The generation of organoperoxy radical by irradiating aqueous solutions of organochlorides depends on the concentration of organochloride, where low concentration of organochloride results in low yield of peroxyl radical. The need of high concentration of organochloride limits the application in cancer therapy as most small molecule organochlorides show liver toxicity at elevated concentrations. To study if the oxidation is feasible at low concentration of organochloride, we proposed a reaction network where the effect of molecular oxygen is included. We hypothesized that oxygen competes with the organochloride to react with aqueous electrons, thereby causing a low yield of peroxyl radical at low organochloride concentrations. However, oxygen is necessary in the peroxyl radical formation pathway, which complicates straightforward prediction of reaction outcome. We developed a mathematic model to simulate the yield of peroxyl radical depending on organochloride and oxygen concentrations. The simulated results indicate that at low organochloride concentration, decreasing oxygen concentration leads to higher yield of peroxyl radical, with a peak at approximately 2% partial pressure of oxygen, and oxygen lower than 2% results in a sharp yield drop of peroxyl radical. Experiments using a thioether as reductant to quantify the peroxyl radical formation show good agreement with simulated data, verifying the proposed network. After irradiation in phosphate buffer saline/organochloride, a thioether caged dye showed a higher uncaging yield than the group without organochloride, demonstrating the viability of using thioether as a radiation sensitive group.

The generation of organoperoxy radical by irradiating aqueous solutions of organochlorides depends on the concentration of organochloride, where low concentration of organochloride results in low yield of peroxyl radical. The need of high concentration of organochloride limits the application in cancer therapy as most small molecule organochlorides show liver toxicity at elevated concentrations. To study if the oxidation is feasible at low concentration of organochloride, we proposed a reaction network where the effect of molecular oxygen is included. We hypothesized that oxygen competes with the organochloride to react with aqueous electrons, thereby causing a low yield of peroxyl radical at low organochloride concentrations. However, oxygen is necessary in the peroxyl radical formation pathway, which complicates straightforward prediction of reaction outcome. We developed a mathematic model to simulate the yield of peroxyl radical depending on organochloride and oxygen concentrations. The simulated results indicate that at low organochloride concentration, decreasing oxygen concentration leads to higher yield of peroxyl radical, with a peak at approximately 2% partial pressure of oxygen, and oxygen lower than 2% results in a sharp yield drop of peroxyl radical. Experiments using a thioether as reductant to quantify the peroxyl radical formation show good agreement with simulated data, verifying the proposed network. After irradiation in phosphate buffer saline/organochloride, a thioether caged dye showed a higher uncaging yield than the group without organochloride, demonstrating the viability of using thioether as a radiation sensitive group.

Monitoring complex catalytic pathways under industrially-relevant conditions is one of the key challenges in catalysis chemistry and technology. Herewith we describe a direct technique called ‘fast scanning-pulse analysis’ (FASPA) that allows the direct characterization and detailed kinetic analysis of intimately interweaved catalytic pathways. The power and potential of the FASPA approach are demonstrated with an industrially relevant methanol-to-hydrocarbons (MTH) process over H-ZSM-5 zeolite. This reaction proceeds via a hydrocarbon pool (HCP) mechanism producing olefins and aromatics. The HCP is built-up upon exposure to methanol during the induction period, followed by a transition regime to a quasi-steady state MTH operation. This FASPA technique allows (sub-)second resolution of the full temporal products response upon a methanol pulse providing direct and quantitative insight into the MTH reactions. Globally two consecutive pathways can be discerned: a very fast primary product formation in the presence of methanol in a narrow active MTH reaction zone, followed by a slower formation of light aromatics, which is closely related to the decomposition and release of HCP species and secondary reactions in absence of methanol in the downstream part of the catalyst bed. The time delay between the appearance of inert tracer and primary products represents the time needed to build-up the HCP in the induction period, where methane is observed prior to other products. The primary products (alkanes, olefins, and light aromatics) are nearly instantaneously formed from the pulsed methanol. These results demonstrate the highly dynamic character of the HCP in the MTH process over H-ZSM-5.

Monitoring complex catalytic pathways under industrially-relevant conditions is one of the key challenges in catalysis chemistry and technology. Herewith we describe a direct technique called ‘fast scanning-pulse analysis’ (FASPA) that allows the direct characterization and detailed kinetic analysis of intimately interweaved catalytic pathways. The power and potential of the FASPA approach are demonstrated with an industrially relevant methanol-to-hydrocarbons (MTH) process over H-ZSM-5 zeolite. This reaction proceeds via a hydrocarbon pool (HCP) mechanism producing olefins and aromatics. The HCP is built-up upon exposure to methanol during the induction period, followed by a transition regime to a quasi-steady state MTH operation. This FASPA technique allows (sub-)second resolution of the full temporal products response upon a methanol pulse providing direct and quantitative insight into the MTH reactions. Globally two consecutive pathways can be discerned: a very fast primary product formation in the presence of methanol in a narrow active MTH reaction zone, followed by a slower formation of light aromatics, which is closely related to the decomposition and release of HCP species and secondary reactions in absence of methanol in the downstream part of the catalyst bed. The time delay between the appearance of inert tracer and primary products represents the time needed to build-up the HCP in the induction period, where methane is observed prior to other products. The primary products (alkanes, olefins, and light aromatics) are nearly instantaneously formed from the pulsed methanol. These results demonstrate the highly dynamic character of the HCP in the MTH process over H-ZSM-5.

There are two folders: Experimental_data and Theoretical_data. The Experimental_data contains the experimental results on metal contents determined by ICP analysis; XRD patterns; unit-cell lattice parameters and crystallinity results of all catalysts; FTIR spectra; MeOH conversion and carbon yields of BTEX and MTA. The Theoretical_data folder contains the results on the genetic algorithm, structures optimization and reaction mechanisms of ethane dehydrogenation. The structure of the theoretical data is described in the README file.

There are two folders: Experimental_data and Theoretical_data. The Experimental_data contains the experimental results on metal contents determined by ICP analysis; XRD patterns; unit-cell lattice parameters and crystallinity results of all catalysts; FTIR spectra; MeOH conversion and carbon yields of BTEX and MTA. The Theoretical_data folder contains the results on the genetic algorithm, structures optimization and reaction mechanisms of ethane dehydrogenation. The structure of the theoretical data is described in the README file.

The dataset contains the processed data of the publication with the above-mentioned title, published in Catalysis Science & Technology (https://doi.org/10.1039/D0CY00817F).