical properties of these molecules has shown a highly systematic trend in the magnitude of CT as a function of increased electron deficiency of the perylene core and solvent polarity. Importantly, just by changing the attachment of electron-donating group from “bay” to “imide” position, we are able to block the CT process. This implies that the positioning of the electron donor at the perylene core strongly influences the kinetics of the photoinduced CT process. In these compounds, the CT process is characterized by the quenching of fluorescence and singlet excited-state lifetimes as compared to model compounds bearing non-electron-donating 4-tert-butylphenoxy groups. Transient absorption spectroscopy did not reveal spectra of CT states. This most likely implies that the CT state is not accumulated, because of the faster charge recombination.@en