Long-Term Characterization of Oxidation Processes in Graphitic Carbon Nitride Photocatalyst Materials via Electron Paramagnetic Resonance Spectroscopy

Graphitic carbon nitride (gCN) materials have been shown to efficiently perform light-induced water splitting, carbon dioxide reduction, and environmental remediation in a cost-effective way. However, gCN suffers from rapid charge-carrier recombination, inefficient light absorption, and poor long-term stability which greatly hinders photocatalytic performance. To determine the underlying catalytic mechanisms and overall contributions that will improve performance, the electronic structure of gCN materials has been investigated using electron paramagnetic resonance (EPR) spectroscopy. Through lineshape analysis and relaxation behavior, evidence of two independent spin species were determined to be present in catalytically active gCN materials. These two contributions to the total lineshape respond independently to light exposure such that the previously established catalytically active spin system remains responsive while the newly observed, superimposed EPR signal is not increased during exposure to light. The time dependence of these two peaks present in gCN EPR spectra recorded sequentially in air over several months demonstrates a steady change in the electronic structure of the gCN framework over time. This light-independent, slowly evolving additional spin center is demonstrated to be the result of oxidative processes occurring as a result of exposure to the environment and is confirmed by forced oxidation experiments. This oxidized gCN exhibits lower H2 production rates and indicates quenching of the overall gCN catalytic activity over longer reaction times. A general model for the newly generated spin centers is given and strategies for the alleviation of oxidative products within the gCN framework are discussed in the context of improving photocatalytic activity over extended durations as required for future functional photocatalytic device development

Long-Term Characterization of Oxidation Processes in Graphitic Carbon Nitride Photocatalyst Materials via Electron Paramagnetic Resonance Spectroscopy

Graphitic carbon nitride (gCN) materials have been shown to efficiently perform light-induced water splitting, carbon dioxide reduction, and environmental remediation in a cost-effective way. However, gCN suffers from rapid charge-carrier recombination, inefficient light absorption, and poor long-term stability which greatly hinders photocatalytic performance. To determine the underlying catalytic mechanisms and overall contributions that will improve performance, the electronic structure of gCN materials has been investigated using electron paramagnetic resonance (EPR) spectroscopy. Through lineshape analysis and relaxation behavior, evidence of two independent spin species were determined to be present in catalytically active gCN materials. These two contributions to the total lineshape respond independently to light exposure such that the previously established catalytically active spin system remains responsive while the newly observed, superimposed EPR signal is not increased during exposure to light. The time dependence of these two peaks present in gCN EPR spectra recorded sequentially in air over several months demonstrates a steady change in the electronic structure of the gCN framework over time. This light-independent, slowly evolving additional spin center is demonstrated to be the result of oxidative processes occurring as a result of exposure to the environment and is confirmed by forced oxidation experiments. This oxidized gCN exhibits lower H2 production rates and indicates quenching of the overall gCN catalytic activity over longer reaction times. A general model for the newly generated spin centers is given and strategies for the alleviation of oxidative products within the gCN framework are discussed in the context of improving photocatalytic activity over extended durations as required for future functional photocatalytic device development

Towards single-cell pulsed EPR using VCO-based EPR-on-a-chip detectors

Electron paramagnetic resonance (EPR) is the gold standard for studying paramagnetic species. As an example, in structural biology, it allows to extract information about distance distributions on the nanometer scale via site-directed spin labeling. Conventional pulsed EPR of biological samples is currently limited to relatively large sample concentrations and cryogenic temperatures, mainly due to low sensitivity and the significant dead time associated with conventional resonator-based EPR setups, essentially precluding in-cell EPR under physiological conditions. This paper presents our latest progress toward single-cell pulsed EPR using VCO-based EPR-on-a-chip (EPRoC) sensors. Together with an analytical model for VCO-based pulsed EPR, we present an experimental scheme to perform dead time- free pulsed EPR measurements using EPRoC detectors. The proposed scheme is validated using extensive numerical simulations and proof-of-concept experiments on the spin dynamics of an organic radical at room temperature using a custom-designed EPRoC detector operating in the Ka-band around 30.4 GHz. Additionally, we discuss methods to improve the excitation field homogeneity and sample handling through chip post-processing and custom-designed microfluidics. Finally, we present our progress towards compact, portable pulsed EPR spectrometers incorporating EPRoC detectors, microfluidics, and custom-designed permanent magnets. Such portable EPR spectrometers can pave the way toward new EPR applications, including point-of care diagnostics

Synthesis and characterization of poly(ester amide amide)s of different alkylene chain lengths

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