Materials Today Chemistry

The document contains additional SEM micrographs of the samples obtained by pyrolysis of ferrocene with 0.2 ml of dichlorobenzene

Source data for publication Polyacrylonitrile‒Chitosan IPN composite scaffolds that closely mimic the human trabecular bone structure for tissue engineering

Collectivity of all measured data mentioned in the article "Spaeth K., Goetz-Neunhoeffer F., Hurle K. - The effect of Cu2+ doping in β-tricalcium phosphate on the hydration mechanism of a brushite cement". Listed are raw and evaluated data of the following methods: Isothermal heatflow calorimetry, In-situ 1H - time domaine - nuclear magnetic resonance, In-situ X-ray diffraction, powder X-ray diffraction, lasergranulometry, pore solution analysis by inductively coupled plasma - mass spectrometry.

XRD, XPS, IR, and PDF data are included as accessible files for the fresh and recovered Pt/LaAlO3-c and LaAlO3-c (where c = calcination temperature of the support at 700, 900, 1100 °C). Characterisation of the fresh materials allowed for identification of amorphous lanthanum carbonate phases in the 700 °C calcined sample that was not present in the higher calcined materials. The recovered Pt/LaAlO3-c were characterised after the aqueous phase reforming (APR) of glycerol to understand effects of real catalytic reactions on material structure. Additionally, the recovered LaAlO3-c were characterised after simulated reactions with acidic reaction products (lactic acid and CO2) to deconvolute the effects of specific reaction products on material stability. It is essential to note that multiple advanced characterisation techniques were required to fully characterise any amorphous content and the early-stage decomposition that occurs during the reactions.

Supplementary files for article The Influence of Phase Purity on the Stability of Pt/LaAlO3 Catalysts in the Aqueous Phase Reforming of Glycerol Supplementary Information Aqueous phase reforming (APR) of waste oxygenates offers the potential for sustainable hydrogen production. However, catalyst stability remains elusive, due to the aggressive hydrothermal conditions employed. Herein, we show that the catalytic performance and stability of Pt supported on LaAlO3 catalysts for glycerol APR is strongly influenced by the phase purity of LaAlO3. Calcination of the support at 700 °C produces the LaAlO3 perovskite phase and an amorphous lanthanum carbonate phase, which can be removed by calcination at higher temperature. Catalysts comprised of phase pure LaAlO3 were notably more active, with a support calcination temperature of 1100 °C resulting in 20.4% glycerol conversion (TOF 686 h−1) in a 2 h batch reaction. Interestingly, all the catalysts, regardless of LaAlO3 phase purity, eventually transform into Pt/LaCO3OH-AlO(OH) during reaction, but only in the presence of evolved carbon dioxide, itself produced from glycerol reforming. Studies using simulated reaction products showed that organic acid products (lactic acid), in the absence of CO2, facilitated La leaching and loss of crystallinity. A carbonate source (CO2) is essential to limit La leaching and form stable Pt/LaCO3OH. Pt supported on LaCO3OH and AlO(OH) are stable and active catalysts during APR reactions. Yet, the rate of perovskite phase decomposition strongly influences the final catalyst performance, with the initially phase impure LaAlO3 decomposing too quickly to facilitate Pt redistribution. LaAlO3 calcined at higher temperatures evolved more slowly and consequently produced more active catalysts.

Aqueous phase reforming (APR) of waste oxygenates offers the potential for sustainable hydrogen production. However, catalyst stability remains elusive, due to the aggressive hydrothermal conditions employed. Herein, we show that the catalytic performance and stability of Pt supported on LaAlO3 catalysts for glycerol APR is strongly influenced by the phase purity of LaAlO3. Calcination of the support at 700 °C produces the LaAlO3 perovskite phase and an amorphous lanthanum carbonate phase, which can be removed by calcination at higher temperature. Catalysts comprised of phase pure LaAlO3 were notably more active, with a support calcination temperature of 1100 °C resulting in 20.4% glycerol conversion (TOF 686 h−1) in a 2 h batch reaction. Interestingly, all the catalysts, regardless of LaAlO3 phase purity, eventually transform into Pt/LaCO3OH-AlO(OH) during reaction, but only in the presence of evolved carbon dioxide, itself produced from glycerol reforming. Studies using simulated reaction products showed that organic acid products (lactic acid), in the absence of CO2, facilitated La leaching and loss of crystallinity. A carbonate source (CO2) is essential to limit La leaching and form stable Pt/LaCO3OH. Pt supported on LaCO3OH and AlO(OH) are stable and active catalysts during APR reactions. Yet, the rate of perovskite phase decomposition strongly influences the final catalyst performance, with the initially phase impure LaAlO3 decomposing too quickly to facilitate Pt redistribution. LaAlO3 calcined at higher temperatures evolved more slowly and consequently produced more active catalysts.

XRD, XPS, IR, and PDF data are included as accessible files for the fresh and recovered Pt/LaAlO3-c and LaAlO3-c (where c = calcination temperature of the support at 700, 900, 1100 °C). Characterisation of the fresh materials allowed for identification of amorphous lanthanum carbonate phases in the 700 °C calcined sample that was not present in the higher calcined materials. The recovered Pt/LaAlO3-c were characterised after the aqueous phase reforming (APR) of glycerol to understand effects of real catalytic reactions on material structure. Additionally, the recovered LaAlO3-c were characterised after simulated reactions with acidic reaction products (lactic acid and CO2) to deconvolute the effects of specific reaction products on material stability. It is essential to note that multiple advanced characterisation techniques were required to fully characterise any amorphous content and the early-stage decomposition that occurs during the reactions.

Supplementary files for article The Influence of Phase Purity on the Stability of Pt/LaAlO3 Catalysts in the Aqueous Phase Reforming of Glycerol Supplementary Information Aqueous phase reforming (APR) of waste oxygenates offers the potential for sustainable hydrogen production. However, catalyst stability remains elusive, due to the aggressive hydrothermal conditions employed. Herein, we show that the catalytic performance and stability of Pt supported on LaAlO3 catalysts for glycerol APR is strongly influenced by the phase purity of LaAlO3. Calcination of the support at 700 °C produces the LaAlO3 perovskite phase and an amorphous lanthanum carbonate phase, which can be removed by calcination at higher temperature. Catalysts comprised of phase pure LaAlO3 were notably more active, with a support calcination temperature of 1100 °C resulting in 20.4% glycerol conversion (TOF 686 h−1) in a 2 h batch reaction. Interestingly, all the catalysts, regardless of LaAlO3 phase purity, eventually transform into Pt/LaCO3OH-AlO(OH) during reaction, but only in the presence of evolved carbon dioxide, itself produced from glycerol reforming. Studies using simulated reaction products showed that organic acid products (lactic acid), in the absence of CO2, facilitated La leaching and loss of crystallinity. A carbonate source (CO2) is essential to limit La leaching and form stable Pt/LaCO3OH. Pt supported on LaCO3OH and AlO(OH) are stable and active catalysts during APR reactions. Yet, the rate of perovskite phase decomposition strongly influences the final catalyst performance, with the initially phase impure LaAlO3 decomposing too quickly to facilitate Pt redistribution. LaAlO3 calcined at higher temperatures evolved more slowly and consequently produced more active catalysts.

Aqueous phase reforming (APR) of waste oxygenates offers the potential for sustainable hydrogen production. However, catalyst stability remains elusive, due to the aggressive hydrothermal conditions employed. Herein, we show that the catalytic performance and stability of Pt supported on LaAlO3 catalysts for glycerol APR is strongly influenced by the phase purity of LaAlO3. Calcination of the support at 700 °C produces the LaAlO3 perovskite phase and an amorphous lanthanum carbonate phase, which can be removed by calcination at higher temperature. Catalysts comprised of phase pure LaAlO3 were notably more active, with a support calcination temperature of 1100 °C resulting in 20.4% glycerol conversion (TOF 686 h−1) in a 2 h batch reaction. Interestingly, all the catalysts, regardless of LaAlO3 phase purity, eventually transform into Pt/LaCO3OH-AlO(OH) during reaction, but only in the presence of evolved carbon dioxide, itself produced from glycerol reforming. Studies using simulated reaction products showed that organic acid products (lactic acid), in the absence of CO2, facilitated La leaching and loss of crystallinity. A carbonate source (CO2) is essential to limit La leaching and form stable Pt/LaCO3OH. Pt supported on LaCO3OH and AlO(OH) are stable and active catalysts during APR reactions. Yet, the rate of perovskite phase decomposition strongly influences the final catalyst performance, with the initially phase impure LaAlO3 decomposing too quickly to facilitate Pt redistribution. LaAlO3 calcined at higher temperatures evolved more slowly and consequently produced more active catalysts.

Related Article: Oier Pajuelo-Corral, Sonia Perez-Yañez, Inigo J. Vitorica-Yrzebal, Garikoitz Beobide, Andoni Zabala-Lekuona, Antonio Rodríguez-Diéguez, José M Seco, Javier Cepeda|2022|Materials Today Chemistry|24|100794|doi:10.1016/j.mtchem.2022.100794