Titanium-based metal-organic framework, NH2-MIL-125(Ti), has been widely investigated for photocatalytic applications but has low activity in the hydrogen evolution reaction (HER). In this work, we show a one-step low-cost postmodification of NH2-MIL-125(Ti) via impregnation of Co(NO3)2. The resulting Co@NH2-MIL-125(Ti) with embedded single-site CoII species, confirmed by XPS and XAS measurements, shows enhanced activity under visible light exposure. The increased H2 production is likely triggered by the presence of active CoI transient sites detected upon collection of pump-flow-probe XANES spectra. Furthermore, both photocatalysts demonstrated a drastic increase in HER performance after consecutive reuse while maintaining their structural integrity and consistent H2 production. Via thorough characterization, we revealed two mechanisms for the formation of highly active proton reduction sites: nondestructive linker elimination resulting in coordinatively unsaturated Ti sites and restructuring of single CoII sites. Overall, this straightforward manner of confinement of CoII cocatalysts within NH2-MIL-125(Ti) offers a highly stable visible-light-responsive photocatalyst.

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CO2 electrolysis might be a key process to utilize intermittent renewable electricity for the sustainable production of hydrocarbon chemicals without relying on fossil fuels. Commonly used carbon-based gas diffusion electrodes (GDEs) enable high Faradaic efficiencies for the desired carbon products at high current densities, but have limited stability. In this study, we explore the adaption of a carbon-free GDE from a Chlor-alkali electrolysis process as a cathode for gas-fed CO2 electrolysis. We determine the impact of electrowetting on the electrochemical performance by analyzing the Faradaic efficiency for CO at industrially relevant current density. The characterization of used GDEs with X-ray photoelectron spectroscopy (XPS) and X-Ray diffraction (XRD) reveals a potential-dependent degradation, which can be explained through chemical polytetrafluorethylene (PTFE) degradation and/or physical erosion of PTFE through the restructuring of the silver surface. Our results further suggest that electrowetting-induced flooding lets the Faradaic efficiency for CO drop below 40% after only 30 min of electrolysis. We conclude that the effect of electrowetting has to be managed more carefully before the investigated carbon-free GDEs can compete with carbon-based GDEs as cathodes for CO2 electrolysis. Further, not only the conductive phase (such as carbon), but also the binder (such as PTFE), should be carefully selected for stable CO2 reduction.@en

In the version of this article, there were errors in Fig. 2a and d. In Fig. 2a, we have changed Cu2+ to Cu(0) in the revised version. While the two references cited in our paper used Cu2+ in their schematics,1,2 we believe that Cu(0) is the correct representation for the electrochemically mediated amine regeneration (EMAR)3. To be clear, the Cu metal anode is oxidized into cupric ions. The cupric ions then bind to the carbamate and displace the CO2 and form a copper–amine complex. The copper–amine complex is then reduced at the cathode where Cu metal is plated out. In Fig. 2d, we have changed the polarity of the cathode and anode in the revised version. A proton is released at the anode, while a hydroxide is released at the cathode. We have also simplified the quinone/hydroquinone chemistry in the revised version to be consistent with proton and hydroxide stoichiometry. The original and revised Fig. 2 images are shown below. The changes have been made to the html and PDF versions of the article.

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